小分子化合物在离子阱质谱中的分子离子反应研究

利用离子阱质谱的原理和特点，研究了小分子醇、醚、胺、醛、酮等有机化合 物（分子量小于200）在离子阱里的分子离子反应，总结了反应特点和规律，并把 它归类为自身化学电离（SCI）反应。以丁酮、丙烯醇为例，采用FTMS对反应产物 离子进行准确质量测定，验证了它们各自的分子离子反应结果。另外，把该类化合 物（30个）SCI反应的质谱图与NIST98库中的标准EI质谱图进行了比较，建立了 SCI质谱图库，提高了在离子阱质谱上对这类小分子化合物定性分析的准确率。     

新型双重电荷转移分子的二阶非线性光学性质的 理论研究

以INDO/SCI方法为基础,按完全态求和(SOS)公式编制了计算分子二阶非线性光学系数β~i~j~k和β~μ的程序。研究了1,2-二氨基-4,5-二硝基苯1和其异构体1,3-二氨基-4,6-二硝基苯2的电子光谱和二阶非线性光学性质。计算表明分子1具有与分子2几乎相等的二阶非线性极化率。但由于分子1的偶极矩明显大于分子2的,故分子1的μβ值比分子2的μβ值大的多。在此基础上,研究了2,3-二(β-苯乙烯基)-5,6-二氰基吡嗪和2,3-二(β-噻吩乙烯基)-5,6-二氰基吡嗪和2,3-二(β-噻吩乙烯基)-5,6二氰基吡嗪衍生物的电子光谱和二阶非线性光学性质。结果表明,这些化合物均具有两个相距很近的强吸收峰,它们对β值的呈加和模式。由于这类化合物特征吸收峰均位于413nm以下且具有大的μβ值,所以,它们是一类很有前途的二阶非线性光学候选材料。     

N－甲基-吡咯烷并[3,4]C60衍生物的结构、电子光谱 和二阶非线性光学性质的 理论研究

利用半经验AM1量子化学方法研究了N－甲基－吡咯烷并[3,4]C60(MPC)及其噻吩取代衍生物(TMPC)的几何结构。电子结构研究表明,MPC及TMPC衍生物的前沿轨道主要由C60部分决定,C60母体与成基团之间存在较强的分子内电荷转移,C60部分是电子受体,而噻吩环部分和吡咯环部分为电子给体。在AM1优化几何构型的基础上,用INDO/SCI方法计算了MPC及TMPC的电子光谱,用完全态求和(SOS)公式计算了其二阶非线性光学性质。结果表明,MPC与TMPC在400nm以上均存在吸收峰,TMPC的这些吸收峰(400nm以上)比MPC的吸收峰强得多,与实验所得结果一致。对于TMPC来说,其二阶非线性光学系数β0值随分子构型不同而有较大的变化,β0值最大可达60×10^-30esu。     

Synthesis and characterization of β-fused porphyrin-BODIPY dyads

Novel dyads in which a porphyrin ring is directly fused through two β-pyrrolic carbons to a BODIPY^® moiety have been prepared using a stepwise approach starting from the copper(II) complex of pyrrolo[2,3-c]-5,10,15,20-tetraphenylporphyrin. Formylation and reaction with 3,5-dimethylpyrrole afforded 8; subsequent BF₂ complexation gave the TPP-BODIPY^® dyad in reasonable yields. Demetalation in TFA/H₂SO₄ led to the corresponding free base 12, opening the way to the subsequent preparation of the Zn complex 13. Both 12 and 13 exhibited complex optical spectra with an intensely red-shifted Q-band. Luminescence spectra displayed a very intense band around 700 nm making these species suitable as near-IR dyes and sensors in biological media. Optical analyses of 12, using the INDO/SCI technique, were performed to obtain information to establish the origin of the novel optical properties. These studies showed that the optical properties of 12 cannot be attributed to deformation of the molecular skeleton, but derive from the increased extension of the conjugation between the TPP and BODIPY^® π-systems.     

Direct INDO/SCI method for excited state calculations

Intermediate neglect of differential overlap (INDO) is the most commonly utilized semiempirical technique for performing excited state calculations on large organic systems such as organic semiconductors and fluorescent dyes. The calculations are typically done at the singles-configuration interaction (SCI) level. Direct methods provide a more efficient means of performing configuration interaction (CI) calculations, and the computational trade offs associated with various approaches to direct-CI theory have been well characterized for ab initio Hamiltonians and high-order CI. However, the INDO and SCI approximations lead to a new set of trade offs. In particular, application of the electron-electron interactions in the atomic basis leads to savings in computational time that scale as the number of atomic orbitals, which for a large organic system can be two to three orders of magnitude. These savings are largest when only a few low-lying excited states are generated and when a full SCI basis, which includes excitations between all filled and empty molecular orbitals, is used. In addition, substantial memory savings are achieved in the direct method by avoiding the evaluation of the two electron integrals in the molecular orbital basis. The method is demonstrated by calculating the absorption spectrum of a poly(paraphenylenevinylene) oligomer containing 16 phenyl rings.     

我国SCI收录刊化学类论文中氢核磁共振数据表达的错误与规范化

调研了近年来包括台湾地区在内我国部分涉及氢核磁共振谱SCI收录刊中1H NMR数据表达的不规范与错误,涵盖化学位移δ、偶合常数J、积分值与归属等各种参数.发现这种表达的不规范与错误已非常普遍与严重,亟待改正与防止再现.为了顺利通畅地学术交流,氢谱数据的表达必须规范化.广大作者特别是编辑同仁对此应高度重视,严格把关.     

