CN102060866A - Rare earth ternary complex as well as preparation method and application thereof - Google Patents
Rare earth ternary complex as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ternary complex formed by rare earth elements and 2-pyridine carboxaldehyde thiosemicarbazone Schiff base and 8-oxyquinoline or derivatives thereof as well as a preparation method and application of the ternary complex as an antibacterial agent. The chemical formula of the rare earth ternary complex is: Ln(L)Hq(NO3)3C2H5OH.CH3OH, Ln(L)(HqM)2(NO3)C2H5OH.CH3OH; Ln(L)(HqS)2(NO3) C2H5OH.CH3OH, wherein the Ln is a rare earth ion; the L is 2-pyridine carboxaldehyde thiosemicarbazone Schiff base; the Hq is 8-oxyquinoline; the HqM is a 8-oxyquinoline derivative connected with an electron donating group on the quinoline ring 2-position; and the HqS is a 8-oxyquinoline derivative connected with an electron withdrawing group on the quinoline ring 5-position. The rare earth ternary complex has the advantages of good chemical stability, heat stability and lipid solubility, strong antibacterial activity and little pollution.
Description
Technical field
The present invention relates to rare earth ternary complex and its production and application, specifically, be a kind of preparation method by the ternary complex that has substituent oxine derivative to form on rare earth element and 2-pyridylaldehyde thiosemicarbazone schiff bases and oxine or the quinoline ring with and as the application of antiseptic-germicide.
Background technology
Human paces have marched toward 21st century, raising along with the human living standard, public health service more and more is subjected to people's attention, and sick and Influenza A H1N1s in 2009 etc. make the public recognize that clear-headedly the hygienic safety problem is related to national and universe's health and safety to the infection of human body from " atypical pneumonia " to 2008 " hand stomatopod " in spring in 2003.Make people be alerted to the fearful property of bacterium, virus and to the worry of human health situation.
Rare earth element and title complex thereof have in life science widely to be used, and people have done a lot of research to this.In the sixties in 20th century, people just find that tiron and sulphosalicylic acid rare earth are potential anti-inflammatory, germ killing drugs, and various subsequently antibacterials constantly are synthesized out.Lu Xiaohong etc. utilize and contain 2-NH in the Methionin molecule
2Group utilizes their sterically hindered and reactive behavior different, and is synthetic and characterized novel rare earth Schiff alkali title complex, and the anti-microbial activity of title complex is studied.Li Jinzhou etc. have synthesized furancarbonyl pyrazolone double-Schiff base rare earth compounding, part and Pr (NO
3)
3Experimental strain is all had certain activity, and behind the formation title complex, anti-microbial effect strengthens (active raising 34～74%).Can strengthen its fungistatic effect because rare earth ion forms title complex, therefore this field progressively causes people's attention and concern in recent years.
Rare earth is as the high yield element of China, be proved to be and had reasonable biological activity, its title complex has important medical value aspect anticoagulation, the rare earth compound solution of lower concentration has antibacterial, anti-inflammatory action, and also there is more application aspects such as this external anti-analgesia, arteriosclerosis.Rare earth ion has the intensive perviousness, can be penetrated into the film inside of microorganism, can carry other ion with anti-microbial activity in the process of its infiltration enters in the film, so that the protein structure of microorganism is destroyed, cause microbial death like this or produce dysfunction, cause microbial death.That Schiff alkali has is antibacterial, sterilization, antitumor, antiviral biological activity, but also can be used as good part.The 2-pyridylaldehyde thiosemicarbazone schiff bases that the present invention selects for use, this heterocycle schiff bases is compared with common schiff bases part, it not only has electron donor(ED)s such as extra N, S, O, and can offer center rare earth coordination ion better stability and bigger steric effect, behind metal ion formation title complex, can improve its biological activity greatly, reduce toxicity.The oxine or derivatives thereof has sterilization and photoluminescent property, itself also is a kind of good part, is widely applied to fields such as antibiotic antitumor drug and luminescent material after forming stable title complex with metal ion.But do not see the ternary complex that forms by 2-pyridylaldehyde thiosemicarbazone schiff bases oxine or derivatives thereof and rare earth relevant report so far as antiseptic-germicide.
