JPS63283743A - High-molecular protective metal colloid - Google Patents

Abstract

PURPOSE:To make bonding and solidifying with a component containing amino group by blending one kind or more of metal colloid particles selected from dispersion mediums and the elements of groups Ib, VIIb and VIII in the periodic table and high-molecules and prepating colloids. CONSTITUTION:High-molecular protective metal colloids are prepared with (a) dispersion mediums, (b) at least one kind of colloid particles selected from the elements of groups Ib, VIIb and VIII in the periodic table and (c) high- molecules. In that case, the high-molecules (c) has structural units represented by the formula I (R<1> represents H, alkyl radical or the like and R<2> represents -(CH2)n'1 (n'1 is an integer of 0-6), by the formula II (R<3> represents H, alkyl radical or the like, and R<4> represents -(CH2)n'1 (n'1 is an integer of 0-6) or the like, and also by the formula III (R<5> represents H, alkyl radical or the like, and R<6> represents hydroxyl radical).

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to polymer-protected metal colloids. More specifically, 1. The present invention relates to a novel metal colloid in which metal colloid particles are protected by a specific polymer. 0. The colloidal particles of the polymer-protected metal colloid of the present invention include:
It easily binds to amino group-containing compounds to provide a stable metal colloid immobilized product, and the resulting immobilized product is used as a solid catalyst with various properties, as well as for research on biological tissues, treatment of various diseases, and for use in royal palaces. It can be advantageously used for such purposes. (Prior Art) It is well known that when gelatin is added to a gold colloid solution, the colloid becomes significantly stable due to the protective action of gelatin and can be evaporated to dryness without color change. In addition, substances that exhibit such a protective effect are called protective colloids. In addition to gelatin, well-known protective colloids include natural polymers such as albumin, gum arabic, protalbic acid, and salvic acid. In addition, research on protective colloids has progressed in recent years, and synthetic polymers such as polyvinylpyrrolidone, polyvinyl ether, and polymethylvinyl ketone have also been shown to act as protective colloids, and in the presence of these synthetic polymers, metal ions in a solution can be It has been reported that upon reduction, a colloid of ultrafine metal particles protected with a synthetic polymer is obtained, and the resulting colloidal metal colloid particles can be used for applications such as catalysts (for example, in the industrialization of polymer catalysts). , pp. 151-179 (1981), CMC). (Problems to be Solved by the Invention) However, metal colloids using the above-mentioned natural polymers or synthetic polymers as protective colloids have various problems. That is, metal colloids using natural polymers such as gelatin as protective colloids have drawbacks such as poor colloid stability and poor reproducibility of the particle size distribution of colloid particles. In addition, in the case of metal colloids that use the synthetic polymers mentioned above as protective colloids, since the reactivity of the synthetic polymers that are protective colloids is low, metal colloid particles protected with these synthetic polymers can be used with other materials. It is difficult to chemically bond and immobilize various substances. Therefore, the use of conventional metal colloids made of these synthetic polymers as optometric colloids is extremely limited, and their practical use has been limited to olefin hydrogenation catalysts. (Means for Solving the Problem) The present inventors have discovered that the metal colloid is not only stable as a metal colloid, but is also firmly immobilized on various other substances, and is used in the conventional polymer-protected metal colloid described above. We have carried out extensive research to develop metal colloids protected by synthetic polymers that can be advantageously used in various useful applications that have not been possible before. As a result 1, the present inventors have found that specific hydrazide polymers, azide polymers, acrylic ester polymers, and acrylamide polymers not only exhibit excellent protective effects against metal colloids, but also that these specific polymers Protected metal colloid particles easily combine with various amino group-containing compounds to provide stable immobilized products, and the resulting immobilized products can be used as solid catalysts, for the treatment and diagnosis of various diseases, and for research on biological tissues. The present invention is based on the above findings. It is therefore an object of the present invention to provide novel polymer-protected metal colloids that can be advantageously used in a wide variety of applications. These and other features, features, and benefits will become apparent from the detailed description provided below. According to the invention. Cta) dispersion medium. (b) colloidal particles of at least one metal selected from the group consisting of elements of groups Ib, Vllb and VIII of the periodic table, and (C) a polymer, the colloidal particles (b) containing the dispersion medium (a ), and the polymer (C) is adsorbed to the colloid particles to protect the colloid particles as a protective colloid,
The polymer contains structural units (i), structural units (ii), and structural units (iii), and the content thereof is 1 to 1, respectively, based on the total amount of structural units (i), (ii), and (iii). 100 mol%, 0-99 mol%. 0 to 99 mol%, and the structural unit (i), the structural unit (
ii) and structural unit (iii) each have the general formula
, (II), (III) [However, R″ is a hydrogen atom, a substituted or unsubstituted carbon number 1
-6 alkyl group, substituted or unsubstituted phenyl group, hydroxyl group, 6o, -co-R or 10-R' (wherein R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or -(COP) )nu −Xn, −(CHa)na
-Yn4-(ctt, )ni -Go-R' (wherein X and Y are each independently 10- or -NH-; n
l*R2 and n are each independently an integer of 0 to 6; R
8 and R4 are each independently 0 or 1; R7 is -NH-
NH,,-A-R" means -NH; A is -〇-
or -3-;R'' is substituted or unsubstituted and has 1 to 1 carbon atoms;
0 alkyl group, substituted or unsubstituted phenyl group, or substituted or unsubstituted succinimide group), R' is the same as R above), R2 is -(CI(,)n,
' -X 'ni'-'(cut)na'-
Y'R4'-(cHi)ns'-Co-R”
(However, X', Y', nl', R2' * R3
'*R4', n%' and R7' are the same as the above-mentioned 1 to 6 alkyl groups, substituted or unsubstituted phenyl groups,
Hydroxyl group, combination 0, -Co-R or -0-R' (however, R and R' are as above), R4 is -(CH,)n,
'-X' n, '-(CHI)n, "-Y' n,
# -(CH,)n,'-Co-R' (however, X'
@Y', nl', n%. ns'', n, JF and n,' are the above-mentioned X, Y, n, respectively. n, , R3, n, and n, and R1 is -A'
-R1°, A' is the same as the above M, and R1 is a hydrogen atom, an alkali metal, an alkaline earth metal, a W1-substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group, and phenyl group, or a substituted or unsubstituted succinimide group]. (However, R1 is a hydrogen atom, l!A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group,
Hydroxyl group, 6→, -CO-R or 10-R' (however, R
and R' are as above), R@ is a hydroxyl group, 6o, -Go
-R or 10-R' (where R and R' are as above), provided that R1 is a hydrogen atom, R' is -Co-NH, and unit(…
) is 0 mole, ul is a hydroxyl group, -C
o -R or 10-R' (where R and R' are as above), and when R7 is -NH-NH, part or all of -NH-NH, the group is -N1 group Furthermore, when R1 is a hydrogen atom or a substituted or unsubstituted furkyl group having 1 to 6 carbon atoms, the structural unit (i), the structural unit (11) and the structural unit (iii)
) content of structural units (i), (ii) and (iii)
1 to 95 mole %, 0 to 90 mole %, and 5 to 99 mole %, respectively, based on the total amount of polymeric protected metal colloids. The metal constituting the colloidal particles of the polymer-protected metal colloid of the present invention is at least one metal selected from the group consisting of elements of groups 1b, , rhodium, palladium, osmium, rhenium, iridium, copper, and nickel. Further, the metal forming the colloidal particles of the polymer-protected metal colloid of the present invention is
The metals mentioned above may be radioactive. For example, radioactive gold, silver, platinum, etc. may be used. The term "metal colloid" herein refers to a dispersion system in which ultrafine metal particles (diameter = 5 to 1000 particles) are dispersed in a liquid such as water or alcohol. In the polymer-protected metal colloid of the present invention. The colloidal particles made of the above metal have the following general formula (I
) 1 to 100 mol%, preferably 10 to 50 mol%, of the structural unit (i), and 0 to 99 mol%, preferably 0 to 50 mol% of the structural unit (11) of general formula (n) and 0 to 99 mol% represented by general formula (m), preferably 30
It is protected by a polymeric protective colloid containing ~90 mol% of structural unit (iii). "protected by the protective colloid of the polymer" means that the polymer adsorbs to the colloid particles, and the protective effect of the polymer as a protective colloid 1. For example, metal colloid particles form a complex with the polymer. for example, 1 at 5 ooo revolutions/min.
This refers to a state in which colloidal particles do not precipitate even after centrifugation for 0 minutes, and as mentioned above, polymers adsorbed to colloidal particles exhibit a protective effect. A part of the polymer may exist dissolved in the dispersion medium without being adsorbed to the colloid particles. [However, nl is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms such as methyl or ethyl, a substituted or unsubstituted phenyl group, a hydroxyl group, ♂7-o, -CO-R or 10-R '(However, R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, or -(CHa)nz Xn, -(CHi)n
a-Yn, -(CH,)n, -Co-R' (however,
X and Y are each independently 10- or -NH-;
, and R5 are each independently an integer of 0 to 6; R2 and n,
are each independently 0 or l; R' is -NH-NH,
, -A -R' or -NH2; A is 10- or -5-; R'' is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted phenyl group; represents an unsubstituted succinimide group), and R
' is the same as R above), R8 is -(cow)ni'
-X'ns'(C1,)na'-Y'
R4'-(CHi)ns'=Go-R"
(However, 'L,, X', Y', J' * R2' +1
13'*R4', ng' and R7/ are the above-mentioned L Y% nx, n** "s, "4-"s, respectively
and R7)], [where R2 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms such as methyl or ethyl, a substituted or unsubstituted phenyl group, a hydroxyl group, a color →, -Co -R or 10-R' (however, R and R' are as above), R4 is -
(CH2)n1'-X'n*' -(CHa)na
'-Y' n, ' -(CH,) n, ' -Co-R
'(However, X', Y'. nz ' % nz ' s na ', n, #
and nl are the above-mentioned X, Y, ni, "*sn3, respectively
, n, and n, and nl is -A'-H11
1, and A' is the same as A above. R1@ is a hydrogen atom, an alkali metal, an alkaline earth metal,
Substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, W1
substituted or unsubstituted); nyl group, or substituted or unsubstituted succinimide group].

[However, Rs is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms such as methyl or ethyl, a II-substituted or unsubstituted phenyl group, a hydroxyl group, 1-C〇-R or 10- R' (However, R and R' are as above), R'
is a hydroxyl group, -Go -R or 10-R' (however,
R and R' are as described above]. In the above general formulas (1), (II), and (m), substituents for alkyl groups having 1 to 6 carbon atoms or 1 to 10 carbon atoms include halogen, alkyl groups having 1 to 6 carbon atoms, hydroxyl groups, Examples include a nitro group, a cyano group, a carboxyl group, and a phenyl group. Substituents for the phenyl group include halogen, alkyl group having 1 to 6 carbon atoms, hydroxyl group,
Examples include a nitro group, a carboxyl group, and a phenyl group. As the substituent for the above succinimide group,
Examples include halogen, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, and a phenyl group. In the present invention, HA is a hydrogen atom and am is 100-
When it is NH and the content of the structural unit (ii) is 0 mol%, R' is a hydroxyl group, -Co-R, or 10-R' (however, R and R' are as described above). a R
When ' is -NH-NH, some or all of -
NH-NH, group may be substituted with -N3 group,
Further, Hall is preferably a substituted or unsubstituted carbon number 1
~10 alkyl groups or substituted or unsubstituted phenyl groups. Furthermore, the structural unit shown in the above general formula (1) (
In i), when nl is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, the structural unit (i), the structural unit (i)
i) and the amount of structural unit (iii) is structural unit (i). 1 to 95 each based on the total amount of (ii) and (iii)
Mol%, preferably 10-50 mol%, 0-90 mol%
, preferably 0 to 50 mol%, and 5 to 99 mol%, preferably 30 to 90 mol%. The molecular weight of the polymer composed of the structural units shown above is preferably 800 to 1,000,000, more preferably 1,500 to 50,000. The molecular weight of this polymer was determined by gel permeation chromatography (GPC).