High-resolution in vivo diffusion tensor imaging of the injured cat spinal cord using self-navigated,interleaved, variable-density spiral acquisition (SNAILS-DTI)

Diffusion tensor magnetic resonance imaging (DTI) is useful for studying the microstructural changes in the spinal cord following traumatic injury; however, image quality is generally poor due to the small size of the spinal cord, physiological motion and susceptibility artifacts. Self-navigated, interleaved, variable-density spiral diffusion tensor imaging (SNAILS-DTI) is a distinctive pulse sequence that bypasses many of the challenges associated with DTI of the spinal cord, particularly if imaging gradient hardware is of conventional quality. In the current study, we have demonstrated the feasibility of implementing SNAILS-DTI on a clinical 3.0-T MR scanner and examined the effect of navigator filter parameters on image quality and reconstruction time. Results demonstrate high-quality, high-resolution (546 μm×546 μm) in vivo DTI images of the cat spinal cord after traumatic spinal cord injury.     

Relationship between shoulder pain and skin temperature measured by infrared thermography in a wheelchair propulsion test

IntroductionWheelchair Users (WCUs) depend on their upper extremities for their daily living. Therefore, it is not unusual to find that shoulder pain (SP) is a problem for WCUs and reduces their participation in sport and leisure activities.ObjectivesThe aims of this study were 1 – to analyse skin temperature measured by infrared thermography (IRT) before (pre-test), one minute after (post-test) and 10 min after (post-10) the kinematic wheelchair propulsion test (T-CIDIF) of athletic wheelchair users; 2 – to evaluate the relationship between shoulder pain (SP) and Skin Temperature Asymmetry (ΔT_sk) before and after (pre-test, post-test, post-10) the T-CIDIF, and to relate the SP with the kinematic variables of the T-CIDIF.Participants & interventions/procedureA volunteer sample of 12 wheelchair athletes completed an exercise test (T-CIDIF) in their own wheelchair. It consisted in a 30-s maximum test performed on two rollers. Two linear transducers connected to the rollers registered the number of propulsions, maximum and mean velocity and power of each arm. SP was assessed with the Wheelchair Users Shoulder Pain Index (WUSPI). Skin temperature (T_sk) of the anterior and posterior upper body was measured before and after the T-CIDIF by using an infrared camera. A total of 26 ROIs were evaluated with respect to the opposite side of the body to identify significant (ΔT_sk).Results/main outcome measure(s)Significant differences were observed between the T_sk of the post-10 and pre-test in 12 ROIs, and between the post-10 and the post-test in most of the ROIs. These differences are attenuated when the ΔT_sk is compared before and after exercise. T_sk tends to initially decrease immediately after the test and then significantly increase after 10 min of completing the T-CIDIF. The ΔT_sk vs SP analysis yielded significant inverse relationships (from r = −0.58 to r = −0.71, p < 0.05) in 5 of the 26 ROI. No significant correlations between propulsion variables and SP questionnaire were found. All T-CIDIF variables were significantly correlated with the temperature asymmetries in multiple ROIs (from r = −0.86 to r = −0.58, from p < 0.05 to p < 0.001).ConclusionsThese results present indications that high performance wheelchair athletes exhibit similar capacity of heat production than able-bodied. The thermographic data inversely correlates with the SP and the kinematic variables, but the last is not related to SP. This work contributes to improve the understanding about temperature changes in wheelchair athletes during exercise, and could be used to assess the efficacy of various sports and rehabilitation programs.     

6,7,8,9-四氢-吩嗪并[2,3]C_(60)衍生物的结构、电子光谱和二阶非线性光学性质的理论研究

利用半经验AM1量子化学方法研究了6, 7, 8, 9-四氢-吩嗪并[2, 3]C60衍生物(1～4)及其异构体5, 6, 7, 8-四氢-9, 10-二氮杂蒽并[2, 3]C60衍生物 (5～8) 的结构。 结果表明,目标分子的前线轨道主要由C60部分决定, C60母体与加成基团之间存在较强的分子内电荷转移, C60部分是电子受体,吩嗪环部分为电子给体。 在AM1优化几何构型的基础上, 用INDO/SCI方法计算了目标分子的电子光谱, 用完全态求和(SOS)公式计算了其二阶非线性光学性质。 计算结果表明, 目标分子在400 nm 以上均存在弱吸收峰, 与实验所得结果一致。 5, 6, 7, 8-四氢-9, 10-二氮杂蒽并[2, 3]C60衍生物(5～8)的二阶非线性光学系数(0)比其异构体6, 7, 8, 9-四氢-吩嗪并[2, 3]C60衍生物(1～4)的大得多。     

基于SCI/ERA方法的高效气动力降阶模型

由正交Walsh函数构造Walsh-单信号-复合-输入,对其作用下的计算流体力学响应采用单信号-复合-输入/特征系统实现算法SCI/ERA(Single-Composite-Input/Eigensystem Realization Algorithm)辨识得到离散时间非定常气动力状态空间降阶模型。通过对Isogai机翼剖面气动弹性算例的计算证明该方法具有和非定常计算流体力学方法相当的精度同时模型维数降低2个数量级;在模型构造时间上,SCI/ERA方法比脉冲/ERA方法计算效率提高24%,同时内存占用减小34%;由理论分析可知当耦合结构模态数目增加时,SCI/ERA方法所需的计算开销增幅远小于脉冲/ERA方法;采用频域平衡特征正交分解BPOD(Balanced Proper Orthogonal Decomposition)方法可以准确地从降阶模型中提取出一个低频二次降阶模型,同时保持与原模型相当的精度。二次降阶后模型维数进一步减小88%。