The hydrolysis process of the anticancer agents novel non-classical transplatinum（ Ⅱ ） with aliphatic amines and the influence of solvent models therein have been studied by using hybrid density functional theory ...The hydrolysis process of the anticancer agents novel non-classical transplatinum（ Ⅱ ） with aliphatic amines and the influence of solvent models therein have been studied by using hybrid density functional theory （B3LYP）. In this study, the stepwise hydrolysis, trans[PtCl2（Am）（isopropylamine）] ＋ 2H2O → trans-[Pt（Am）（isopropylamine）（OH2）2]^2＋＋ 2Cl^-, was explored. Implicit solvent effects were incorporated through polarized continuum models. The stationary points on the potential energy surfaces for the first and second hydrolysis steps,proceeding via a general SN2 pathway, were fully optimized and characterized. It was found that the first hydrolysis reaction is easier than the second one and the hydrolysis of trans- [PtCl2-（isopropylamine）2] is the easiest in our studying systems. The result can assist in under- tanding the hydrolysis mechanism of trans-[PtCl2（Am）（isopropylamine）] and designing novel Pt-based anticancer drugs.展开更多
Herein we give a theoretical study of the hydrolysis processes of a novel anticancer drug trans-[PtCl2（3-pico）（ipa）] （3-pico=3-methylpyridine, ipa=isopropylamine）. Two different models, model 1 relative to isola...Herein we give a theoretical study of the hydrolysis processes of a novel anticancer drug trans-[PtCl2（3-pico）（ipa）] （3-pico=3-methylpyridine, ipa=isopropylamine）. Two different models, model 1 relative to isolated reactant/product （R/P, wherein R=platinum complex＋H2O, P=platinum complex＋Cl^-） and model 2 relative to reactant complex/product complex （RC/PC, wherein RC=（platinum complex）（H2O）, PC=（platinum complex）（CI^-） are employed and the geometric structures are optimized at the B3LYP level of DFT method. It is found that the processes of the reactions follow the established theory for ligand substitution in square planar complexes; the geometries of the transition states （TS） agree with the previous related work and all of the reactions are endothermic. The effects originating from the inclusion of the attacking water/released chloride into the second coordination shell of platinum in RC/PC play an important role in the thermodynamic and kinetic profiles of the reactions, that is, the barrier heights of the reactions of model 2 are increased by -26.3 and -23.8 kJ/mol for step1 and step2 respectively, and the endothermicity is considerably decreased by -420.5 and -771.2 kJ/mol compared to model 1 in the gas phase. The consideration of the bulk solvation effects increase the barrier heights for both steps of model 1 by -27.6 and -6.7 kJ/mol respectively, whereas it reduces the barrier heights by -7.9 and -29.3 kJ/mol for model 2. The reaction energies are all decreased, especially for model i, indicating more stable complexes solvated in the bulk aqueous solution than in the gas phase. Additionally, to get an accurate energy picture of the title complex, the relative free energies derived from the DFT-SCRF （density functional theory self-consistent field） calculations are compared with the relative total energies. The results are that activation energies rise for the first hydrolysis and fall for the second hydrolysis for all the systems, and for all the systems, the barrier height of the second hydrolysis is always higher than that of the first step. The rate constants indicate that transplatin analogue is kinetically comparable to cisplatin and its analogue in the hydrolysis process.展开更多
Strong room-temperature photoluminescence from the adducts of C60 reacting with five different aliphatic amines, namely propylethylamine (PPA), n-butyl amine (BTA), n-heptylamine (HPA) and dodecylamine (DDA) and dieth...Strong room-temperature photoluminescence from the adducts of C60 reacting with five different aliphatic amines, namely propylethylamine (PPA), n-butyl amine (BTA), n-heptylamine (HPA) and dodecylamine (DDA) and diethylamine (DEA), was firstly found from their toluene solution at relatively shorter wavelength around 519 nm.The fluorescence intensity has a good correlation with the length of n-alkyl group chain, the steric position and concentration of different amines and setting of solution as well as the UV-radiation. Their fluorescence quenching by concentration and by aromatic electron-donor N,N-dimethylaniline (DMA) were first investigated and determined.展开更多