It can be measured by Dispersion media for the polymer-protected metal colloid of the present invention generally include water, linear or branched alcohols having 1 to 10 carbon atoms, and water-soluble ethers such as dioxane.
and mixtures thereof. Preferred are water, methanol and ethanol and mixtures thereof. The amount of the dispersion medium used is preferably 10 to 500 moles, more preferably 50 to 500 moles, per 1M metal particles of the colloidal particles. Further, the amount of the above-mentioned polymer which is a protective colloid is preferably 1 to 100 as the total number of moles of structural units (i), (ii) and (iii) per 1M metal molecules of the colloidal particles.
o mol, more preferably 5 to 50 mol. The polymer-protected metal colloid of the present invention can be produced, for example, by the method described below, but is not limited to these methods. Method! = A metal ion-containing solution is prepared by dissolving a metal compound corresponding to the metal component of the polymer-protected metal colloid to be produced in a solvent. The metal compound used may be one that is soluble in a solvent in the presence of a polymer, such as halides and nitrates. Sulfates, carbonates, hydroxides, etc. are used. As the solvent, water, linear or branched alcohols having 1 to 10 carbon atoms, water-soluble ethers such as dioxane, and mixtures thereof are generally used, preferably water, methanol, and ethanol. and mixtures thereof are used. The amount of the solvent in this case is preferably 10 to 5000 mol, more preferably 50 to 500 mol, per 1 fM metal element. Next, a polymer consisting of the structural units shown above is added to the prepared solution. The amount of polymer added is preferably 1 to 1000 mol as the total number of moles of structural units (i), (ii), and (iii) per 1 metal atom. The amount is preferably 5 to 50 moles. The polymer-protected metal colloid of the present invention is obtained by reducing the polymer-containing solution thus obtained. Although the reduction treatment method is not particularly critical, it is generally carried out using photoreduction or a reducing agent. For example, when the reduction treatment is performed by photoreduction. After freezing and degassing the polymer-containing metal solution obtained above several times, the degassing solution was heated with a high-pressure mercury lamp and a low-pressure mercury lamp. This is carried out by irradiating with a tungsten lamp, an argon laser, etc., generally for 1 minute to 50 hours, preferably for 30 minutes to 30 hours. On the other hand, when performing sangen treatment using a reducing agent. A reducing agent is added to the polymer-containing metal solution obtained above at a molar ratio of 1 to 50. Preferably 1.5-10
The polymer-protected metal colloid of the present invention can be obtained by adding at a ratio of 1 to 100°C and stirring at 10 to 100°C for 1 minute to 10 hours. In this case, the reducing agent used is generally formaldehyde, hydrazine, sodium borohydride, alcohol having 1 to 6 carbon atoms, etc. (For example, New Experimental Chemistry Course 15, Oxidation and Reduction [■], pp. 29-332) 1977
), Maruzen Co., Ltd.], the reduction treatment may also be carried out by bringing hydrogen into contact with the aqueous solution. Method ■: Precursor of a polymer consisting of the structural units threaded above [i.e., a precursor of a polymer (polymer group) in which R7 is -NH-NH; Hl is -A -R'' (A and R A precursor of a polymer (polymer B) where R7 is -NH); and a precursor of a polymer (polymer C) where R7 is -NH] are produced by the method described below.This precursor A metal colloid solution protected with each precursor of polymers A, B, and C is prepared by the same method as method 1 except that each of these is used in place of the polymer in method!.Each colloid solution thus obtained are treated as follows to obtain the polymer colloid of the present invention. That is, a polymer protected with a precursor of polymer A (a polymer in which R' is -N)I-NH) In the case of a colloid, by subjecting this colloid solution to hydrazine treatment, the precursor of polymer A is hydrazidized, and the polymer-protected metal colloid of the present invention is obtained. Adding hydrazine to the colloidal solution obtained above at a ratio of 0.1 to 100 mol per 1 mol of the structural unit (ii) represented by the above general formula (ff) in
Temperature of 10°C or higher and lower than the boiling point of the solvent, preferably 3°C
This can be carried out by stirring at 0 to 80°C for generally 30 minutes to 10 hours. In the case of a colloid protected with a precursor of polymer B (a polymer in which R' is -AR''), this colloid solution is subjected to esterification or thioesterification treatment to form polymer B.
The polymer-protected metal colloid of the present invention is obtained by esterifying or thioesterifying the precursor. The esterification and thioesterification methods are not particularly limited, and may be carried out by the conventional method 1, for example, by refluxing in the presence of an alcohol or thioalcohol using an acid as a catalyst to remove the generated water, or by reacting with thionyl chloride. After this, alcohol or thioalcohol may be applied. [For example, New Experimental Chemistry Course 14. Synthesis and Reactions of Organic Compounds [■], pp. 1000-1062 (1977), published by Maruzen Co., Ltd.]. In the case of a colloid protected with a precursor of polymer C (a polymer in which R' is -NH), this -colloid solution is treated with ammonia to transform the precursor of polymer C into an amide group-containing precursor. By making it into a polymer, the polymer-protected metal colloid of the present invention can be obtained. The ammonia treatment is performed, for example, by the structural unit (ii) represented by the above general formula (II) in the polymer precursor.
Ammonia is added in the form of an aqueous solution to the above-obtained colloidal solution at a ratio of 0.1 to 100 mol per 1 mol of the amount of ammonia, or alternatively, ammonia gas is blown into the colloidal solution. A temperature of 0°C or higher and lower than the boiling point of the solvent, preferably 10°C
This can be carried out by stirring at ~80°C for generally 30 minutes to 10 hours. [For example, New Experimental Chemistry Course 14. Synthesis and reactions of organic compounds [■]. See pages 1134-1189 (1977), published by Maruzen Co., Ltd.]. Method (2): A metal ion-containing solution is obtained in the same manner as the above-mentioned method (2). This solution is subjected to a reduction treatment in the same manner as in Method ① to obtain a metal colloid. Add to this a polymer consisting of the structural units shown above, preferably 1 to 1000 moles, more preferably In addition to the metal colloid, the polymer-protected metal colloid of the present invention can be obtained in a proportion of 5 to 50 moles. (The following is a blank space) A polymer containing the structural unit shown above can be produced by a conventional method. An example of its manufacturing method is shown below. R7 is -NH-NH; A 1 to 100 mol% of a monomer represented by the following general formula (IV);
For example, polymerization using a radical initiator, photopolymerization,
After polymerizing by radiation polymerization, cationic polymerization, etc. to obtain a precursor of the polymer (polymer A) as a protective colloid used in the present invention, this is reacted with hydrazine to form a hydrazide, thereby forming polymer A. can be obtained. [However, zl is a hydrogen atom, substituted or unsubstituted carbon number 1
-6 alkyl groups, substituted or unsubstituted phenyl groups, hydroxyl groups, gutters. , -co-z" or 10-21' (however, 21' is a carbon number of 1, such as methyl, ethyl, and propyl)
~10 alkyl groups or -(CH,)m, -X's,
-(CH,)m, -Y"m, -(C1,)m, -GO-
NH-NH, (where xl and Yl are each independently 10- or -NO-', rai, proverb, and - are each independently an integer from 0 to 6; -2 and vote are each independently 0 or 1), and zl is an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, and propyl, or -(CHx1m
□'-X"m2'-(CHI)113' -
Y” ' ■4 ' - (cut) intestine,' -
co-α' (however, x1' and Y'' are each independently 10- or -NH-; α' is -NH,, -γ'-β'
(However, γ' is 10- or -S-; β' is hydrogen, an atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a phenyl group, a nitro group, or an alkyl group. a substituted or unsubstituted phenyl group such as a phenyl group substituted with a phenyl group, a substituted or unsubstituted succinimide group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group)
, ■, '1ms' and I each independently represent an integer of 0 to 6, ' and ■4' each independently represent 0 or 1)) zl is -(CH2)mu' -X "ll='
-(CI,)m3'-'l'''m,' -(CH,
)m,' -C0-α (However, ILz and Y■ are each independently 10-formed.

[Or -NH-; α is -NHa, -γ-β (However, γ is 10- or -S-; β is a hydrogen atom, an alkali metal, an alkaline earth metal, a substituted or unsubstituted carbon number 1 ~10 alkyl groups, phenyl groups, nitro groups, substituted or unsubstituted phenyl groups such as phenyl groups substituted with alkyl groups, or substituted or unsubstituted succinimide groups, preferably substituted or unsubstituted carbon atoms of 1 to 10 an alkyl group, a phenyl group, or a phenyl group substituted with a nitro group or an alkyl group, etc.), m1#, m, # and m♂ each independently represent an integer of 0 to 6; each independently indicates 0 or 1)]. [However, zl is a hydrogen atom or a substituted or unsubstituted alkyl having 1 to 6 carbon atoms such as methyl and ethyl -zL-(
However, zl' and zLN are as above)]. Typical examples of monomer compounds represented by the general formula (IVI) include acrylamide, methacrylamide, N-dimethylacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, and methacrylic acid. Substituted or unsubstituted acrylic esters and methacrylic esters, such as phenyl, varanitrophenyl ester of acrylic acid, varanitrophenyl ester of methacrylic acid, trifluoroethyl ester of acrylic acid and trifluoroethyl ester of methacrylic acid, Examples include thiophenyl ester, 4-nitrothiophenyl ester of methacrylic acid, succinimide ester of acrylic acid, and succinimide ester of methacrylic acid.On the other hand, as a representative example of the monomer compound represented by general formula (V), Examples include N-vinylpyrrolidone, substituted N-vinylpyrrolidone, vinyl alcohol, methyl vinyl ether, ethyl vinyl ether, and methyl vinyl ketone.Compounds represented by general formula (IV) and compounds represented by general formula (V) The copolymerization with can be carried out by a conventional method, for example, radical polymerization using benzoyl peroxide, azobisisobutylnitrile, potassium beroxonisulfate, etc. as a polymerization initiator, photopolymerization, radiation polymerization, cationic polymerization, etc. [For example, New Experimental Chemistry Course 19. Polymer Chemistry [I
], pp. 46-48 (1978), Maruzen Co., Ltd.],
still. When obtaining a copolymer containing structural unit (i) and structural unit (ii) or a copolymer containing structural unit (i), structural unit (ii) and structural unit (iii), the general formula ( The ratio of the monomer represented by mV) to the monomer represented by general formula (V) varies depending on the type of monomer used, but is generally a molar ratio of 0.1:100. The polymer obtained by the above method (precursor of a polymer used as a protective colloid) is reacted with hydrazine,
A polymer (polymer A) in which 7 is -NH-NH is obtained. The reaction between hydrazine and the polymer obtained by the above method involves dissolving the polymer in water, a linear or branched alcohol having 1 to 10 carbon atoms, a water-soluble ether such as dioxane, and mixtures thereof. Then, hydrazine is added to the structural unit (ii) represented by the above general formula (II) in the polymer! Added at a ratio of 0.1 to 100 mol to 1 mol 1
A temperature of 0°C or higher and lower than the boiling point of the solvent, preferably 30°C
The reaction is generally carried out for 30 minutes to 10 hours at ~80°C. In the above reaction, when one polymer is a homopolymer of the compound of the above general formula (IV), one α group (however, α is as described above) contained in the polymer is completely decomposed with hydrazine to -NH -NH, In one case, the structural unit (
i) is obtained, partially containing -NH-NH
, a polymer consisting of structural units (1) and (11) is obtained. On the other hand, when the polymer is a copolymer of the above compound (IV) and [■], the -NH -NH
, when converted into groups, a polymer containing structural units (i) and (ii) is obtained; (iii
) is obtained. R7 is -A-R'' B 1 to 100 mol% of a monomer represented by the following general formula (VI) and 0 to 99 mol% of a monomer represented by the following general formula [■] For example, polymerization using a radical initiator, photopolymerization,
Polymer B can be obtained by polymerizing by radiation polymerization, cationic polymerization, or the like. In addition, the following general formula [■
] and 0 to 99 mol% of a monomer represented by the following general formula [■], for example, by polymerization using a radical initiator, photopolymerization, radiation polymerization. , and cationic polymerization to obtain a precursor of the polymer (polymer B) as a protective metal colloid used in the present invention, which can then be reacted with alcohol or thioalcohol. . z [However, z5 and 2@ are the same as R1 and R2, respectively]
. [However, 2? and zl are the same as R1 and R@, respectively]
