JPS58172392A - Imidazole-coordinated hem complex included in cyclodextrin and gas-absorbing and desorbing agent - Google Patents

Abstract

PURPOSE:To provide the titled imidazole-coordinated hem complex composed of an imidazole derivative having a specific substituent group at the 1-N atom and hem bonded with the 3-N atom through a coordinate bond, having low toxicity, good biocompatibility, and capable of keeping the gas absorbability even in an aqueous solution. CONSTITUTION:For example, the halide of formula X-A-B [X is halogen; A is -(CH2)n- or -SO2- (n is 0-3); B is 1-10C hydrocarbon group] is bonded to an imidazole compound of formula I (R<1> is methyl; R<2> and R<3> are H or methyl) by the dehydrohalogenation reaction. The resultant imidazole derivative of formula II (e.g. 1-phenetyl-2-methylimidazole) is mixed with an aqueous solution of cyclodextrin, and dried. The included imidazole can be obtained by removing the free imidazole from the dried product with a solvent. The included compound is mixed with hem [e.g. a complex of porphyrin and Fe(II)] in a solvent to obtain the objective complex.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heme complex coordinated with an imidazole derivative and a gas adsorption/desorption agent.

Many heme complexes have been known as substances that have the ability to reversibly adsorb and desorb gas molecules such as oxygen, carbon oxides, and nitrogen oxides. However, in general, the constituent components of known heme complexes are often materials with poor biocompatibility, such as synthetic porphyrins or basic ligands with structures far different from those in vivo, and moreover, There are few materials that can maintain gas adsorption/desorption ability.

Therefore, an object of the present invention is to provide an imidazole derivative-coordinated heme complex that is biocompatible, has superior ability to adsorb and desorb gas molecules, and can maintain its function even in aqueous liquid.

The complex of the present invention is an imidazole derivative encapsulated in a cyclodextrin, which has a substituent on the nitrogen atom at the 1-position that has a size and hydrophobicity that allow it to be included in the cavity of the cyclodextrin. It is a cyclodextrin inclusion imidazole-coordinated heme complex in which heme is bound to the nitrogen atom through a coordination bond.

The above cyclodextrin has 6, 7 or 8 D-
Glucobylanose units are cyclically glucosidically bonded, and are called α-cyclodextrin (6 units), β-cyclodextrin (7 units), and γ-cyclodextrin (8 units) depending on the number of D-gelcopynose units. It's swollen. This cyclodextrin has a nearly cylindrical structure,
The inside of the cavity is a water canal. In this invention, α−
Cyclodextrins are preferred.

The imidazole derivatives included in such cyclodextrins are lipophilic and have a size and hydrophobicity that allow them to be included in the cavities of the cyclodextrin, i.e.,
It has a substituent on the nitrogen atom at the 1st position that can stably exist within the cavity. Such imidazole derivatives preferably have the formula (wherein R1 is a methyl group, R2 and R5 are each independently hydrogen or a methyl group, A is +Cl2-) -1 or -M-1nUO to an integer of 3, and B is 1 Hydrocarbon group having 1 to 10 carbon atoms or its terminal hydrogen atom 1
(a group in which 5 is substituted with a c1-C5 hydrocarbon ester of carboxylic acid or a 7-talimide).

Specific examples include 1-7enethyl-2-methylimidazole, l-cyclohexyl-2-me, chirui, mida/-/l/, 1-47-)-2-methylimidazole, l-tosyl -2-methylimidazole, 1-(2
-Ethoxylic? N-11-(4,5-dimethyl)imidazolyl)pentylphthalimide, 11-+1-(2-methyl)imidazolyl)cundecanoate, or 1,2-dimethylimidazole.

The term "inclusion" used in this specification means that the entire imidazole derivative or its 1-position substituent exists relatively stably within the cavity of the cyclodextrin.

In the complex of this invention, the heme that is coordinately bonded to the above-mentioned ikibutazole is connected to the porphyrin and F@(II) or F-
(to), and is a complex with F@(n
) is preferred. The central iron of such heme is coordinately bonded to the nitrogen atom at the 3-position of the imidazole derivative. This heme includes complexes of various hemin and other porphyrins in the body and iron.