The mechanisms of action on monofunctional guanine adducts of analogues of transplatin with aliphatic amine ligands,such as trans-[Pt（Am）（isopropylamine）（G）（H2O）] where Am represents dimethylamine,propylamine ...The mechanisms of action on monofunctional guanine adducts of analogues of transplatin with aliphatic amine ligands,such as trans-[Pt（Am）（isopropylamine）（G）（H2O）] where Am represents dimethylamine,propylamine or isopropylamine and their cis isomers reacting with sulfur- and nitrogen-containing amino acid residues,were explored. Histidine and lysine residues are chosen as the model ligands of nitrogen-containing amino acid residues of proteins; meanwhile,methionine and cysteine residues are chosen as the model ligands of sulfur-containing amino acid residues of proteins. A dominating preference for sulfur-containing ligand over nitrogen-containing ligand is established. The calculated smallest activation barrier for sulfur-containing ligand is 9.9,and 21.1 kcal/mol for nitrogen-containing ligand in aqueous solution,and both of them have trans configurations. The difference in activation energy is 11.2 kcal/mol,indicating the platination of sulfur-containing amino acid residues is faster by seven to eight orders of magnitude than that of nitrogen-containing amino acid residues.展开更多
Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,...Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2. Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2. Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.展开更多
The first example of sono-photocatalytic bond formation was reported.With both visible light and ultrasound wave as the energy,various 3-aminoquinoxalin-2(1H)-ones were efficiently obtained with good functional group ...The first example of sono-photocatalytic bond formation was reported.With both visible light and ultrasound wave as the energy,various 3-aminoquinoxalin-2(1H)-ones were efficiently obtained with good functional group tolerance in the absence of any additive or external photocatalyst.Compared with the conventional photocatalysis,sono-photocatalysis not only dramatically improved the reaction rates and yields,but also reduced energy consumption.展开更多
The interaction of hypocrellin, including hypocrellin A (HA) and hypocrellin B (HB), with aliphatic amines in deaerated solutions has been studied by ESR and nanosecond transient absorption spectra. In polar solvents,...The interaction of hypocrellin, including hypocrellin A (HA) and hypocrellin B (HB), with aliphatic amines in deaerated solutions has been studied by ESR and nanosecond transient absorption spectra. In polar solvents, the acid-base interaction between hypocrellin and amines was observed without irradiation. The signals of semiquinone radical anions of hypocrellm and the spin-trapping adduct of α-phenyl-N-tertbutyl-ratrone (PNB) with the aminoalkyl radicals have been detected in photoinduced ESR studies. The transient absorption of excited triplet state of HA and semiquinone radical anion of HA have been observed in laser flash photolysis studies.展开更多
Crystallization is an unsolved challenge in the chemistry of covalent triazine frameworks(CTFs) due to the poorly controlled simultaneous polymerization and crystallization processes. Herein, the synthesis of crystall...Crystallization is an unsolved challenge in the chemistry of covalent triazine frameworks(CTFs) due to the poorly controlled simultaneous polymerization and crystallization processes. Herein, the synthesis of crystalline CTFs via the introduction of aliphatic amine as a dynamic modulator is reported. By optimizing the amount of aliphatic amine, the crystallization process can be controlled in an open system, resulting in the synthesis of crystalline CTFs. These crystalline CTFs exhibit much better photocatalytic hydrogen evolution performance, with highly ordered CTF-1-C3 demonstrating superior performance(10 mmol g^(-1)h^(-1)) compared with most reported CTF-1. This approach also allows for the preparation of various crystalline CTFs.展开更多
"One-step"method for the synthesis of secondary aliphatic amine substituted nitrobenzaldehyde was developed.In the presence of Pd catalyst,halogenated nitrobenzaldehyde could be smoothly coupled with seconda..."One-step"method for the synthesis of secondary aliphatic amine substituted nitrobenzaldehyde was developed.In the presence of Pd catalyst,halogenated nitrobenzaldehyde could be smoothly coupled with secondary aliphatic amine to give the target product in hexamethylphosphamide(HMPT) media without the protection of aldehyde groups.展开更多
