甲卡西酮光谱性质的密度泛函模拟与指认

采用密度泛函理论的DFT/B3LYP方法和6-311+G(d,p)基组,对甲卡西酮(C10H13NO)的UV-Vis光谱,ECD光谱,IR光谱,拉曼光谱,1HNMR光谱和荧光光谱进行了理论模拟和指认。自然电荷计算表明,胺基N和甲基C原子很可能是其发挥药理活性的亲电和亲核反应中心。     

聚对苯二甲酸乙二醇酯反式及左右式构象互变机理研究

采用红外光谱(IR光谱)研究了聚对苯二甲酸乙二醇酯(PET)分子结构。PET亚甲基变角振动模式(δCH2)主要包括:PET亚甲基左右式变角振动模式(δCH2-左右式)和PET亚甲基反式变角振动模式(δCH2-反式)。以PET/δCH2-左右式和PET/δCH2-反式为研究对象,进行了变温红外光谱(TD-IR光谱)研究。实验发现:随着测定温度的升高,PET/δCH2-左右式和PET/δCH2-反式对应的红外吸收频率及强度均有明显的改变,而玻璃化温度(Tg)是一个临界温度。采用二维红外光谱(2D-IR谱),进一步开展了PET反式及左右式构象互变机理研究。拓展了三级IR光谱(包括:IR光谱、TD-IR光谱和2D-IR光谱)在重要的高分子材料(PET)结构及构象转变的研究范围。     

1-氯-2,2,2-三氟乙基二氟甲基醚红外光谱研究

1-氯-2,2,2-三氟乙基二氟甲基醚(以下简称异氟醚)是一类重要的吸入性麻醉剂。采用3种中红外(MIR)光谱(透射中红外(T-MIR)光谱、衰减全反射中红外(ATR-MIR)光谱、漫反射中红外(DR-MIR)光谱)和4种MIR光谱(一维MIR光谱、二阶导数MIR光谱、四阶导数MIR光谱、去卷积MIR光谱)计算方法开展了异氟醚的分子结构研究。试验发现:异氟醚的红外吸收模式主要包括异氟醚分子CF_2不对称伸缩振动模式(ν_(asCF_2-异氟醚))、异氟醚分子CF_2对称伸缩振动模式(ν_(sCF_2-异氟醚))、异氟醚分子CF_3不对称伸缩振动模式(ν_(asCF_3-异氟醚))和异氟醚分子CF_3对称伸缩振动模式(ν_(sCF_3-异氟醚))等。试验同时发现:3种MIR光谱中,异氟醚DR-MIR光谱质量要优于相应的ATR-MIR光谱和T-MIR光谱;而4种MIR光谱的计算方法中,异氟醚去卷积MIR光谱的谱图质量要优于相应的一维MIR光谱、二阶导数MIR光谱和四阶导数MIR光谱。研究拓展了MIR光谱在重要的氟烃类化合物(异氟醚)结构研究中的应用范围。     

分子光开关钌配合物[Ru（phen）2（phehat）]^2＋的光谱研究

运用TDDFT方法,分子光开关钌配合物[Ru（phen）2（phehat）]^2＋的UV—Vis光谱得以计算和理论解释。计算表明在水溶液环境下对钌配合物进行计算,实验结果和计算结果一致。而且,溶液条件下计算的UV-Vis光谱的结果能较好的指认该配合物实验光谱的^1MLCT和^1LLCT性质。     

CARS光谱技术在炸药测温领域中的应用

阐述了 CARS光谱技术的基本概念 ,将之引入到对爆轰过程的研究领域 ,论证了将 CARS光谱技术应用于炸药温度测量的可行性 ,并设计了实验方案。此外 ,还计算了氮的理论 CARS光谱     