. [However, zl and 21'' are the same as R3 and R4, respectively]. Typical examples of monomer compounds represented by general formula (VI) include methyl acrylate and methyl methacrylate. Ethyl acrylate, ethyl methacrylate, and acrylate.・Substituted or unsubstituted acrylic esters and methacryl, such as phenyl runate, phenyl methacrylate, varanitrophenyl acrylic acid, varanitrophenyl methacrylic acid, trifluoroethyl acrylic acid, and trifluoroethyl ester of methacrylic acid. Acid ester. Examples include thiophenyl ester of acrylic acid, 4-nitrothiophenyl ester of methacrylic acid, succinimide ester of acrylic acid, succinimide ester of methacrylic acid, etc. On the other hand, monomers represented by the general formula [■] Representative examples of the compound include N-vinylpyrrolidone, substituted N-vinylpyrrolidone, vinyl alcohol, methyl vinyl ether, ethyl vinyl ether, and methyl vinyl ketone.In addition, monomers represented by the general formula [■] Representative examples of the compound include acrylic acid, methacrylic acid, alkali metal salts or alkaline earth metal salts of acrylic acid, and alkali metal salts or alkaline earth metal salts of methacrylic acid.Represented by the general formula [■] Copolymerization of the compound with the compound represented by the general formula [■] or copolymerization of the compound represented by the general formula [■] with the compound represented by the general formula (■) can be carried out by a conventional method, such as benzoyl peroxide, azo It can be carried out by radical polymerization, photopolymerization, radiation polymerization, cationic polymerization, etc. using bisisobutylnitrile, potassium beroxonisulfate, etc. as a polymerization initiator. [For example, New Experimental Chemistry Course 19. Polymer Chemistry (!), No. 46 -48 pages (1978
), published by Maruzen Co., Ltd.), and the ratio of the amount of the monomer represented by the general formula [■] or general formula [■] to the monomer represented by the general formula (■] depends on the monomer used. Although it varies depending on the type of polymer, the molar ratio is generally 0.1:100. In addition, the compound represented by the general formula [■] and the compound represented by the general formula [■] are copolymerized, and the compound represented by the general formula [■] is protected in the present invention. After obtaining a precursor of a polymer (polymer B) to be used as a colloid, in order to obtain a polymer to be used as a protective colloid from this precursor, the obtained polymer precursor is subjected to esterification or thioesterification treatment. There are no particular limitations on the methods of esterification and thioesterification, and for example, the precursor may be refluxed in the presence of an alcohol or thioalcohol using an acid as a catalyst to remove the water produced. After reacting with thionyl chloride, alcohol or thioalcohol may be reacted. [For example, New Experimental Chemistry Course 14. Synthesis and Reaction of Organic Compounds [■], pp. 1000-1062 (1977), Maruzen. Co., Ltd.], typical examples of alcohols used here include methanol, ethanol, propyl alcohol, butanol, phenol, cresol, 4-nitrophenol, and 2,2,2-trifluoroethanol. In addition, as the thioalcohol, thiophenol, 4-nitrothiophenol, thiobutanol, etc. can be used. In the above esterification or thioertherification, the precursor is a homopolymer of the compound of the general formula [■] If it is,
When the carboxyl groups contained in the precursor are completely esterified or thioesterified, a polymer consisting of structural unit (i) can be obtained. When partially esterified, structural units (i) and (
...) is obtained.゛On the other hand, when the precursor is a copolymer with the above general formula [■)k(■], when the carboxyl group contained in the precursor is completely eruterized or thioesterified, the structural unit (1) and (ffl)
When a polymer consisting of structural unit (i) and structural unit (1) is obtained and partially esterified or thioesterified, structural unit (i)
1) and a structural unit (U) is obtained. R7 is -NH C 1 to 100 mol% of a monomer represented by the following general formula (IK) and the following general formula (X Polymer C can be obtained by polymerizing 0 to 99 mol% of the monomer represented by ), for example, by polymerization using a radical initiator, photopolymerization, radiation polymerization, cationic polymerization, etc. For example, 1 to 100 mol% of a monomer represented by the following general formula [Summer] and 0 to 99 mol% of a monomer represented by the following general formula (X) are polymerized using a radical initiator. , a polymer (polymer C) that is polymerized by photopolymerization, radiation polymerization, cationic polymerization, etc. and used as a protective colloid in the present invention.
It can also be obtained by obtaining a precursor of and then reacting it with ammonia. [However, zLIL and z18 are the same as R1 and R2, respectively]. [However, zll and z14 are the above R1 and R, respectively.
6], [However, zls and zll are the above R″ and R, respectively.
Same as 4]. Representative examples of compounds represented by the general formula CIK) include acrylamide, methacryla, mido, N,N-dimethylacrylamide. On the other hand, representative examples of the compound represented by the general formula (X) include N-vinylpyrrolidone, substituted N-vinylpyrrolidone,
Examples include vinyl alcohol, methyl vinyl ether, ethyl vinyl ether, and methyl vinyl ketone. Representative examples of the compound represented by the general formula (XI) include acrylic acid, methacrylic acid, alkali metal salts or alkaline earth metal salts of acrylic acid, alkali metal salts or alkaline earth metal salts of methacrylic acid, methyl acrylate. , methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, phenyl methacrylate, varanitrophenyl ester of acrylic acid, varanitrophenyl ester of methacrylic acid, trifluoroethyl ester of acrylic acid and trifluoro methacrylate Substituted or unsubstituted acrylic esters and methacrylic esters such as ethyl esters. Examples include thiophenyl ester of acrylic acid, thiophenyl ester of methacrylic acid, succinimide ester of acrylic acid, and succinimide ester of methacrylic acid. The copolymerization of the compound represented by the general formula CIIC) and the compound represented by the general formula (X) or the copolymerization of the compound represented by the general formula [Wataru] and the compound represented by the general formula (X) can be carried out by a conventional method. For example, radical polymerization using penzoyl peroxide, azobisisobutylnitrile, potassium beroxonisulfate, etc. as a polymerization initiator, photopolymerization, radiation polymerization, cationic polymerization, etc. can be carried out. [For example, New Experimental Chemistry Course 19. Polymer Chemistry [■], pp. 46-48 (19
78), published by Maruzen Co., Ltd.], and the ratio of the usage amount of the monomer represented by the general formula (IK) or the general formula (X[] to the monomer represented by the general formula (X) is Although it varies depending on the type of monomer used, the molar ratio is generally 0.1:100.A protective colloid is obtained by copolymerizing a compound represented by the general formula [X] and a compound represented by the general formula (X). After obtaining a precursor of the polymer (polymer C) used as The method of ammonia treatment is not particularly limited and may be a conventional method, such as dissolving the precursor in water, a linear or branched alcohol having 1 to 10 carbon atoms, a water-soluble ether such as dioxane, or a mixture thereof. Thereafter, ammonia is added in the form of an aqueous solution at a ratio of 0.1 to 100 mol per mol of the structural unit (ii) represented by the general formula (II) above, or ammonia gas is blown into the solution. ℃
temperature above and below the boiling point of the solvent, preferably 10 to 8
The reaction is generally carried out at 0° C. for 30 minutes to 10 hours at normal pressure. or,
Ammonia treatment may be performed under pressure. In the above ammonia treatment, if the -A'-null group contained in one polymer (A' and HAg+ are as described above) is completely reacted with ammonia and converted into -NH, the structural unit A polymer consisting of (1) and Oo is obtained, and when partially converted to -NH, a polymer containing structural units (i), (11) and (iii) is obtained. The polymer-protected metal colloid of the present invention obtained as described above is very stable over a long period of time. The colloidal particles bind to various amino group-containing compounds to give stable immobilized substances, and the resulting immobilized substances can be used as solid catalysts with various properties, in the treatment and diagnosis of various diseases, in the study of biological tissues, and in biological systems. It can be advantageously used for various purposes such as inducing mutations in. (Left below) Immobilization of the polymer-protected metal colloid of the present invention onto an amino group-containing compound is as follows:
This is carried out by bringing the amino group in the amino group-containing compound into contact with the polymer adsorbed on the colloid particles by bringing it into contact with the amino group-containing compound and forming a chemical bond between the amino group-containing compound and the polymer. be able to. The contact between the polymer-protected metal colloid and the 7-mino group-containing compound can be carried out, for example, in a solvent using means such as stirring. The contact time is generally 10 minutes to 30 hours, preferably 30 minutes to 10 hours. Any amino group-containing compound can be used as long as it has an amino group for immobilization of the polymer-protected metal colloid. Examples thereof include homopolymers or copolymers of vinyl compounds having primary and/or secondary amino groups, nucleic acids, or proteins. Typical examples of homopolymers or copolymers include poly(
Aminostyrene polymers such as 4-aminostyrene) and copolymers of 4-aminostyrene and styrene, and crosslinked products thereof 1 For example, ion exchange resins having primary and/or secondary amino groups, polyallylamine and crosslinked products thereof and aminoalkyl (CZ-CS) polyacrylamide. Examples of amino group-containing compounds include nucleic acids containing amino groups such as DNA and RNA;
Nucleic acids such as thymidylic acid into which amino groups have been introduced; hormones such as eitumerase, peroxidase, urease, ATPase, and insulin. Examples include antigens and antibodies; carbohydrates such as heparin, mucopolysaccharides, and keratan sulfate into which amino groups have been introduced; and lipids into which amino groups have been introduced. In the case of a compound that does not have an amino group, an amino group can be chemically introduced into the compound and used as an amino group-containing compound. The amount of the amino group-containing compound used is the amount of the hydrazide group, ester group, thioester group, and amide group in the polymer that is the protective colloid with respect to the polymer-protecting metal colloid.
0.1-100 mole to mole, preferably 1-10
It is a mole. As the solvent, water, linear or branched alcohols having 1 to 6 carbon atoms, and mixtures thereof are generally used, and preferably water, methanol, ethanol, and mixtures thereof are used. The amount of the solvent is generally 10 to 1000 mol, preferably 50 to 300 mol, per 1 mol of amino groups in the amino group-containing compound. The immobilization reaction can generally be carried out at -20 to 100°C, but when immobilizing to natural polymers such as proteins, the immobilization reaction is carried out at a low temperature of -10 to 20°C to prevent denaturation of the natural polymer. It is preferable to do this. The pH when performing the immobilization reaction is not critical and is generally pH
4 to 10. R7 of the polymer in the polymer antiseptic metal colloid to be brought into contact with the amino group-containing compound is -NH-NH or -NH. In the case of The polymer-protected metal colloid particles can be immobilized on the amino group-containing compound via the residues of the bifunctional compound by contacting the polymer-protected metal colloid with the amino group-containing compound. In this manner, the reactivity of the polymer-protected metal colloid can be increased by reacting the polymer-protected metal colloid with the above bifunctional compound prior to contacting the polymer-protected metal colloid with the amino group-containing compound. Examples of bifunctional compounds reactive with amino groups include compounds having two functional groups selected from aldehyde groups, isocyanate groups, maleimide groups, coded acetamide groups, and diazobenzidine groups. A specific example is 0HC-(C1la)
Dialdehydes such as glutaraldehyde represented by n-CHO (where n is an integer of 0 to 7), hexamethylene diisocyanate, N,N'-ethylene bismaleimide, N. N'-polymethylene biiodoacetamide, bisdiazobenzidine, etc. can be mentioned. The reaction between the polymer-protected metal colloid and the above compound is carried out by reacting the polymer-protected metal colloid with the above compound in a solvent such as water, a linear or branched alcohol having 1 to 6 carbon atoms, or a mixture thereof. This can be carried out by stirring at a temperature of 1 to 20 hours. The amount of the difunctional compound used at this time is 1 to 50 mol, preferably 1 mol, per 1 mol of the hydrazide group and amide group in the polymer that is the protective colloid.
．． 5-20 moles. The amount of solvent is generally 5 to 2 per mole of difunctional compound.
00 moles. After separating the obtained reaction product from the reaction mixture, or as a reaction mixture, it can be immobilized by contacting it with an amino group-containing compound under the same conditions as the above-mentioned contact between the polymer-protected metal colloid and the amino group-containing compound. can. Furthermore, the polymer-protected metal colloid and the amino group-containing compound are brought into contact with each other in the presence of the above-mentioned bifunctional compound that is reactive with amino groups, so that the particles of the polymer-protected metal colloid are
It may be immobilized on the amino group-containing compound.The amount of the amino group-containing compound used in this case is 0 to 1 mole of the hydrazide group and amide group in the polymer that is the protective colloid with respect to the polymer-protecting metal colloid. .1 to 100 mol, preferably 1 to 10 mol, and the amount of difunctionalized metal is 1 to 50 mol, preferably per 1 mol of hydrazide group and amide group in the polymer that is the protective colloid. is 1.5-20
This contacting can generally be carried out in a solvent. As the solvent, water, linear or branched alcohols having 1 to 6 carbon atoms, and mixtures thereof are generally used, and preferably water, methanol, ethanol, and mixtures thereof are used. The amount of the solvent is generally 10 to 1000 mol, preferably 50 to 300 mol, per 1 mol of the amino group in the amino group-containing compound.The reaction temperature is generally 0.
