Theoretical Study on the Reaction Mechanism of Ketene CH2CO with Isocyanate NCO Radical

The bimolecular single collision reaction potential energy surface of an isocyanate NCO radical with a ketene CH2CO molecule was investigated by means of B3LYP and QCISD（T） methods. The computed results indicate that two possible reaction channels exist on the surface. One is an addition-elimination reaction process, in which the CH2CO molecule is attacked by the nitrogen atom at its methylene carbon atom to lead to the formation of the intermediate OCNCH2CO followed by a C-C rupture channel to the products CH2NCO＋CO. The other is a direct hydrogen abstraction channel from CHzCO by the NCO radical to afford the products HCCO＋HNCO. Because of a higher barrier in the hydrogen abstraction reaction than in the addition-elimination reaction, the direct hydrogen abstraction pathway can only be considered as a secondary reaction channel in the reaction kinetics of NCO＋ CH2CO. The predicted results are in good agreement with previous experimental and theoretical investigations.     

Theoretical Study on the Structures and Stability of Isomers and Complex of[Si,C,O,O] Sytem

A detailed singlet potential energy surface(PES) of [Si,C,O,O] system including a van der Waals (vdW) comples SiO……CO2,eight isomers,and twelve transiton states is investigated by MP2 and QCISD(T) (single-point)methods.At the final QCISD(T)/6-311 G(2df)//MP2/6-311G(d) level with zero-point energy included,the complex SiO……CO is found to be thermodynamically and kinetically the most stable species.Although eight ismoers are located as local energy minima,they are rather unstable toward isomerization to the dissociation fragments or comples.For the reaction of silocon atoms with carbon dioxide,two competitive reaction channels are found,and the primary pathway,which leads to the products of SiO and CO fragments,is the direct oxygen-abstraction process from carbon dioxide by silicon atom with a41.16 kJ/mol reaction barrier height.Our predications are in good agreement with previous experimental and theoretical studies.     

磷炔R-C≡P(R=-BH2,-CH3,-NH2,-OH)及其异构体的稳定性

采用 B3LYP和 CCSD(T)方法对 R-C≡ P(R=-BH2, -CH3,-NH2, -OH)体系进行了理论研究 .结果表明,含 C≡ P三键的异构体 BH2-C≡ P和 CH3-C≡ P在各自的体系中分别是热力学最稳定的结构 .而在 HO-C≡ P和 NH2-C≡ P体系中,热力学最稳定的结构却是 H-P=C=O和含 C≡ N三键的 N≡ C-PH2.动力学理论研究表明,没有相关实验研究的 R-C≡ P(R=-BH2,NH2)体系中共有 5种异构体是动力学稳定的 .在 HO-C≡ P体系的 2种动力学稳定的异构体中, H-P=C=O连接方式的异构体已被实验所证实,而另外一种 HO-C≡ P连接方式的异构体的动力学稳定性较高,实验中可以观察到 .对于 CH3C≡ P体系,研究所预示的 2种动力学稳定的异构体中 CH3-C≡ P已被实验证实,从理论上推测另一种动力学稳定性较高的异构体 HC≡ C-PH2在实验中也可以检测到.     

[Si,N,C,O]2+异构体结构、相对稳定性与解离

在UB3LYP/6-311G(d)和UCCSD(T)/6-311 + G(2df)(单点)水平下得到了[Si, N, C,O]²⁺体系的15种异构体, 对它们的结构进行了分析, 并给出了能量较低的离子碎片方式. 计算结果表明线型异构体SiNCO²⁺ (²Π )是[Si,N,C,O]²⁺体系中热力学最稳定的物种, 其次是线型的SiOCN²⁺(²Π ), SiCNO²⁺(²Π )和含NCO三元环的异构体SiC(NO)(²A″ ). 几个动力学相对较稳定的异构体的稳定性顺序为SiNCO²⁺> SiCNO²⁺(²Π )> SiOCN²⁺> SiC(NO)²⁺ >OSiNC²⁺(²Π ). 对异构化过程及离子碎片方式的分析结果说明线型异构体SiNCO²⁺是相关质谱实验中的主要物种, 而且是亚稳态的, 在质谱条件下可以解离成离子碎片.     

Fe3+-TiO2/SiO2光催化降解罗丹明B的研究

以硅胶为载体,采用溶胶-凝胶法制备了不同掺杂量的Fe3+-TiO2/SiO2光催化剂,并采用SEM,Raman和DRS等手段对其进行了分析和表征.以氙灯为光源,通过对可溶性染料罗丹明B的降解反应,考察了Fe3+-TiO2/SiO2催化剂的光催化活性,探讨了光催化反应中溶液pH值和起始浓度对催化反应的影响.     

