CN106902355B - Water-soluble polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound and preparation method thereof - Google Patents
Water-soluble polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-soluble polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound and a preparation method thereof, wherein the structural formula of the compound is shown in the specification
Wherein L' represents any one of dimethyl sulfoxide, pyridine and triphenylphosphine, and m is the polymerization degree of an ethylene glycol structural unit; the compound is prepared from Ru3(CO)12The polyethylene glycol monomethyl ether succinate and the ligand are prepared by reaction, and the preparation method is simple. The compound can improve the water solubility and biocompatibility of the saw horse structure and reduce the toxicity of molecules in a breakthrough manner by greatly increasing the chain links of bridging polyethylene glycol monomethyl ether, can quickly release CO molecules under the irradiation of ultraviolet light when water is used as a transmitter, and can also spontaneously release CO under the condition of no light stimulation, thereby having potential application prospects in the field of medicaments.
Description
Technical Field
The invention belongs to the technical field of medicine synthesis, and particularly relates to a water-soluble polyethylene glycol carboxylate bridged sawn horse ruthenium carbonyl compound and a preparation method thereof.
Background
Carbon monoxide (CO) is widely recognized as a highly toxic and deadly gas molecule due to its strong affinity for hemoglobin. CO poisoning events occur frequently because they are colorless, odorless, and difficult to identify. Although CO has high toxicity, scientific research in recent years also indicates that CO can be generated in organisms through the decomposition of human heme and other series of metabolic activities, plays an important physiological or pathological role and is an important messenger molecule. The CO carrier and carbon monoxide releasing molecules (CORMs) can be used as a new method for transmitting CO in a physiological environment. However, most of the CORMs in the prior art have poor water solubility, need organic solvent to dissolve and then release CO for research, and are difficult to be used in biological systems taking water as a medium.
Lewis et al first discovered carboxylic acids with Ru2(CO)4The double metal framework structure is in a bridging coordination form. In 1977, H.Schumann et al, obtained a single crystal structure of a ruthenium carbonyl of saw horse with propionic acid bridge spanning axial coordination of tri-tert-butylphosphine containing two electrons, and verified the double coordination mode. In the structure, the multifunctional carboxylic acid and the ligand containing N, P, S atoms are used as coordination outside, and the stability and the biological responsiveness of the double-layer saw horse structure can be respectively regulated and controlled. In recent years, the structure of ruthenium (S) sawmancarbonyl has begun to be applied in the research fields of biomedicine, catalysis, materials, etc. (Dalton Trans,1997, 4351-4356).
M.J.
The panel found that water soluble CORM-3 coordinates rapidly to the protein and loses all non-carbonyl ligands and one molecule of CO, forming a protein CORM adduct. In solution systems, intracellularly and in rats, the adduct spontaneously releases CO, exhibiting anti-inflammatory effects. The selection of the backbone structure of the functional polymer, in combination with the CORM guide, can modulate the water solubility and targeted release properties of the target CORMs (angelw. chem.,2015, volume 127, 1188-1191).
Disclosure of Invention
The invention aims to overcome the defect of poor water solubility of the existing saw horse structure, and provides a nonionic water-soluble polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound which has good thermal stability, low toxicity, good water solubility and biocompatibility and can realize the slow release of carbon monoxide, and a preparation method of the compound.
The technical scheme for solving the technical problems is that the structural formula of the water-soluble polyethylene glycol carboxylate bridged sawn horse carbonyl ruthenium compound is as follows:
the structural formula of the compound is as follows:
in the structural formula, L' represents any one of dimethyl sulfoxide, pyridine and triphenylphosphine, m is the polymerization degree of an ethylene glycol structural unit, and the molecular formula of the compound is [ Ru2(CO)4(μ2-η2-O2CCH2CH2CO2-mPEGn)2(η1-L′)2]In the molecular formula, mPEG represents polyethylene glycol monomethyl ether, n is the number average molecular weight of the polyethylene glycol monomethyl ether, the value of n is 1000-10000, and the preferable value of n is 2000-5000.