-100°C, and immobilization is achieved by stirring for 1 to 20 hours. As described above, the polymer-protected metal colloid is reacted with the above bifunctional compound prior to contact with the amino group-containing compound, or the polymer-protected metal colloid and the amino group-containing compound are reacted with the above bifunctional compound. By contacting in the presence of a compound, the reactivity of the polymer-protected metal colloid can be increased. When R7 of the polymer in the polymer-protected metal colloid to be brought into contact with the amino group-containing compound is -NH-NH,
Prior to contacting the polymer-protected metal colloid with the amino group-containing compound, the polymer-protected metal colloid is reacted with nitrous acid or a nitrite salt, such as sodium nitrite, to form an azide, and the resulting product is converted into an azide containing an amino group. Particles of the polymer-protected metal colloid may be immobilized on the amino group-containing compound by contacting the polymer-protected metal colloid with nitrous acid or nitrite. 1 to 10 moles of nitrous acid or nitrite per mole of hydrazide group in a certain polymer is added to water,
This can be carried out by stirring at 10 to 60° C. for 1 to 10 hours in a solvent such as a linear or branched alcohol having 1 to 6 carbon atoms, or a mixture thereof. The amount of solvent is generally from 5 to 200 moles per mole of nitrous acid or nitrite. After the resulting reaction product is separated from the reaction mixture, it is immobilized by contacting it with an amino group-containing compound under the same conditions as the above-mentioned contact between the polymer-protected metal colloid and the amino group-containing compound. . Furthermore, particles of the polymer-protected metal colloid may be immobilized on the amino group-containing compound by bringing the polymer-protected metal colloid into contact with the amino group-containing compound in the presence of nitrite or nitrite. The amount of nitrous acid or nitrite used in this case is 1 to 10 mol per 1 mol of hydrazide group in the polymer, and the amount of the amino group-containing compound is 1 to 10 mol per mol of hydrazide group in the polymer. The amount is 0.1 to 100 mol, preferably 1 to 10 mol. This contact can generally be carried out in a solvent. As a solvent, is water, carbon number 1~
6, a straight chain or branched alcohol, a mixture thereof, etc. are used, and the amount thereof is generally 5 to 200 mol per 1 mol of nitrous acid or nitrite.The reaction temperature is generally 0 to 100 mol. ℃, and immobilization is achieved by stirring for 1 to 20 hours. As mentioned above, the polymer-protected metal colloid may be reacted with nitrous acid or nitrite prior to contact with the amino group-containing compound, or the polymer-protected metal colloid and the amino group-containing compound may be reacted with nitrous acid or nitrite. By contacting in the presence of nitrate, the reactivity of the polymeric metal colloid can be increased. In the contact between the polymer-protected metal colloid and the amino group-containing compound, it can be confirmed as follows that the polymer-protected metal colloid particles are fixed to the amino group-containing compound. If the amino group-containing compound is insoluble in the solvent, the color of the liquid phase (for example, a copolymer of acrylamide and N-vinyl-2-pyrrolidone) may change during contact of the amino group-containing compound with the polymer-protected metal colloid. In the case of a platinum colloid protected with a hydrazide, the color (blackish brown) gradually becomes lighter, and it can be confirmed by the coloration of insoluble amino group-containing compounds. Alternatively, after one reaction, the product may be sufficiently washed with water or alcohol, dissolved in aqua regia, etc., and subjected to atomic absorption spectrometry to confirm the presence of metals. On the other hand, when the amino group-containing compound is soluble in the solvent, the colloid particles bond to the dissolved amino group-containing compound to form an immobilized substance. The reaction mixture containing the generated immobilized product is subjected to gel permeation chromatography, and a peak appears at a position different from that of the starting amino group-containing compound and the polymer contained in the polymer-protected metal colloid. You can check it. When the amino group-containing compound is an enzyme, confirmation can be made by flowing the reaction mixture through a column on which a substrate specific to the enzyme is immobilized, and by adsorbing the immobilized substance on the column. The immobilized polymer-protected metal colloid obtained as described above can be used for various purposes as it is dispersed in a solvent. Depending on the situation, it may be used after being separated by various filtration means, column chromatography, or the like. As mentioned above, the polymer-protected metal colloid of the present invention can be advantageously used in a wide variety of applications, such as:
By immobilizing polymer-protected metal colloid particles on a solvent-insoluble amino group-containing compound such as an ion exchange resin made of polyallylamine and its crosslinked product or polyaminostyrene and its crosslinked product described above, hydrogenation of olefin can be achieved. Solid catalysts that are effective for hydrogenation, hydrogenation of dienes, hydration of nitriles, etc. can be produced. After use, such a solid catalyst can be easily separated from the reaction mixture by decantation, passing, or the like. The recovered catalyst can be repeatedly reused. Furthermore, polymer-protected metal colloid particles are immobilized on amino groups contained in enzymes, nucleic acids, antigens, antibodies, etc., and used for research on biological tissues and treatment and diagnosis of various diseases. It can be used for purposes such as inducing mutations in microorganisms.6For example, the structure of the complex of tropomyosin and troponin, which exists in muscle tissue, has been studied using various methods such as X-ray diffraction. However, since trobonin cannot be seen with an electron microscope, the binding state of troponin and tropomyosin can be directly examined using an electron microscope. I couldn't figure it out. However, when troponin on which polymer-protected metal colloidal particles are immobilized is reacted with tropomyosin to form a complex, it is observed using an electron microscope. Polymer-protected metal colloid particles immobilized on trobonin are observed using an electron microscope, and the bonding position between tropomyosin and trobonin can be directly confirmed using an electron microscope. In addition, when the metal of the polymer-protected metal colloid is a radioactive metal such as radioactive gold, platinum, or silver, antibodies to which the polymer-protected metal colloid particles are immobilized can be administered into the body to diagnose cancer or to Treatment can be performed. Also, polymers fixed to oligomers of nucleic acids that have cytosine and/or adenine residues in the part unrelated to genetic information (nonsense code part), or that have amino groups introduced by chemical modification into the nonsense code part. Protective radioactive metal colloids can be introduced into bacteria such as Escherichia coli or yeast, which are used as hosts when producing polypeptides through genetic engineering, and then cultured to induce mutations in the host using the radiation emitted by the radioactive metal. , high temperature stability. Mutant strains improved in terms of acid resistance, alkali resistance, increased growth rate, etc. can be obtained. (The following is a blank space) (Examples) The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. 01L 1.5g of acrylamide, 22g of N- in 16g of water
Add vinyl-2-pyrrolidone and 0.05g benzoyl peroxide. The resulting mixture is stirred at 80° C. for 12 hours to obtain a copolymer of acrylamide and N-vinyl-2-pyrrolidone. NMR spectrum analysis of the resulting copolymer revealed that the acrylamide content in the copolymer was 37.
It turns out that it is in moles. 2 g of the copolymer synthesized above was dissolved in 50 ffi1 water and heated on a 50°C water bath for 45 minutes, then 9 g of hydrazine l hydrate was added thereto, and the mixture was heated to 50°C while stirring with a magnetic stirrer. Let it react for 6 hours. Add 1000g of this solution to 1
．． When poured into 4-dioxane, a white precipitate forms. After removing the supernatant by decantation, the supernatant is vacuum dried to obtain a purified hydrazided acrylamide-N-vinyl-2-pyrrolidone copolymer. The hydrazide group in this copolymer was added using biochemistry (
Biochemistry, published in 1969, volume 8, page 4074, the amount is 0.38 milliequivalent per gram of copolymer. In addition, the molecular weight of the hydrazide copolymer obtained above was measured by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo ■ Co., Ltd. Hpw-soon column (filling material: TS
K-GEL) ; solvent, water] is about 28. Go
0.11 g of the hydrazide copolymer was added to 50 m of a mixed solvent of ethanol and water (volume ratio = 1:1).
Dissolve in l. Add 5 ml of a 1.1 x 10'' 1 mol/liter aqueous potassium tetrachloroplatinate solution to this. After freezing and degassing twice, while stirring using a magnetic stirrer,
Irradiated with light for 2 hours using a 500W high-pressure mercury lamp to obtain platinum colloid protected by a hydrazide copolymer as a blackish brown homogeneous solution.Measurement using a HU-12A transmission electron microscope at Hitachi Membrane Manufacturing Co., Ltd. It can be seen that the platinum colloid particles with a particle size of 30 mm are well dispersed. This colloid is extremely stable, with no platinum colloid particles precipitated even after centrifugation at 5,000 rpm for 10 minutes, and no platinum colloid particles formed even after being left at room temperature for more than a month. do not have. LL 5 g of a 14% 11% glutaraldebide aqueous solution was added to the platinum colloid protected with the hydrazide copolymer obtained in Example 1, and after reacting at pH 7, 2, and 32°C for 12 hours, Sephadex was added. (Sephadex) G-25 column (Pharmacia tS, Sweden). To the purified product obtained, troponin 5B collected from a rabbit was added and reacted at 4°C for 12 hours to form polymer-protected platinum colloid particles. is fixed on trobonin. A part of the resulting reaction solution was subjected to gel permeation chromatography [Analysis conditions: PV-S manufactured by Toyo Soda Kogyo Co., Ltd.
ooo column (filling material: TSK-GEL); solvent, water]
When analyzed, a peak appears at a position different from that of trobonin and the polymer present in the colloid, confirming that the polymer-protected platinum colloid particles are immobilized on troponin. At this time, a fraction of the m chemotactic product is collected and the amount of immobilized troponin is determined by amino acid analysis. As a result, it was found that 0.04 mole of troponin was immobilized per mole of the structural unit containing a glutaraldehyde group in the polymer.Next, 20 g of the reaction solution obtained above was mixed with loose crystals of rabbit tropomyosin. Add 50mg, pH 7
, 5°C for 12 hours at 4°C to obtain a complex of troponin and trobomyosin on which polymer-protected colloidal platinum particles are immobilized. This complex was stained with 1% uranyl acetate and subjected to an electron microscope JEM100-CX (JEOL, magnification: x3).
0), 5OO). The results are shown in Figure 1. As is clear from Figure 1, polymer-protected platinum microparticles and tropomyosin immobilized on troponin were observed under a microscope.
The bonding position between troponin and tropomyosin can be directly observed using an electron microscope. As described above, by using the polymer optometric metal colloid of the present invention as a label, it is possible to observe the state of bonding between proteins in living tissues using an electron microscope. A hydrazide copolymer was obtained in the same manner as in Example 1. 0.047 g of the hydrazide copolymer was dissolved in 15 ml of a mixed solvent of ethanol and water (volume ratio = 1:l). Add 5 ml of an aqueous solution of potassium tetrachloroplatinate of 4 x 10-" mol/liter to this. After freezing and degassing twice, stir at 500 V using a magnetic stirrer.
Light is irradiated using a high-pressure mercury lamp. The color of the solution gradually becomes blackish brown, and after 2 hours, a platinum colloid protected by the hydrazide copolymer is obtained as a blackish brown homogeneous solution. When the resulting colloid was measured using a new model HU-12A transmission electron microscope manufactured by Hitachi, it was found that platinum particles with an average particle size of 40 mm were well dispersed. 7.215. to the platinum colloid obtained in Example 2. Styrenic weakly basic anion exchange resin (Mitsubishi Kasei DIAI)
ON VA20; Apparent density 39-45g/n; Replacement capacity 2.5w+eq/1al1 or more; Effective diameter 0.35-0
．． 55 mm) and 100 ml of phosphate buffer (pH 7) containing 0.24 wt% glutaraldehyde and 75°C.
Stir for 28 hours. The color of the resin gradually becomes blackish brown,
Furthermore, the blackish brown color of the liquid phase gradually becomes lighter, indicating that the ultrafine platinum particles are immobilized on the resin.Then, the resin is separated in a furnace, thoroughly washed with water, and then dried in vacuum. Take 2g of resin fixed with ultrafine platinum particles and add 50g of it.
