CN102617620B - One class contains antibiosis rare earth ternary complexes of heterocyclic ligand and its preparation method and application - Google Patents
One class contains antibiosis rare earth ternary complexes of heterocyclic ligand and its preparation method and application Download PDFInfo
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- CN102617620B CN102617620B CN201210058821.1A CN201210058821A CN102617620B CN 102617620 B CN102617620 B CN 102617620B CN 201210058821 A CN201210058821 A CN 201210058821A CN 102617620 B CN102617620 B CN 102617620B
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Abstract
The invention discloses a class and contain high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand and its preparation method and application, its chemical constitution is RE (Assb) (Hq)
25H
2o, RE are rare earth; Assb is thiazolamine salicylaldehyde Schiff's base; Hq is oxine.A class of the present invention has strong bacteriostatic activity containing the high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand, it is all greater than 30mm to the antibacterial circle diameter of intestinal bacteria and streptococcus aureus, there is good chemical stability, thermostability and fat-soluble simultaneously, can be used as antiseptic-germicide and be applied to antibacterial field.
Description
Technical field
The present invention relates to a class and contain high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand and its preparation method and application, specifically, be that rare earth ion and thiazolamine salicylaldehyde Schiff's base and oxine form the preparation method of ternary complex and the application in antibacterial field.
Background technology
Along with the fast development of science and technology, hygiene medical treatment level have also been obtained very large progress, also more and more pays close attention to hygiene and health situation while people's living standard improves constantly.But the public health security that current mankind faces threatens and but grows with each passing day, and SARS, " bird flu ", " mad cow disease ", " foot and mouth disease ", " superbacteria " come one after another, and bring the fear that people are huge, and world's public health security situation causes anxiety.The preventing and controlling of public health medical field seem particularly important, and therefore, anti-bacteria and anti-virus research becomes current study hotspot.
From 18 the end of the century rare earth element found successively, be now widely used in the fields such as biological medicine, material, electronics, aviation, agricultural, be described as " industrial monosodium glutamate ".Rare earth ion, due to its special electron structure, can suppress the Metabolic activity of mushroom, has the effects such as antibacterial, anti-inflammatory, analgesia.Rare earth element and title complex thereof are widely used in life science, become the focus of current research.There are some researches show, compared with many organic synthesis medicines or transition metal complex, the toxicity of rare earth compounding is low, does not find cylinder accumulation by oral or external application rare earth compounding.
Research shows, Schiff's base and metal complexes thereof have good antibacterial and antiviral biological activity, become one of study hotspot in recent years.A kind of part that the present invention selects-thiazolamine salicylaldehyde Schiff's base is a class wherein with stronger bacteriostatic activity as Schiff bases containing sulfur, thiazole also has stronger pharmacologically active simultaneously, much antibiotic is as having thiazole ring in the molecule of penicillin, Sulphathiazole, if introduced by thiazole ring in complex molecule, then have stronger biological activity.
Another part-oxine that the present invention selects also has good antibiotic bioactive, and correlative study shows, the formation of oxine energy anti-bacteria cytolemma, thus plays germicidal action, is widely used as excellent sterilant.N, O in oxine, with lone-pair electron, are a kind of good parts, can increase the conjugated system of title complex, make the fat-soluble enhancing of title complex, strengthen its bacteriostasis.
Heterogeneous ring compound is that a class has bioactive compound widely, and research shows that many heterogeneous ring compounds have sterilization, anti-inflammatory, the biological activity such as antiviral, thus receives much concern.After heterogeneous ring compound and rare earth ion form title complex, due to synergistic effect, the anti-microbial effect of rare earth compounding will strengthen.
In sum, the ternary complex that rare earth ion of the present invention and thiazolamine salicylaldehyde Schiff's base and oxine are formed is with a wide range of applications in antibacterial field.
Summary of the invention
Technical problem to be solved by this invention is to provide rare earth ion and thiazolamine salicylaldehyde Schiff's base and oxine and forms ternary complex and preparation method thereof and the application in antibacterial field.
Technical problem to be solved by this invention is achieved through the following technical solutions:
One class is containing the high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand, and its chemical constitution is RE (Assb) (Hq)
25H
2o, wherein RE is rare earth, and Assb is thiazolamine salicylaldehyde Schiff's base, and Hq is oxine, and its structural formula can be expressed as:
Described rare earth ion is selected from La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+and Y
3+in one or more.
