五多原子的 cyclotriphosphazene ligands 为他们的劈开活动被综合并且测试到原生质标志 DNA。所有被 MS 这些新混合物证实, <SUP>1</SUP > H NMR, <SUP>31</SUP > P NMR, <SUP>13</SUP > C NMR...五多原子的 cyclotriphosphazene ligands 为他们的劈开活动被综合并且测试到原生质标志 DNA。所有被 MS 这些新混合物证实, <SUP>1</SUP > H NMR, <SUP>31</SUP > P NMR, <SUP>13</SUP > C NMR 和红外。pUC19 DNA 的劈开上的初步的研究面对金属建筑群被执行。结果表明这些建筑群能在生理的条件下面充当强大的催化剂。建筑群 3b + Cu 能有效地劈开 DNA 到 nicked 形式,给水解作用在生理的条件下面的 0.08/h 的率常数。acid–;基础催化 DNA phosphate-diester 水解作用机制也被建议。展开更多
Two artificial minic polypeptides which are synthetic analogues of natural products with DNA affinity were synthesized, and theirs cleavage activity with DNA were examined. The structures of these compounds was confir...Two artificial minic polypeptides which are synthetic analogues of natural products with DNA affinity were synthesized, and theirs cleavage activity with DNA were examined. The structures of these compounds was confirmed by 1H NMR, MS and IR.展开更多
The a-L-rhamnopyranosyl phosphomonoesters conjugated with L-amino acid methyl esters were stereoselectively synthesized in a convenient route by utilizing H-phosphonate intermediate.
It was found that phosphorylation of small peptide could improve the sensitivity in mass spectrometry. Density functional theory calculations showed that the energy for the protonation of N-(O, O(-dimethyl) phosphoryl...It was found that phosphorylation of small peptide could improve the sensitivity in mass spectrometry. Density functional theory calculations showed that the energy for the protonation of N-(O, O(-dimethyl) phosphoryl glycylglycine is lower than that of glycylglycine. These could help to understanding the experimental results.展开更多
A series of N-phosphoryl branched peptides were synthesized by coupling of various N-phosphoryl amino acids to L-Lysine methyl ester, and their structures were confirmed by 31P NMR, 1H NMR, MS and elemental analysis. ...A series of N-phosphoryl branched peptides were synthesized by coupling of various N-phosphoryl amino acids to L-Lysine methyl ester, and their structures were confirmed by 31P NMR, 1H NMR, MS and elemental analysis. The results of cell biological tests indicated that compound 1d and 1e obviously inhibited the growth of both K562 and A2780 cells.展开更多
The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between a-COOH and b-COOH in phosphoryl aspartic acid was studied by theo...The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between a-COOH and b-COOH in phosphoryl aspartic acid was studied by theoretical study (Hartree-Fock and Density Functional methods) in this paper. The intermediates II containing five-membered ring were more stable than III with six-membered ring. While for intermediates III, the isomers with six-membered ring in apical-equatorial spanning arrangement were more stable than those with di-equatorial spanning arrangement. At B3LYP/6-31G** level, it was shown that transition states IV and V involving a-COOH or b-COOH group had energy barriers of DE = 58.67 kJmol-1 and 103.94 kJmol-1, respectively. These results were in agreement with the experimental data. So the a-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not b-COOH group.展开更多
Nucleosides were phosphorylated with different N-(O, O-diisopropyl) phosphoryl amino acids to give nucleoside mono phosphates in aqueous solution. 2’, 3’. and 5’-isomers had been confirmed by comparison with authen...Nucleosides were phosphorylated with different N-(O, O-diisopropyl) phosphoryl amino acids to give nucleoside mono phosphates in aqueous solution. 2’, 3’. and 5’-isomers had been confirmed by comparison with authentic samples on the basis of HPLC analysis. The conversion percentage of nucleoside indicated that N- (O, O-diisopropyl) phosphoryl aspartic acid reacted with adenosine and guanosine at a much higher rate than other kinds of N- phosphoryl amino acids, while phosphorylation of cytidine and uridine was relatively easy by using N- (O.O- diisopropyl) phosphoryl threonine. The result could give some clue to the prebiotic code origin of nucleic acid and protein.展开更多
Different hydroxy substituted coumarins were successfully phosphorylated with diisopropylphophite (DIPPH) by the Atherton-Todd reaction in 76-89% yields. Moreover, the reaction activities of different hydroxys of the ...Different hydroxy substituted coumarins were successfully phosphorylated with diisopropylphophite (DIPPH) by the Atherton-Todd reaction in 76-89% yields. Moreover, the reaction activities of different hydroxys of the coumarins in the Atherton-Todd reaction were studied.展开更多