The preparation method of the water-soluble polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound comprises the following steps: under the protection of anhydrous oxygen-free inert gas, Ru is added3(CO)12And polyethylene glycol monomethyl ether succinate (mPEG)n-OOCCH2CH2-COOH) is added into toluene according to the molar ratio of 1: 2-4, the mixture reacts for 6-12 hours at the temperature of 110-130 ℃, and then the reaction liquid is cooled to 40-60 ℃; dissolving a ligand in a mixed solvent of dichloromethane and methanol in a volume ratio of 1:1, adding the mixed solvent into a reaction solution, and stirring for reaction for 1-3 hours, wherein the addition amount of the ligand is Ru3(CO)122-4 times of the molar weight; after the reaction is finished, filtering, drying and purifying to obtain the water-soluble polyethylene glycol carboxylate bridged sawhorse carbonyl ruthenium compound, wherein the specific reaction equation is as follows:
in the above production method, Ru is preferred3(CO)12The molar ratio of the compound to polyethylene glycol monomethyl ether succinate and the ligand is 1:3: 3.
The polyethylene glycol monomethyl ether succinate is prepared by taking toluene as a solvent, carrying out reflux reaction on polyethylene glycol monomethyl ether with the number average molecular weight of 1000-10000, succinic anhydride and triethylamine according to the molar ratio of 2:4:3 at 60 ℃ for 8 hours, wherein the number average molecular weight of the polyethylene glycol monomethyl ether part is 1000-10000, and the number average molecular weight of the polyethylene glycol monomethyl ether part is preferably 2000-5000.
The ligand is any one of dimethyl sulfoxide, pyridine and triphenylphosphine.
The invention has the following beneficial effects:
1. according to the invention, the bridging ligand of the saw horse structure with poor water solubility is subjected to pegylation modification, so that the thermal stability and biocompatibility of the saw horse structure are increased, the toxicity of molecules is reduced, and the water solubility of the molecules is greatly increased.
2. The synthesis method is simple, the obtained PEGylated saw horse type compound can rapidly release CO molecules under the irradiation of ultraviolet light, and the good water solubility is the knock-out brick of the compound in the field of medicine application.
3. The half-life period of the pegylation saw horse type compound is more than 150 s.
Drawings
FIG. 1 shows logP and t of a polyethylene glycol carboxylate bridged-sawhorse ruthenium carbonyl compound prepared in the steps 1-61/2A histogram of the relationship.
FIG. 2 is a bar graph of the effect of PEG-carboxylate bridged bis (saw) ruthenium carbonyl compounds prepared in example 1 on cell viability at various concentrations of RAW 264.7.
FIG. 3 is a bar graph of the effect of PEG-carboxylate bridged bis (saw) ruthenium carbonyl compounds prepared in example 1 on cell viability at various concentrations of HT 29.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Preparing a polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound with the molecular formula as follows:
[Ru2(CO)4(μ2-η2-O2CCH2CH2CO2-mPEG2000)2(η1-SO(CH3)2)2]
200mg (0.31mmol) of Ru are weighed out3(CO)12And 1.9688g (0.93mmol) of polyethylene glycol monomethyl ether succinate (mPEG)2000-OOCCH2CH2-COOH) was placed in a Schlenk flask using vacuum line operating technique at N2Adding 5mL of dry toluene as a solvent under protection, heating and refluxing at 120 ℃ for 8 hours, and then cooling the reaction solution to 50 ℃; dissolving 66.05 mu L (0.93mmol) of dimethyl sulfoxide in 2mL of mixed solvent of dichloromethane and methanol in a volume ratio of 1:1, adding the mixture into the reaction solution cooled to 50 ℃, stirring and reacting at 50 ℃ for 2 hours, filtering after the reaction is finished, adding anhydrous ether into the filtrate, putting the filtrate into a refrigerator, leaching after precipitation, and drying in vacuum at room temperature to obtain 244mg of dark yellow powder, namely the polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound with the yield of 56%.
The structural characterization data of the obtained product are: IR (CH)2Cl2,cm-1):V(co)＝2047vs,2002m,1973vs,V(co-ester)＝1736m,V(co-acid)＝1574m,1444m；1H NMR(400MHz,CDCl3)δ4.17(t,4H,CH2),3.88-3.42(m,PEG),3.36(s,6H,OCH3),2.56(dd,8H,CH2CH2CO2),2.07(s,12H,CH3)；13C NMR(101MHz,CDCl3)δ200.12(CO),186.01(COOCH2),172.28(COO),71.90(PEG),70.53(PEG),68.92(PEG),63.85(PEG),58.98(OCH3),41.93(CH3),31.51(CH2),30.16(CH2)。
Example 2
Preparing a polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound with the molecular formula as follows:
[Ru2(CO)4(μ2-η2-O2CCH2CH2CO2-mPEG2000)2(η1-NC5H5)2]
in example 1, dimethyl sulfoxide used was replaced with equimolar pyridine, and the other steps were the same as in example 1 to obtain 276mg of a pale green powdery solid, i.e., a polyethylene glycol carboxylate bridged bis-saw horse carbonyl ruthenium compound, with a yield of 48%.