In addition title complex being prepared into nano level diameter, is because general bacterium-sized about about micron, therefore, prepares the antiseptic-germicide with nano-scale and can make the active easier cell interior that enters mutually, makes the membranolysis of cell.Secondly, the volume effect of nanoparticle uniqueness can improve active distribution consistency degree mutually greatly with surface-area effects, and it is long-pending to increase its surface in contact with cell, thereby further improves biological activity, and the minimizing dosage reduces cost; Utilize the quantum size effect of nanoparticle and macro quanta tunnel effect etc. can improve its electronics and level structure characteristic, to improve antibacterial ability.
Summary of the invention
The purpose of this invention is to provide technical problem to be solved and provide ternary complex that a class forms by rare earth element, 2-pyridylaldehyde thiosemicarbazone schiff bases, oxine or derivatives thereof and preparation method thereof and its application as antiseptic-germicide.
Purpose of the present invention can be achieved through the following technical solutions.
The rare earth ternary complex, its chemical formula is: Ln (L) Hq (NO
3)
3C
2H
5OHCH
3OH, Ln (L) (HqM)
2(NO
3) C
2H
5OHCH
3OH; Ln (L) (HqS)
2(NO
3) C
2H
5OHCH
3OH, wherein: Ln is a rare earth ion; L is a 2-pyridylaldehyde thiosemicarbazone schiff bases; Hq is an oxine; HqM is the oxine derivative that is connected to electron-donating group on the quinoline ring 2-position; HqS is the oxine derivative that is connected to electron withdrawing group on the quinoline ring 5-position.
Described rare earth ion is preferably from La
3+, Ce
3+, Pr
3+, Nd
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Y
3+, Er
3+, Tm
3+And Yb
3+In one or more.
The chemical structural formula of described Hq, HqM and HqS can by
Expression; Wherein, the substituent R in the chemical structural formula of Hq
1, R
2Be hydrogen atom; Substituent R in the chemical structural formula of HqM
1Be electron-donating groups such as methyl, R
2Be hydrogen atom; Substituent R in the chemical structural formula of HqS
1Be hydrogen atom, R
2Be electron-withdrawing groups such as sulfonic group, nitro.
The preparation method of above-mentioned ternary complex, its concrete steps are as follows:
(1) preparation of part 2-pyridylaldehyde thiosemicarbazone schiff bases
The mol ratio of 2-pyridylaldehyde and thiosemicarbazide is 1: 1, with both ethanol solution at 70～80 ℃ of backflow 4h, after reaction finishes, cooling has the crystalline white solid to separate out, and filters, with washing with alcohol three times, the solid that obtains places vacuum drying oven inner drying 4～6h, get final product pure product.Reaction equation is as follows:
(2) preparation of rare earth ternary complexes
Under the condition of reflux, Ln (NO
3)
36H
2O (Ln=La
3+, Ce
3+, Pr
3+, Nd
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Y
3+, Er
3+, Tm
3+And Yb
3+In a kind of, can be two or more combinations also, such as rare earth La
3+And Eu
3+, Pr
3+And Nd
3+, Nd
3+And Sm
3+, Y
3+And Er
3+Even 15 kinds of rare earth elements is whole) methanol solution slowly be added drop-wise in the hot ethanol solution by the 2-pyridylaldehyde thiosemicarbazone schiff bases part of step (1) preparation, stirring and refluxing 2～4h, the ethanol solution that in this mixing solutions, dropwise adds the oxine or derivatives thereof again, it is muddy that solution becomes at once, continue stirring and refluxing 2～4h then, rare earth nitrate, 2-pyridylaldehyde thiosemicarbazone schiff bases, the mol ratio of oxine or derivatives thereof is 1: 1: 3, be cooled to suction filtration after the room temperature, respectively wash three times with dehydrated alcohol and redistilled water, behind gained title complex vacuum-drying 4～8h, it is stand-by to place moisture eliminator to preserve.
Preferred 0.5～the 2mol/L of concentration of described 2-pyridylaldehyde and thiosemicarbazide ethanolic soln.
Preferred 0.2～the 2mol/L of concentration concentration of the methanol solution of described rare earth nitrate.
Preferred 0.1～the 1.8mol/L of concentration of the ethanolic soln of described 2-pyridylaldehyde thiosemicarbazone schiff bases.
Preferred 0.1～the 1.8mol/L of the concentration of the ethanolic soln of described oxine or derivatives thereof.
The average particle size range of described rare earth ternary complexes is 50～500nm.
