Sites of Protonation and Unimolecular Fragmentation of Protonated N-Hydroxyphthalimide in the Gas Phase

ＳｉｔｅｓｏｆＰｒｏｔｏｎａｔｉｏｎａｎｄＵｎｉｍｏｌｅｃｕｌａｒＦｒａｇｍｅｎｔａ┐ｔｉｏｎｏｆＰｒｏｔｏｎａｔｅｄＮ┐ＨｙｄｒｏｘｙｐｈｔｈａｌｉｍｉｄｅｉｎｔｈｅＧａｓＰｈａｓｅＳＨＥＹｉ－ｍｉｎ，ＳＵＮＹｕ－ｑｕａｎ，ＪＩＹｉ－ｐｉｎｇａｎｄ...

Ab Initio and RRKM Study of the Unimolecular Decomposition of Five-membered Ring Heterocyclic (X:O,S,N-H)

Quantum mechanical and Rice-Ramsperger-Kassel-Marcus （RRKM） calculations are carried out to study the thermal unimolecular decomposition of 2,5-dihydrofuran （1）,2,5dihydrothiophene （2）,and 3-pyrroline （3） at the MPW1PW91/6-31＋＋G level of theory,and the results are in good agreement with the experimental values.The predicted high pressure limit rate constants （k（T）） in various states of activation energy and pre-exponential （S1：（A（calc.）,E a（calc.））,S2：（A （calc.）,E a（exp.））,and S3：（A （exp.）,E a（calc.））） for the thermal decomposition processes 1-3 were evaluated.Also,the fall-off pressures （P1/2） for compounds 1-3 in the states 1-3 are found to be （1.24×10-2,1.09×10-3,and 4.19×10-2mmHg）,（1.24×10-2,1.63×10-3,and 2.79×10-2mmHg）,and （1.24×10-2,1.63×10-3,and 4.19×10-2 mmHg）,respectively.As the fall-off pressure of thermal decomposition process of compounds 1-3 is in the following order：P1/2（3）〉 P1/2（1）〉 P1/2 （2）,the decomposition rates are as below：rate（3） 〈rate（1）〈rate（2）.

THEORETICAL STUDIES ON THE UNIMOLECULAR DISSOCIATION OF METHYLFORMATE CATION

The unimolecular dissociation of methylformate free radical cation(CH_3OCHO^+) was studied by ab initio theoretical calculations, Molecular orbital and state correlation diagrams have been examined in the ground and lower excited states. The dissociation mechanism has been explained along the reaction paths. For two possible dissociation pathways in the ground and lower excited states, the activation barriers and reaction heats have been calculated by MCSCF method respectively.

Preparation and Unimolecular-Micellization Behavior of Homopolymer of Surface-Active Monomer AMC14AB

(2-acrylamido ) 乙醇 tetradecyl dimethylammonium 溴化物(AMC 14 AB ) 是在水的答案的 polymerized 形成人聚合物 P (AMC 14 AB ) 。P 的物理化学的性质(AMC 14 AB ) 主要与荧光灯的探查方法，表面紧张测量和 conductom-etry 在水的答案被学习。试验性的结果证明 P 的聚集形态学(AMC 14 AB ) 在里面水的答案是期望的 unimolecular micelle。与常规多分子的 micelle 系统不同， P 的 unimolecular micelle 系统( AMC 14 AB )不仅显示出批评 micellar 集中( CMC = 0 )，(即一旦增加了纯水，表面紧张在恶意立即减少密度怎么小)，而且表面紧张几乎呆在一样，集中增加。那是说，在表面紧张和集中之间的关系曲线上没有 mutational 点。而且， P 的 unimolecular micelle 系统(AMC 14 AB ) 没有 Krafft 温度，即只要它在水里被溶解，在任何温度， unimolecular 微粒将形成。除这以外，为恐水病的有机物质的增溶， P 的 unimolecular micelle 系统( AMC 14 AB )与普通多分子的 micelle 系统显然不同，没在在甲苯 solubi-lizaion 数量和 P 之间的关系曲线上有转弯的点( AMC 14 AB )集中，并且 P 的 unimolecular-micelle 系统的增溶的能力( AMC 14 AB )为恐水病的有机物质比普通表面活化剂的常规多分子的 micelle 答案的高得多，例如 centyl 修剪乙醇铵溴化物。

单分子胶束的制备及应用研究进展

单分子胶束由单个分子构成且有核-壳结构的胶束,这种独特的结构,使其显示出优异的稳定性,在稀释的条件下,不会发生解离。单分子胶束因其在复杂多变的微环境中具有良好的热力学稳定性和尺寸分布均匀性,使得单分子胶束在药物运输、靶向释放、染料去除、荧光标记、无机纳米颗粒模板的制备、能量收集和储存等方面都有重要应用。本文从不同聚合物结构及功能方向,综述了单分子胶束制备及应用的研究进展。