After stirring overnight at 30° C. in aqua regia, the amount of platinum in the liquid phase is measured using an AA-646 atomic absorption spectrometer manufactured by Shimadzu Corporation. It can be seen that 1.7 x 10-' milligram atoms of platinum are fixed per 411111 g. Hydrogenation of cyclohexene was carried out using methanol as a solvent at 30° C. and 1 atm hydrogen pressure using the resin on which the ultrafine platinum particles were fixed as a catalyst. That is, 20 ml of methanol was placed in an eggplant flask. 82 mg of cyclohexene and 0.1 g of the resin on which the ultrafine platinum particles obtained above are immobilized are added and stirred. Hydrogen is introduced therein at a pressure of 1 atm and hydrogenation of cyclohexene is carried out at 30°C. As a result, hydrogenation proceeds rapidly, with an initial hydrogenation rate of 0.11 mol 1 per gram atom of supported platinum. Seconds. After the reaction, the catalyst is easily recovered by decandation, and no change in activity is observed even when the recovered catalyst is reused.
The same procedure as in Example 1 was carried out except that uCQ s) was used to prepare hydrazide acrylamide-N-vinyl-2-
A gold colloid is prepared using a pyrrolidone copolymer (hydrazidized copolymer) as a protective colloid. The resulting colloid was measured using a HU-12A transmission electron microscope manufactured by Hitachi Rakusho. It can be seen that the gold particles with an average particle size of 120 are well dispersed. This colloid is very stable and can be rotated at 5000 rpm7.
Even after centrifugation for 10 minutes, no gold particles were precipitated, and even after being left at room temperature for more than one month, no gold particles were precipitated. After adding hydrochloric acid aqueous solution to the colloid obtained in Example 3 to make it acidic, add 0.5N sodium nitrite aqueous solution 1
g and reacted at 0° C. for 1 hour to azidate the hydrazide groups in the hydrazidized polymer to obtain a gold colloid protected by the azidated copolymer. Separately, 5 g of the carbohydrate mannan and 1 g of ethyleneimine are reacted at 60° C. for 3 hours to introduce a 7-mino group into the carbohydrate mannan. This was added to a gold colloid solution containing the azide copolymer obtained above as a protective colloid, and the mixture was heated at 20°C for 10 min.
Allow time to react. The product was analyzed by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo ■ pv-
5ooo column (filling material: τ5K-GEL); solvent,
water], and a peak appears at a position different from that of the polymers present in the aminated mannan and colloid, indicating that the colloidal particles protected by the azidated copolymer are fixed to the aminated mannan. is confirmed. At this time, a fraction of the immobilized product is collected and the amount of immobilized aminated mannan is determined by elemental analysis. The results show that 0.02 mol of aminated mannan is fixed per 1 mol of 714 molecules of the azide group-containing structural unit. Hydrazated acrylamide-N-vinyl-2-pyrrolidone copolymer was obtained by carrying out the same operation as in Example 1 except for using radioactive chloroauric acid (H""AuCJl, ) instead of potassium tetrachloroplatinate. A colloid of radioactive gold is prepared using the copolymer (hydrazidated copolymer) as a protective colloid. When the resulting colloid was measured using a new model HU-12A transmission electron microscope manufactured by Hitachi, it was found that radioactive gold particles with an average particle size of 140 mm were well dispersed. This colloid is extremely stable, and no radioactive gold particles precipitate when centrifuged at 5,000 rpm for 10 minutes, and no radioactive gold particles precipitate when left at room temperature for more than a month. I can't. After adding hydrochloric acid aqueous solution to the colloid obtained in Example 4 to make it acidic, add 1 g of 0.5N sodium nitrite aqueous solution.
The mixture is reacted at 0° C. for 1 hour to azidate the hydrazide groups in the hydrazide polymer, thereby obtaining an azidated copolymer and a radioactive gold colloid protected with . Separately, amino groups are introduced into the carbohydrate mannan by reacting the carbohydrate mannan with ethyleneimine in the same manner as in Application Example 3. This is added to a radioactive gold colloid containing the azide copolymer obtained above as a protective colloid, and the mixture is reacted at 20° C. for 10 hours. The product was analyzed by gel permeation chromatography [Analysis conditions: pw manufactured by Toyo Soda Kogyo Co., Ltd.]
5ooo column (filling material: TSK-GEL; solvent, water), a peak appears at a position different from that of the aminated mannan and the polymer present in the colloid.
It is confirmed that the colloidal particles of radioactive gold protected by the azidated copolymer are immobilized on the heptaminated mannan. At this time, a fraction of the immobilized product is collected and subjected to single-element analysis to determine the amount of immobilized aminated mannan. The results show that 0.03 mole of aminated mannan is fixed per mole of the azide group-containing structural unit of the polymer. 【Leave】111. 10.0g of methanol. 1-methoxy-1-aminocarbomethylethylene and 100. of benzoyl peroxide. The resulting mixture is stirred at 60° C. for 12 hours to polymerize. The obtained polymer was reacted with hydrazine monohydrate in the same manner as in Example 1 to obtain a hydrazide polymer.The content of hydrazide groups in the polymer was determined according to Bio-chamistry Magazine, 19
When measured by the method described in 1969, Volume 8, page 4074, it is 0.63 milliequivalent per tg of copolymer. Moreover, when the molecular weight of the hydrazide polymer obtained above is measured by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo Co., Ltd. PV-SOOO column (filling material: TSK-GEL); solvent, water] Approximately 3
,000. The same procedure as in Example 1 was carried out except for using the hydrazide polymer obtained above, and a platinum colloid with the hydrazide polymer as a protective colloid was prepared. lll1. When the resulting colloid was measured using a Hitachi Model 11HU-12A transmission electron microscope, it was found that platinum particles with an average particle size of 40 mm were well dispersed. This colloid is extremely stable, and no platinum particles precipitate even when centrifuged at 5,000 rpm for 10 minutes, and no platinum particles precipitate at all even when left at room temperature for more than a month. . Add 5 g of methyl vinyl ether and 50 g of 4-pentenoic acid amide to 200 g of methanol. The resulting mixture is copolymerized by irradiating gamma rays for 20 hours. NMR spectrum analysis of the resulting polymer revealed that the content of 4-pentenoic acid amide in the polymer was 16 moles. Hydrazation is carried out in the same manner as in Example 1 except that the copolymer obtained above is used. The content of hydrazide groups in the polymer was determined by biochemistry (
Biochemistry) magazine, published in 1969, No. 8
roll. When measured by the method described on page 4074, it is 0.12 milliequivalent per gram of copolymer.
The molecular weight of the hydrazide copolymer obtained above was determined by gel permeation chromatography (analysis conditions: Toyo Soda Kogyo (II) PV-5ooo column (filling material:
When measured with TSK-GEL); solvent, water], it is approximately 4,
It is 500. A hydrazide copolymer was produced in the same manner as in Example 1, except that silver nitrate was used instead of potassium tetrachloroplatinate and the above hydrazide copolymer was used instead of the hydrazide acrylamide-N-vinyl-2-pyrrolidone copolymer. Prepare a colloid-protected silver colloid. When the resulting colloid was measured using a new model HU-12A transmission electron microscope manufactured by Hitachi, it was found that silver particles with an average particle size of 80 mm were well dispersed. The colloid obtained is very stable, and no silver particles precipitate even after centrifugation at 5,000 rpm for 10 minutes, and even when left at room temperature for more than a month.
No formation of precipitates of 11 particles was observed. 1 g of 0.5N nitrous acid aqueous solution was added to the colloidal solution obtained in Example 6, and the reaction was carried out at 0°C for 20 minutes to azidate the hydrazide group in the hydrazide polymer, and form an azidated copolymer. Obtain protected silver colloid. Add 100 g of albumin and stir at 10°C overnight. The product was analyzed by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo Co., Ltd. 1pv-5000]
Column (filling material: TSK-GEL); solvent, water], and a peak appeared at a position different from that of albumin and the polymers present in the colloid. It can be seen that the particles are fixed. At this time, a fraction of the immobilized product is collected and the amount of immobilized albumin is determined by amino acid analysis. the result,
0.0 per mole of azide group-containing structural unit of polymer
It can be seen that 1 mole of albumin is immobilized. A gold colloid protected with a hydrazide acrylamide-N-vinyl-2-pyrrolidone copolymer is then prepared in the same manner as in Example 3. Next, add hydrochloric acid aqueous solution to this colloid to make it acidic, and then add 1 g of 0.5N sodium nitrite aqueous solution to make it acidic.
The reaction is carried out at .degree. C. for 1 hour to azidize the hydrazide group in the hydrazidated polymer to obtain a gold colloid protected by the azidated copolymer. 100mg instead of mannan, a carbohydrate with amino groups introduced
The same operation as in Application Example 3 was carried out except that concanavalin A was used, and the gold colloid protected by the azidated copolymer was reacted with concanavalin A. The resulting product was subjected to gel permeation chromatography [ Analysis conditions: Toyo Soda Kogyo Co., Ltd. PV-5OOO column (filling material: TSK-GEL); solvent, water], and a peak appeared at a position different from that of concanavalin A and the polymer present in the colloid. , it can be seen that the colloidal gold particles protected by the azidated copolymer are immobilized on concanavalin A. At this time, a fraction of the immobilized product is collected and the amount of concanavalin A immobilized is determined by amino acid analysis. The results show that 0.03 mol of concanavalin A is immobilized per 1 mol of the azide group-containing structural unit of the polymer. Niwafu Salmon I A radioactive gold colloid protected with a hydrazide acrylamide-N-vinyl-2-pyrrolidone copolymer is prepared by carrying out the same operation as in Example 4. Next, add an aqueous solution of hydrochloric acid to this colloid to make it acidic (pH
1), add 0.5N sodium nitrite aqueous solution 1.
is added and reacted at 0° C. for 1 hour to azidate the hydrazide groups in the hydrazidated polymer to obtain a radioactive gold colloid protected by the azidated copolymer. 100mg instead of mannan, a carbohydrate with amino groups introduced
The same procedure as in Application Example 3 was carried out except that concanavalin A was used, and the radioactive gold colloid protected by the azidated copolymer was reacted with concanavalin A. The resulting product was subjected to gel permeation chromatography.

[Analysis conditions: Toyo Soda Kogyo ■ pv-5ooo column (
Filler: TSK-GIEL); Solvent. water], and a peak appears at a position different from that of the polymers present in coccanavalin A and the colloid, indicating that the radioactive gold colloid particles protected by the azidated copolymer are immobilized on concanavalin A. Recognize. At this time, a fraction of the immobilized product is collected and the amount of concanavalin A immobilized is determined by amino acid analysis. As a result, it was found that 0.04 mol of concanavalin A was immobilized per 1 mol of the azide group-containing structural unit of the polymer. 1 Arashi ■U 100g of methanol, 1g of acrylic acid thiophenyl ester, 20g of N-vinyl-2-pyrrolidone and 0
．． Add 5g of benzoyl peroxide. The resulting mixture is stirred at 80° C. for 24 hours to obtain a copolymer of acrylic acid thiophenyl ester and N-vinyl-2-pyrrolidone. This copolymer and hydrazine are reacted in the same manner as in Example 1 to obtain a hydrazide acrylic acid thiophenyl ester-N-vinyl-2-pyrrolidone copolymer (hydrazide copolymer). The content of hydrazide groups in this copolymer was determined by biochemist
ry), published in 1969, volume 8, page 4074, 1 g of copolymer.
It is 0.38 milliequivalent per fi. In addition, the molecular weight of the hydrazidated copolymer obtained above was determined by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo ■ Co., Ltd.
w -5ooo column (filling material: TSK-GEL);
Solvent, water] is approximately 25,000. By carrying out the same operations as in Example 1 except for using this copolymer, a platinum colloid protected by a hydrazide polymer, which is a blackish brown homogeneous solution, is obtained. When the resulting colloid was measured using a Hitachi fAHU-12A transmission electron microscope, it was found that the platinum particles with an average particle size of 110 mm were well dispersed. No precipitation of platinum particles was observed even after centrifugation for 10 minutes, and no precipitation of platinum particles was observed even after being left at room temperature for more than 1 month. The platinum colloid obtained in Example 7 was reacted with sodium nitrite in the same manner as in Application Example 3, except that the platinum colloid obtained in Example 7 was used to obtain a platinum colloid protected by an azidated copolymer. Platinum colloid is reacted with heptaminated mannan in the same manner as in Application Example 3 except that the above-mentioned platinum colloid is used. The product was analyzed by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo PM-5000 Power 5AC packing material: TSK-GEL]; solvent, water].