The antibacterial experiment result shows that rare earth ternary complexes of the present invention all has good antibacterial activity to intestinal bacteria, streptococcus aureus, belongs to broad spectrum antimicrobicide.Because the size of general germ or bacterium is about about 0.5～5 micron, therefore particle size range is that the rare earth ternary complexes of 50～500nm can make the active easier bacterium inside that enters mutually, make the membranolysis of bacterium, and kill effectively and suppress virus and bacteria, have efficient, fast, the characteristics of lasting and broad-spectrum antimicrobial.
Compared with prior art, beneficial effect of the present invention is as follows:
1) rare earth ternary complexes of the present invention is to have good chemical stability and thermostability with coordinate bond bonded rare earth 2-pyridylaldehyde thiosemicarbazone schiff bases oxine or derivatives thereof ternary complex, can stand 600 ℃ high temperature, can use at normal temperatures, storage and transport.
2) preparation technology of rare earth ternary complexes of the present invention is simple, mild condition, and no toxic and harmful produces in the manufacturing processed, and is less to the pollution of environment.
3) rare earth ternary complexes of the present invention has good fat-solublely, makes it enter the cytolemma of bacterium and bacterium is played lethal effect easilier.
4) ternary complex of the present invention is different relevant to the group that is connected on the antibacterial circle diameter of intestinal bacteria and streptococcus aureus and the oxine derivative, find by contrast, oxine rare earth ternary complexes anti-microbial activity is best, can reach＞30mm, minimal inhibitory concentration can reach≤60 μ gmL
-1The anti-microbial activity that is connected to oxine derivative (as the 2-methyl-oxine) rare earth ternary complexes of electron-donating group also belongs to strong anti-microbial activity, but slightly poorer than the anti-microbial activity of oxine rare earth ternary complexes; The anti-microbial activity that is connected to oxine derivative (as the 5-sulfonic acid-oxine) rare earth ternary complexes of electron withdrawing group does not all have the above two good, belongs to medium anti-microbial activity.Experimental result shows that this particle size range is that the rare earth ternary complexes of 50～500nm has stronger anti-microbial activity, and antibacterial ability all is better than any single part.
Description of drawings
The ultraviolet figure that Fig. 1, Fig. 2, Fig. 3 record in the DMF of 1mmol/L solution for the prepared rare earth ternary complexes of embodiment 1 and part thereof; Wherein, Fig. 1: La (L) Hq (NO
3)
3C
2H
5OHCH
3OH; Fig. 2: La (L) (HqM)
2(NO
3) C
2H
5OHCH
3OH; Fig. 3: La (L) (HqS)
2(NO
3) C
2H
5OHCH
3OH
Fig. 4 is the differential thermal thermal multigraph of the prepared rare earth ternary complexes of embodiment 6;
Fig. 5 is the transmission electron microscope photo of the prepared rare earth ternary complexes of embodiment 4;
Fig. 6 is that embodiment 3 prepared rare earth ternary complexes and parts thereof are schemed colibacillary antibacterial ring contrast, among the figure: a:Y (NO)
36H
2O; B:L (2-pyridylaldehyde thiosemicarbazone schiff bases); C: control group; The d:8-hydroxyquinoline; E:Y (L) Hq (NO
3)
3C
2H
5OHCH
3OH.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, as operational manual, or the condition of advising according to manufacturer.All inorganic chemical reagents and organic solvent are available from Shanghai chemical reagent factory; Intestinal bacteria and streptococcus aureus provide by Shanghai Pharmaceutical Inst., Chinese Academy of Sciences.
Embodiment 1
(1) preparation of part 2-pyridylaldehyde thiosemicarbazone schiff bases
0.05mol 2-pyridylaldehyde is dissolved in the 50mL dehydrated alcohol, place the 150mL round-bottomed flask, under agitation in this solution, slowly drip the ethanol solution of 4.557g (0.05mol) thiosemicarbazide, at 70～80 ℃ of backflow 4h, after reaction finishes, cooling, there is the crystalline white solid to separate out, filters, use washing with alcohol three times, the solid that obtains places vacuum drying oven inner drying drying 4～6h, get final product pure product.(productive rate: 89%; Fusing point: 197.2～197.3)
(2) preparation of rare earth ternary complexes
Take by weighing 0.18g (1mmol) 2-pyridylaldehyde thiosemicarbazone schiff bases and be dissolved in the hot ethanol solution of 5mL, under the condition of reflux, will contain 1mmol Ln (NO
3)
36H
2The methanol solution of O slowly is added drop-wise in the above-mentioned solution, stirring and refluxing 4h, in this mixing solutions, slowly drip the ethanol solution of the oxine that contains 3mmol again, it is muddy that solution becomes at once, continue stirring and refluxing 4h then, be cooled to suction filtration after the room temperature, respectively wash three times, obtain Ln (L) Hq (NO with dehydrated alcohol and redistilled water
3)
3C
2H
5OHCH
3OH, with the vacuum-drying of gained title complex be placed in the moisture eliminator preserve stand-by.