氟橡胶的红外光谱研究

采用红外(IR)光谱,包括一维红外光谱、二阶导数红外光谱、四阶导数红外光谱和去卷积红外光谱对氟橡胶(FKM)的分子结构进行了研究。试验发现:氟橡胶的红外吸收模式主要包括CH2不对称伸缩振动模式(νasCH2-FKM)、CH2对称伸缩振动模式(νsCH2-FKM)、CH2弯曲伸缩振动模式(δCH2-FKM)、CF2不对称伸缩振动模式(νasCF2-FKM)、CF2对称伸缩振动模式(νsCF2-FKM)和CFCl伸缩振动模式(νCFCl-FKM)等。研究发现:氟橡胶的去卷积IR光谱的谱图分辨能力要优于相应的一维IR光谱、二阶导数IR光谱和四阶导数IR光谱。此研究拓展了IR光谱在氟橡胶结构及应用研究的范围。     

钴卟啉轴向配位反应的紫外可见及圆二色谱研究

用紫外-可见光谱和圆二色谱研究了氯乙酸胆甾酯钴卟啉和桥联冠醚钴卟啉在CHCl3中的光谱行为,探讨了氯乙酸胆甾酯钴卟啉和桥联冠醚钴卟啉与咪唑、苯骈咪唑轴向配位前后的光谱变化。实验结果表明:在反应体系中不同的配体具有不同的最佳浓度:氯乙酸胆甾酯钴卟啉体系中,咪唑、苯骈咪唑的最佳浓度分别为7.5×10-4mol/L,2.5×10-4mol/L,低于最佳浓度时有利于增强CD光谱的强度和对称性,高于最佳浓度则减弱了CD光谱的强度并且使峰形变复杂;同时卟啉和咪唑类分子的结构均对反应体系的紫外-可见光谱和圆二色光谱的峰形、强度和波长产生影响。     

菲并咪唑类席夫碱双核卟啉的合成及性能

以9,10-菲醌、对苯二甲醛、对氟苯甲醛、对甲氧基苯甲醛、对硝基苯甲醛及吡咯等为主要原料,设计合成了双核卟啉(P2-PPI).通过FT-IR光谱、1HNMR和13CNMR表征了其结构,利用UV-Vis光谱、荧光光谱测试了其光谱特征.UV-Vis光谱测试表明,双核卟啉(P2-PPI)Soret带的摩尔消光系数是对应单核卟啉(P1)的2.85倍,光谱吸收范围显著变宽;在浓度测试范围内,双核卟啉(P2-PPI)的聚集形态未改变.同浓度下,荧光光谱测试表明,双核卟啉(P2-PPI)中菲并咪唑部分的荧光强度仅为菲并咪唑前驱体的1/3,卟啉单元的荧光强度是单体卟啉的2倍.通过循环伏安法测试并比较了P2-PPI和P1的电化学性质,并结合光化学带隙计算了ELUMO和EHOMO值,分别与TiO2和I-/I3-氧化还原电对能级匹配.     

功能性钌配合物[Ru(phen)_2(mdpz)]~(2+)的电子吸收光谱研究

运用含时密度泛函(TDDFT)方法,对功能性钌配合物[Ru(phen)2(mdpz)]2+的UV-Vis光谱进行计算和理论解释。计算结果表明在乙氰溶液环境下的计算结果与实验结果符合较好。并且,乙氰溶液条件下计算的UV-Vis光谱的结果能较好的指认该配合物实验光谱的1MLCT和1LLCT性质。     

Meso-四(对-甲基苯基)卟啉金属络合物的光电性质研究

本文采用Adler法合成Meso-四(对-甲基苯基)卟啉(TMPP),采用两步法合成Meso-四(对-甲基苯基)金属卟啉(TMPP-Mn/Fe/Co/Ni/Cu/Zn),利用红外光谱、紫外-可见光谱和荧光光谱对它们进行结构表征及光性能研究分析,并用循环伏安特性试验法进行电化学性质研究分析。     