In this paper, chiral discrimination in N-(O,O-dialkyl)phosphoamino acid monolayers at the air/water interface was studied and it was revealed that the D:L=1:1 racemic monolayer of N- (O, O-dihexadecyl)phosphoalanine ...In this paper, chiral discrimination in N-(O,O-dialkyl)phosphoamino acid monolayers at the air/water interface was studied and it was revealed that the D:L=1:1 racemic monolayer of N- (O, O-dihexadecyl)phosphoalanine is packed more densely in solid phase while shows a higher LE to LC transition pressure than the enantiomeric ones.展开更多
In this paper, we described an improved electrochemical method for synthesis of some 1-aryl-2-pyrrolidinecarbonitrile derivatives bearing an electron-withdrawing group (NO2). The electrochemical synthesis of titile co...In this paper, we described an improved electrochemical method for synthesis of some 1-aryl-2-pyrrolidinecarbonitrile derivatives bearing an electron-withdrawing group (NO2). The electrochemical synthesis of titile compounds has been successfully performed in an undivided cell in reasonable yields.展开更多
The reaction between D-glucose. D-ribose and 2. 2. 2-trimethoxy-4. 5-diphenyl-2. 2dihydro-1. 3. 2-dioxaphospholene stere investigated by 31P NMR and FAB-MS. The resultsshowed that there were a lot of differences in th...The reaction between D-glucose. D-ribose and 2. 2. 2-trimethoxy-4. 5-diphenyl-2. 2dihydro-1. 3. 2-dioxaphospholene stere investigated by 31P NMR and FAB-MS. The resultsshowed that there were a lot of differences in the reactions via pentacoordinate phosphoruscompound. and it should give significant clue to the metabolism of carbohydrate phosphate innature.展开更多
In order to explain the high activity of N-phosphoryl-α-amino acids, ab initio and MNDO calculations are performed to study the reaction pathway of the intermediate formation from N-dimethylphosphoryl-α-alanine (DMP...In order to explain the high activity of N-phosphoryl-α-amino acids, ab initio and MNDO calculations are performed to study the reaction pathway of the intermediate formation from N-dimethylphosphoryl-α-alanine (DMP-α-Ala) and the structures and energies involved in the reaction.展开更多
Reaction of Zn(ClO4)2·6H2O with septadentate 2,6-bis[bis(2-benzimidazolylme-thyl)amino methyl]-4-methylphenol (Hbbap) and sodium isonicotinate yielded a dinuclear zinc complex[Zn2(bbap) (Iso) (Hiso)] (ClO4)2·...Reaction of Zn(ClO4)2·6H2O with septadentate 2,6-bis[bis(2-benzimidazolylme-thyl)amino methyl]-4-methylphenol (Hbbap) and sodium isonicotinate yielded a dinuclear zinc complex[Zn2(bbap) (Iso) (Hiso)] (ClO4)2·[Zn2 (bbap) (Iso) (H2O)] (ClO4)2·4H2O(1a·1b·4H2O). Hiso isisonicotinic acid and Iso is isonicotinate anion. The structure has been established by X-raycrystallography and shows that the two zinc ions are bridged by the phenoxy unit of bbap- ligand,and the presence of unusual monodentate O-coordination of carboxylate group from isonicotinicacid. The coordination geometry around the zinc ion is approximately trigonal bipyramidal.展开更多
Newlase F is a rude enzyme which contains triacylglycerol lipase and acid protease. Hydrolysis of dipeptide heptyl esters with Newlase F was studied in phosphate buffer-organic solvent by HPLC. When the Newlase F’s l...Newlase F is a rude enzyme which contains triacylglycerol lipase and acid protease. Hydrolysis of dipeptide heptyl esters with Newlase F was studied in phosphate buffer-organic solvent by HPLC. When the Newlase F’s level reached 5 mg/mL under mild condition (pH 7.0, 30(C), the lipase had the highest activity. The reaction was also affected greatly by organic solvents and their concentrations. It is found that protease in Newlase F does not hydrolyze amide bond under this condition (pH 7.0, r.t.).展开更多
An efficient and novel method for synthesizing 3′,5′-dithio-2′-deoxyguanosine was described.In this method normal guanosine was used as the starting material.A very efficient procedure was used to synthesize 2-O-to...An efficient and novel method for synthesizing 3′,5′-dithio-2′-deoxyguanosine was described.In this method normal guanosine was used as the starting material.A very efficient procedure was used to synthesize 2-O-tosylguanosine 1,which used 0.1 eq.DBTO instead of 2 eq.1 was treated with LTBH to give 9-(2-deoxy-β-D-threo-pentofuranosyl)guanine 2.2 could be easily turned to the target compound.展开更多
Oxyphosphorane reacted with glucose to give disaccharide which was confirmed by FAB-MS and 13C-NMR. The mechanism for formation of oligosaccharides through the participation of phosphorus was
基金supports from the NNSFC(Nos.20602032,20732004 and 20572061).
