H+HCNO反应势能面的理论研究

在CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p)+ZPVE水平下, 对反应H＋HCNO进行了研究. 建立了反应势能面, 揭示了该反应的反应机理, 通过H迁移、N—O键或C—N键断裂等多步反应, 得到4种产物, 其中最主要产物为P1(HCN+OH).     

THEORETICAL APPROACHES TO PROTEIN STRUCTURE-FUNCTION ANALYSIS (Ⅰ)——DIRECTED PERTURBATION CONFORMATIONAL ANALYSIS

A new computational technique called directed perturbation conformational analysis has been developed for use in protein model building and structure-function studies. Designed to perform an efficient local search of a macromolecular potential energy surface, the algorithm can be used to locate multiple energy minimum conformers via low energy transition state structures from a single starting or trial structure. The algorithm contains developments to stabilize transition state optimizations for systems described by many degrees of freedom displaying anharmonic potential energy surfaces. It has been found to be efficient in the generation of alternative equilibrium structures from a given trial structure when compared with those generated from a standard molecular dynamics simulation of N-acetyl, N'-methyl-deca-L-alaninamide.     

Electronic structure of substituted bicycloheptanones (camphors)

He I photoelectron spectra of some camphor derivatives have been recorded and are assigned on the basis of correlations with the spectra of related molecules. The spectra reported in this work together with those reported previously form a camphor database for study of electronic structure interactions between functional groups themselves and between groups and the bicycloalkane skeleton. The unsymmetrical camphor skeleton is found to be a poor relay for σ−π interactions.     

聚醚砜紫外光氧化降解的ESR研究

与聚砜相比,聚醚砜(PES)由于没有异丙基,因而具有更好的耐热性和耐辐射性。Lyons等曾用ESR方法研究了聚砜在γ射线辐照下的降解,发现辐射产生的自由基主要是苯氧基(ArO·)、苯砜基(ArSO_2)、过氧基(ROO·)和环已二烯自由基。本文用ESR方法研究了PES的光氧化降解过程并提出了可能的降解机理。     

Potential energy surfaces for low-lying electronic states of SO2

The potential energy surfaces for the nine low-lying electronic states of SO₂ have been constructed by using the multi-reference second order perturbation theory (MRPT2) with the basis set cc-pVTZ. The optimized geometries and the adiabatic excitation energies of these states are in good agreement with experiments and previous calculations. The crossings and avoided crossings displayed in the potential energy surfaces are expounded.     

Crystallographic study of interaction between adspecies on metal surfaces

The interaction among adsorbed atoms and molecules (adspecies) on metal surfaces plays a decisive role in catalytic reactions. Such interaction may cause structural changes of the local adsorption geometry which, together with spectroscopic and energetic data, may afford useful physical and chemical insights into the basic mechanisms of surface processes. When the adsorption geometry of a single adspecies is considered as a function of coverage, a deeper understanding of the nature of the adsorbate-substrate bonding can be obtained. Depending on the adsorbate coverage, the magnitude of adsorbate-induced relaxations and reconstructions vary widely. Occasionally, chemisorption systems transform gradually into adsorbate-substrate compounds, such as oxides, nitrides, hydrides, and sulfides. For the case of adsorption of different adspecies, coadsorption, structural data can make a vital contribution to our understanding of reaction intermediates, the promotion effect in heterogeneously catalyzed reactions, and the formation of ultra-thin compound films.     