In the aforesaid method, L is a 2-pyridylaldehyde thiosemicarbazone schiff bases, and Hq is an oxine, and Ln can be La
3+, Ce
3+, Pr
3+, Nd
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Y
3+, Er
3+, Tm
3+And Yb
3+In a kind of, can be more than one combination also, such as rare earth La
3+And Ce
3+, Pr
3+And Nd
3+, Nd
3+And Sm
3+, Eu
3+And Er
3+, even 15 kinds of rare earth elements is whole, n kind Ln (NO
3)
36H
2When O was raw material, its reaction conditions was identical with process.
Embodiment 2～12
The difference of following examples and embodiment 1 is: it is different to prepare rare earth ternary complexes used Ln part and Hq part, and the oxine derivative that specific practice needs only identical mole number replaces oxine, and concrete ginseng being shown in Table 1.All the other contents are all with identical described in the embodiment 1.
The ultraviolet data that Fig. 1-Fig. 3 records in DMF solution for the prepared rare earth ternary complexes of embodiment 1 and part thereof, the ternary complex that can find identical ligands from uv atlas has similar spectrogram, and the spectrogram of title complex and the spectrogram of part have tangible difference.It is respectively 260nm and 324nm that schiff base ligand has two absorption peaks, red shift has all taken place in these two absorption peaks after forming title complex, this may be because when ligating atom and rare-earth ion coordination, distortion to a certain degree takes place in part, the delocalization conjugative effect weakens, the two key character of CH=N increase, and make this band than part red shift (as Fig. 1) be arranged.Oxine has two strong absorption peaks to be respectively 242nm at 316nm, forms latter two absorption peak of title complex all die down (as Fig. 1); 2-methyl-oxine has a weak absorption peak at the 224nm place, a strong and big absorption peak is arranged at the 305nm place, and behind the formation title complex, the absorption peak strength of title complex is big, but not wide (as Fig. 2); 5-sulfonic acid-oxine has a strong and narrow absorption peak at the 268nm place, have at the 323nm place a little less than in the of one but than the absorption peak of broad, form title complex after, the absorption peak (as Fig. 3) a little less than one of 328nm place formation.It is relevant with electron-withdrawing group to produce the electron-donating group that these different absorption peaks may be mainly have with oxine and derivative thereof.
Though the power of these absorption peaks, size are all different, red shift has all taken place in these peaks.This is because after forming title complex, p-π key conjugated degree strengthens in the molecule, energy is reduced, thereby produce the red shift phenomenon.
By above analysis, we can judge that coordination has taken place for each part and rare earth ion.
Fig. 4 is the differential thermal thermal multigraph of the prepared rare earth ternary complexes of embodiment 6, in the time of 71～211 ℃, a little endotherm(ic)peak is arranged, on the TG curve, weightlessness is arranged simultaneously, promptly be that title complex loses methyl alcohol and alcoholic acid process, and lose methyl alcohol, the alcoholic acid amount is consistent with results of elemental analyses.Title complex begins oxygenolysis subsequently, occurs two exothermic peaks on the DTA curve, the proceed step by step during oxygenolysis of this explanation title complex.The decomposing oxidation exothermic peak of fs is 211～501 ℃, is accompanied by a little exothermic effect peak; The decomposing oxidation exothermic peak of subordinate phase is 522～601 ℃, and is accompanied by a peak of a strong exothermic effect.Generation corresponding to decomposition, oxidation and the metal oxide of part in the title complex.After 600 ℃, each title complex just gradually decomposes fully, and the decomposition of title complex and oxidation stop, and decomposes fully to become corresponding rare earth oxide RE
2O
3, show that title complex has certain thermostability.The percentage of actual title complex weightlessness coincide basically with theoretical weightless percentage.
Fig. 5 is the TEM figure of the prepared rare earth ternary complexes of embodiment 4, and intermediary nuclear is metal ion, and outer bread part, and the pattern of whole particle is very clear, and the particle diameter major part of particle is about 100～500nm.Illustrate that the synthetic title complex is nano level.