文摘五多原子的 cyclotriphosphazene ligands 为他们的劈开活动被综合并且测试到原生质标志 DNA。所有被 MS 这些新混合物证实, <SUP>1</SUP > H NMR, <SUP>31</SUP > P NMR, <SUP>13</SUP > C NMR 和红外。pUC19 DNA 的劈开上的初步的研究面对金属建筑群被执行。结果表明这些建筑群能在生理的条件下面充当强大的催化剂。建筑群 3b + Cu 能有效地劈开 DNA 到 nicked 形式,给水解作用在生理的条件下面的 0.08/h 的率常数。acid–;基础催化 DNA phosphate-diester 水解作用机制也被建议。
文摘Two artificial minic polypeptides which are synthetic analogues of natural products with DNA affinity were synthesized, and theirs cleavage activity with DNA were examined. The structures of these compounds was confirmed by 1H NMR, MS and IR.
基金The authors would like to thank the financial supports from the NNSF of China(No.201 72033),the Ministry of Science and Technology,the Ministry of Education and Tsinghua University.
文摘The a-L-rhamnopyranosyl phosphomonoesters conjugated with L-amino acid methyl esters were stereoselectively synthesized in a convenient route by utilizing H-phosphonate intermediate.
基金The authors thank the National Natural Science Foundation of China(No.39870415)the Ministry of Science and Technology of China,the Education Ministry of China and Tsinghua University for financial suport.
文摘It was found that phosphorylation of small peptide could improve the sensitivity in mass spectrometry. Density functional theory calculations showed that the energy for the protonation of N-(O, O(-dimethyl) phosphoryl glycylglycine is lower than that of glycylglycine. These could help to understanding the experimental results.
基金This work is supported by Natural Science Foundation of Beijing City (7002006). Elemental analyses were performed by Institute of Chemistry Chinese Academy of Science.
文摘A series of N-phosphoryl branched peptides were synthesized by coupling of various N-phosphoryl amino acids to L-Lysine methyl ester, and their structures were confirmed by 31P NMR, 1H NMR, MS and elemental analysis. The results of cell biological tests indicated that compound 1d and 1e obviously inhibited the growth of both K562 and A2780 cells.
基金the National Natural Science Foundation of China (No. 29802006) the Teaching and Research Award Program for Outstanding Young Teachers in Higher Education Institutions of MOE P.R.C. and Tsinghua University.
文摘The bio-mimic reactions of N-phosphoryl amino acids are very important in the study of many biochemical processes. The difference of reactivity between a-COOH and b-COOH in phosphoryl aspartic acid was studied by theoretical study (Hartree-Fock and Density Functional methods) in this paper. The intermediates II containing five-membered ring were more stable than III with six-membered ring. While for intermediates III, the isomers with six-membered ring in apical-equatorial spanning arrangement were more stable than those with di-equatorial spanning arrangement. At B3LYP/6-31G** level, it was shown that transition states IV and V involving a-COOH or b-COOH group had energy barriers of DE = 58.67 kJmol-1 and 103.94 kJmol-1, respectively. These results were in agreement with the experimental data. So the a-COOH group was involved in form of the intramolecular penta-coordinate phosphoric-carboxylic mixed anhydride intermediates, but not b-COOH group.
基金This prqiect was supported by the National Natural Science Foundation of China, National Science Technology Committee of Chi
文摘Nucleosides were phosphorylated with different N-(O, O-diisopropyl) phosphoryl amino acids to give nucleoside mono phosphates in aqueous solution. 2’, 3’. and 5’-isomers had been confirmed by comparison with authentic samples on the basis of HPLC analysis. The conversion percentage of nucleoside indicated that N- (O, O-diisopropyl) phosphoryl aspartic acid reacted with adenosine and guanosine at a much higher rate than other kinds of N- phosphoryl amino acids, while phosphorylation of cytidine and uridine was relatively easy by using N- (O.O- diisopropyl) phosphoryl threonine. The result could give some clue to the prebiotic code origin of nucleic acid and protein.