Preparation and characterization of CdS and CdS/polyacrylonitrile nanocomposites by γ‐irradiation and emulsion polymerization

CdS and CdS/polyacrylonitrile (PAN) nanocomposites were prepared by γ‐irradiation and emulsion polymerization. The CdS and CdS/PAN nanocomposites were characterized by powder X‐ray diffraction, infrared spectroscopy, Fourier transform Raman spectroscopy, transmission electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, and thermal analysis (thermogravimetric analysis/dynamic thermal analysis). In photoluminescence spectroscopy analysis, the maximum peak of CdS/PAN nanocomposites prepared by γ‐irradiation and emulsion polymerization was at about 485 nm, whereas the maximum peak of CdS nanocomposites was at about 460 nm. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2335–2342, 2004     

Porous calcium titanate and sorption and desorption of water under ambient conditions: a study by conventional and synchronous luminescence spectroscopy

We report chemical synthesis and characterization of micro/mesoporous CaTiO₃ by X-ray diffraction (XRD), nitrogen sorption/desorption, small angle XRD, diffuse reflectance optical spectroscopy, and luminescence spectroscopy under ambient conditions. We determined the energies of absorption and emission transitions through electronic midgap states in micro/mesoporous calcium titanate by optical spectroscopy, “conventional” photoluminescence (PL) spectroscopy and, for the first time, synchronous luminescence spectroscopy at 25?°C. Micro/mesoporous CaTiO₃ reversibly sorbs and desorbs water vapor in ambient air, with water sorption capacity being close to the total pore volume. The luminescence of micro/mesoporous CaTiO₃ in visible range at room temperature is repeatedly significantly increased upon desorption of water and decreased (quenched) upon sorption of water vapor in air, due to the interactions of the adsorbate with electronic surface midgap states.     

Raman Study of the Relationship between Room-Temperature Tetragonality and the Curie Point of Barium Titanate

Variable-temperature Raman spectroscopy showed that, in progressively finer BaTiO₃ powders, the Curie point increased as the room temperature tetragonality decreased. The influence of crystallite size distribution on the range of tetragonalities present in a powder was clearly evident in both phase transitions, as observed by Raman spectroscopy and room-temperature X-ray diffraction patterns. Titanium K -edge X-ray absorption spectroscopy could not distinguish between the cubic and tetragonal structures of BaTiO₃, at 300°C and room temperature, respectively.     

Fabrication of Pt–Cu/RGO hybrids and their electrochemical performance for the oxidation of methanol and formic acid in acid media

Pt–Cu/reduced graphene oxide (Pt–Cu/RGO) hybrids with different Pt/Cu ratios were prepared by the reduction of H₂PtCl₆ and CuSO₄ by NaBH₄ in the presence of graphene oxide (GO). The Pt–Cu nanoparticles were characterized by transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The reduction of GO was verified by ultraviolet–visible absorption spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Compared to Pt/RGO, the Pt–Cu/RGO hybrids have superior electrocatalytic activity and stability for the oxidation of methanol and formic acid. Thus they should have potential applications in direct methanol and formic acid fuel cells.     

Mn-P共掺杂氮化碳的制备及其光催化性能研究

采用四水氯化锰、磷酸氢二铵和三聚氰胺为原料制备了Mn-P共掺杂的石墨相氮化碳(g-C3 N4).使用X射线衍射光谱(XRD)、扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)、光致荧光光谱(PL)、紫外-可见漫反射光谱(UV-Vis DRS)、电化学阻抗谱(EIS)、瞬态光电流响应等分析测试手段对制备的催化剂...     