As stated above, the cyclodextrin inclusion imidazonyl-coordinated heme complex of the present invention is an iron complex of porphyrin, which is a biological component, and cyclodextrin, which is a polysaccharide that is highly safe in the body. LDs by internal administration
o 1.00 P/'kl/ (α-cyclodextrin), 0.788p/ to # (/-zriOy"kistrin): D, W, Frank et al., American
Journal of Pathology83(2)
, 367 (1976)) and fat-soluble imidazole derivatives. Some fat-soluble imidazoles have pharmacological effects9, and toxicity tests have been carried out extensively, and the results show that they are generally highly toxic and expected to be reduced.

In general, the complex of imidazole and heme is represented by the formula (where F7 is a porphyrin planar structure and N is its iron (It) complex), and has a low spin hexacoordination structure, but is based on steric hindrance. An imidazole derivative having tf
The complex of 2-methylimidazole and heme is represented by the formula (where z is a porphyrin structure with the center bulging upward, and 2aa7 is an iron (■) complex of this),
It has a high spin five-coordination structure.

In the heme complex with a low spin hexacoordination structure of formula (1), when it comes into contact with oxygen, in order for oxygen to coordinate, it must coordinate to the sixth coordination dust of the central iron and then displace imidazole. However, in the latter heme complex with a high-spin pentacoordination structure of formula (U), the sixth coordination dust of the central iron is empty, and gas molecules such as oxygen are quickly released. Can be combined. Furthermore, in the low-spin hexacoordination structure heme of formula (1), the approach of oxygen molecules is extremely difficult! It is generally said that type 1 oxidative degradation is also likely to occur, and considering these points, the latter high spin type 5 is necessary for heme complexes to stably and reversibly bond with gas molecules such as oxygen. A coordination structure is preferable, and this is because in in vivo hemoglobin and myoglobin, heme binds to only one axial base, has a high-spin pentacoordination structure, and has the function of stably capturing oxygen molecules. be.

By the way, imidazole derivatives having sterically hindered groups are
Compared to imidazole, which does not have a sterically hindered group, its coordination bond with heme is generally significantly weaker, and in order to stably form a five-coordinate structure of heme using imidazole, a large molar excess of heme is required. It is necessary to use Therefore, it is extremely difficult to apply the complex having the structure of formula (II) to living organisms, considering only the toxicity of imidazole itself.

On the other hand, in the cyclodextrin-clathrated imidabule derivatives of the present invention, which are constituents of the @-body, even if the imidazole derivative has a sterically hindered group, the coordination bond strength as a result of inclusion with cyclodextrin is significantly improved. That is, for heme having a low spin five-coordination structure shown by the formula (1), for example, the formula (
Here, when a minute amount of a cyclodextrin inclusion imidazole derivative represented by θ is cyclodextrin and A and B are as described above is applied, a high-spin type five-coordinated heme complex is preferentially produced. Therefore, the amount of the imidazole derivative itself can be small, and since the imidazole derivative is included in cyclodextrin, its toxicity is low and it also has biocompatibility.

In order to obtain the cyclodextrin inclusion imidazole coordinated heme complex of the present invention having such characteristics, for example, X-
A-B (wherein, It is combined by the known 1-position substituent introduction reaction (dehydrohalogenation reaction) K of imidazole, and an aqueous solution having an appropriate concentration below the saturation concentration of cyclodextrin at a ratio of 2 times molar or less based on the above formula The mixture is mixed and stirred at around room temperature for several hours, and then freeze-dried. After further drying under reduced pressure at around 50°C, the unclathrated imidazole conductor is washed with a suitable low-boiling point organic solvent (such as diethyl ether) that dissolves the unclathrated imidazole conductor but does not dissolve the clathrated imidazole derivative. Remove clathrate imidazole. The obtained clathrate imidazole is dried under reduced pressure at 50° C. to a constant weight to obtain a desired cyclodextrin clathrate imidazole derivative. lastly,
This clathrate imidazole derivative is dissolved in water or in a unipolar aprotic solvent (e.g., N,N-dimethylformamide, N,
The cyclodextrin inclusion imidazole-coordinated heme complex of the present invention can be obtained by mixing heme in a mixed solvent of N-dimethylacetamide and water in an equimolar amount or more relative to heme.

The complex of this invention adsorbs and captures gases such as oxygen, carbon oxide, and nitrogen oxides when it is passed through the solution, and immediately releases the adsorbed gases when an inert gas is passed through it or when it is placed under reduced pressure. do.

This can be done repeatedly. Since the present invention has such ability and high biocompatibility, it can be applied, for example, as a material for artificial blood. It can also be used as a catalyst for chemical reactions such as redox reactions and oxygen addition reactions, particularly as a homogeneous aqueous phase catalyst.

Hereinafter, this invention will be explained in detail with reference to Examples.

