The Crystal Structure of Platyphylline and Molecular Conformational Analysis of Integerrimine

The title compounds platyphylline (C₁₈H₂₉NO₅.0.5H₂O) and integerrimine (C₁₈H₂₅NO₆) have been isolated from the serial parts of the Senecio species. the crystal and molecular structures of platyphylline have been determined. the compound crystallises in orthorhombic space group, P2₁2₁2₁. the pyrrolizidine nucleus exhibits exo-buckling conformation. the molecular geometry was stabilized by C-H[ddot]O and C-H[ddot]N hydrogen bonds. a search for the low energy conformations of integerrimine as a similar alkaloid was also carried out. Force field calculations were undertaken by the MM3 program and some particular conformations were computed with the semi-emprical molecular orbital methods by the AMI and PM3 programs.     

Emission Spectrum and Resistivity of Low Power Plasma Weld Arcs

Emission spectra from plasma arc welds were observed under a variety of current, voltage, polarity, and standoffs. If reverse polarity (welding torch positive) welds are struck below 50 amperes most of the power is deposited at the electrode rather than the workpiece because of low carrier density within the arc. Straight polarity, on the other hand, suffers no such limitation because of electrons created in the pilot arc used to start the weld process.     

Spectroscopic and Structural Studies of Complex of [CU(DIEN)(CNGE)(ONO2)2] (Dien=Diethylenetriamine,CNGE=Cyanoguanid)

The electronic absorption spectrum (diffuse reflection spectrum) of the crystal of [Cu(dien)(cnge)(ONO₂)₂] has been measured. The experimental results are interpreted quantitatively with ligand field theory and the radial wave function of non-free copper (II), and our calculation values coincide well with the experimental results. As a result, the d-d absorption spectrum was explained satisfactorily. In particular, the structural characterizations whose degree of distortion of crystal structures of three Copper(II) complexes is different in this paper, are also discussed with their spectral behaviors. The experimental data provides significant correlation between the spectra and degree of distortion of coordination structures.     

Spectra,Magnetic Property and Coordination Structure Study on Polymeric Copper(II) Iodo Complex of Diethylenetriamne

Abstract

Polymeric [Cu(dien)Ix] (dien = diethylenetriamine) was prepared. Its electronic absorption spectrum and photoacoustic spectrum were recorded at room temperature. They were compared with each other and the results were discussed quantitatively with respect to ligand field theory (LFT) and the radical scaling wave function of a non-free copper(II) ion. The theoretical values are in agreement with the observed ones. In addition. the ESR spectra of the title complex were measured at 77k and room temperature, respectively. They were compared with each other and characterized. Therefore, the electronic structure was also investigated with its spectra behaviors and PLFT. The spectra and the theoretical analysis about the title complex suggest there is a weak interaction between the Cu-Cu. It can be interpreted with using Kahn's theory. The g (= 2.0942) is greater than 2.040, conforming to a ground state configuration with unpaired electron in the dx²?y² orbital.     

丁氟螨酯的波谱学数据解析与结构确证

丁氟螨酯是一种新型杀螨剂,具有高效、低残留的特点.本文对其红外吸收光谱（IR）、紫外吸收光谱（UV）、质谱（MS）及核磁共振（NMR）波谱（包括¹H NMR、¹³C NMR、DEPT、¹H-¹H COSY、¹H-¹³C HSQC、¹H-¹³C HMBC）进行了测定,分析了其UV和IR谱图特征吸收峰对应的基团,并对其¹H和¹³C NMR信号进行了归属,确证了丁氟螨酯的结构.该研究将为丁氟螨酯的其他相关研究提供参考.     

