共查询到20条相似文献，搜索用时 31 毫秒
1.
采用密度泛函理论和MonteCarlo模拟方法研究了2-氨基-2-咪唑啉在气相和水中的异构现象和质子迁移反应.考虑了直接迁移和水助催化迁移等两种质子迁移途径.气相中稳定点的几何结构和热力学性质是在B3LYP/6-311+G**理论水平上计算得到的.溶剂效应的研究结果表明,水作为溶剂可降低直接迁移途径的速率,有利于水助催化反应途径的进行. 相似文献
2.
3.
有机溶剂对ICP—AES分析性能影响的研究 总被引：3，自引：0，他引：3
研究了有机溶剂对电感耦合等离子体－原子发射光谱（ＩＣＰ－ＡＥＳ）分析性能的影响。ＭｏｎｔｅＣａｒｏｌ模拟结果和实验结果表明，只要选择合适的操作参数，有机溶剂直接引入ＩＣＰ不仅不会影响ＩＣＰ的稳定性，还会提高某些元素的灵敏度，从而提高了ＩＣＰ－ＡＥＳ的分析性能。 相似文献
4.
2-羟基咪唑在气相和水中的异构平衡和质子迁移的从头算计算和Monte Carlo模拟 总被引：1，自引：0，他引：1
采用从头算方法在MP2/6-31＋G*水平上研究了2-羟基咪唑分子在孤立分子和一水合物的异构体的相对稳定性和可能的质子迁移反应, 分析了一个水分子的参与对2-羟基咪唑分子异构体的相对稳定性和质子迁移速率的影响, 采用Monte Carlo模拟方法研究了反应体系在水溶液中反应的溶剂化效应. 结果表明: 2-羟基咪唑分子的孤立分子和一水合物的最稳定异构体相同, 都为酮式. 直接质子迁移反应在水溶液中活化能垒有轻微增加, 但产物能量得到降低; 水助催化质子迁移反应在水溶液中的活化能垒和产物能量都得到明显降低. 综合气相和水相的计算结果, 2-羟基咪唑水助催化的质子迁移反应较易进行, 且在水溶液中进行容易, 可以很容易被实验观察到. 相似文献
5.
Proton transfer reactions were studied in all titratable pairs of amino acid side chains where, under physiologically reasonable conditions, one amino acid may function as a donor and the other one as an acceptor. Energy barriers for shifting the proton from donor to acceptor atom were calculated by electronic structure methods at the MP2/6-31++G(d,p) level, and the well-known double-well potentials were characterized. The energy difference between both minima can be expressed by a parabola using as argument the donor-acceptor distance R(DA). In this work, the fit parameters of the quadratic expression are determined for each donor-acceptor pair. Moreover, it was found previously that the energy barriers of the reactions can be expressed by an analytical expression depending on the distance between donor and acceptor and the energy difference between donor and acceptor bound states. The validity of this approach is supported by the extensive new data set. This new parameterization of proton transfer barriers between titratable amino acid side chains allows us to very efficiently estimate proton transfer probabilities in molecular modelling studies or during classical molecular dynamics simulation of biomolecular systems. 相似文献
6.
Some substituted 2‐amino‐2‐chromenes were synthesized by the reaction of arylidenemalononitriles with 1‐naphthol or 2‐naphthol in the presence of sodium hydroxide as catalyst under solvent‐free condition. 相似文献
7.
8.
Ling Chen Hao Zhang Prof. Mei Pan Dr. Zhang‐Wen Wei Hai‐Ping Wang Ya‐Nan Fan Prof. Cheng‐Yong Su 《化学:亚洲杂志》2016,11(12):1765-1769
We report herein an unprecedented example of a luminescent SmIII metal–organic framework (Sm‐MOF), in which both the visible and near‐infrared (NIR) emissions of Sm3+ ions are able to be sensitized by an excited‐state intramolecular proton transfer (ESIPT) ligand. Due to the solvent‐mediated interchange between enol and keto excited states of the ligand and subsequent energy transfer rate to Sm3+ ions, the luminescent decay lifetime of the Sm‐MOF can be tuned in different solvent‐grinding systems. 相似文献
9.