Bioreducible unimolecular micelles based on amphiphilic multiarm hyperbranched copolymers for triggered drug release

A novel type of bioreducible amphiphilic multiarm hyperbranched copolymer (H40-star-PLA-SS-PEG) based on Boltorn H40 core,poly(L-lactide) (PLA) inner-shell,and poly(ethylene glycol) (PEG) outer-shell with disulfide-linkages between the hydrophobic and hydrophilic moieties was developed as unimolecular micelles for controlled drug release triggered by reduction.The obtained H40-star-PLA-SS-PEG was characterized in detail by nuclear magnetic resonance (NMR),Fourier transform infrared (FTIR),gel permeation chromatography (GPC),differential scanning calorimeter (DSC),and thermal gravimetric analysis (TGA).Transmission electron microscopy (TEM) and dynamic light scattering (DLS) analyses suggested that H40-star-PLA-SS-PEG formed stable unimolecular micelles in aqueous solution with an average diameter of 19 nm.Interestingly,these micelles aggregated into large particles rapidly in response to 10 mM dithiothreitol (DTT),most likely due to shedding of the hydrophilic PEG outer-shell through reductive cleavage of the disulfide bonds.As a hydrophobic anticancer model drug,doxorubicin (DOX) was encapsulated into these reductive unimolecular micelles.In vitro release studies revealed that under the reduction-stimulus,the detachment of PEG outer-shell in DOX-loaded micelles resulted in a rapid drug release.Flow cytometry and confocal laser scanning microscopy (CLSM) measurements indicated that these DOX-loaded micelles were easily internalized by living cells.Methyl tetrazolium (MTT) assay demonstrated a markedly enhanced drug efficacy of DOX-loaded H40-star-PLA-SS-PEG micelles as compared to free DOX.All of these results show that these bioreducible unimolecular micelles are promising carriers for the triggered intracellular delivery of hydrophobic anticancer drugs.

Cylindrical polymer brushes-anisotropic unimolecular micelle drug delivery system for enhancing the effectiveness of chemotherapy

Polymer systems can be designed into different structures and morphologies according to their physical and chemical performance requirements,and are considered as one of the most promising controlled delivery systems that can effectively improve the cancer therapeutic index.However,the majority of the polymer delivery systems are designed to be simple spherical nanostructures.To explore morphology/size-oriented delivery performance optimization,here,we synthesized three novel cylindrical polymer brushes(CPBs)by atom transfer radical polymerization(ATRP),which were cellulose-g-(CPT-b-OEGMA)(CCO)with different lengths(~86,~40,and~21 nm).The CPBs are composed of bio-degradable cellulose as the carrier,poly(ethylene glycol)methyl ether methacrylate(OEGMA)as hydrophily block,and glutathione(GSH)-responsive hydrophobic camptothecin(CPT)monomer as loaded anticancer drug.By controlling the chain length of the initiator,three kinds of polymeric prodrugs with different lengths(CCO-1,CCO-2,and CCO-3)could be self-organized into unimolecular micelles in water.We carried out comparative studies of three polymers,whose results verified that the shorter CPBs exhibited higher drug release efficiency,more cellular uptake,and enhanced tumor permeability,accompanied by shortened blood circulation time and lower tumor accumulation.As evidenced by in vivo experiments,the shorter CPBs exhibited higher anti-tumor efficiency,revealing that the size advantage has a higher priority than the anisotropic structure advantage.This provided vital information as to design an anisotropic polymer-based drug delivery system for cancer therapy.

CO product distribution in the unimolecular dissociation of HCO

The unimolecular dissociation of HCO ground state was investigated with the time-dependent full-quantum symplectic propagation based on the newest potential energy surface of the system. Calculated energy and widths of HCO resonance states agree well with those in the literature. CO product distribution was systematically investigated. A simple model was presented to interpret the rovibrational distributions in HCO dissociation.

Self-organization of unimolecular micelles in beam stream for functional mesoporous metal oxide nanofibers