The structural characterization data of the obtained product are: IR (CH)2Cl2,cm-1):V(co)＝2024vs,1973m,1940vs,V(co-ester)＝1735m,V(co-acid)＝1581m,1448m；1H NMR(400MHz,CDCl3)δ8.67(d,4H,NC5H5),7.84(t,2H,NC5H5),7.51-7.40(m,4H,NC5H5),4.12(t,4H,CH2),3.84-3.40(m,PEG),3.36(s,6H,OCH3),2.52-2.56(dd,8H,CH2CH2CO2),2.37(s,4H,CH2)；13C NMR(101MHz,CDCl3)δ203.97(CO),184.74(COOCH2),172.60(COO),151.78(NC5H5),137.40(NC5H5),124.90(NC5H5),71.90(PEG),70.53(PEG),69.02(PEG),63.45(PEG),58.99(OCH3),31.57(CH2),30.51(CH2)。
Example 3
Preparing a polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound with the molecular formula as follows:
[Ru2(CO)4(μ2-η2-O2CCH2CH2CO2-mPEG2000)2(η1-PPh3)2]
in example 1, dimethyl sulfoxide used was replaced with equimolar triphenylphosphine and the other steps were the same as in example 1 to obtain 285mg of a bright yellow powdery solid, i.e., a polyethylene glycol carboxylate bridged bis-saw horse carbonyl ruthenium compound, with a yield of 61%.
The structural characterization data of the obtained product are: IR (CH)2Cl2,cm-1):V(co)＝2024vs,1979m,1956vs,V(co-ester)＝1734m,V(co-acid)＝1577m,1456m；1H NMR(400MHz,CDCl3)δ7.48(dd,12H,Ph),7.37(d,18H,Ph),4.08-4.03(m,4H,CH2),3.82-3.42(m,PEG),3.35(s,6H,OCH3),2.22(t,8H,CH2CH2CO2),2.02(t,4H,CH2)；13C NMR(101MHz,CDCl3)δ205.23(CO),186.39(COOCH2),172.59(COO),133.74(Ph),133.12(Ph),129.74(Ph),128.23(Ph),71.92(PEG),70.55(PEG),69.05(PEG),63.30(PEG),59.01(OCH3),31.71(CH2),29.84(CH2)。
Example 4
Preparing a polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound with the molecular formula as follows:
[Ru2(CO)4(μ2-η2-O2CCH2CH2CO2-mPEG5000)2(η1-SO(CH3)2)2]
in example 1, mPEG was used2000-OOCCH2CH2Equimolar mPEG for-COOH5000-OOCCH2CH2-COOH substitution, the other steps being the same as in example 1, to give 456mg of a pale yellow powdery solid, i.e., a polyethylene glycol carboxylate bridged bis-saw ruthenium carbonyl compound, in a yield of 69%.
The structural characterization data of the obtained product are: IR (CH)2Cl2,cm-1):V(co)＝2047vs,2002m,1973vs,V(co-ester)＝1736m,V(co-acid)＝1606m,1403m；1H NMR(400MHz,CDCl3)δ4.75(s,8H,CH2),4.16(t,4H,CH2),3.80-3.39(m,PEG),3.36(s,6H,OCH3),2.60(s,8H,CH2CH2CO2),2.11(s,6H,CH3)；13C NMR(101MHz,CDCl3)δ201.21(CO),186.75(COOCH2),172.33(COO),71.99(PEG),70.57(PEG),69.02(PEG),63.75(PEG),58.99(OCH3),42.03(CH3),31.61(CH2),29.96(CH2)。
Example 5
Preparing a polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound with the molecular formula as follows:
[Ru2(CO)4(μ2-η2-O2CCH2CH2CO2-mPEG5000)2(η1-NC5H5)2]
in example 4, dimethyl sulfoxide used was replaced with equimolar pyridine, and the other steps were the same as in example 1 to obtain 481mg of a bright yellow powdery solid, i.e., a polyethylene glycol carboxylate bridged saw horse carbonyl ruthenium compound, in a yield of 72%.