Spectral,X-ray diffraction,surface morphological and thermal studies of gamma-irradiated potassium bis(oxalato)zincate(II)dihydrate

ABSTRACT

Potassium bis(oxalato)zincate(II)dihydrate was prepared and characterized. The sample was irradiated with ⁶⁰Co gamma rays up to 900?kGy. Infrared, Raman and photoluminescence spectra, X-ray diffraction pattern, surface morphology by AFM and SEM and non-isothermal decomposition of the complex were studied before and after irradiation. Spectral studies suggested significant radiation damage. X-ray diffraction studies showed reduction in unit cell volume and average crystallite size. Both unirradiated and irradiated samples of the complex belong to the hexagonal crystal system. Surface morphology of the complex changed upon irradiation. Thermal decomposition was enhanced.     

内/外部励磁方式下高温超导环的俘获场特性

高温超导磁体在闭环运行时,可以提供稳定磁场,但是由于高温超导带材无法实现无阻焊接,成为高温超导磁体闭环运行的技术瓶颈.本文利用第二代高温超导带材制备闭环超导环,采用内部励磁和外部励磁对超导环进行励磁,在液氮温度中(77 K)测量超导环的中心俘获磁场.结果表明超导环在内部励磁俘获的磁场值比外部励磁俘获的磁场值高;外部励磁中,超导环中插入铁芯柱能提高俘获场;内部励磁中,超导环在螺线管闭环运行俘获的磁场值比开环运行俘获的磁场值高.结果对于高温超导闭环磁体励磁和高温超导带材磁通动力学研究具有很重要参考价值.     

二芳基马来酸酐吸收光谱的计算研究

在B3LYP/6-311++G(3df, 3pd)//b3LYP/6-31G(d)和TD/6-31G(d)//B3LYP/6-31G(d)水平上对二芳基马来酸酐的电子吸收光谱进行了研究。2,3-(2,4-二甲基噻吩-3)马来酸酐的开式结构和闭式结构的S₁, S₂和S₃跃迁的计算结果分别为390, 360.5, 339.4; 584.6, 395.8, 370.2 nm; 与类似物2,3-(2,4,5 -三甲基噻吩-3)马来酸酐的开式结构和闭式结构的S₁和S₂, 实验值390,331; 552, 386 nm一致。振子相对强度计算结果与吸收峰强度一致。     

Trigonally-compressed octahedral geometry of hexaamminecobalt(III) complex cation in aqueous solution investigated from the electronic spectra

Electronic spectra of hexaamminecobalt(III) complex cation in aqueous solution were analyzed to obtain spectral components. Subsequently, based on the spectral components, the coordination geometry around the cobalt(III) ion was investigated, using the reverse angular overlap model method. The result indicates that the geometry is a trigonally compressed octahedron with the polar angle of 57.9?±?1.0° under D_3d symmetry, where the polar angle is the angle between the trigonal axis and the Co–N bond. From this angle, the top and side N–Co–N bond angles are calculated as 94.4° and 85.6°, respectively. The density functional theory computation supported this trigonally compressed structure in aqueous solution.     

Novel and Validated Spectrophotometric Matrix Matching Method for Simple and Rapid Determination of Chromium in Oily Media

N,N’-bis(4-methoxysalicylidene) ethylenediamine is proposed as analytical reagent for the direct determination of chromium in original matrix of liquid oils. The method is based on the complexation of N,N’-bis(4-methoxysalicylidene) ethylenediamine and chromium in n-hexane∶acetone (1∶4) medium and spectrophotometric determination at 355 nm against reagent blank. Complexation of MSE and chromium is completed in 20 seconds at molar ratio 1∶1. The molar absorptivity and the formation constant of the complex are determined as 9 740 L·mol-1·cm-1 and 3.6(±0.1)×105, respectively. Beer’s law is obeyed in range 0.02～1.50 mg·L-1 chromium concentration. Limits of detection and quantification of the suggested method were 7.5 and 25.1 μg·kg-1, respectively. The accuracy and precision of the method was checked by finding mean recovery and relative standard deviation by oil-based chromium standard analysis as 96.4%±1.4% and 1.5%, respectively. The practical applicability of elaborate method was tested using oil-based chromium standard spiked and unspiked corn, sunflower, soybean, olive and canola oils.     