Example 1 1) Phenethyl chloride 28.111 (0.2 mol), 2-methylimidazole 32.8p (0.4 mol)
were mixed and reacted at 200°C for 5 hours. After cooling, the reactant t200d is dissolved in chloroform. Add this to the same amount of 1
096- After sequentially washing with Na2Co, aqueous solution, and the same amount of water, it was left to dry over anhydrous sodium carbonate, and the solvent was distilled off under reduced pressure.

The residual oil was distilled under reduced pressure under a nitrogen stream (bp 159-1
60° C. (5 mHg)) to obtain 15.35′ of 1-7enethyl-2-methylimidazole (yield: 41.0%).

NMR (TMS, CD (J3), 2.10 (- doublet, 3H1-CH,), 2.80 (triplet, 2H%)
J==7) 1z, CH2φ), 3.97 (triple line 1
．． 2H%J”7HzSCH2CH2φ), 6.64 (double line, IHSJ=IHz, proton at 5th position of imidazole ring), 6.79 (double line, IHSJ=IHz, proton at 4th position of imidazole ring), 6.84-7 .22 (multiple □
111 line, 5H, φ-H) pp Kame MS rn/@ 186 (M±) 11) α-Cyclodextrin 2.92 F (3
1.12 P (6X
10−3 mol) is added. After stirring at room temperature for 3 hours, the mixture is freeze-dried and further dried under reduced pressure at 50° C. for 8 hours.

The obtained powder was washed twice with 50-〇 diethyl ether, and then dried under reduced pressure at 50°C for further 12 hours to obtain 1-phenetide-2-methylimidagul and α-cyclodextrin (IJ) as a white powder. A molecular ratio of 4.0 OP (quantitative yield) of the 1 clathrate compound is obtained.

Tetramethylsilane (TMS) in heavy water solvent (D20)
) (The following two tables were obtained from the results of measuring PM enomidazole.

Table 1 1 1.909 1.772 0.1372
6.971 6.892 0.07936.8
22 6.740 0.0824 4.164
4.088 0.0765 3.014
2.938 0.0766 7.027 6
．． 912 0.1157 7.308 7.1
84 0.1248 7.262 7.172
0.090 (In the above, α-CD is coated with α-cyclodextrin, and PMI is coated with l-phenethyl-2-methylimidazole.) 2 3.635 3.503 0
．． 1323 3.997 3.812
0.1854 3.601 3.
456 0.1455 3.891
3.67'I O,214 In Table 1,
The phenyl group and methyl group gloton of 1-phenethyl-2-methylimidazole are clathrates and are subject to high magnetic field shift.
It can be seen that these groups are contained within the hydrophobic cavity. In addition, in Table 2, the protons at the 3rd and 5th positions on the inner surface of the cavity of α-cyclodextrin are shifted by a high magnetic field in the case of the inclusion complex, and these protons have a hydrophobic interaction with the phenyl group and the methyl group. It was inferred that this was the case. Furthermore, in the m-spectrum of the inclusion complex, for example, the 1st groton signal of α-cyclodextrin (5
,065ppm) and the methyl group proton signal of 1-7enethyl-2-methylimidazole (1,909ppm
) was 6:3, which confirmed that the inclusion ratio was 1:1.

111) Dissolve hemin in V5-Na2CO, -NaHCO, buffer solution (PI-1 = 10.0) to prepare a 10-5M hematin aqueous solution. Na28204 was added to the solution under nitrogen atmosphere in a molar amount 20 times that of hematin, and the visible absorption spectrum in the wavelength range of 350 to 700 nm was measured. Then 50.100 each for hematin
, 200, 500, and 1000 times the molar amount of α-cyclodextrin inclusion 1-7enethyl-2-methylimidazole was allowed to coexist, and then Na2S2O4 reduction was performed under the same conditions as above, and the spectrum was measured. From the obtained continuous change spectrum, the complex equilibrium constant of the complex formed between heme and the inclusion ligand is determined by the Mill@r-Dorough equation as =7.
648102 no moj-' is found and then. This value is
When compared to the case where 1.2-dimethylimidazole is used as a ligand and the ratio is 2.8×10'no·mo/', the ability to coordinate to heme is significantly improved.