The use of linear amphiphilic block copolymers as templates is an important method for the preparation of mesoporous materials.However,the obtained assemblies are usually sensitive to synthetic conditions,which impedes the preparation of such mesoporous materials in certain environments.Herein,we report a universal strategy applying an amphiphilic multiarm triblock copolymer in the preparation of mesoporous metal oxide nanofibers(NFs)using one metal oxide(TiO_(2),ZrO_(2),WO_(3),CeO_(2)),or two(TiO_(2)/WO 3,TiO_(2)/ZrO_(2),TiO_(2)/CeO_(2))and three(TiO_(2)/WO_(3)/CuO)metal oxides as composites.The template consists of modified β-cyclodextrin as the center of the macromolecule which is attached sequentially to a block of polystyrene,poly(acrylic acid),and poly(ethylene oxide).Under electrospinning conditions,stable unimolecular micelles are formed and effectively co-assemble with metal ions to form fibrous nanostructures.As indicated by various characterization methods,the synthesized TiO_(2) and its derived composite NFs maintain a straight and continuous fibrous structure after calcination,and TiO_(2) NFs exhibit uniform mesopores of 10.8 nm in diameter and a large Brunauer-Emmett-Teller surface area of 143.3 m^(2)g^(−1).Benefiting from the characteristic structure,still present after modification,Pt-decorated mesoporous TiO_(2) NFs display excellent ability in the visible-light photocatalytic degradation of tetracycline,which is superior to the commercial P25 catalyst.This study reveals a promising strategy for the preparation of fibrous mesoporous metal oxides.

A three-dimensional ratiometric sensing strategy on unimolecular fluorescence—thermally activated delayed fluorescence dual emission

With the support by the National Natural Science Foundation of China and partially by the National Key Research and Development Program of China,the research team led by Prof.Zhu LiangLiang(朱亮亮)at the State Key Laboratory of Molecular Engineering of Polymers,Department of Macromolecular Science,Fudan University,cooperated with the research team led by Prof.

Theoretical calculations of the unimolecular canonical rate constants

Microcanonical rate constants k(E) and canonical rate constants k(T) for unimolecular reactions have been obtained through the calculations of cumulative reaction probabilities N(E) with the unsymmetrical Eckart potential tunneling correction. By way of example, the reactions HCN→CNH (I) and FNC→NCF (II) have been employed. For reaction (I), the calculated rate constants are in agreement with the experimental data; for reaction (II), the results are in accordance with the rate constants kCVT/MEPSAG(T) calculated by the common program POLYRATE.

Effect of intramolecular energy transfer on the rate of unimolecular isomerization: HCN --HNC

This paper reports calculations of the rate of isomerization of HCN - HCN based on the theory of Gary and Rice as extended by Zhao and Rice. The major task is to determine the effect of intramolecular energy transfer on the prediction of the rate of isomerization. Both the full three-dimensional (3D) system and the reduced two-dimensional (2D) system obtained from freezing CN bond at 1.159 A are analyzed to check the validity of the freezing bond approximation. Meanwhile, RRKM rates are calculated to test RRKM choice of the transition state by comparing to Gary-Rice three-state model. The comparison shows that the rates from 2D model and 3D model are differing up to 20% with 2D rates consistently larger. The intramolecular energy transfer modifies the isomerization rate for HCN system up to 30% that is modestly small by the expectation. The isomerization rate predicted from RRKM theory is greater than those of Gary-Rice three-state model theory up to 65%, and it overstimates the rates under all considerations, including the contribution from intramolecular energy transfer, for the studied system by about a factor of 2.

A New Formulation of the Lindemann Mechanism of Unimolecular Reactions

A new formulation of the Lindemann mechanism of unimolecular reactions in gaseous phase is presented,without the use of steady state hypothesis. It is hereby shown that the nature of applicability of steady state hypothesis in the regime of high reactant gas pressure is different from that in the regime of low gas pressure. In the former case it is an equilibrium approximation,while in the latter case it is a highly reactive intermediate approximation in no connection with a steady state. Furthermore for the latter case it is shown that in the classical formulation of Lindemann mechanism the use of steady state hypothesis is an ad hoc assumption. A highly reactive intermediate in the sense that its concentration is very small during the whole course of reaction is a necessary condition for the applicability of very reactive intermediate approximation. When the two distinctive nature of the applicability of steady state hypothesis is mixed-up,wrong or useless conclusion may be arrived at. The only possible case of realizing a true steady state in a complex reaction is pointed out.

Single-Metal-Atom Polymeric Unimolecular Micelles for Switchable Photocatalytic H_(2) Evolution

Developing“green”catalytic systems with desirable performance such as good water solubility,recyclability,and switchability is a great challenge.Here,to address this challenge,we extend the concept of polymeric unimolecular micelles(a typical selfassembled structure)to the construction of a stimuli-responsive and recoverable molecular catalyst with single-metal atoms that exhibits switchable photocatalytic activity for water splitting.

