Quantum states of hydrogen transfer and vibration in malonaldehyde

New ab initio results on the 21D potential energy surface of malonaldehyde and a quantum mechanical treatment of the hydrogen transfer motion and its interaction with all vibrations are presented. An explicit approximate reaction path, close to the minimum energy path but matching the reactive normal mode near equilibrium, allows one to predict the ground state tunnelling frequency even when using small basis sets. With a barrier of 1144 cm^?1 (3.27kcal mol-¹) the tunnelling splitting is predicted to be 22.0cm^?1 for the parent species and 3.8 cm^?1 for the species deuterated in the hydrogen bond, in good agreement with the observed values 21.6 and 2.9 cm^?1, respectively. Predicted energy levels for excited states of the hydrogen transfer motion and for the non-reactive vibrations suggest a re-examination of the vibrational spectra and an extension of the number of vibrational factors in the basis set to improve the results for the vibrationally excited states.     

Electrophysiological correlates of associative learning in smokers: a higher-order conditioning experiment

Background  

Classical conditioning has been suggested to play an important role in the development, maintenance, and relapse of tobacco smoking. Several studies have shown that initially neutral stimuli that are directly paired with smoking are able to elicit conditioned responses. However, there have been few human studies that demonstrate the contribution of higher-order conditioning to smoking addiction, although it is assumed that higher-order conditioning predominates learning in the outside world. In the present study a higher-order conditioning task was designed in which brain responses of smokers and non-smokers were conditioned by pairing smoking-related and neutral stimuli (CS1_smoke and CS1_neutral) with two geometrical figures (CS2_smoke and CS2_neutral). ERPs were recorded to all CSs.     

Microwave spectra and structure of an isoxazole-water complex

The rotational spectrum of a hydrogen-bonded isoxazole-water complex has been measured between 6–18 GHz with a pulsed nozzle Fourier transform microwave spectrometer. In addition to isoxazole-H₂O, the complexes with HDO and D₂O as well as isoxazole-¹⁵ N-H₂O have been investigated in order to determine the structure of the complex. Rotational constants, quartic centrifugal distortion constants and quadrupole coupling constants, where applicable, have been fitted to the measured transition frequencies of the isotopomers. Structural data, which have been deduced from the planar moments of inertia and the quadrupole coupling constants of the isotopomers, have established conclusively that water binds to nitrogen in the ring plane of isoxazole. Ab initio calculations have revealed that complexes with a hydrogen-bond to nitrogen or to oxygen are both stable. The complex with water attached to nitrogen has been found to be more strongly bound than that with water attached to oxygen. Small splittings of the rotational transitions of the two complexes with H₂O have been interpreted as being the result of an internal rotation of water with respect to isoxazole.     

Activation of the pre-supplementary motor area but not inferior prefrontal cortex in association with short stop signal reaction time – an intra-subject analysis

Background  

Our previous work described the neural processes of motor response inhibition during a stop signal task (SST). Employing the race model, we computed the stop signal reaction time (SSRT) to index individuals' ability in inhibitory control. The pre-supplementary motor area (preSMA), which shows greater activity in individuals with short as compared to those with long SSRT, plays a role in mediating response inhibition. In contrast, the right inferior prefrontal cortex (rIFC) showed greater activity during stop success as compared to stop error. Here we further pursued this functional differentiation of preSMA and rIFC on the basis of an intra-subject approach.     

吡啶与7-苯乙酰氨基-3-氯甲基头孢烷烯酸对甲氧基苄酯碘代物亲核取代反应动力学

以7-苯乙酰氨基-3-氯甲基头孢烷烯酸对甲氧基苄酯(GCLE)和吡啶为原料合成头孢他啶中间体7-苯乙酰氨基-3-吡啶甲基头孢-4-羧酸对甲氧苄酯,用高效液相色谱仪监测了吡啶与GCLE碘取代物在二氯甲烷、丙酮、四氢呋喃、乙酸乙酯和DMF混合液中的亲核取代反应,反应动力学行为可用SN2机理解释.在一定的溶剂中不同温度的速率常数可用Arrhenius方程很好的关联,求得了指前因子,初步讨论了反应的溶剂效应,得出在不同溶剂中亲核取代反应活性顺序为:丙酮＞四氢呋喃＞乙酸乙酯-DMF混合液＞二氯甲烷.     