The appearance of a peak at a position different from that of the polymer present in the aminated mannan and colloid confirms that the platinum colloid particles protected by the azidated copolymer are fixed to the aminated mannan. At this time, a fraction of the immobilized product is collected and the amount of immobilized aminated mannan is determined by elemental analysis. The results show that 0.04 mole of aminated mannan is fixed per mole of the azide group-containing structural unit of the polymer. (Left below) 0.8 g of ethyl acrylate, 22 g of N-vinyl-2-pyrrolidone, and 0.05 g of benzoyl peroxide are added to 1611 of water. The resulting mixture was stirred at 80° C. for 12 hours to obtain a copolymer of ethyl acrylate and N-vinyl-2-pyrrolidone. Elemental analysis of the resulting copolymer revealed that the ethyl acrylate content in the copolymer was 32 mol%. . The molecular weight of the copolymer obtained above was determined by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo Co., Ltd. p.
v-5ooo column (filling material: TSK-GEL); solvent, water] is approximately 28,000 when measured with 9th order 0.
11 g of copolymer and 14.4 g of rhodium chloride were mixed in 50 m of a mixed solvent of ethanol and water (volume ratio +=1:1).
Dissolve in l. When this solution is heated under reflux for 1 hour, a copolymer-protected rhodium colloid is obtained as a blackish brown homogeneous solution.0 When measured using a Hitachi HU-12A transmission electron microscope, the average particle size of the rhodium colloid is 50. It can be seen that the colloidal particles are well dispersed. This colloid is extremely stable, and no rhodium colloid particles precipitate even when centrifuged at 5,000 rpm for 10 minutes, and no rhodium particles precipitate at all even when left at room temperature for more than a month. do not have. ``Eggplant''■11 Polyacrylamide gel having aminoethyl group [Bio-Rad Laboratories
Aminoethyl Biogel (Am
inoathyl Bio-Gel)P-150)Ig
5311 water and stirred for 6 hours. Twenty rhodium colloids obtained in Example 8 were added to this, and stirring was continued at room temperature. After 3 days, the gel becomes black and the liquid phase is clear and colorless. Even when the liquid phase was analyzed by atomic absorption, no rhodium was detected, indicating that all of the rhonlam atoms were fixed in the gel. Further, elemental analysis of the immobilized product obtained above was performed, and the results showed that 0.09 mol of gel was immobilized per 1 mol of ester group-containing structural unit of the polymer. Even when the gel on which colloidal particles are immobilized is washed with water at pH 2-13, no outflow or detachment of the colloidal particles is observed. Using this gel as a catalyst, ethyl vinyl ether, acrylonitrile, cyclohexene, mesityl oxide, and
Hydrogenation of 1-hexene is carried out in methanol at 30° C. and 1 atm hydrogen pressure, that is, 20 ml of methanol is placed in an eggplant flask. Hydrogenated substance 0.1. Add 0.1 g of the resin on which the colloidal particles obtained above are fixed, and stir. Hydrogen is introduced there at a pressure of 1 atm and hydrogenation is carried out at 30°C. As a result, hydrogenation proceeds rapidly. The initial rates of hydrogenation of the substrates ethyl vinyl ether, acrylonitrile, cyclohexene, mesityl oxide, and l-hexene were 170, 92, 72, and 56, respectively.
75 mmolH,/gram atom Rh-5, and the values of the commercially available (Nippon Engelhard Co., Ltd. H) measured under the same conditions were 22, 12° 1G, and 4.7, respectively. and 2.0 times. After the hydrogenation reaction, the gel is separated by decantation, and using this gel as a catalyst, hydrogenation of cyclohexene is carried out under the same conditions as above. Hydrogenation proceeds rapidly, with an initial hydrogenation rate of 72.5 oi1. /gram atom Rh.S, the first
It is the same as the value in the second catalytic reaction. That is, it is clear that the gel having rhodium colloid particles fixed thereon has high hydrogenation catalytic activity and can be used repeatedly. 0.8g of methyl acrylate in 16ml of ethanol,
Add 22 g of N-vinyl-2-pyrrolidone and 0.05 g of benzoyl peroxide. The resulting mixture was heated to 80°C.
After stirring for 12 hours, methyl acrylate and N-vinyl-2
- Obtaining a copolymer with pyrrolidone. Elemental analysis of the resulting copolymer revealed that the methyl acrylate content in the copolymer was 32 mol%. The molecular weight of the copolymer obtained above was determined by gel permeation chromatography [Analysis conditions: P manufactured by Toyo Soda Kogyo
V-5000 force 5A (filling material: TSK-GEL)
; When measured with solvent, water], it is approximately 28. 0.11 g of the 6-order copolymer of Goo and 14.4 μg of rhodium chloride were mixed in a mixed solvent of ethanol and water (volume ratio = i:g so m
Dissolve in l. When this solution is heated and refluxed for 1 hour, a copolymer-protected rhodium colloid is obtained as a blackish brown homogeneous solution. Rhodium colloid particles with an average particle diameter of 50 nm are measured using a Hitachi HU-12A transmission electron microscope. It can be seen that they are well dispersed. This colloid is very stable and soo. Even after centrifugation for 10 minutes at a rotation speed of 7 minutes, no rhodium colloid particles were precipitated, and even after being left at room temperature for more than a month, no rhodium particle precipitates were observed. Colloidal particles of rhodium colloid obtained in Eggplant ALL Main Example 9 are immobilized on polyacrylamide gel having aminoethyl groups in the same manner as in Application Example 9. Elemental analysis of the obtained immobilized product reveals that 0.09 mol of gel is immobilized per 1 mol of the ester group-containing structural unit of the polymer. Even if the gel on which colloidal particles are fixed is repeatedly washed with water of pi 2 to 13, no outflow and detachment of the colloidal particles is observed. Using this gel as a catalyst, ethyl vinyl ether, acrylonitrile, cyclohexene,
Mesityl oxide and 1-hexene are hydrogenated. As a result, ethyl vinyl ether, acrylonitrile, cyclohexene. The initial hydrogenation rates of mesityl oxide and 1-hexene were 170.92, 72.56, and 75 mol, respectively.
H,/gram atom Rh-5, each having a value of 22.
12.10.4.7 and 2.0 times. After increasing the hydrogenation pressure, the gel was separated by decantation, and using this as a catalyst, cyclohexene was hydrogenated under the same conditions as above. Hydrogenation proceeded rapidly, with an initial hydrogenation rate of 72 mmolH,/ is a gram atom Rh-5,
The value is the same as that in the first catalytic reaction. That is, it is clear that the gel having rhodium colloid particles fixed thereon has high hydrogenation catalytic activity and can be used repeatedly. 10 g of N-vinyl-2-pyrrolidone and 1 g of acrylic acid 4-nitrophenyl ester are added to 100 g of methanol. After adding 0.1 g of azobisisobutyronitrile to the resulting mixture, the mixture was stirred at 70° C. for 12 hours to polymerize. Elemental analysis of the resulting copolymer revealed that the content of acrylic acid 4-nitrophenyl ester in the copolymer was 31 mol%. The molecular weight of the copolymer obtained above was measured by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo Vslpw-soo. When measured using a column (filling material: TS-GEL); solvent, water], it is approximately 15,000. 0.11 g of copolymer of N-vinyl-2-pyrrolidone and acrylic acid 4-nitrophenyl ester obtained above
50ml of a mixed solvent of ethanol and water (volume ratio = 1:1)
Dissolve in 1. Add 5 + wl of an aqueous solution of potassium tetrachloroplatinate of I A platinum colloid protected by the above copolymer is obtained as a homogeneous solution of the copolymer.
When measured using an A-type transmission electron microscope, the average particle size is 4.
It can be seen that the platinum particles of 0 are well dispersed. The resulting colloid is very stable and 1 at 5000 revolutions/min.
No precipitation of platinum particles occurs even after centrifugation for 0 minutes, and no precipitation of platinum particles is observed even after being left at room temperature for more than 1 month. 7.215 g of styrene-based weakly basic anion exchange resin (DI made by Mitsubishi Kasei) was added to the platinum colloid obtained in Example 10.
AION VA20: Apparent density 39-45g/fl
; Exchange capacity 2.5*eq/s n or more; Effective diameter 0.35
~0.55 mm) and stirred at 75°C for 28 hours. The color of the resin gradually becomes blackish brown, indicating that the ultrafine platinum particles are immobilized on the resin. Thereafter, the resin is separated, thoroughly washed with water, and then vacuum dried. Hydrogenation of cyclohexene was carried out under the same conditions as in Application Example 9 except for using these ultrafine platinum particles. Hydrogenation progresses rapidly, initial hydrogenation rate is 36n+mol
H. 7 gram atoms pt-s. After the reaction, the catalyst is easily recovered by decandation, and even if the recovered catalyst is reused, no change in activity is observed. Gold using methyl acrylate-N-vinyl-2-pyrrolidone copolymer as a protective colloid was carried out in the same manner as in Example 8, except that chloroauric acid (HAuCn4) was used instead of rhodium chloride. Prepare a colloid of When the resulting colloid was measured using a Hitachi Model 11HU-12A transmission electron microscope, it was found that gold particles with an average particle size of 80 mm were well dispersed. This colloid is very stable and 1 minute at 5000 rotations.
No precipitation of gold particles occurred even after centrifugation for 0 minutes, and
Even if the sample was left at room temperature for more than a month, no gold particle precipitation was observed. Natsago Kako 1 1g of carbohydrate mannan and 5g of ethyleneimine at 50℃
The mixture is reacted for 12 hours to introduce amino groups into the carbohydrate mannan. This was added to the gold colloidal solution obtained in Example 11 and reacted at 20°C for 10 hours. The product was analyzed by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo Co., Ltd. pV-5000 column (packing material: TSK-GEL
); solvent, water], and a peak appeared at a position different from that of the polymer present in the aminated mannan and colloid, indicating that it was protected by N-vinyl-2-pyrrolidone-methyl acrylate copolymer. It is confirmed that the colloidal particles are immobilized on the aminated mannan. At this time, a fraction of the immobilized product is collected and the amount of immobilized aminated mannan is determined by elemental analysis. As a result, it was found that 0.06 mol of 7-minated mannan was fixed per 1 mol of the ester group-containing structural unit of the polymer. Radioactive chloroauric acid (H'”AuC) instead of rhodium chloride
A radioactive gold colloid using methyl acrylate-N-vinyl-2-pyrrolidone copolymer as a protective colloid is prepared by carrying out the same operation as in Example 8 except for using Q. The resulting colloid is Hitachi 1! )(U-12A
When measured using a transmission electron microscope, the average particle size is 70
It can be seen that the human radioactive gold particles are well dispersed. This colloid is very stable and 10
No precipitation of radioactive gold particles occurs even after centrifugation for minutes.