Unimolecular Transmembrane Na^(+) Channels Constructed by Pore-Forming Helical Polymers with a 2.3A Aperture

To understand the relationships between channel size and ion selectivity,we have developed a new type of artificial ion channel based on pore-forming helical polymers consisting of phenanthrolineoxadiazole units with a pore aperture 2.3A close to the diameter of the Na^(+)ion(2.04A).Successful preparation of high molecular weight helical polymers(HP1)gives rise to a 4.6 nm long artificial unimolecular transmembrane channel.The transport property of artificial channel HP1 was elaborately investigated by means of vesicle-based kinetic assay and symmetry/asymmetry bilayer membrane(BLM)experiments as well.These results unambiguously demonstrate that HP1 is a Na^(+)-selective channel with extremely high transport activity(EC_(50)=0.017 mol% relative to lipid).Moreover,the Na^(+)/K^(+)selectivity ratio of HP1 reaches 1.9,as determined by asymmetry BLM experiments.Owing to the narrowest 2.3A size constraint so far,HP1 transport naked Na^(+)ion across the membrane,which represents a different Na^(+)transport mode from that of natural Na^(+)channels,which transports partially hydrated Na^(+)ions during transmembrane conduction.This study provides crucial insights on the chemical basis of ion selectivity in the field of ion channels.

Theoretical studies on silathione and its unimolecular reactions

The unimolecular reactions of silathione:(a)dehydrogenation,(b)trans-isomerization, (c)cis-isomerization,are investigated by ab initio MO calculations using RHF/4-31G basis set.The geometries and energies of the reactant,transition states and products have been determined on the singlet potential energy surface of the ground state.The reaction ergodography along the intrinsic reaction coordinate(IRC)for the three reactions has also been performed.

Theoretical studies on ammonia oxide and its unimolecular reactions

The unimolccular reactions of ammonia oxide H_3NO,isomerization and dehydrogenation, are investigated by ab initio MO calculations with the 4-31G basis set.The geometries and energies of the reactant,transition states and products have been determined on the singlet potential energy sur- face.The reaction ergodography along the intrinsic reaction coordinate(IRC)for the two reactions have been performed.The vibrational frequency correlation diagram of the two reactions are analyzed along the IRC.

合成水杨酸-交联聚苯乙烯螯合树脂的新途径

采用氯甲基化试剂1,4-二氯甲氧基丁烷对交联聚苯乙烯(CPS)微球实施了氯甲基化反应,然后使5-氨基水杨酸(ASA)与氯甲基化交联聚苯乙烯微球表面的苄氯基团发生亲核取代反应,制得了氨基水杨酸-交联聚苯乙烯(ASA-CPS)螯合树脂。考察了主要反应条件对取代反应的影响,初步试验了ASA-CPS对金属离子的螯合性能。结果表明:ASA-CPS对Fe(Ⅲ)离子具有很强的螯合能力,吸附容量达3.77 mmol/g。

离子/中性复合物中间体研究进展

对离子／中性（碎片）复合物的形成、特征、反应、研究方法和近年来取得的重要成就及其应用进展进行了综述．简述了另一类特殊形式的离子／中性（碎片）复合物质子键合复合物．

Glucagon-like peptide-1/glucose-dependent insulinotropic polypeptide dual receptor agonist DA-CH5 is superior to exendin-4 in protecting neurons in the 6-hydroxydopamine rat Parkinson model

Patients with Parkinson's disease(PD) have impaired insulin signaling in the brain. Incretin hormones, including glucagon-like peptide-1(GLP-1) and glucose-dependent insulinotropic polypeptide(GIP), can re-sensitize insulin signaling. In a recent phase II clinical trial, the first GLP-1 mimic, exendin-4, has shown reliable curative effect in patients with PD. DA-CH5 is a novel GLP-1/GIP receptor unimolecular coagonist with a novel peptide sequence added to cross the blood-brain barrier. Here we showed that both exendin-4 and DA-CH5 protected against 6-hydroxydopamine(6-OHDA) cytotoxicity, inhibited apoptosis, improved mitogenesis and induced autophagy flux in SH-SY5Y cells via activation of the insulin receptor substrate-1(IRS-1)/alpha serine/threonine-protein kinase(Akt)/c AMP response element-binding protein(CREB) pathway. We also found that DA-CH5(10 nmol/kg) daily intraperitoneal administration for 30 days post-lesion alleviated motor dysfunction in rats and prevented stereotactic unilateral administration of 6-OHDA induced dopaminergic neurons loss in the substantia nigra pars compacta. However, DA-CH5 showed curative effects in reducing the levels of α-synuclein and the levels of pro-inflammatory cytokines(tumor necrosis factor-α, interleukin-1β). It was also more effective than exendin-4 in inhibiting apoptotic process and protecting mitochondrial functions. In addition, insulin resistance was largely alleviated and the expression of autophagy-related proteins was upregulated in PD model rats after DA-CH5 treatment. These results in this study indicate DA-CH5 plays a therapeutic role in the 6-OHDAunilaterally lesioned PD rat model and is superior to GLP-1 analogue exendin-4. The study was approved by the Animal Ethics Committee of Shanxi Medical University of China.