IV) Hematin 10-5M according to the procedure described above,
P4/'5-Na2C in imidazole 10 M
05-Na HCOs solution (P)I = 10.0) was prepared and reduced by adding nithionic acid to a plate under a nitrogen gas atmosphere to obtain λmax 426° 528, 558 nm.
A visible absorption spectrum of a low-spin hexacoordination structure was observed. When V5 amount of α-cyclodextrin inclusion 1-7enethyl-2-methylimidazole ligand of imidazole was added to the obtained solution. , the previous spectrum quickly shifted to λm□432, 557 nm, indicating the formation of a high-spin pentacoordination complex. The ability to coordinate to heme was shown to be even better than that of imidazole without sterically hindered groups,9 and it has characteristics that are completely different from conventional low-molecular-weight ligands.

■) Hemin 1.2X10-'M, α-cyclodextrin inclusion 17enethyl-2-methylimidazole 2.4X
10 M N,N-dimethylformamide/water (PI
(=7)=9/1 (ma/ma) The solution was reduced by adding 6 times the mole of Na 2 S 204 to hemin under a nitrogen atmosphere. The obtained heme complex solution was cooled to -30°C,
When atmospheric pressure oxygen was introduced, a visible spectrum change immediately occurred, and an oxygen complex spectrum of λmax 41015451577 was obtained. When nitrogen gas was blown into this, the visible spectrum changed to the original reduced form (λrn,!43
2,557 nm). When carbon monoxide was blown into the obtained heme complex, a carbon monoxide complex svector of λm□418.538.566 was observed. These visible spectral behaviors are comparable to spectral changes associated with gas adsorption and desorption of hemoglobin in water at room temperature (Table 3).

Table 3 Inclusion ligand heme 432557418538566 4
%rio to 10545577 430.5564
18539570 414542578 imidazole,
In systems using conventional low-molecular-weight ligands such as 2-methylimidazole, under the same conditions as above, either no oxygen complexes are formed and they are rapidly oxidized, or the half-life of the oxygen complex is less than a few minutes. In comparison, it is an improved heme complex with a longer half-life and a more stable oxygen bond.

Examples 2-8 Several imidazole derivatives with hydrophobic substituents were prepared and cyclodext v"?m according to the method of Example 1.
I was brought into contact with it. The coordination ability of the prepared clathrate imidazole to heme (#i stability constant) and the gas adsorption properties of the clathrate imidazole coordination heme complex were also investigated using exactly the same method as used in Example 1. Details are shown in Table 4.

In the table, the imidazoles of /4 and A6 were included with the addition of a small amount of acetic acid. The stability of the generated oxygen complex is higher as the complex stability constant is larger, and 7f14 with smaller these values
It was unstable when using imidazole clathrates of 8 and 8.

The imidazole crocodile conductors of Examples 2 to 7 were each synthesized as follows.

cyclohexylmethylbromide 35.49 (0,2-
&), 2-methylimidazole 32.81! (0,4
After mixing and reacting at 200°C for 8 hours, 1-cyclohexyl-2-methylimidazole 25. Oj' (yield 70.0%) was obtained.

NMR (TMS, CDCj,), 0.6 to 2.0 (wide multiplet, 11H, (bar Σ5.2.35 (-multiplet, 3H
, -CH,), 3.61 (double line, 2H, J=7Hz1
CH2-), 6.69 (- heavy line, H1 imidazole ring 5-position proton), 6.81 (- heavy line, H1 imimezole ring 4-position groton) ppmMS m/* 178 (S
) dish benzyl chloride 25.39 (0.2 mol), 2-methylimidazole 16.4 jl (0.2 mol) n
-! Add to 100 d of ethanol, add sodium hydroxide 9.
After boiling under reflux for 3 hours in the presence of 6F, distillation under reduced pressure (bp 146
~153°C (9111Hg)) L, 1-benzyl-2-
Methylimidazole 17.7F<yield 51.5%) was obtained.

NMR (TMS, CD (J3), 2.31 (- double line,
3 H, -CH5), 5.00 (- double line, 2 H, -C
H2-), 6.82 (double line, IH.

imidazole ring 5-position proton), 1 line at 6.93, IH
, imidazole ring 4-position proton), 6.9-7.4 (
Multiplet, 5H1φ-H)pprn MS rn/s 172 (M+,) 2-methylimidazole 16 in 100d of anhydrous pyridine
．． 4P(0,2F), p-)luenesulfonyl chloride 38. Add IP and stir overnight at room temperature. After distilling off the solvent under reduced pressure, the residue is treated in a conventional manner and recrystallized from diethyl ether-petroleum ether to obtain 1-tosyl-2-methylimidazole 36.8 F (yield 78%).