The structural characterization data of the obtained product are: IR (CH)2Cl2,cm-1):V(co)＝2024vs,1792m,1940vs,V(co-ester)＝1735m,V(co-acid)＝1601m,1451m；1H NMR(400MHz,CDCl3)δ8.64(d,4H,NC5H5),7.81(t,2H,NC5H5),7.46-7.37(m,4H,NC5H5),4.08(d,4H,CH2),3.93-3.38(m,PEG),3.33(s,6H,OCH3),2.49(d,8H,CH2CH2CO2)；13C NMR(101MHz,CDCl3)δ205.49(CO),186.30(COOCH2),174.22(COO),153.18(NC5H5),138.81(NC5H5),126.31(NC5H5),73.29(PEG),71.91(PEG),70.42(PEG),64.85(PEG),60.37(OCH3),32.97(CH2),31.92(CH2)。
Example 6
Preparing a polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound with the molecular formula as follows:
[Ru2(CO)4(μ2-η2-O2CCH2CH2CO2-mPEG5000)2(η1-PPh3)2]
in example 4, dimethyl sulfoxide used was replaced with equimolar pyridine, and the other steps were the same as in example 1 to obtain 486mg of a bright yellow powdery solid, i.e., a polyethylene glycol carboxylate bridged bis-saw horse carbonyl ruthenium compound, in a yield of 71%.
The structural characterization data of the obtained product are: IR (CH)2Cl2,cm-1):V(co)＝2024vs,1979m,1951vs,V(co-ester)＝1735m,V(co-acid)＝1577m,1470m；1H NMR(400MHz,CDCl3)δ7.48(s,12H,Ph),7.37(s,18H,Ph),4.05(s,4H,CH2),3.90-3.41(m,PEG),3.35(s,6H,OCH3),2.21(s,8H,CH2CH2CO2),2.02(d,4H,CH2)；13C NMR(101MHz,CDCl3)δ206.63(CO),187.98(COOCH2),173.97(COO),135.14(Ph),134.53(Ph),131.14(Ph),129.63(Ph),73.33(PEG),71.96(PEG),70.45(PEG),64.70(PEG),60.40(OCH3),33.11(CH2),31.24(CH2)。
In order to prove the beneficial effects of the invention, the inventor performs various performance tests on the polyethylene glycol carboxylate bridged sawn horse carbonyl ruthenium compound (hereinafter referred to as an object to be tested) prepared in the embodiments 1 to 6, wherein the specific test conditions are as follows:
1. water solubility test
The water solubility of the test substances was measured by the oil-water partition coefficient measurement method, and the results are shown in FIG. 1 and Table 1.
Table 1 water solubility test results
As can be seen from Table 1 and FIG. 1, the water solubility of the PEGylated carboxylic acid ester bridged across-saw ruthenium carbonyl compound of the present invention is good.
2. Cytotoxicity assays
Using the pegylated carboxylate bridged bis-saw ruthenium carbonyl compound prepared in example 1, as exemplified by mouse mononuclear macrophage leukemia cells (RAW264.7) and human colorectal cancer cells (HT29), the following experiments were performed:
(1) cell processing
A frozen RAW264.7 cell line is taken, quickly thawed at 37 ℃, centrifuged at 1000 rpm for 5 minutes, washed 1-2 times by using a culture medium (because substances harmful to cell propagation and growth are added in the freezing process), resuspended by using the culture medium and centrifuged again, the obtained RAW264.7 cells are added into a complete culture medium for culture, the culture medium is changed once a day, the cell growth condition is observed, and the cell is reserved after full growth.