The median size of the rare earth ternary complexes of the part of participation reaction and generation among table 1 embodiment 1～12
Embodiment 13
The substratum diffusion process
(1) principle: utilize antiseptic-germicide constantly to dissolve and form the different concns gradient, to show its anti-microbial effect through agar diffusion.
(2) operation steps:
1. the preparation of antiseptic-germicide: rare earth compounding is dissolved with DMF, add the emulsification of a small amount of tween 80 solubilising, be mixed with the suspension agent of 0.005mol/L, oxine, 2-methyl-oxine, 5-sulfonic acid-oxine, 5-nitro-oxine, Ln (NO
3)
36H
2O, Schiff's base are mixed with the solution of 0.005mol/L respectively.
2. antibiotic preparation: get aseptic and exsiccant filter paper (bore dia 5mm), then filter paper is wrapped to be placed in the Sterilizers with double-deck newspaper and sterilize, after sterilization has been got well, put in the incubator (37 ℃) standby after the oven dry.
3. the inoculation of test organisms: dip in aseptic cotton carrier that to get concentration be 5 * 10
5CfumL
-1～5 * 10
6CfumL
-1The test organisms suspension is evenly smeared 3 times on the nutrient agar surface.Whenever smear 1 time, flat board should rotate 60 °, at last cotton swab is smeared a week around plate edge.Build plate, put drying at room temperature 5min.
4. the antiseptic-germicide print pastes and puts: paste with the aseptic nipper coupongs and be put in the microbiological contamination planar surface, the negative contrast print of a paster drips antimicrobial 20 μ L on other the every paster, after subsides are put well, gently press print with aseptic nipper, makes it be close to planar surface.Build culture dish, put 37 ℃ of incubators, observations behind cultivation 18h～24h, antibacterial ring is an annulus transparent on the nutrient agar, the bacterium that do not grow is with vernier caliper measurement inhibition zone diameter (comprising paster) and record.Test repeats 3 times.
(3) estimate regulation: 3 times repeated experiments all has bacteriostatic action person as a result, and it is qualified to be judged to; Negative control group should not have antibacterial ring and produces, otherwise test invalid.
(4) bacteriostasis property evaluation: experiment judges by the inhibition zone size whether it has antibacterial ability.Antibacterial circle diameter is less than or equal to 7mm person, is no bacteriostatic action.Antibacterial circle diameter is greater than 7mm person, for weak bacteriostatic action is arranged; Inhibition zone is medium antibacterial at 10～20mm; Antibacterial circle diameter represents to have strong fungistatic effect greater than 20mm.
The antibacterial ring test data of prepared rare earth ternary complexes among table 2 embodiment 1～12
As shown in Table 2: in the prepared rare earth ternary complexes, the rare earth ternary complexes 〉=20mm of oxine; The oxine derivative to the inhibition zone diameter of intestinal bacteria (ATCC8099) and streptococcus aureus (ATCC6538) basically between 10mm～20mm.
Fig. 6 is that embodiment 3 prepared rare earth ternary complexes and parts thereof are schemed colibacillary antibacterial ring contrast, among the figure: a:Y (NO)
36H
2O; B:L (2-pyridylaldehyde thiosemicarbazone schiff bases); C: control group; The d:8-hydroxyquinoline; E:Y (L) Hq (NO
3)
3C
2H
5OHCH
3OH
Embodiment 14
Dilution nutrient broth method
(1) principle
This test with the antiseptic-germicide mixed dissolution of different concns in nutrient broth medium (being used for microbial culture) or husky fort broth culture (being used for fungus culture), inoculated bacteria or fungi then, whether growth by bacterium, determine that antiseptic-germicide suppresses to be tried the minimum concentration of bacterium or fungal growth, be minimal inhibitory concentration (Minimal Inhibitory Concentration, MIC).
(2) experimental procedure
(1) antiseptic-germicide with different mass is dissolved in respectively in the 100mL nutrient broth medium;
(2) pipette a certain amount of bacterial suspension inoculation in the Erlenmeyer flask of the nutrient broth that contains antiseptic-germicide, make its concentration reach 1 * 10
5～5 * 10
6CfumL
-1As the test group sample; In kind be inoculated in the Erlenmeyer flask of the nutrient broth that do not contain antiseptic-germicide or husky fort meat soup, as the positive controls sample; Get only contain 100mL nutrient broth medium or husky fort broth culture Erlenmeyer flask as negative control group;
(3) test group sample, positive controls sample and negative control group sample are placed in 37 ℃ of incubators cultivate 18h-24h, observations;
(4) test should be carried out live bacterial count with bacteria suspension in the test, 30～300cfu is effective counting region on the nutrient agar flat board, determines final MIC.