Investigation of semiflexible coil‐like chains in the process of partitioning with a slit in a solvent of variable thermodynamic quality has shown two key results. For semiflexible chains in a good solvent, the effect of chain stiffness played a role only at low concentrations. However, the situation is different with interacting chains where the effect of stiffness is also observed at higher concentrations. For theta chains, the partitioning into a slit in dilute solutions is lower for semiflexible than for flexible chains, while for higher concentrations this order is reversed. The packing ability of semiflexible chains at higher concentrations is enhanced in the theta system. Interestingly, stretching of chains on penetration into the slit is observed at higher concentrations. Decomposition of free energy change on partitioning into entropy and energy contributions gives more information on the details of partitioning of these systems, especially the differentiation between dilute and moderate concentration regimes. A positive change of partitioning entropy in the theta solvent in the semidilute regime for both flexible and semiflexible chains is noteworthy. This is related to breaking favorable interactions between chains on penetration into the slit. 相似文献
10.
Proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) reactions of the phenoxyl/phenol couple are studied theoretically by using wave function theory (WFT) as well as DFT methods. At the complete active space self-consistent field (CASSCF) level, geometry optimization is found to give two transition states (TSs); one is the PCET type with two benzene rings being nearly coplanar, and the other is the HAT type with two benzene rings taking a stacking structure. Geometry optimization at the (semilocal) DFT level, on the other hand, is found to give only one transition state (i.e., the PCET-type one) and fail to obtain the stacking TS structure. By comparing various levels of theories (including long-range corrected DFT functionals), we demonstrate that the Hartree-Fock exchange at long range plays a critical role in obtaining the sufficient stacking stabilization of the present open-shell system, and that the sole addition of empirical dispersion correction to semilocal DFT functionals may not be adequate for describing such a stacking interaction. Next, we investigate the solvent effect on the PCET and HAT TS thus obtained using the reference interaction site model self-consistent field (RISM-SCF) method. The results suggest that the free energy barrier increases with increasing polarity of the solvent, and that the solvent effects are stronger for the PCET TS than the stacking HAT TS pathway. The reason for this is discussed based on the dipole moment of different TS structures in solution. 相似文献
11.
12.
Gang Yang Xiaomin Wu Yuangang Zu Chengbu Liu Yujie Fu Lijun Zhou 《International journal of quantum chemistry》2009,109(2):320-327
Ab initio calculations at MP2 level of theory were used to study the proton transfer at the carboxylic sites of amino acids, in the isolated, mono‐ and di‐hydrated forms. In the case of water dimer, two interaction modes with glycine neutral structures (see Fig. 3 ) were explored, corresponding to the concerted and stepwise reaction pathways. Their transition states can be described as (H2O? H? OH2)+ [Fig. 4 (a)] and (H2O‐‐‐H? OH2)+ [Fig. 4 (b)], respectively. The energy analysis indicated that the concerted pathway is preferred. In the isolated, mono‐ and di‐hydrated glycine complexes, the activation barriers of the proton transfer at the carboxylic sites were calculated to be 34.49, 16.59, and 13.36 kcal mol?1, respectively. It was thus shown that the proton transfer is significantly assisted and catalyzed by water monomer so that it can take place at room temperature. Instead, the further addition of water molecules plays solvent effects rather than catalytic effects to this proton transfer process. The above results obtained with discrete water molecules were supported by the solvent continuum calculated data. It was also observed that the heavy dependence of the solvent continuum models on dipole moments may produce misleading results. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 相似文献
13.
Yongbing Song Run Jiang Zheng Wang Lang Wang Yuhua Yin Baohui Li An‐Chang Shi 《Macromolecular theory and simulations》2016,25(6):559-570
The self‐assembled morphologies of cyclic amphiphiles, which are composed of a long hydrophobic block and a short hydrophilic block, in selective solutions are studied by using a simulated annealing method. The morphological dependence of the aggregates on solvent quality is investigated. The topology effects are studied by comparing results from linear counterparts of the amphiphiles. It is observed that, in addition to spherical micelles, cylindrical micelles, disklike micelles, vesicles, and large compound micelles, muticompartment vesicles with several fluidic cores can be formed by the cyclic systems. The morphologies are regulated by the interaction parameter εAS between the hydrophobic block and solvents. Furthermore, it is revealed that the differences of characteristics of the self‐assembled aggregates originate from the difference in architectural constraint. The wide region of forming multicompartment vesicles suggests that cyclic amphiphilic macromolecules could be a suitable candidate for applications to deliver multiple functional components by compartmentalizing different components in different confined space of vesicles. 相似文献
14.