(2) Cell viability assay
After RAW264.7 cells are overgrown, the cell concentration is adjusted to 5 × 104one/mL, inoculated in a 96-well plate at 100. mu.L/well, at 37 ℃ with 5% CO2Culturing in an incubator for 24 hours. Then add in groups of experiments in 96-well platesDifferent concentrations of (0, 50, 100, 200, 300, 400, 500. mu. mol/L) PEGylated carboxylate bridged across saw horse ruthenium carbonyl compound, 150. mu.L per well, triplicate wells per group, were added and incubated for 2 hours. Subsequently, the cultured cells of different concentrations were irradiated with 365nm ultraviolet light for 20 minutes and not irradiated, and left in the dark for 8 hours before MTT detection: mu.L of tetrazolium salt (MTT) was added to each well at 37 ℃ with 5% CO2Culturing in incubator for 4 hr in dark place, sucking out liquid in the well, adding 200 μ L DMSO, shaking at room temperature for 10 min in shaking table, measuring OD value at the same time point with enzyme labeling instrument at 492nm wavelength, and analyzing cell proliferation effect with the measured OD value, with the test result shown in FIG. 2 and FIG. 3.
From the MTT results, it can be seen that: IC under RAW264.7 cell light conditions50IC value of 572.8. mu. mol/L under the condition that RAW264.7 cells are not lighted50The value was 539.9. mu. mol/L; IC of HT-29 cells in the absence of light50526.9. mu. mol/L, and after light-induced induction, cell IC50It was 637.6. mu. mol/L.
As can be seen from the experimental results of FIG. 2, the viability of the cells after the 365nm light source is reduced from 76.7% to 12.7% along with the increase of the concentration. Similar to the apoptosis trend in the dark. Indicating that cytotoxicity decreased with increasing concentration.
As can be seen from the experimental results of FIG. 3, the cell viability was gradually decreased as the concentration of the released molecules was increased, whereas the cell viability was decreased by 31.9% as the concentration of the released molecules was increased from 250. mu. mol/L to 500. mu. mol/L, and was 29.7% as the concentration reached 1000. mu. mol/L. Indicating that cytotoxicity decreased with increasing concentration.
Claims (5)
1. A water-soluble polyethylene glycol carboxylate bridged saw horse ruthenium carbonyl compound is characterized in that the structural formula of the compound is as follows:
in the structural formula, L' represents any one of dimethyl sulfoxide, pyridine and triphenylphosphineM is the degree of polymerization of ethylene glycol structural unit, and the molecular formula of the compound is [ Ru2(CO)4(μ2-η2-O2CCH2CH2CO2-mPEGn)2(η1-L′)2]In the molecular formula, mPEG represents polyethylene glycol monomethyl ether, n is the number average molecular weight of the polyethylene glycol monomethyl ether, and the value of n is 1000-10000.
2. The water-soluble polyethylene glycol carboxylate bridged bis-saw ruthenium carbonyl compound of claim 1, wherein: the value of n is 2000-5000.
3. A method for preparing the water-soluble polyethylene glycol carboxylate bridged saw-spanning ruthenium carbonyl compound according to claim 1, which is characterized in that: under the protection of anhydrous oxygen-free inert gas, Ru is added3(CO)12Adding the mixture and polyethylene glycol monomethyl ether succinate into toluene according to the molar ratio of 1: 2-4, reacting for 6-12 hours at 110-130 ℃, and then cooling the reaction solution to 40-60 ℃; dissolving a ligand in a mixed solvent of dichloromethane and methanol in a volume ratio of 1:1, adding the mixed solvent into a reaction solution, and stirring for reaction for 1-3 hours, wherein the addition amount of the ligand is Ru3(CO)122-4 times of the molar weight; after the reaction is finished, filtering, drying and purifying to obtain a water-soluble polyethylene glycol carboxylate bridged sawhorse carbonyl ruthenium compound;
the number average molecular weight of the polyethylene glycol monomethyl ether part in the polyethylene glycol monomethyl ether succinate is 1000-10000;
the ligand is any one of dimethyl sulfoxide, pyridine and triphenylphosphine.
4. The method for preparing the water-soluble polyethylene glycol carboxylate bridged bis-saw ruthenium carbonyl compound according to claim 3, wherein the method comprises the following steps: the Ru3(CO)12The molar ratio of the compound to polyethylene glycol monomethyl ether succinate and the ligand is 1:3: 3.
5. The method for preparing the water-soluble polyethylene glycol carboxylate bridged saw-spanning ruthenium carbonyl compound according to claim 3 or 4, wherein the method comprises the following steps: the number average molecular weight of the polyethylene glycol monomethyl ether part in the polyethylene glycol monomethyl ether succinate is 2000-5000.
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