The preparation method of the above-mentioned high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand, concrete steps are as follows:
(1) in the ethanol solution of thiazolamine salicylaldehyde Schiff's base, anhydrous Na is added
2cO
3control at 6-7 by the pH value of solution, heated solution, to 50-80 DEG C, stirs 20-50min;
(2) in above-mentioned solution, drip the ethanol solution of rare earth nitrate, continue reaction 2-4h, wherein, rare earth nitrate: the mol ratio of thiazolamine salicylaldehyde Schiff's base is 1: 1-1: 1.1;
(3) in above-mentioned solution, drip the ethanol solution of oxine, continue reaction 2-4h, separate out and precipitate to obtain target product, wherein rare earth nitrate: the mol ratio of oxine is 1: 2-1: 2.2.
By absolute ethanol washing 2-4 time of step (3) gained precipitation, then use dehydrated alcohol recrystallization 1-3 time, 20-50 DEG C of vacuum-drying 4-8h, target product of can purifying.
The preparation method of described thiazolamine salicylaldehyde Schiff's base is as follows:
(1) ethanol solution of thiazolamine is heated to 50-80 DEG C, adds the salicylic aldehyde with thiazolamine same molar under agitation, 50-80 DEG C of reaction 2-4h;
(2) remove 3/4-4/5 ethanol, leave standstill cooling 18-24h, separate out precipitation, suction filtration, by filter residue dehydrated alcohol recrystallization 1-3 time, obtain thiazolamine salicylaldehyde Schiff's base;
Reaction equation is as follows:
Compared with prior art, beneficial effect of the present invention is as follows:
A class of the present invention has good fat-soluble containing the high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand, easy permeates cell membranes enters bacterium inside, suppresses and kills bacterium;
A class of the present invention has good chemical stability and thermostability containing the high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand, is convenient to preserve, use and transport;
Antibacterial tests result shows that a class of the present invention all has stronger bacteriostatic action containing the high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand to intestinal bacteria and streptococcus aureus, belong to broad spectrum antimicrobicide, all 30mm is greater than to the antibacterial circle diameter of above-mentioned two kinds of bacteriums, the bacteriostatic action of rare earth ternary complexes is obviously better than part, intestinal bacteria are better than to the bacteriostatic action of streptococcus aureus, can be used as antiseptic-germicide and be applied to antibacterial field;
A class of the present invention is simple containing the preparation technology of the high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand, and productive rate is high, and non-toxic by-products produces, and pollute little, raw materials cost is lower, easily realizes suitability for industrialized production.
Accompanying drawing explanation
The ultraviolet spectrogram of the part thiazolamine salicylaldehyde Schiff's base of Fig. 1 prepared by the embodiment of the present invention 1.
The ultraviolet spectrogram of the high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 2 prepared by the embodiment of the present invention 1.
The x-ray photoelectron spectroscopy figure of the high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 3 prepared by the embodiment of the present invention 1.
Differential thermal-the thermal multigraph of the high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 4 prepared by the embodiment of the present invention 1.
The high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 5 prepared by the embodiment of the present invention 1 is to colibacillary antibacterial loop graph.
The high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 6 prepared by the embodiment of the present invention 1 is to the antibacterial loop graph of streptococcus aureus.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.
The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, as operational manual, or according to the condition that manufacturer advises.All inorganic chemical reagents and organic solvent are purchased from Solution on Chemical Reagents in Shanghai company limited of traditional Chinese medicines group; Intestinal bacteria and streptococcus aureus provide by Shanghai Pharmaceutical Inst., Chinese Academy of Sciences.
Embodiment 1:
Ethanol solution 100mL being contained 20mmol2-aminothiazole is heated to 78 DEG C under magnetic stirring, 20mmol salicylic aldehyde is dripped with the rate of addition of 1-2mL/min in above-mentioned solution, 78 DEG C of back flow reaction 4h, air distillation boils off 4/5 ethanol, leave standstill cooling 24h, separate out yellow mercury oxide, suction filtration, by filter residue dehydrated alcohol recrystallization 3 times, obtain yellow needle-like crystals (fusing point: 78.1-78.3 DEG C).Productive rate: 83.2%.
The ultraviolet spectrogram of the part thiazolamine salicylaldehyde Schiff's base of Fig. 1 prepared by the present embodiment.As can be known from Fig. 1, the principal character absorption peak of thiazolamine salicylaldehyde Schiff's base all there occurs considerable change compared with raw material thiazolamine.Thiazolamine has a strong absorption peak at 265nm place, and there is stronger absorption peak at thiazolamine salicylaldehyde Schiff's base 213,235,277 and 367nm place.The ultraviolet absorption peak that this explanation thiazolamine and salicylic aldehyde generation condensation reaction generate each main functional group of thiazolamine salicylaldehyde Schiff's base there occurs obvious displacement.