掺铥氟磷玻璃的结构、热学性质和光谱性质

制备了不同Al(PO3)3含量的掺铥系列氟磷玻璃,研究了其结构、热稳定性和光谱性质。随着Al(PO3)3含量的增加,该系列玻璃的密度降低,折射率增加,差热分析表明,转变温度、析晶起始温度、析晶峰温度和熔化温度增加。Al(PO3)3摩尔浓度在7%~9%时析晶稳定性最佳。采用归一化的拉曼光谱分析了材料的结构和声子状况,对于该系列氟磷玻璃,Al(PO3)3含量的增加不会影响声子能量,但使声子密度增大。测试了样品的吸收光谱,Tm3 的3H6→3F4在第三通信窗口的L波段有明显吸收。与在其它玻璃基质中相比,Tm3 的3F4能级对应能量偏高,3H4能级对应能量偏低,使得3H4→3F4跃迁波长较大,接近于增益迁移光纤放大器的放大波长。扎得奥菲而特(Judd-Ofelt)理论分析表明随着Al(PO3)3含量增加,离子强度参量Ω2增大,Ω6保持相对稳定,Tm3 的能级寿命降低。     

一种测量磁光阱中冷原子密度和温度的新方法

报道了对磁光阱中冷铯原子吸收谱的实验观察,由于冷原子的多普勒增宽远小于激光发态超精细分裂,实验观察到三个孤立的吸收峰（Cs,6S1/2,F=4→6P3／2,F＝3,4,5,）其吸收系数比为3：7：12,这与相应跃迁振子强度一致。利用吸收信号测量了冷原子云的密度.结果与荧光探测法在10％的精度内符合;用吸收信号测量了冷原子的温度,测量结果与用荧光飞行时间法和释放捕捉法的结果吻合。     

一个评价光谱估计精度的新参数

研究了对多光谱成像系统进行光谱估计的精度评价的问题。在给出光谱估计偏指数定义的基础上,提出了多光谱图像获取系统的光谱估计性能的评价的新方法——系统光谱匹配偏度指数法。该方法用一个指标来定量评价两光谱向量的光谱匹配程度,避免了以往评价参数的复杂性,同时反映了光谱反射率估计曲线实际测量曲线之间的差异程度。采用一典型多光谱相机对Macbeth色卡的24个典型光谱仿真估计所得的24个光谱对数值模拟,验证了光谱反射率估计匹配偏度指数能全面的反映光谱反射率的估计精度的设想;并拿17个多光谱估计系统的仿真估计的光谱数据,计算了它们的系统光谱估计偏度指数,计算结果有很好的一致性。结果还显示,系统光谱估计偏度指数还可用作对多光谱相机光谱估计性能进行等级划分的依据。     

(C6H5R)Mo (CO)3复合体系结构的密度泛函研究

用量子化学DFT-B3LYP方法在IANL2DZ基组水平上对标题复合物体系的可能构型进行了自由优化,在此基础上进行了频率分析,得到了复合物的电子结构和红外光谱.原子净电荷、前沿轨道能量都表明,Mo(CO)3和C6H5R结合时电子从苯环向Mo转移,形成电荷转移复合物.复合物的键长、Wiberg键级表明,它们之间的结合方式和氢键的结合方式相似,且属强氢键.复合物的红外特征振动频率位于212cm-1～224 cm-1,对应于Mo(CO)3的金属垂直于C6H5R中的苯环平面的来回振动,同时形成复合物后,原来位于3200 cm-1左右的峰活性消失.     

苯乙烯化苯酚的密度泛函研究

以苯乙烯化苯酚(SP-2)为研究对象,采用密度泛函理论的M06-2X/6-311g(d,p)方法,进行了分子结构优化.在此基础上,对其分子轨道、能级、最高占据轨道(HOMO)和最低空轨道(LUMO)、红外光谱(IR)、核磁共振谱(NMR)、紫外-可见吸收光谱(UV-Vis)进行了模拟计算.根据能级和分子轨道计算结果,主要讨论了苯乙烯化苯酚的最高占据轨道(HOMO)和最低空轨道(LUMO)的特点;获得了红外光谱(IR)、核磁共振谱(NMR)、紫外-可见吸收光谱(UV-Vis)计算结果,并对谱图数据进行了分析讨论.     