The Partitioning Mechanism of Phenazine Ethosulfate into Polymer Film Electrodes

Phenazine ethosulfate (PES⁺) partitioning into the AQ55 cation‐exchange polymer has been demonstrated by immersion and continuous electrochemical cycling experiments. Cyclic voltammetric waveshapes indicate that both the reduction of PES⁺ and the oxidation of PESH are diffusion‐controlled when incorporated into the polymer film. This is in dramatic contrast to the behavior exhibited at bare glassy carbon where the reduction of PES⁺ is diffusion‐controlled but the oxidation of PESH is characteristic of a surface‐confined redox process. The straightforward determination of the partition coefficient is complicated by the uncertainty associated with accurately knowing the thickness of the swollen polymer. Therefore Randles‐Sevcik data for the reduction of PES⁺ at the bare and polymer‐modified electrode were compared to qualitatively assess the extent of possible partitioning, which was determined to be on the order of 10¹–10². The partition coefficient was determined to be 9.1±0.4, a value in agreement with qualitative assessment. Partitioning was found to be sensitive to the cations present in solution with the order of extractability of PES⁺ from solutions of Li⁺, Na⁺, and K⁺, increasing in the order: Li⁺>Na⁺>K⁺. Continuous cycling experiments suggest PES⁺ partitions into the film during the reductive cycle to restore the equilibrium concentration in the film caused by the electrochemical consumption of the species.     

Vibrational spectra and ab initio molecular orbital calculations of the novel anti-cancer drug combretastatin A-4 prodrug

The NIR-FT Raman and FT-IR spectral studies of the novel antineoplastic and antiangiogenesis substance comprestatin A-4 prodrug (CA4P) were carried out. The equilibrium geometry, various bonding features and harmonic vibrational frequencies of CA4P have been investigated with the help of B3LYP density functional theory (DFT) method. The most preferred cis-configuration for its bioactivity has been demonstrated on the basis of torsional potential energy surface (PES) scan studies. Stability of the molecule arising from hyperconjugative interactions leading to its bioactivity, charge delocalization and mesomeric effects have been analyzed using natural bond orbital (NBO) analysis. Detailed assignments of the vibrational spectra have been made with the aid of theoretically predicted vibrational frequencies. The optimized geometry shows near-planarity of phenyl rings and perpendicular conformation of meta substituted methoxy group. The vibrational analysis confirms the differently acting ring modes, steric repulsion, pi conjugation and back-donation.     

纳米二氧化锆改性聚醚砜的研究

互联网的高速发展对通讯速度和通讯容量提出了越来越高的要求,也对基础性的材料科学提出同样的挑战。目前的信息高速传输网络主干线主要采用石英玻璃光纤,由于其光纤芯极细（8～62μm）,因而对光纤连接器的性能要求极高,而光纤连接器性能的好坏又直接影响到通讯的速度及容量。     

Mechanism and kinetics of the reaction of the 2-propargyl radical with ammonia

Gas-phase mechanism and kinetics of the reactions of the 2-propargyl radical (H₂CCCH), an important intermediate in combustion processes, with ammonia were investigated using ab initio molecular orbital theory at the coupled-cluster CCSD(T)//B3LYP/6-311++G(3df,2p) method in conjunction with transition state theory (TST), variational transition state theory (VTST), and Rice–Ramsperger–Kassel–Macus (RRKM) calculations for rate constants. The potential energy surface (PES) constructed shows that the C₃H₃ + NH₃ reaction has four main entrances, including two H-abstraction and two addition channels in which the former are energetically more favorable. The H-abstraction channels occur via energy barriers of 24 (T0/P2) and 26 kcal/mol (T0/P3) forming loose van de Waals complexes, COM_1 (12 kcal/mol) and COM_2 (14 kcal/mol), respectively. These complexes can easily be decomposed via barrier-less processes resulting HCCCH₃ + NH₂ (P2, 14 kcal/mol) and HCCCH₃ + NH₂ (P3, 15 kcal/mol), respectively. The additional channels occur initially by formation of two intermediate states, H₂CCCHNH₃ (35 kcal/mol) and H₂CC(NH₃)CH (37 kcal/mol) via energy barriers of 37 and 40 kcal/mol at T0/1 and T0/5, respectively, followed by isomerization and decomposition yielding 21 different products. These processes are fully depicted in an as-complete-as-possible PES. The rate constants and product branching ratios for the low-energy channels calculated show that the C₃H₃ + NH₃ reaction is almost pressure-independent. For the temperature range of 300–2000 K, the HCCCH₃ + NH₂ is the major product, whereas the minor one, HCCCH₃ + NH₂, has more contribution when temperature increases. Theoretical results on the mechanism and kinetics of the reaction considered may be helpful for future experiments as well as for understanding the role of the propargyl radical in combustion chemistry.