流动注射化学发光法测定针剂中呋脲苄青霉素钠

基于碱性介质中,在以铁氰化钾作为催化剂和发光剂,亚铁氰化钾作为发光抑制剂,无过氧化氢时,呋脲苄青霉素钠与鲁米诺能够直接发生化学反应,提出了快速测定呋脲苄青霉素钠的流动注射化学发光法。结果表明:在最佳条件下,呋脲苄青霉素钠浓度在6.5×10-6～8.0×10-4mol.L-1范围内呈线性,方法的检出限(3s/k)为3.3×10-6mol.L-1,对浓度为5.0×10-4mol.L-1的呋脲苄青霉素钠标准溶液连续测定11次,测定值的相对标准偏差为0.9%。以粉针剂样品为基体,用标准加入法检验方法的回收率,测得结果在96.8%～98.3%之间。     

Study of ψ(4415) in the QPC model

Some authors consider the ψ(4415) to be the 4S or 5S excited tate of a cc pair. Starting from this assumption, we study he decays of the ψ(4415) to DD, D^*D^*, D_SD_S, D_S^*D_S^*, and get the corresponding branching ratios in terms of the Quark-Pair-Creation (QPC) model. Compared with the experimental data, we find that the results of 4S state agree much better than those of the 5S state. Therefore, it is more reasonable to assume the ψ(4415) to be a 4S state.     

Nonlinear Local Lyapunov Exponent and Quantification of Local Predictability

Nonlinear local Lyapunov exponent （NLLE） is applied to quantitatively determine the local predictability limit of chaotic systems. As an example, we find that the local predictability limit of Henon attractor varies considerably with time, and some underlying phase-spatial structure does not appear. The local predictability limit of initially adjacent points in phase space may be completely different. This will cause difficulties in making the long-time analogue forecast.     

弹丸高速撞击压力容器损伤实验研究

微流星体及空间碎片的高速撞击威胁着航天器的安全运行。而压力容器是航天器上受微流星体及空间碎片撞击威胁最大的关键部件之一。对压力容器的高速撞击能导致其发生破裂而过早终止航天器的使命。本文的目的是通过实验研究,确定高速撞击条件下压力容器发生具有撕裂的简单穿孔和裂纹失稳破裂的界限。实验样件选择6063铝合金管焊接制成。高速撞击实验采用铝柱状弹丸和球形弹丸在3km/s左右的速度下正撞击铝压力容器,铝压力容器的压力从0～30Bar变化来探索获得不同损伤形式的压力条件。给出了铝压力容器前、后壁从穿孔到裂纹失稳破裂的实验结果。未防护充水铝压力容器的主要损伤是其前壁的裂纹失稳破裂。而防护充水铝压力容器在前璧未穿孔时未发生破裂。未防护充气压力容器在给定的实验条件下前璧未发生破裂而后璧发生破裂。防护充气压力容器在小防护间距时前璧发生破裂。     

顺丁烯二酸β-环糊精酯-N-乙烯基吡咯烷酮水溶性聚合物的合成及其吸附疏水性药物的研究

以γ射线引发顺丁烯二酸β-环糊精酯(CDM)和N-乙烯基吡咯烷酮(NVP)发生自由基链式反应,制备了顺丁烯二酸β-环糊精酯-N-乙烯基吡咯烷酮聚合物(CDM-NVP).优化后的CDM-NVP聚合物的合成条件为: CDM∶NVP为1∶0.7(w/w, CDM 3.6 g 和 NVP 2.52 g),辐照剂量4 kGy,DMF溶液用量为20 mL.在此条件下制备聚合物的产率为84%,重均分子量为20 kDa.结果表明,此聚合物可以同纳他霉素(NM)和多菌灵(MBC)形成稳定复合物.研究了复合物抑菌活性,测定了其表观稳定常数.利用紫外光谱、核磁图谱和相溶解度对药物复合物进行结构表征.303 K下,NM-CDM-NVP和 MBC-CDM-NVP复合物的表观稳定系数分别为12988.54和865.94 L/mol.抑菌实验结果表明,NM-CDM-NVP和 MBC-CDM-NVP复合物可以显著提高NM和MBC的溶解性和抑菌活性.