Esteban Vöhringer‐Martinez Alejandro Toro‐Labbé 《Journal of computational chemistry》2010,31(14):2642-2649
15.
Yves Termonia 《Journal of Polymer Science.Polymer Physics》2010,48(6):687-692
The issue of chain confinement in nanocomposites remains largely unanswered because experimental systems are plagued by additional complicating variables such as particle–polymer interactions and free volume increases brought upon by the addition of the particles. Using computer simulation of high length chain polymers, we show that simple excluded volume interactions between polymer and nanoparticles lead to a wealth of changes in the diffusion coefficient and entanglement density of the chains. This opens up the possibility of using nanoparticles for tuning polymer properties, such as toughness, melt viscosity, and transient rubberlike behavior. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 687–692, 2010 相似文献
16.
Monte Carlo模拟研究高分子单链在基体中扩散的拓扑效应 总被引：1，自引：0，他引：1
高分子流体的性质同高分子的链结构及其动力学行为密切相关. 在高分子共混物中,共混组分的性质不仅依赖于自身的拓扑结构,还受到其它组分分子拓扑的影响. 本文中采用基于格子模型的Monte Carlo模拟方法研究了在高分子基体中扩散的4种不同拓扑组合（环形或线形高分子链）体系中目标单链的静态和动态性质. 结果发现,环形目标单链的性质受基体分子拓扑结构的影响要大于线形目标单链;其中环/线这一拓扑组合中目标单链的扩散机理相比其本体已经发生了较大改变,链末端在其中起了重要作用. 此外,我们对引起这一现象出现的可能原因做了分析. 相似文献
17.
18.
Pi‐Tai Chou 《中国化学会会志》2001,48(4):651-682
Contemporary progress regarding guest/host types of excited‐state double proton transfer has been reviewed, among which are the biprotonic transfer within doubly H‐bonded host/guest complexes, the transfer through a solvent bridge relay, the intramolecular double proton transfer and solvation dynamics coupled proton transfer. Of particular emphases are the photophysical and photochemical properties of excited‐state double proton transfer (ESDPT) in 7‐azaindole and its corresponding analogues. From the chemical aspect, two types of ESDPT reaction, namely the catalytic and non‐catalytic types of ESDPT, have been classified and reviewed separately. For the case of static host/guest hydrogen‐bonded complexes both hydrogen‐bonding strength and configuration (i.e. geometry) play key roles in accounting for the reaction dynamics. In addition to the dynamical concern, excited‐state thermodynamics are of importance to fine‐tune the proton transfer reaction in the non‐catalytic host/guest type of ESDPT. The mechanisms of protic solvent assisted ESDPT, depending on host molecules and proton‐transfer models, have been reviewed where the plausible resolution is deduced. Particular attention has been given to the excited‐state proton transfer dynamics in pure water, aiming at its future perspective in biological applications. Finally, the differentiation in mechanism between solvent diffusive reorganization and solvent relaxation to affect the host/guest ESPT dynamics is made and discussed in de tail. 相似文献
19.
采用Monte Carlo方法研究了分子量多分散性对AB型嵌段共聚物相行为的影响.通过调整嵌段共聚物中组分含量,考察了整体多分散性和单嵌段多分散性对嵌段共聚物共混物的有序-无序转变(Order-disorder transition,ODT)、形貌及链尺寸的影响.研究结果表明,多分散度的增大使无序相向较大xN区域略微移动,形成的片层结构厚度增加.在形成微观有序形貌后,较大分散度时各亚组分的链会得到更大的伸展,表明分子链堆积受挫的程度减小,因此,涨落作用受到的抑制作用减小,无序相区向更低温度区域移动. 相似文献
20.
Xiubin Ren Xiangyun Guo . College of Chemistry Chemical Engineering Xi’an University of Science Technology Xi’an Shaanxi China . State Key Laboratory of Coal Conversion Institute of Coal Chemistry Chinese Academy of Sciences Taiyuan Shanxi 《天然气化学杂志》2011,20(5):503-506
Monte Carlo method was applied to simulate the oscillatory behavior during partial oxidation of methane under non-isothermal condition. The simulation was performed to examine the influences of heat transfer constant and particle size on the kinetic oscillation. The oscillatory period and amplitude were observed to increase with the increase of heat transfer constant. The increase of catalyst particle size was found to result in short oscillatory period and more or less regular oscillations combined with the formation of oxide down to L=100. 相似文献