A potential trackable bone filler: Preparation and characterization

This study reported the synthesis of fluorescent hydroxyapatite/alginate/carbon quantum dots (HA/Alg/CQDs) nanocomposites via the co-precipitation technique. The N-doped CQDs as a new class of fluorescent materials were prepared by the citric acid pyrolysis method, with an average size around 4 nm. Physical, chemical, and optical properties of the synthesized nanocomposites were investigated by X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FTIR), atomic force microscopy (AFM), field-emission scanning electron microscopy (FESEM), UV–visible spectroscopy, and photoluminescence (PL) spectroscopy, respectively. The PL spectroscopy data verified the favorable in vitro luminescent emission of the HA/Alg/CQDs nanocomposites in comparison with HA/Alg and HA samples. The XRD patterns of the prepared samples confirmed the formation of crystalline HA in all composites, possessing a Ca/P ratio around 1.5 as obtained by EDX elemental analysis. The FESEM analysis exhibited HA nanoplates that homogeneously distributed throughout the alginate matrix. Therefore, the synthesized nanocomposites could be regarded as potential trackable drug carriers for hard tissue engineering applications.     

Ethylene diamine-grafted carbon nanotubes: A promising catalyst support for methanol electro-oxidation

In this paper, carbon nanotubes (CNTs) were modified by ethylene diamine (ED) and then used as the support of the Pt-Ru catalyst. The cyclic voltammetry (CV) and Fourier transform infrared spectroscopy were employed to study the interaction between ED and CNTs. The morphology and elemental composition of the as-prepared Pt-Ru/ED/CNT electrode were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. The electrocatalytic properties of the Pt-Ru/ED/CNT electrode for methanol electro-oxidation were investigated by CV, polarization method and electrochemical impedance spectroscopy. The long-term stability of the Pt-Ru/ED/CNT electrode was also evaluated. Compared with the Pt-Ru/CNT electrode, the Pt-Ru/ED/CNT electrode exhibits excellent electrocatalytic properties and long-term stability. These results show that the ED-grafted CNTs are the promising catalyst support for methanol electro-oxidation.     

氨丙基低聚硅倍半氧烷及其酰胺化产物的合成与表征

由3-氨基丙基三甲氧基硅烷（NH₂-propyl-silane）出发,在碱催化条件下采用水解缩合一锅法合成了笼形氨丙基硅倍半氧烷（NH₂-propyl-POSS）。红外光谱、核磁共振、电喷雾飞行质谱（ESI-TOF）表征结果表明,合成产物NH₂-propyl-POSS是不同大小笼形结构的混合物,其中T8、T9、T10笼形结构含量较高。由NH₂-propyl-POSS分别与乙酸和丙炔酸进行酰胺化反应,进一步合成了乙酰基丙基POSS（CH₃-CONH-POSS）和丙炔酰基丙基POSS（CH≡C—CONH-POSS）,并通过红外光谱、氢谱、碳谱分析表征了其结构。X射线衍射分析结果表明,3种POSS均为非晶态结构。通过热重分析可知,NH₂-propyl-POSS具有较高的热稳定性。将NH₂-propyl-POSS用于提高环氧树脂（EP）的热稳定性,添加量为5 %（质量分数,下同）时,EP/NH₂-propyl-POSS共混物的玻璃化转变温度（T_g）提高至180.7 ℃,极限氧指数（LOI）为25.2 %。     

碳酸钙三级红外光谱研究

采用红外（IR）光谱技术开展了碳酸钙的结构研究。实验发现,碳酸钙的红外吸收模式包括碳酸钙CO₃不对称伸缩振动模式（ν）、碳酸钙 CO₃对称伸缩振动模式（ν）、碳酸钙CO₃面外弯曲振动模式（r）和碳酸钙CO₃面内弯曲振动模式（β）等。采用变温红外（TD-IR）光谱开展了碳酸钙的热稳定性研究。在293~393 K的温度范围内,碳酸钙主要官能团对应的吸收强度及频率都有一定的改变。采用二维红外（2D-IR）光谱进一步研究了碳酸钙ν、r和β吸收峰变化快慢的信息,证明了三级红外（IR）光谱在重要的无机盐（碳酸钙）结构及热稳定性研究中的重要作用。