Direct C(sp3)-H functionalization of N-unprotected aliphatic amines represents one of the most efficient and straightforward strategies for amine synthesis.Despite some recent progress in this field,the NH2-directed y...Direct C(sp3)-H functionalization of N-unprotected aliphatic amines represents one of the most efficient and straightforward strategies for amine synthesis.Despite some recent progress in this field,the NH2-directed y-C(sp3)-H arylation of primary aliphatic amines exceptα-amino esters remained an unmet challenge.In this report,we established a simple and efficient method for site-selective C(sp3)-H arylation of primary aliphatic amines by aryl iodides.In the presence of only 5 mol%Pd(OAc)2,a wide range of aliphatic amines including O-benzyl and O-silyl amino alcohols were arylated at y-orδ-positions by aryl iodides containing a broad scope of functional groups.The synthetic application of this method had also been demonstrated by large-scale synthesis,the synthesis of a fingolimod analogue,and the conjugation with natural D-menthol and fluorescent 1,8-naphthalimide.展开更多
基金This work was supported by the Science Foundation of Jinan University (639)
文摘The hydrolysis process of the anticancer agents novel non-classical transplatinum（ Ⅱ ） with aliphatic amines and the influence of solvent models therein have been studied by using hybrid density functional theory （B3LYP）. In this study, the stepwise hydrolysis, trans[PtCl2（Am）（isopropylamine）] ＋ 2H2O → trans-[Pt（Am）（isopropylamine）（OH2）2]^2＋＋ 2Cl^-, was explored. Implicit solvent effects were incorporated through polarized continuum models. The stationary points on the potential energy surfaces for the first and second hydrolysis steps,proceeding via a general SN2 pathway, were fully optimized and characterized. It was found that the first hydrolysis reaction is easier than the second one and the hydrolysis of trans- [PtCl2-（isopropylamine）2] is the easiest in our studying systems. The result can assist in under- tanding the hydrolysis mechanism of trans-[PtCl2（Am）（isopropylamine）] and designing novel Pt-based anticancer drugs.
文摘Herein we give a theoretical study of the hydrolysis processes of a novel anticancer drug trans-[PtCl2（3-pico）（ipa）] （3-pico=3-methylpyridine, ipa=isopropylamine）. Two different models, model 1 relative to isolated reactant/product （R/P, wherein R=platinum complex＋H2O, P=platinum complex＋Cl^-） and model 2 relative to reactant complex/product complex （RC/PC, wherein RC=（platinum complex）（H2O）, PC=（platinum complex）（CI^-） are employed and the geometric structures are optimized at the B3LYP level of DFT method. It is found that the processes of the reactions follow the established theory for ligand substitution in square planar complexes; the geometries of the transition states （TS） agree with the previous related work and all of the reactions are endothermic. The effects originating from the inclusion of the attacking water/released chloride into the second coordination shell of platinum in RC/PC play an important role in the thermodynamic and kinetic profiles of the reactions, that is, the barrier heights of the reactions of model 2 are increased by -26.3 and -23.8 kJ/mol for step1 and step2 respectively, and the endothermicity is considerably decreased by -420.5 and -771.2 kJ/mol compared to model 1 in the gas phase. The consideration of the bulk solvation effects increase the barrier heights for both steps of model 1 by -27.6 and -6.7 kJ/mol respectively, whereas it reduces the barrier heights by -7.9 and -29.3 kJ/mol for model 2. The reaction energies are all decreased, especially for model i, indicating more stable complexes solvated in the bulk aqueous solution than in the gas phase. Additionally, to get an accurate energy picture of the title complex, the relative free energies derived from the DFT-SCRF （density functional theory self-consistent field） calculations are compared with the relative total energies. The results are that activation energies rise for the first hydrolysis and fall for the second hydrolysis for all the systems, and for all the systems, the barrier height of the second hydrolysis is always higher than that of the first step. The rate constants indicate that transplatin analogue is kinetically comparable to cisplatin and its analogue in the hydrolysis process.
文摘Strong room-temperature photoluminescence from the adducts of C60 reacting with five different aliphatic amines, namely propylethylamine (PPA), n-butyl amine (BTA), n-heptylamine (HPA) and dodecylamine (DDA) and diethylamine (DEA), was firstly found from their toluene solution at relatively shorter wavelength around 519 nm.The fluorescence intensity has a good correlation with the length of n-alkyl group chain, the steric position and concentration of different amines and setting of solution as well as the UV-radiation. Their fluorescence quenching by concentration and by aromatic electron-donor N,N-dimethylaniline (DMA) were first investigated and determined.