IR(KBr)1375.1200~1155i'(y
30) NMR (TMS, CDC), ), 2.40 (-
Heavy line, 3H, imidazole ring -Cl, ), 2.48(
-Double line, 3H, phenyl ring -CH,), 6.79 (double line, Hl imidazole ring 5th position 7.30 (double line, H
11' midazole ring 4th position Zoroto 2-methylimidazole 16.4 F (0.2 mol)
, 21.3 P CO 0.4 mol of acrylonitrile were mixed, and the mixture was refluxed for 3 hours at the boiling point, and then excess 7 acrylonitrile was distilled off under reduced pressure. The residue was dissolved in 95% ethanol,
Concentrated hydrochloric acid 2011/ was added and boiling refluxed for 4 hours. Neutralize by adding 10% Na 2 CO 3 aqueous solution while cooling with water.

After extracting three times with chloroform 3001, it was dried over N1□CO1 and treated with water. After distilling off the P liquid under reduced pressure, the residue is crystallized on dry ice at methanol temperature, and the obtained pale yellow crystals are ground in diethyl ether to collect P. Dry under reduced pressure over P2O5 at room temperature to obtain 1-(2-ethoxycargenyl).
16.89 ethyl-2-methylimidazole (yield 4
6%).

IR (KBr) 1740 (C,-01 ester>1
185 (C, -0.
, imidazole ring -CH,), 2.64 (triple line, 2H
, -Cdan2CH2CO□-), 4.06 (quartet, 2H
, -CH,CH,), 4.11 (triple line, 2H.

CH2CH2C0□-), 6.87, 6.85 (each double line, 2H, imidazole ring proton) pDw.

M8 w', 182 (M, ) Reflux (1) Mix acetoin 25P1 formamide 1251 and reflux at boiling point for 4 hours. After cooling, fractional distillation under reduced pressure, bp 16
After collecting 5°C (11m11P), it was recrystallized from diethyl ether-methanol to obtain 4.5-trimethylimidazole 13.5P (yield: 49.5m).

MS w'e 96 (M, ) NMR (TMS, CD (J,) 1.82 (- heavy line, 6H, -CH,), 6.74 (- heavy line, H1 imidazole ring 2-position proton), 11 .04 (wide line, H, NH
)ppm.

(1)) Potassium phthalimide 6, Of was suspended in pentamethylene bromide 250P and heated at 200°C for 12
Time heating stirring reaction. Subsequently, unreacted pentamethylene mite was removed by steam distillation.

Add diethyl ether and water to the residue and shake vigorously.

The diethyl ether layer was separated, and the aqueous layer was further extracted with diethyl ether twice, and the diethyl ether solution was collected and washed with water, followed by drying in an apparatus over anhydrous sodium sulfate overnight. After filtration, the solvent component was distilled off under reduced pressure, and the residue was recrystallized from ethanol to obtain N-(5-bromopentyl)phthalimide 48F (yield: 50%).

IR (KBr) 1780.1720m-' (C-6.
phthalimidocardenyl) NMR (TMS, CDC
),) 2.1-1.3 (multiple line, !load, 61,
NCH2(CH2), CI(2Br), 3.38
(triplet, 2H1-CH2B r ), 3.66 (triplet, 2H,'NCH2-), 8.27 (multiplet, 4H,
φ-H) ppm.

MS rn/@296 (M,) (ill) 10 parts of 4.5-dimethylimidazole are dissolved in tetrahydrofuran, 50% sodium hydride 6.4F is added under nitrogen, and the mixture is refluxed at boiling point for 1 hour. N-(
A solution of 35.5F of 5-pro, moventil) 7-talimide in tetrahydrofuran (150R1) was added dropwise at room temperature over 1 hour, and then the mixture was refluxed at the boiling point for 3 hours. After removing the insoluble components and distilling off the solvent components under reduced pressure, a silica gel column (6c+m6X45
cIn, CHCj〆CH,0H=20/1 (ma/ma) solvent) to obtain N-11-(4,5-methyl)imidazolyl)pentylphthalimide 18F (yield 55.6%). Ta.

IR(KBr)1775.1720cM (C-o
' Phthalimidokaryl) NMR (TMS,
CDC), ) 1.3 to 1.7 (wide, multiple lines, 4H
, φ-H) ppm.

MS rrV・311 (resistant) (7) 11-Bromoundecanoic acid 2511't Benzene lOO
' 11-Bromoundeca/acid methyl ester 23F (
A yield of 87.5% is obtained.