Be dissolved in 10mL dehydrated alcohol by 3mmol2-aminothiazole salicylaldehyde Schiff's base, magnetic agitation, adds 0.6mmol anhydrous Na
2cO
3, dissolve, measure pH value control pH 6 ~ 7, be heated to 78 DEG C, magnetic agitation 30min, then in above-mentioned solution, drip the ethanol solution of 10mL containing 3mmol rare earth lanthanum nitrate, rate of addition is 1-2mL/min, magnetic agitation, 78 DEG C of back flow reaction 4h, slowly drip the ethanol solution of 20mL containing 6mmol8-hydroxyquinoline again, rate of addition is 1-2mL/min, magnetic agitation, 78 DEG C of back flow reaction 4h, separate out precipitation, leave standstill cooling, suction filtration, by filter residue absolute ethanol washing 3 times, again by filter residue dehydrated alcohol recrystallization 3 times, 30 DEG C of vacuum-drying 4h, obtain target product.Productive rate: 78.9%.
The ultraviolet spectrogram of the high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 2 prepared by the present embodiment.As can be seen from Figure 2, the principal character absorption peak of rare earth ternary complexes has compared obvious difference with part lanthanum nitrate, thiazolamine salicylaldehyde Schiff's base with oxine.Lanthanum nitrate has the last one absorption peak and has a weak absorbing peak at 285nm place at 230nm place, thiazolamine salicylaldehyde Schiff's base has stronger absorption peak in 213,235,277 and 367nm place, oxine has stronger absorption peak in 246 and 312nm place, and rare earth ternary complexes has stronger absorption peak and has more weak wide absorption peak band at 300-350nm and 445-500nm place in 225,260 and 375nm place.This illustrates that the ultraviolet absorption peak of lanthanum ion and part thiazolamine salicylaldehyde Schiff's base and each main functional group of oxine generation coordination reaction there occurs obvious displacement.
The x-ray photoelectron energy spectrogram of the high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 3 prepared by the present embodiment.This title complex has two of lanthanum ion strong absorption peaks in 838.11 and 855.11eV electron binding energy place, Sauerstoffatom strong absorption peak is had at 531.11eV electron binding energy place, there is nitrogen-atoms on heterocycle stronger absorption peak at 399.11eV electron binding energy place, and there is no the charateristic avsorption band of nitrate ion at about 407eV electron binding energy place.N, O atom generation coordination reaction in lanthanum ion and part thiazolamine salicylaldehyde Schiff's base and oxine, electron binding energy changes, and the nitrate ion in raw material lanthanum nitrate does not participate in coordination, further demonstrate that structure and the chemical constitution of this rare earth ternary complexes.
Differential thermal-the thermal multigraph of the high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 4 prepared by the present embodiment.Be in the air atmosphere of 50mLmin-1 at flow velocity, with α-Al
2o
3do reference, temperature rise rate 10 DEG C of min-1, measure TG-DTA within the scope of 25 DEG C ~ 1000 DEG C.There is dehydration endotherm peak at 90-110 DEG C in this rare earth ternary complexes, and with weightlessness, illustrating that the water molecules in title complex has neither part nor lot in coordination, is crystal water; Having there is decomposition oxidation heat liberation peak at 286,433,545,630 DEG C in this rare earth ternary complexes, and with there is remarkable weightlessness, title complex framework collapse, decomposes oxidation; The final product of thermolysis should be lanthanum trioxide.The rate of weight loss of this rare earth ternary complexes conforms to theoretical value, and this title complex has good thermostability simultaneously, and heat decomposition temperature is 252 DEG C.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, and difference is that rare earth nitrate used is praseodymium nitrate.Productive rate: 76.5%.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, and difference is that selected rare earth nitrate is samaric nitrate.Productive rate: 80.3%.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, and difference is that selected rare earth nitrate is Yttrium trinitrate.Productive rate: 79.2%.
In above-described embodiment, rare earth ion can be La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+and Y
3+in any one or multiple.
Anti-microbial property test and evaluation:
Test adopts substratum diffusion process, utilizes antiseptic-germicide constantly to dissolve and forms different concns gradient, to show its anti-microbial effect through agar diffusion.
Operation steps is: rare earth nitrate, thiazolamine salicylaldehyde Schiff's base, oxine and rare earth ternary complexes redistilled water or a small amount of DMF are dissolved, be mixed with the solution of 0.005mol/L, test the bacteriostatic action to intestinal bacteria and staphylococcus aureus respectively.Adopt substratum diffusion process, in 37 DEG C of incubators after 18-24h cultivates, measure its antibacterial circle diameter with vernier callipers.