(3) MIC result passes judgment on regulation and anti-microbial property evaluation
It is generally acknowledged that working as the activity of testing with bacteria suspension is 5 * 10
5～5 * 10
6CfumL
-1The time, positive controls has bacterium or fungal growth (occurring muddy), negative control group asepsis growth (entire body is transparent), the pairing antiseptic-germicide concentration of high dilution of test group asepsis growth, for this sample to being tried the MIC of bacterium.According to standard code, as the MIC≤800 μ gmL of analyte
-1The time, think that promptly this analyte has antibacterial effect, and more little its anti-microbial property of MIC is good more.
The minimal inhibitory concentration testing data of the rare earth ternary complexes that table 3 the foregoing description is prepared
As can be known from the above table: according to " disinfection technology standard " standard that Ministry of Health of the People's Republic of China 2006 issues, (1) part and title complex all have restraining effect to intestinal bacteria and streptococcus aureus.In part oxine and derivative thereof, the germ resistance of 2-methyl-oxine slightly is better than oxine and 5-sulfonic acid-oxine; In this three serial title complex, Ln (L) Hq (NO
3)
3C
2H
5O HCH
3The anti-microbial activity of OH significantly is better than Ln (L) (HqM)
2(NO
3) C
2H
5OHCH
3OH and Ln (L) are (HqS)
2(NO
3) C
2H
5OHCH
3OH.(2) at serial Ln (L) Hq (NO
3)
3C
2H
5OHCH
3Among the OH, anti-microbial activity Y＞La＞Nd, title complex are better than each part far away; At serial Ln (L) (HqM)
2(NO
3) C
2H
5OHCH
3Among the OH, anti-microbial activity Nd＞Y＞La, the anti-microbial activity of title complex slightly is better than each title complex; At serial Ln (L) (HqS)
2(NO
3) C
2H
5OHCH
3Among the OH, the anti-microbial activity of title complex is not enhanced, and is similar basically with part.(3) for identical central ion, anti-microbial activity La (L) Hq (NO
3)
3C
2H
5OHCH
3OH＞La (L) (HqM)
2(NO
3) C
2H
5OHCH
3OH＞La (L) (HqS)
2(NO
3) C
2H
5OHCH
3OH, this is mainly relevant with part oxine and derivative thereof.The result shows to have power supply or electrophilic group on the oxine, can reduce the biological activity of title complex, and it is bigger to contain the influence of electron-withdrawing group.
Claims (10)
1. rare earth ternary complex, it is characterized in that: its chemical formula is: Ln (L) Hq (NO
3)
3C
2H
5OHCH
3OH, Ln (L) are (HqM)
2(NO
3) C
2H
5OHCH
3OH or Ln (L) are (HqS)
2(NO
3) C
2H
5OHCH
3OH; Wherein: Ln is a rare earth ion; L is a 2-pyridylaldehyde thiosemicarbazone schiff bases; Hq is an oxine; HqM is the oxine derivative that is connected to electron-donating group on the quinoline ring 2-position; HqS is the oxine derivative that is connected to electron withdrawing group on the quinoline ring 5-position.
2. rare earth ternary complex according to claim 1 is characterized in that: described rare earth ion is selected from La
3+, Ce
3+, Pr
3+, Nd
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Y
3+, Er
3+, Tm
3+And Yb
3+In one or more.
3. rare earth ternary complex according to claim 1 is characterized in that: the chemical structural formula of Hq, HqM and HqS can by
Expression; Substituent R in the chemical structural formula of Hq
1, R
2Be hydrogen atom; Substituent R in the chemical structural formula of HqM
1Be electron-donating groups such as methyl, R
2Be hydrogen atom; Substituent R in the chemical structural formula of HqS
1Be hydrogen atom, R
2Be electron-withdrawing groups such as sulfonic group, nitro.