2-Methylimidazole 8.2P to NaH2,4P/D
Add slowly to the suspension of MF2001j.

After the addition, the mixture was heated at 90° C. for 1 hour, and the obtained fC1l-bromoundecanoic acid methyl ester was first added dropwise.

Subsequently, the mixture was heated and stirred at 90°C for 2 hours, and then operated in a conventional manner. Silica gel column (6cInφX 27cm, CHCj7
C) Purification using sOH=9/1 (ma/ma) to obtain methyl 11-11-(2-methyl)imidazolyl)undecanoei) 9.5F (yield 41%).

IRC liquid film) 1740 m-' (ν.., ester) N
MR (TMS, CDC), ), 1.28 (- double line,
12H.

:;NCH2CH2(C!!2)6CH2CH2CO□
-), 1.68 (multiplet, wide, 4H,, Jcu2cdan, (CH2)6Cdan2C12CO2-), 2.31 (triplet, 2H, -CH2Co2-), 2.37 (-multiplet, 3H.

Imidazole ring -CH,), 3.66 (- doublet, 3H.

-C00CH,), 3.80 (triple line, 2H,:;NC
H2-), 6.80 (double line, H1 imidazole ring 5-position proton), 6.90 (double line% H% imidazole ring 4
position proton) ppm.

MS Iv/l! 1280 (M,) Applicant's agent: Patent attorney Suzue TakehikoContinued from page 1 0 shots clear person Hiroyuki Nishide 2-16 Saginomiya, Nakano-ku, Tokyo No. 6 0 shots: Hidetoshi Tsuchida 1-141 Sekimachi, Nerima-ku, Tokyo 770-

Claims (1)

[Scope of Claims] (3) An imidazole derivative clathrated in cyclodextrin, which has a substituent on the nitrogen atom at the 1-position having a size and hydrophobicity that allows it to be included in the cavity of cyclodextrin. A cyclodextrin inclusion imidazole-coordinated heme complex in which heme is bonded to the nitrogen atom in the position by a coordination bond. (2) The complex according to claim 1, wherein the cyclodextrin is α-7 clodextrin. (3) The imidazole derivative has the formula (where R1 is a methyl group, R2 and Rs are each independently hydrogen or a methyl group, A is +CH2-), n1 is a hydrocarbon group having 1 to 10 carbon atoms, or one terminal hydrogen atom is a carbon group. 3. The complex according to claim 1 or 2, which is represented by C1<, 9 groups substituted with a hydrocarbon ester or phthalimide) of phosphoric acid. (4) The imidazole derivative is 1-phenethyl-2-
Methylimidazole, 1-cyclobekyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-tosyl-2-methylimidazole, 1-(2-ethoxycarpyl)-2-#-ruimidazole Zor,
Claim 3, which is N-1l-(4,5-trimethyl)imidazolyl)pentylphthalimide, 1l-tl-(2-methyl)imidagril)undecanoate, or 1,2-tumethylimidazole. Complex. (5) Iron(II) of porphyrin whose heme is a biological component
or the complex according to any one of claims 1 to 4, which is an iron complex. (6) An imidazole derivative encapsulated in a cyclodextrin, which has a substituent on the nitrogen atom at the 1st position that has a size and hydrophobicity that allow it to be included in the cavity of the cyclodextrin, but on the nitrogen atom at the 3rd position. Heme is a coordination bond 9
A gas adsorption/desorption agent consisting of a bound cyclodextrin inclusion imidazole coordination heme complex. (7) The gas adsorption/desorption agent according to claim 6, wherein the cyclodextrin is α-cyclodextrin. (8) The imidazole derivative has the formula (where R1 is a methyl group, R2 and R3 are each independently hydrogen or a methyl group, and A is ÷CH2+n. 7. The gas adsorption/desorption agent according to claim 6 or 7, wherein the group is substituted with a C1-C5 hydrocarbon ester of an acid or a group substituted with 7-talimide. (9) The imidazole derivative is 1-7enethyl-2-
Methylimidazole, 1-cyclohexyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-tosyl-2-methylimidazole, 1-(2-ethoxycaryl)ethyl-2-methylimidazole,
Claim 1 is N-(1-(4,5-trimethyl)imidazolyl)pe/tylphthalimide, 11-1l-(2-methyl)imidazolyl)undecanoate, or 1,2-dimethylimidazole. Gas adsorption/desorption agent as described. C1l Iron (I) of porphyrins in which heme is a biological component
The gas adsorption/desorption agent according to any one of claims 6 to 9, which is an iron complex.