Inhibition zone result passes judgment on regulation and anti-microbial property evaluation:
To repeat experiment negative control group for 3 times to produce without inhibition zone, antiseptic-germicide sample strip all has fungistatic effect, and it is qualified to be judged to; Otherwise it is invalid to test.Judge whether antiseptic-germicide has antibacterial ability by antibacterial circle diameter size.According to " People's Republic of China's chemical industry standard: inorganic antiseptic performance and evaluation ", antibacterial circle diameter is less than or equal to 7mm person, is judged to without bacteriostatic action; Antibacterial circle diameter is greater than 7mm person, has weak bacteriostatic action; Inhibition zone, 10-20mm person, has moderate antibacterial effect; Antibacterial circle diameter is greater than 20mm person, has strong bacteriostatic action.
Table 1 prepared by embodiment 1-4 containing the high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand and the inhibition zone data sheet of part thereof.
Table 1
The high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 5 prepared by embodiment 1 is to colibacillary antibacterial loop graph; The high-efficiency antimicrobial rare earth ternary complexes containing heterocyclic ligand of Fig. 6 prepared by embodiment 1 is to the antibacterial loop graph of streptococcus aureus.Have respectively in above-mentioned Fig. 5, Fig. 65 inhibition zones (above for blank, left side be lanthanum nitrate, in be lanthanum ternary complex, the right side is thiazolamine salicylaldehyde Schiff's base, time is oxine).
Anti-microbial property test adopts the test of substratum diffusion process, and the anti-bacterial result is in table 1 and Fig. 5, Fig. 6.From table 1 and Fig. 5, Fig. 6: a class of the present invention is all greater than 30mm containing the antibacterial circle diameter of high-efficiency antimicrobial rare earth ternary complexes to intestinal bacteria and streptococcus aureus of heterocyclic ligand, the bacteriostatic action of rare earth ternary complexes is obviously better than part, is better than intestinal bacteria to the bacteriostatic action of streptococcus aureus.Therefore, according to " disinfection technology standard " standard that Ministry of Health of the People's Republic of China 2006 issues, a class of the present invention all has stronger bacteriostatic action containing the high-efficiency antimicrobial rare earth ternary complexes of heterocyclic ligand to intestinal bacteria and streptococcus aureus, belong to broad spectrum antimicrobicide, can be used as antiseptic-germicide and be applied to antibacterial field.
Above-described embodiment is interpreted as only being not used in for illustration of the present invention limiting the scope of the invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalence changes and modification fall into the scope of the claims in the present invention equally.
Claims (2)
1. a class is containing the antibiosis rare earth ternary complexes of heterocyclic ligand, and it is characterized in that, its chemical constitution is RE (Assb) (Hq)
25H
2o, wherein RE is rare earth, and Assb is thiazolamine salicylaldehyde Schiff's base, and Hq is oxine, and its structural formula can be expressed as:
Described rare earth ion is selected from La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+and Y
3+in one or more;
Above-mentioned its concrete steps of ternary complex preparation method are as follows:
(1) in the ethanol solution of thiazolamine salicylaldehyde Schiff's base, anhydrous Na is added
2cO
3control at 6-7 by the pH value of solution, heated solution, to 50-80 DEG C, stirs 20-50min; The preparation method of described thiazolamine salicylaldehyde Schiff's base is as follows: the ethanol solution of thiazolamine is heated to 50-80 DEG C, adds the salicylic aldehyde with thiazolamine same molar under agitation, 50-80 DEG C of reaction 2-4h; Removing 3/4-4/5 ethanol, leaves standstill cooling 18-24h, separates out precipitation, suction filtration, by filter residue dehydrated alcohol recrystallization 1-3 time, obtains thiazolamine salicylaldehyde Schiff's base;
(2) in above-mentioned solution, drip the ethanol solution of rare earth nitrate, continue reaction 2-4h, wherein, rare earth nitrate: the mol ratio of thiazolamine salicylaldehyde Schiff's base is 1:1-1:1.1;
(3) in above-mentioned solution, drip the ethanol solution of oxine, continue reaction 2-4h, precipitation precipitates to obtain target product, absolute ethanol washing 2-4 time of gained precipitation, use dehydrated alcohol recrystallization 1-3 time again, 20-50 DEG C of vacuum-drying 4-8h, wherein rare earth nitrate: the mol ratio of oxine is 1:2-1:2.2.
2. a class according to claim 1 contains the antibiosis rare earth ternary complexes of heterocyclic ligand for the preparation of the antiseptic-germicide suppressing intestinal bacteria and streptococcus aureus.
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