PDT光敏剂HA在不同液相体系下的光谱特性研究

为了对候选光敏剂竹红菌甲素(HA)进行改性并保持其优异的敏化特性,对HA的光谱特性和激发态性质作了进一步的指认。系统研究了HA在不同液相体系下的吸收和荧光光谱,对指认HA的光谱和电子跃迁的机制提出了新的依据,结果表明,吸收带I产生于π-π*跃迁,吸收带Ⅱ和Ⅲ产生于P-π共轭所导致的L→aπ跃迁的电子振动结构;荧光发射带I和Ⅱ是产生于同一跃迁机制S1(L,aπ)→S0的正常荧光的振动结构。     

胭脂红和苋菜红分子结构与光谱性质的对比研究

应用英国Edinburgh FLS920P稳态-瞬态荧光光谱仪,对互为同分异构体的胭脂红、苋菜红分子的吸收光谱和荧光光谱实验检测,得到二者的光谱特性参数,并进行对比。分别采用密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）对这两种分子的基态和激发态结构进行优化,将所得基态分子构型进行频率计算,结果显示均无虚频存在,进而比较两分子构型在不同能态下的差异。在此基础上,应用TD-DFT并结合极化连续介质模型（PCM）在6-311++G(d, p)水平上分别计算二者的吸收光谱和荧光光谱,对两种分子的发光机制、荧光光谱特性差异与分子结构的关系进行了分析。结果表明,两种分子的基态结构均为非平面,它们中的两个萘环不共面,存在一定的夹角;苋菜红含有分子内氢键,且氢键所在萘环的平面性要优于胭脂红分子对应的萘环部分;激发态时二者各自的两个萘环均共平面。量子化学计算得到的光谱理论值与实验结果较为吻合,说明优化所得胭脂红与苋菜红的分子构型基本合理。与苋菜红相比,胭脂红右侧萘环结构的平面性稍差,分子从激发态跃迁回到基态经历了更多的振动和转动,损耗了更多的能量,导致用来产生荧光光子的能量减少,因此,胭脂红的荧光发射波长更长。本文首次得到胭脂红、苋菜红分子基态与激发态下的分子结构信息,并找出二者光谱特性差异的原因,结果可为研究同分异构体分子的光谱特性与分子结构的关系提供参考。     

Aggregation and spectral properties of Mg(II) tetracarboxyphthalocyanine in aqueous solutions and solid xerogels

Based on spectroscopic studies of magnesium(II) tetracarboxyphthalocyanine molecules in liquid solutions, we have determined the role of the carboxyl groups and the aqueous medium during formation of associates. We have shown that the Q band of the associated form is split into two components of frequency separated by ∼250 cm⁻¹. The effect of the nature of the gel matrices on the spectral luminescence properties of magnesium(II) tetracarboxyphthalocyanine has been studied by incorporating the pigment into a series of xerogels differing in the chemical structure of the inorganic framework and the nanopore surface area. We discuss the reasons for the appearance of associated forms of the pigment in different xerogels. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 211–217, March–April, 2007.     

紫外吸收温差光谱特性与化合物的电子跃迁类型

用紫外吸收变温光谱差减法获得化合物的紫外吸收温差光谱（UVSDT）。测量了系列化合物的温差光谱。结果表明,UVSDT具有很强的特征性：n→σ^*电子跃迁的UVSDT单边红移,温差增大峰强度增加、红移增大;n-π^*电子跃迁的UVSDT为正、负两峰、温差增大,正负两峰各自向正、负方向增强;π-π^*电子跃迁的UVSDT为负峰,温差增大,峰强负向增大,峰位不移动。