基金The authors thank the financial supports from the National Natural Science Foundation of China(No.20132020)the Ministry of Science and Technology,the Chinese Ministry of Education and Zhengzhou University.
文摘Different hydroxy substituted coumarins were successfully phosphorylated with diisopropylphophite (DIPPH) by the Atherton-Todd reaction in 76-89% yields. Moreover, the reaction activities of different hydroxys of the coumarins in the Atherton-Todd reaction were studied.
文摘In this paper, chiral discrimination in N-(O,O-dialkyl)phosphoamino acid monolayers at the air/water interface was studied and it was revealed that the D:L=1:1 racemic monolayer of N- (O, O-dihexadecyl)phosphoalanine is packed more densely in solid phase while shows a higher LE to LC transition pressure than the enantiomeric ones.
基金The authors would like to thank the financial support of Beijing TH-UNIS-Insight Co.Ltd.and the National Natural Science Foundation of China (No.20132020) the Ministry of Science and Technology, the Chinese Ministry of Education and Tsinghua University.
文摘In this paper, we described an improved electrochemical method for synthesis of some 1-aryl-2-pyrrolidinecarbonitrile derivatives bearing an electron-withdrawing group (NO2). The electrochemical synthesis of titile compounds has been successfully performed in an undivided cell in reasonable yields.
文摘The reaction between D-glucose. D-ribose and 2. 2. 2-trimethoxy-4. 5-diphenyl-2. 2dihydro-1. 3. 2-dioxaphospholene stere investigated by 31P NMR and FAB-MS. The resultsshowed that there were a lot of differences in the reactions via pentacoordinate phosphoruscompound. and it should give significant clue to the metabolism of carbohydrate phosphate innature.
文摘In order to explain the high activity of N-phosphoryl-α-amino acids, ab initio and MNDO calculations are performed to study the reaction pathway of the intermediate formation from N-dimethylphosphoryl-α-alanine (DMP-α-Ala) and the structures and energies involved in the reaction.
文摘Reaction of Zn(ClO4)2·6H2O with septadentate 2,6-bis[bis(2-benzimidazolylme-thyl)amino methyl]-4-methylphenol (Hbbap) and sodium isonicotinate yielded a dinuclear zinc complex[Zn2(bbap) (Iso) (Hiso)] (ClO4)2·[Zn2 (bbap) (Iso) (H2O)] (ClO4)2·4H2O(1a·1b·4H2O). Hiso isisonicotinic acid and Iso is isonicotinate anion. The structure has been established by X-raycrystallography and shows that the two zinc ions are bridged by the phenoxy unit of bbap- ligand,and the presence of unusual monodentate O-coordination of carboxylate group from isonicotinicacid. The coordination geometry around the zinc ion is approximately trigonal bipyramidal.
基金the National Natural Science Foundation of China(Nos.20572061,20672104)the Chinese Ministry of Education and Zhengzhou University for financial support.
文摘Newlase F is a rude enzyme which contains triacylglycerol lipase and acid protease. Hydrolysis of dipeptide heptyl esters with Newlase F was studied in phosphate buffer-organic solvent by HPLC. When the Newlase F’s level reached 5 mg/mL under mild condition (pH 7.0, 30(C), the lipase had the highest activity. The reaction was also affected greatly by organic solvents and their concentrations. It is found that protease in Newlase F does not hydrolyze amide bond under this condition (pH 7.0, r.t.).
基金supported by the National Natural Science Foundation of China(No.20872078)the Basic Science Research Foundation of Tsinghua University(No.JC 2001046)
文摘An efficient and novel method for synthesizing 3′,5′-dithio-2′-deoxyguanosine was described.In this method normal guanosine was used as the starting material.A very efficient procedure was used to synthesize 2-O-tosylguanosine 1,which used 0.1 eq.DBTO instead of 2 eq.1 was treated with LTBH to give 9-(2-deoxy-β-D-threo-pentofuranosyl)guanine 2.2 could be easily turned to the target compound.
文摘Oxyphosphorane reacted with glucose to give disaccharide which was confirmed by FAB-MS and 13C-NMR. The mechanism for formation of oligosaccharides through the participation of phosphorus was