4. prepare the method for the described rare earth ternary complexes of claim 1, it is characterized in that: its concrete steps are as follows:
(1) preparation of part 2-pyridylaldehyde thiosemicarbazone schiff bases
The mol ratio of 2-pyridylaldehyde and thiosemicarbazide is 1: 1, with both ethanol solution at 70～80 ℃ of backflow 4h, after reaction finishes, cooling has the crystalline white solid to separate out, and filters, with washing with alcohol three times, the solid that obtains places vacuum drying oven inner drying 4～6h, get final product pure product; Reaction equation is as follows:
(2) preparation of rare earth ternary complexes
Under the condition of reflux, Ln (NO
3)
36H
2O (Ln=La
3+, Ce
3+, Pr
3+, Nd
3+, Pm
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Y
3+, Er
3+, Tm
3+And Yb
3+In a kind of, can be two or more combinations also, such as rare earth La
3+And Eu
3+, Pr
3+And Nd
3+, Nd
3+And Sm
3+, Y
3+And Er
3+Even 15 kinds of rare earth elements is whole) methanol solution slowly be added drop-wise in the hot ethanol solution by the 2-pyridylaldehyde thiosemicarbazone schiff bases part of step (1) preparation, stirring and refluxing 2～4h, the ethanol solution that in this mixing solutions, dropwise adds the oxine or derivatives thereof again, it is muddy that solution becomes at once, continue stirring and refluxing 2～4h then, rare earth nitrate, 2-pyridylaldehyde thiosemicarbazone schiff bases, the mol ratio of oxine or derivatives thereof is 1: 1: 3, be cooled to suction filtration after the room temperature, respectively wash three times with dehydrated alcohol and redistilled water, behind gained title complex vacuum-drying 4～8h, it is stand-by to place moisture eliminator to preserve.
5. the method for rare earth ternary complexes according to claim 4, it is characterized in that: the concentration of described 2-pyridylaldehyde and thiosemicarbazide ethanolic soln is 0.5～2mol/L.
6. the method for rare earth ternary complexes according to claim 4, it is characterized in that: the concentration concentration of the methanol solution of described rare earth nitrate is 0.2～2mol/L.
7. the method for rare earth ternary complexes according to claim 4, it is characterized in that: the concentration of the ethanolic soln of described 2-pyridylaldehyde thiosemicarbazone schiff bases is 0.1～1.8mol/L.
8. the method for rare earth ternary complexes according to claim 4, it is characterized in that: the concentration of the ethanolic soln of described oxine or derivatives thereof is 0.1～1.8mol/L.
9. the method for rare earth ternary complexes according to claim 4, it is characterized in that: the average particle size range of the rare earth ternary complexes in described is 50～500nm.
10. rare earth ternary complex according to claim 1 is characterized in that: the broad spectrum antimicrobicide that can be applicable to intestinal bacteria, streptococcus aureus.
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| CN102617620A (en) * | 2012-03-07 | 2012-08-01 | 上海师范大学 | Heterocyclic ligand-containing efficiently-antibacterial rare earth ternary complexes, and preparation method and application thereof |
| CN102643297A (en) * | 2012-03-07 | 2012-08-22 | 上海师范大学 | Antibacterial copper ternary complex with fluorescence and preparation method and application thereof |
| CN107501310A (en) * | 2017-09-07 | 2017-12-22 | 蚌埠医学院 | Three core rare earth compoundings and its solvothermal preparation method and application based on schiff base ligand |
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| CN102417516A (en) * | 2011-05-30 | 2012-04-18 | 上海师范大学 | 2-pyridylaldehyde thiosemicarbazone Schiff base/8-hydroxyquinoline/rare earth ternary complex, and preparation method and application thereof |
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| CN102643297A (en) * | 2012-03-07 | 2012-08-22 | 上海师范大学 | Antibacterial copper ternary complex with fluorescence and preparation method and application thereof |
| CN102643297B (en) * | 2012-03-07 | 2015-07-15 | 上海师范大学 | Antibacterial copper ternary complex with fluorescence and preparation method and application thereof |
| CN102617620B (en) * | 2012-03-07 | 2015-12-16 | 上海师范大学 | One class contains antibiosis rare earth ternary complexes of heterocyclic ligand and its preparation method and application |
| CN107501310A (en) * | 2017-09-07 | 2017-12-22 | 蚌埠医学院 | Three core rare earth compoundings and its solvothermal preparation method and application based on schiff base ligand |
| CN115197247A (en) * | 2022-07-15 | 2022-10-18 | 太原师范学院 | Rare earth complex with broad-spectrum antibacterial function and preparation method and application thereof |
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