文摘The mechanisms of action on monofunctional guanine adducts of analogues of transplatin with aliphatic amine ligands,such as trans-[Pt（Am）（isopropylamine）（G）（H2O）] where Am represents dimethylamine,propylamine or isopropylamine and their cis isomers reacting with sulfur- and nitrogen-containing amino acid residues,were explored. Histidine and lysine residues are chosen as the model ligands of nitrogen-containing amino acid residues of proteins; meanwhile,methionine and cysteine residues are chosen as the model ligands of sulfur-containing amino acid residues of proteins. A dominating preference for sulfur-containing ligand over nitrogen-containing ligand is established. The calculated smallest activation barrier for sulfur-containing ligand is 9.9,and 21.1 kcal/mol for nitrogen-containing ligand in aqueous solution,and both of them have trans configurations. The difference in activation energy is 11.2 kcal/mol,indicating the platination of sulfur-containing amino acid residues is faster by seven to eight orders of magnitude than that of nitrogen-containing amino acid residues.
文摘Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2. Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2. Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.
基金financial support from the University of South China。
文摘The first example of sono-photocatalytic bond formation was reported.With both visible light and ultrasound wave as the energy,various 3-aminoquinoxalin-2(1H)-ones were efficiently obtained with good functional group tolerance in the absence of any additive or external photocatalyst.Compared with the conventional photocatalysis,sono-photocatalysis not only dramatically improved the reaction rates and yields,but also reduced energy consumption.
基金Project supported by the National Natural Science Foundation of China
文摘The interaction of hypocrellin, including hypocrellin A (HA) and hypocrellin B (HB), with aliphatic amines in deaerated solutions has been studied by ESR and nanosecond transient absorption spectra. In polar solvents, the acid-base interaction between hypocrellin and amines was observed without irradiation. The signals of semiquinone radical anions of hypocrellm and the spin-trapping adduct of α-phenyl-N-tertbutyl-ratrone (PNB) with the aminoalkyl radicals have been detected in photoinduced ESR studies. The transient absorption of excited triplet state of HA and semiquinone radical anion of HA have been observed in laser flash photolysis studies.
基金supported by the National Natural Science Foundation of China (21975086, 52203259)the International S&T Cooperation Program of China (22161142005, 2018YFE0117300)。
文摘Crystallization is an unsolved challenge in the chemistry of covalent triazine frameworks(CTFs) due to the poorly controlled simultaneous polymerization and crystallization processes. Herein, the synthesis of crystalline CTFs via the introduction of aliphatic amine as a dynamic modulator is reported. By optimizing the amount of aliphatic amine, the crystallization process can be controlled in an open system, resulting in the synthesis of crystalline CTFs. These crystalline CTFs exhibit much better photocatalytic hydrogen evolution performance, with highly ordered CTF-1-C3 demonstrating superior performance(10 mmol g^(-1)h^(-1)) compared with most reported CTF-1. This approach also allows for the preparation of various crystalline CTFs.
基金financial support by the open project program of Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education of China(No.09HJYH04)Hunan Science & Technology Department Project(No.2009FJ3166)
文摘"One-step"method for the synthesis of secondary aliphatic amine substituted nitrobenzaldehyde was developed.In the presence of Pd catalyst,halogenated nitrobenzaldehyde could be smoothly coupled with secondary aliphatic amine to give the target product in hexamethylphosphamide(HMPT) media without the protection of aldehyde groups.
基金the National Natural Science Foundation of China(No.21502006)Beijing National Laboratory for Molecular Sciences and Beijing Institute of Technology(BIT)for financial support。
文摘Direct C(sp3)-H functionalization of N-unprotected aliphatic amines represents one of the most efficient and straightforward strategies for amine synthesis.Despite some recent progress in this field,the NH2-directed y-C(sp3)-H arylation of primary aliphatic amines exceptα-amino esters remained an unmet challenge.In this report,we established a simple and efficient method for site-selective C(sp3)-H arylation of primary aliphatic amines by aryl iodides.In the presence of only 5 mol%Pd(OAc)2,a wide range of aliphatic amines including O-benzyl and O-silyl amino alcohols were arylated at y-orδ-positions by aryl iodides containing a broad scope of functional groups.The synthetic application of this method had also been demonstrated by large-scale synthesis,the synthesis of a fingolimod analogue,and the conjugation with natural D-menthol and fluorescent 1,8-naphthalimide.