Cs的覆盖度对Cs/石墨烯的结构稳定性和场发射性能影响

采用密度泛函理论方法,对Cs以不同覆盖度吸附在石墨烯表面时系统的结构稳定性和场发射性能进行了研究。计算结果表明单原子Cs吸附在石墨烯表面的碳六元环的中心位置时系统的能量最低。随着Cs的覆盖度增加,碱金属Cs与石墨烯之间的吸附作用逐渐增强,(4×4)R 0°和(2×2)R 0°结构是稳定的。由于碱金属Cs的修饰作用,Cs/石墨烯体系的功函明显下降,且随着碱金属Cs的覆盖度增大,系统的功函逐渐减小。态密度的计算结果表明功函的下降主要与Cs和石墨烯之间的电子转移有关。随着覆盖度的增大,石墨烯的电子态逐渐向低能方向移动,系统的费米能级升高并导致材料的功函下降。     

Characterizing neural activities evoked by manual acupuncture through spiking irregularity measures

The neural system characterizes information in external stimulations by different spiking patterns. In order to examine how neural spiking patterns are related to acupuncture manipulations, experiments are designed in such a way that different types of manual acupuncture （MA） manipulations are taken at the ＇Zusanli＇ point of experimental rats, and the induced electrical signals in the spinal dorsal root ganglion are detected and recorded. The interspike interval （ISI） statistical histogram is fitted by the gamma distribution, which has two parameters： one is the time-dependent firing rate and the other is a shape parameter characterizing the spiking irregularities. The shape parameter is the measure of spiking irregularities and can be used to identify the type of MA manipulations. The coefficient of variation is mostly used to measure the spike time irregularity, but it overestimates the irregularity in the case of pronounced firing rate changes. However, experiments show that each acupuncture manipulation will lead to changes in the firing rate. So we combine four relatively rate- independent measures to study the irregularity of spike trains evoked by different types of MA manipulations. Results suggest that the MA manipulations possess unique spiking statistics and characteristics and can be distinguished according to the spiking irregularity measures. These studies have offered new insights into the coding processes and information transfer of acupuncture.     

Effective suppression of beta oscillation in Parkinsonian state via a noisy direct delayed feedback control scheme

This work explores the function of the noisy direct delayed feedback(NDDF)control strategy in suppressing the pathological oscillations in the basal ganglia(BG)with Parkinson’s disease(PD).Deep brain stimulation(DBS)alleviates the PD state fantastically.However,due to its unclear mechanism and open-loop characteristic,it is challenging to further improve its effects with lower energy expenditure.The noise stimulus performs competitively in alleviating the PD state theoretically,but it cannot adapt to the neural condition timely and automatically due to its open-loop control scheme.The direct delayed feedback(DDF)control strategy is able to disturb excessive synchronous effectively.Therefore,the NDDF control strategy is proposed and researched based on a BG computational model,which can reflect the intrinsic properties of the BG neurons and their connections with thalamic neurons.Simulation results show that the NDDF control strategy with optimal parameters is effective in removing the pathological beta oscillations.By comparison,we find the NDDF control strategy performs more excellent than DDF in alleviating PD state.Additionally,we define the multiple-NDDF control strategy and find that the multiple-NDDF with appropriate parameters performs better than NDDF.The obtained results contribute to the cure for PD symptoms by optimizing the noise-induced improvement of the BG dysfunction.     

HPO3异构体结构与稳定性

使用密度泛函方法(B3LYP)和6-311 G(3df,3pd)基组计算得到了HPO3体系的9个异构体与11个过渡态,并用内禀反应坐标理论验证了异构体的异构化过程．结果表明,在HPO3体系中,只有热力学最稳定的平面型异构体HOFO2(E1),(cis,cis)构象的HOOPO(E3)和立体的具有Cs对称性的异构体HP(O)O2(E7)具有较高的动力学稳定性,理论预测结果与实验一致．另外2个立体的HOFO2连接方式的异构体(E2和E4)由于解离为HO(Ⅱ) OPO(^2A1)的解离能较低,因此不能稳定存在。     

多价态共存的Ag-TiO2光催化剂的制备及光催化活性

在避光条件下采用溶胶凝胶法制备了Ag-TiO2光催化剂,通过XRD, Raman, PL和XPS表征及对光催化降解罗丹明B的性能评价,发现Ag的掺入抑制了TiO2锐钛矿相的晶化,促进了TiO2由锐钛矿相向金红石相的转变.随着掺Ag量的增加,PL光谱强度下降,这说明Ag掺入抑制了光生电子空穴的复合.在较低掺杂浓度区(Ag/Ti atom＜3%)以Ag+的迁移、扩散为主,在较高浓度掺杂区(Ag/Ti atom≥3%) Ag+的迁移、扩散和表面还原共存,在浅表层扩散阈值附近(Ag/Ti atom=3%～5%), Ag-TiO2光催化剂既有丰富的浅表层电子捕获阱,又有利于电子向表面还原态Ag的导出,使光生电子和空穴的复合得到有效的抑制,从而使光催化效率显著提高.当掺杂浓度大于阈值时,Ag-TiO2催化剂的催化活性降低.