Further, even if the sample was left at room temperature for more than one month, no precipitation of radioactive gold particles was observed. 011" - 100 g of 10 g of N-vinyl-2-pyrrolidone and 1 g of acrylic acid 2,2.2-trifluoroethyl ester
of methanol. After adding 0.1 g of azobisisobutyronitrile to the resulting mixture, the mixture was stirred at 70° C. for 12 hours for copolymerization. Elemental analysis of the resulting copolymer revealed that the content of acrylic acid 2,2,2-trifluoroester in the copolymer was 28% by mole. The molecular weight of the copolymer obtained above was determined by gel permeation chromatography [Dividing conditions: Toyo Soda Kogyo 1111PI
I-5000 (column packing material: TSK-GEL)
; solvent, water] is approximately 25,060. The outer ring is the same as in Example 10, using silver nitrate instead of potassium tetrachloroplatinate and the above copolymer instead of the copolymer of acrylic acid 4-nitrophenyl ester and N-vinyl-2-pyrrolidone. A copolymer-protected silver colloid is prepared by the following procedure. When the resulting colloid was measured using a transmission electron microscope model HU-12A manufactured by Hitachi, it was found that silver particles with an average particle size of 40 mm were well dispersed. This colloid is extremely stable, and no silver grains precipitate even when centrifuged at 5,000 rpm for 10 minutes, and no silver grains precipitate at all even when left at room temperature for more than a month. . 100 mg of albumin was added to the colloid obtained in Example 13 and stirred overnight at 10°C. The product was analyzed by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo Co., Ltd. pv-5ooo column (filling material: TSK-GE
L); solvent, water], and a peak appears at a position different from that of the polymers present in albumin and colloid, indicating that silver particles protected by a copolymer are fixed to albumin. . At this time, a fraction of the immobilized product is collected and subjected to amino acid analysis to determine the amount of albumin immobilized. The results show that 0.05 mole of albumin is fixed per mole of the ester group-containing structural unit of the polymer. Chloroauric acid (HAuCfl 4) instead of rhodium chloride
A gold colloid using an ethyl acrylate-N-vinyl-2-pyrrolidone copolymer as a protective colloid is prepared by carrying out the same operation as in Example 8 except that . When the resulting colloid was measured using a transmission electron microscope model 11HU-12A manufactured by Hitachi, Ltd., it was found that gold particles with an average particle size of 80 mm were well dispersed. This colloid is very stable and 1 at 5000 rpm for 7 minutes.
No precipitation of gold particles occurred even after centrifugation for 0 minutes, and
Even if the sample was left at room temperature for more than a month, no gold particle precipitation was observed. 100mg instead of mannan, a carbohydrate introduced with amino groups
The copolymer-protected gold colloid obtained in Example 14 is reacted with concanavalin A in the same manner as in Application Example 12, except that concanavalin A is used. The resulting product is subjected to gel permeation. It was analyzed by chromatography [Analysis conditions: Toyo Soda Kogyo m@pw-sooo column (filling material: TSK-GEL); solvent, water], and peaks were found at specific positions for concanavalin A and the polymers present in the colloid. This appearance indicates that the gold colloid particles protected by the copolymer are fixed to concanavalin^. At this time, collect a fraction of the immobilized product. Amino acid analysis is performed to determine the amount of concanavalin A immobilized. As a result, it was found that 0.08 mol of huncanavalin A was immobilized per 1 mol of the structural unit containing an ester group of the polymer. 111J- Add 10 g of methyl vinyl ether and Ig of methacrylic acid to 100 g of methanol. O to the resulting mixture
, Ig, and then stirred at 80° C. for 12 hours to copolymerize. 1 g of the resulting copolymer was refluxed in 10 g of thionyl chloride for 8 hours to convert the carboxyl groups in the copolymer into acid chloride groups. After addition to pyridine, the copolymer having 4-nitrophenyl ester groups is prepared by reacting under reflux for 2 hours. Elemental analysis of the resulting product shows that the content of 4-nitrophenyl ester of acrylic acid in the copolymer is 32 mol2. The molecular weight of the copolymer obtained above was determined by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo Co., Ltd. p.
w -5ooo column (packing material: TSK-GEL)
; solvent, water] is about ss, ooo. The copolymer was prepared in the same manner as in Example 8, except that the above copolymer having a 4-nitrophenyl ester group was used instead of the copolymer of N-vinyl-2-pyrrolidone and ethyl acrylate. Obtaining Protected Rhodium Colloid When the obtained colloid was measured using a Hitachi Model 11HU-12A transmission electron microscope vIl, it was found that rhodium particles with an average particle size of 25 mm were well dispersed. This colloid is very stable, with 10
No precipitation of rhodium colloid particles occurs even after centrifugation for a minute, and no precipitation of rhodium particles is observed even after being left at room temperature for more than one month. To 100 g of methanol, 1 g of acrylic acid thiophenyl ester, 10 g of N-vinyl-2-pyrrolidone and 0
．． Add 1 g of benzoyl peroxide. The resulting mixture is stirred at 80° C. for 12 hours to obtain a copolymer of acrylic acid thiophenyl ester and N-vinyl-2-pyrrolidone. Elemental analysis of the resulting copolymer revealed that the content of acrylic acid thiophenyl ester in the copolymer was 36 mol2. Further, the molecular weight of the copolymer obtained above was determined by gel permeation chromatography [Analysis conditions: pw-soo manufactured by Toyo Soda Kogyo ■. Column (filling material: TSK-GEL); solvent, water]: approx. 35. It's Goo. - By performing the same operation as in Example 8 except for using this copolymer, a copolymer-protected rhodium colloid is obtained as a blackish brown homogeneous solution. When the resulting colloid was measured using a new model HU-12A transmission electron microscope manufactured by Hitachi, the average diameter of the colloid particles was 25. This colloid is extremely stable, with no rhodium particles precipitated even when centrifuged at 5000 rpm for 10 minutes, and no rhodium particles precipitated at all even when left at room temperature for more than a month. . A rhodium colloid protected with a copolymer of acrylic acid thiophenyl ester and N-vinyl-2-pyrrolidone is obtained by the same method as in Example 16. Rhodium colloid is reacted with aminated mannan in the same manner as in Application Example 12 except that the above-mentioned rhodium colloid is used. The product was analyzed by gel permeation chromatography and the peaks were located at different positions than the aminated mannan and the polymer present in the colloid, indicating that N-vinyl-2-pyrrolidone and thiophenyl acrylate. It is confirmed that the colloidal particles protected by the copolymer with ester are fixed on the aminated mannan. At this time, a fraction of the immobilized product is collected and analyzed by elemental analysis to determine the amount of immobilized aminated mannan. the result,
0.0% per mole of ester group-containing structural unit of the polymer.
It can be seen that 0.8 mol of aminated mannan is fixed. (Left below) Add Ig of acrylamide, 10g of methyl vinyl ketone, and 0.1g of benzoyl peroxide to 100g of water. The resulting mixture is stirred at 80° C. for 12 hours to obtain a copolymer of acrylamide and methyl vinyl ketone. NMR spectrum analysis of the resulting copolymer revealed that the acrylamide content in the copolymer was 28 mol%. The molecular weight of the copolymer obtained above was measured by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo M iipw-sooo column (filling material: TSK-GE
L); solvent, water] is approximately 32,000. Next, 0.1 g of this copolymer was dissolved in Soul, a mixed solvent of ethanol and water (volume ratio = 1:1), and 1.1
Add 5 ml of an aqueous solution of potassium tetrachloroplatinate of 1 liter of lo-''mol. After freezing and degassing twice,
While stirring using a magnetic stirrer, light is irradiated using a high-pressure mercury lamp for 2 hours to obtain a copolymer-protected platinum colloid as a dark brown homogeneous solution. Observation using a new H, U-12A transmission electron microscope manufactured by Hitachi revealed that platinum particles with an average particle size of 40 mm were well dispersed. This colloid is extremely stable; no platinum colloid particles precipitate even after centrifugation at 5,000 rpm for 10 minutes, and no platinum colloid particles are observed to form even after being left at room temperature for more than a month. do not have. 1 g of aminoethylated polyacrylamide gel (Bio-
Rad Laboratoriesid, amount of aminoethyl residue in dry state, 1.74 mEffi/Ig) is sufficiently swollen in 50 ml of water. Platinum colloid 20a+1 obtained in Example 17, whose pH was adjusted to 5 with hydrochloric acid, was added here. When the mixture was stirred at 20°C, the color of the resin gradually became blackish brown. Furthermore, the blackish brown color of the liquid phase gradually becomes lighter, indicating that the ultrafine platinum particles are immobilized on the resin. After 3 days, the liquid phase became almost transparent, indicating that the ultrafine platinum particles were completely fixed to the resin. Further, the immobilized product obtained above is analyzed by atomic absorption spectrometry to determine the amount of platinum immobilized. As a result, 2. It can be seen that OX 10-'' milligrams of platinum is fixed and oxidized.Using the resin on which these ultrafine platinum particles are fixed as a catalyst, cyclohexene is hydrogenated at 30℃ and methanol as a solvent under conditions of hydrogen pressure of 1 atm. That is, 20 pieces of methanol (1.86 mg of cyclohexene) and 0.1 g of @! fat on which the ultrafine platinum particles obtained above were fixed were placed in an eggplant flask and stirred.Hydrogen was introduced therein at a pressure of 1 atm, and the mixture was heated at 30°C. Hydrogenation of cyclohexene is carried out, resulting in rapid hydrogenation, with an initial rate of hydrogenation of 0.20 mol/sec per gram atom of supported platinum. After the reaction, the catalyst is easily recovered by decandation. Even if the recovered catalyst is reused, no change in activity is observed.Marim Platinum colloid using a copolymer of acrylamide and methyl vinyl ketone as a protective colloid was prepared in the same manner as in Example 17. After adjusting the pH of this platinum colloid to 5 with hydrochloric acid, it becomes 7.21.
5g of styrene-based weakly basic anion exchange resin (Mitsubishi Kasei MDIAION lA20; apparent density 39-45g/
Q; exchange capacity 2.5 vaeq/m 11 or more; effective diameter 0.35-0.55 mm) and 0.24% of 100 mfl
Add a glutaraldehyde aqueous solution (pH 7, phosphate buffer) and stir at 75°C for 28 hours. The color of the resin gradually becomes blackish brown, and the blackish brown of the liquid phase gradually becomes lighter, indicating that the ultrafine platinum particles are fixed to the resin. Thereafter, the resin is separated in a furnace, thoroughly washed with water, and then vacuum dried. After taking 2 g of resin fixed with ultrafine platinum particles and stirring it in aqua regia overnight, the amount of platinum in the liquid phase was measured by Shimadzu Corporation.
Measured using a Model 646 atomic absorption spectrometer. 1 per section of resin
．． It can be seen that 0 s and 10 −4 milligram atoms of platinum are fixed. Hydrogenation of cyclohexene is carried out using methanol as a solvent at 30° C. and 1 atm hydrogen pressure using the resin on which the ultrafine platinum particles are fixed as a catalyst, that is. 20ml of methanol in an eggplant flask. Cyclohexene 8
6 mg and 0.6 mg of the resin fixed with the ultrafine platinum particles obtained above.
Add 1g and stir. Hydrogen was introduced there at a pressure of 1 atm and hydrogenation of cyclohexene was carried out at 30°C. As a result, hydrogenation proceeded rapidly, with an initial hydrogenation rate of 0.11 mol/sec per gram atom of supported platinum. It is. After the reaction, the catalyst is easily recovered by decantation, and no change in activity is observed even when the recovered catalyst is reused. 1 vomit 1'' - Chloroauric acid (HA) instead of potassium tetrachloroplatinate
A gold colloid using an acrylamide-methyl vinyl ketone copolymer as a protective colloid is prepared in the same manner as in Example 17 except that uCQ 4) is used. The resulting colloid is manufactured by Hitachi i! When measured using a HU-12A transmission electron microscope. It can be seen that the gold particles with an average particle size of 80 are well dispersed. This colloid is extremely stable and no gold particles precipitate even after centrifugation for 10 minutes at 5,000 rpm for 7 minutes.
Further, even if it is left at room temperature for more than one month, no formation of gold particle precipitation is observed. 11" - 1g of carbohydrate mannan and 5g of ethyleneimine at 50℃
Amino groups are introduced into the carbohydrate mannan by reacting for 12 hours. This was added to the colloidal gold solution obtained in Example 18 which was brought to pH 5 with hydrochloric acid, and then added to it for 10 minutes at 20°C.
Allow time to react. The product was analyzed by gel permeation chromatography [Analysis conditions: pw-so manufactured by Toyo Soda Kogyo
oo column (filling material: Ts-GEL); solvent, water]
Analysis revealed that a peak appeared at a position different from that of the polymer present in the aminated mannan and colloid, indicating that the colloidal particles protected by the acrylamide-methyl vinyl ketone copolymer were fixed to the aminated mannan. It is confirmed that At this time, a fraction of the immobilized product was collected and single-element analysis was performed. Determine the fixed amount of aminated mannan. The results show that 0.06 mol of aminated mannan is fixed per 1 mol of the amide group-containing structural unit of the polymer. 1 LL1 The same procedure as in Example 17 was carried out except that radioactive chloroauric acid (H"'AuCQ, ) was used instead of potassium tetrachloroplatinate, and acrylamide-methyl vinyl ketone copolymer was used as a protective colloid. Prepare a radioactive gold colloid.
