Hydrolysis Process of the Anticancer Agents Novel Non-classical trans-Platinum(Ⅱ) with Aliphatic Amines

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.

Strong Room-Temperature Photoluminescence from the Novel Adduct of C_(60) with Aliphatic Amines

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.

Sono-photocatalytic amination of quinoxalin-2(1H)-ones with aliphatic amines

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.

Native amine-directed site-selective C(sp^3)-H arylation of primary aliphatic amines with aryl iodides

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.

The Oxirane Ring Opening of 2,3-endo-epoxybicyclo[3. 2 .0] hept-6-one by Amines at Alumina Surface

Stereospecific (trans) and regioselective nucleophilic opening of the title epoxide (I) by different amines at the alumina surface are described.

Hydrolysis of New Transplatin Analogue Containing One Aliphatic and One Planar Heterocyclic Amine Ligand： A Density Functional Theory Study

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.

Intercalation assisted liquid phase production of disulfide zirconium nanosheets for efficient electrocatalytic dinitrogen reduction to ammonia

Disulfide zirconium(ZrS_(2)) is a two-dimensional(2D) transition metal disulfide and has given rise to extensive attention because of its distinctive electronic structure and properties.However,mass production of high quality of ZrS_(2)nanosheets to realize their practical application remains a challenge.Here,we have successfully exfoliated the bulk ZrS_(2)powder with the thickness of micron into single and few-layer nanosheets through liquid-phase exfoliation in N-methylpyrrolidone(NMP) assisted via aliphatic amines as intercalators.It is found that the exfoliation yield is as high as 27.3%,which is the record value for the exfoliation of ZrS_(2)nanosheets from bulk ZrS_(2)powder,and 77.1% of ZrS_(2)nanosheets are 2-3 layers.The molecular geometric size and aliphatic amine basicity have important impact on the exfoliation.Furthermore,the ZrS_(2)nanosheets have been used as catalyst in the electrocatalytic dinitrogen reduction with the NH3yield of 57.75 μg h^(-1)mg_(cat.)^(-1),which is twice that by ZrS_(2)nanofibers reported in literature and three times that by the bulk ZrS_(2)powder.Therefore,the liquid phase exfoliation strategy reported here has great potential in mass production of ZrS_(2)nanosheets for high activity electrocatalysis.

Protecting-group-free amination of halogenated nitrobenzaldehyde with palladium catalyst

"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.

Crystalline covalent triazine frameworks manipulated by aliphatic amine modulator

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.

Theoretical Study on the Mechanisms of Action of Sulfurand Nitrogen-containing Amino Acid Residues with Monofunctional Guanine Adduct Formed by Antitumor Drugs trans-[PtCl_2(Am)(isopropylamine)] (Am = Isopropylamine,Dimethylamine and Propylamine) and Their

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.

The effect of altering crosslinker chemistry during interfacial polymerization on the performance of nanofiltration membranes for desalination, organic, and micropollutants removal

Chemistry of the polyamide active layer of a desalination membrane is critical in determining both its physical and chemical properties.In this study,we designed and fabricated three novel membranes with different active layers using the crosslinkers:terephthaloyl chloride,isophthaloyl chloride,and trimesoyl chloride.The crosslinkers were reacted with an aqueous solution of an aliphatic tetra-amine.Because these crosslinkers differ in their structures and crosslinking mechanisms during interfacial polymerization,the resultant membranes also possess different structural properties.The water contact angle of the fabricated membranes also varies;the water contact angles of 4A-3P-TPC@PSF/PET,4A-3P-TMC@PSF/PET,and 4A-3P-IPC@PSF/PET,are 68.9°,65.6°,and 53.9°,respectively.Similarly,the desalination performance of resultant membranes also showed variations,with 4A-3P-TPC@PSF/PET,4A-3P-IPC@PSF/PET,and 4A-3P-TMC@PSF/PET having a permeate flux of 17.14,25.70,and 30.90 L·m^(−2)·h^(−1),respectively,at 2.5 MPa.The 4A-3P-TPC@PSF/PET membrane exhibited extensive crosslinking with aliphatic linear amine,and cationic dye rhodamine B,MgCl_(2),and amitriptyline rejection rates of 98.6%,92.7%and 80.9%,respectively.The 4A-3P-TMC@PSF/PET membrane showed mediocre performance,while 4A-3P-IPC@PSF/PET membrane showed even lower performance,with a 35%rejection of methyl orange dye.