When measured using an A-type transmission electron microscope, the average particle size was 9.
It can be seen that the radioactive gold particles of 0 people are well dispersed. This colloid is very stable and 1 at 5000 revolutions/min.
No precipitate of radioactive gold particles was observed even after centrifugation for 0 minutes, and no precipitate of radioactive gold particles was observed even after being left at room temperature for more than 1 month. Using the same method as in Application Example 18, the carbohydrate mannan and ethyleneimine are reacted to introduce amino groups into the carbohydrate mannan. This was added to the radioactive gold colloid obtained in Example 19 which had been adjusted to pH 5 with hydrochloric acid, and heated to 20°C for 10 minutes.
Allow time to react. The product was analyzed by gel permeation chromatography [Analysis conditions: pw-so manufactured by Toyo Soda Kogyo
oo column (filling material: TSK-GEL); solvent, water]
Analysis shows that a peak appears at a position different from that of the aminated mannan and the polymer present in the colloid, indicating that the colloidal particles of radioactive gold protected by the acrylamide-methyl vinyl ketone copolymer are converted into the heptaminated mannan. It is confirmed that it is fixed. At this time, a fraction of the immobilized product is collected and subjected to elemental analysis to determine the amount of immobilized aminated mannan. As a result, the amide group-containing structural unit 1 of the polymer
It can be seen that 0.06 mol of 7-minated mannan is fixed per mole. Ig acrylamide, 10 g of methyl vinyl ether, and 0.1 g of benzoyl peroxide are added to 100 g of a water-methanol mixed solvent (water/methanol volume ratio = 1:1). The resulting mixture is stirred at 60° C. for 12 hours to polymerize. NMR spectrum analysis of the resulting copolymer revealed that the acrylamide content in the copolymer was 34 mol%.
It can be seen that it is. The molecular weight of the copolymer obtained above was determined by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo PV-SOOO column (packing material: T
Approximately 35,00 when measured with SK-GEL); solvent, water]
It is 0. A platinum colloid is prepared in the same manner as in Example 17 except for using the obtained polymer. The obtained colloid is very stable, and no platinum particles precipitate even when centrifuged for 10 minutes at 500 rpm for 7 minutes, and no platinum particles precipitate at all even when left at room temperature for more than a month. do not have. 100 g of water-methanol mixed solvent (water/methanol volume ratio = 1:1), 10 g of methyl vinyl ether, 1 g
of methacrylamide and 0.1 g of benzoyl peroxide are added. The resulting mixture is copolymerized by stirring at 80° C. for 12 hours. A silver colloid is prepared in the same manner as in Example 17, except that silver nitrate is used instead of potassium tetrachloroplatinate and the above copolymer is used instead of the acrylamide-methyl vinyl ketone copolymer. The resulting colloid was measured using a new Hitachi HU-12A transmission electron microscope. It can be seen that the silver particles with an average particle size of 80 are well dispersed. This colloid is very stable and does not produce any silver precipitation even after centrifugation at 5000 rpm for 10 minutes.
Even if the sample was left at room temperature for more than a month, no silver particle precipitation was observed. The colloidal solution obtained in Example 21 was adjusted to pH 5 with hydrochloric acid, and then 10 Qmg of albumin was added and stirred overnight at 10°C. The product was analyzed by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo ■lpw-soo
o column (filling material: TSK-GEL); solvent, water]
When analyzed, a peak appears at a position different from that of the polymers present in albumin and colloids. It can be seen that silver particles protected by methacrylamide-methyl vinyl ether copolymer are fixed to albumin. At this time, a fraction of the immobilized product is collected and subjected to amino acid analysis to determine the amount of albumin immobilized. The results show that 0.09 mol of albumin is immobilized per 1 mol of the amide group-containing structural unit of the polymer. Mistake ■Also, instead of the main potassium tetrachloroplatinate, chloroauric acid (HA
A gold colloid using an acrylamide-methyl vinyl ketone copolymer as a protective colloid is prepared in the same manner as in Example 17 except that uCn4) is used. The resulting colloid was measured using a Hitachi 1IHU-12A transmission electron microscope. It can be seen that the gold particles with an average particle size of 80 are well dispersed. This colloid is extremely stable, and no gold particles precipitate even after centrifugation at 5,000 rpm for 10 minutes.
Further, even if it is left at room temperature for more than one month, no formation of gold particle precipitation is observed.廠亙■ 100mg in place of carbohydrate mannan with amino groups introduced
The same procedure as in Application Example 18 was carried out except that concanavalin A was used, and the acrylamide-methyl vinyl ketone copolymer-protected gold colloid obtained in Example 22 was reacted with concanavalin. tion chromatography [Analysis conditions: Toyo Soda Kogyo PV-SOOO column (packing material: τ5K-GEL)
): solvent, water], and a peak appears at a position different from that of concanavalin A and the polymer present in the colloid, indicating that the copolymer-protected gold colloidal particles are fixed to concanavalin A. At this time, a fraction of the immobilized product is collected and subjected to amino acid analysis to determine the amount of concanavalin A immobilized. As a result, it was found that 0.02 mol of concanavalin A was immobilized per 1 mol of the amide group-containing structural unit of the polymer. A radioactive gold colloid protected with an acrylamide-methyl vinyl ketone copolymer is prepared by carrying out the same operation as in Example 19. 100mg as a substitute for mannan, a carbohydrate with amino groups introduced.
The same procedure as in Application Example 18 was carried out except that Concanavalin A was used. Reaction 1 of the radioactive gold colloid protected with the above copolymer and Concanavalin A was carried out. The resulting product was subjected to gel permeation chromatography. [Analysis conditions: Toyo Soda Kogyo Co., Ltd. pw-sooo column (filling material: TSK-GEL); solvent, water], and a peak appeared at a position different from that of concanavalin A and the polymer present in the colloid. , it can be seen that the copolymer-protected radioactive gold colloid particles are immobilized on concanavalin A. At this time, a fraction of the immobilized product is collected and subjected to amino acid analysis to determine the amount of concanavalin A immobilized. The results show that 0.04 mole of concanavalin A is immobilized per mole of the amide group-containing structural unit of the polymer. Mugisato I The same procedure as in Example 18 was carried out to prepare a gold colloid protected with an acrylamide-methyl vinyl ketone copolymer. The reaction between the acrylamide-methyl vinyl ketone copolymer-protected gold colloid and concanavalin A was carried out in the same manner as in Application Example 18, except that 100 μm of concanavalin A was used instead of the carbohydrate mannan into which an amino group was introduced. The resulting product was analyzed by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo Co., Ltd. P%l-500]
Copolymer-protected gold colloid. It can be seen that the particles are immobilized on concanavalin A. At this time, a fraction of the immobilized product is collected and subjected to amino acid analysis to determine the amount of concanavalin A immobilized. The results show that 0.02 mol of concanavalin^ is immobilized per 1 mol of the amide group-containing structural unit of the polymer. A radioactive gold colloid protected with an acrylamide-methyl vinyl ketone copolymer is prepared by carrying out the same operation as in Example 19. The reaction between the radioactive gold colloid protected by the above copolymer and concanavalin A is carried out in the same manner as in Application Example 19, except that 100 μm of concanavalin A is used instead of the carbohydrate mannan into which an amino group has been introduced. The resulting product was analyzed by gel permeation chromatography [Analysis conditions: Toyo Soda Kogyo PV-5OOO column (filling material: TSK-GEL); solvent, water] to determine the presence of concanavalin A and the colloid. It can be seen that the copolymer-protected radioactive gold colloid particles are immobilized on concanavalin A by the appearance of a peak at a specific position relative to the polymer. At this time, a fraction of the immobilized product is collected and subjected to amino acid analysis to determine the amount of concanavalin A immobilized. As a result, it was found that 0.04 mol of huncanabalin^ was immobilized per 1 mol of the amide group-containing structural unit of the polymer. (Effects of the Invention) As described above, the polymer-insulating metal colloid according to the present invention is not only stable as a metal colloid, but also easily binds and immobilizes various amino group-containing compounds, and can be used in various compounds. In addition to being used as a solid catalyst with special properties, it can also be advantageously used in research on living tissues and in the treatment and diagnosis of various diseases.

[Brief explanation of the drawing]

FIG. 1 shows a complex of troponin and tropomyosin on which particles of the polymer-protected metal colloid of the present invention are immobilized.

Claims (6)

[Claims] (1) (a) dispersion medium; (b) colloidal particles of at least one metal selected from the group consisting of elements of groups Ib, VIIb and VIII of the periodic table;
and (c) a polymer, the colloidal particles (b) are dispersed in the dispersion medium (a) to form a metal colloid, and the polymer (c) is adsorbed to the colloidal particles to form a protective colloid. In a polymer-protected metal colloid formed by protecting the colloid particles as,
The polymer contains structural units (i), structural units (ii), and structural units (iii), and the content thereof is 1 to 1, respectively, based on the total amount of structural units (i), (ii), and (iii). 100 mol%, 0 to 99 mol%, and 0 to 99 mol%, and the structural units (i), structural units (ii), and structural units (iii) have general formulas [I], [II], and [II], respectively.
I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [However, R^1 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group ,
There are hydroxyl groups, ▲mathematical formulas, chemical formulas, tables, etc.▼, -CO-
R or -O-R' {However, R is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or -(CH_2)n_1
-Xn_2-(CH_2)n_3-Yn_4-(CH_
2) n_5-CO-R^7 (However, X and Y are each independently -O- or -NH-; n_1, n_3 and n_5
are each independently an integer of 0 to 6; n_2 and n_4 are each independently 0 or 1; R^7 is -NH-NH_2, -A
-R^■ or -NH_2; A is -O- or -
R'
is the same as R}, R^2 is -(CH_2)n_1'
-X'n_2'-(CH_2)n_3'-Y'n_4'
-(CH_2)n_5'-CO-R^7' (However, X'
, Y', n_1', n_2', n_3', n_4', n
_5,' and R^7' are the above X, Y, n_1, respectively
, n_2, n_3, n_4, n_5 and R^7)
], ▲Mathematical formulas, chemical formulas, tables, etc.▼[II] [However, R^3 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group ,
There are hydroxyl groups, ▲mathematical formulas, chemical formulas, tables, etc.▼, -CO-
R or -O-R' (however, R and R' are as above)
, R^4 is -(CH_2)n_1"-X"n_2"-(
CH_2)n_3″-Y″n_4″-(CH_2)n_
5″-CO-R^9 (However, X″, Y″, n_1″, n
_2″, n_3″, n_4″ and n_5″ are the above-mentioned X, Y, n_1, n_2, n_3, n_4 and n_
5, R^9 indicates -A'-R^1^0,
A′ is the same as A above, R^1^0 is a hydrogen atom,
represents an alkali metal, an alkaline earth metal, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted succinimide group], ▲ formula, There are chemical formulas, tables, etc.▼［
III] [However, R^5 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group,
There are hydroxyl groups, ▲mathematical formulas, chemical formulas, tables, etc.▼, -CO-
R or -O-R' (however, R and R' are as above)
, R^6 is a hydroxyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, -CO-R or -O-R' (where R and R' are as above), provided that R^1 is a hydrogen atom and R^2 is -CO-NH_2. and when the content of the structural unit (ii) is 0 mol%, R^6
is a hydroxyl group, -CO-R or -O-R' (where R and R' are as above), and R^7 is -NH-NH_
2, some or all of the -NH-NH_2 groups may be substituted with -N_3 groups, and furthermore, R^1 is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. In some cases, the structural unit (i), the structural unit (ii)
) and the content of the structural unit (iii) is the structural unit (i),
1 to 95 each based on the total amount of (ii) and (iii)
mol%, 0-90 mol% and 5-99 mol%. (2) The polymer-protected metal colloid according to claim 1, wherein R^7 is -NH-NH_2. (3) The polymer-protected metal colloid according to claim 1, wherein R^7 is -A-R^■ (where A and R^■ are as described above). (4) The polymer-protected metal colloid according to claim 1, wherein R^7 is -NH_2. (5) The metal is gold, silver, platinum, ruthenium, rhodium,
palladium, osmium, rhenium, iridium, copper,
The polymer-protected metal colloid according to any one of claims 1 to 4, which is selected from the group consisting of nickel. (6) The polymer-protected metal colloid according to claim 5, wherein the metal is selected from radioactive gold, silver and platinum.