PVK/C_(60)组合体系薄膜的拉曼光谱和荧光光谱研究

我们采用物理喷束淀积技术制备了Ｃ６０、Ｃ７０及聚乙烯咔唑ＰＶＫ／Ｃ６０的混合和分层薄膜，拉曼光谱的测量表明，这种技术所制备的富勒烯薄膜中，富勒烯的笼型结构仍保持完整，而在ＰＶＫ／Ｃ６０组合薄膜中，拉曼光谱及荧光光谱测量表明：在ＰＶＫ和Ｃ６０分子之间存在激发传递过程，在混合膜中，这种激发传递过程要明显强于分层组合薄膜。     

高聚物—富勒烯体系薄膜微微秒三倍频效应研究

采用５０ｐｓ的１．０６ｕｍ的基频光，对用物理喷束沉积方法制备的聚乙烯咔唑Ｐｏｌｙ－富勒烯组合薄膜进行三倍频信号测量。在ＰＶＫ／Ｃ６０分层膜与混合膜中观测到三倍频信号增强，考虑到两者之间的电荷转移效应，在分层膜中，把该三阶非线性增强归因于ＰＶＫ与富勒烯Ｃ６０之间的电荷转移所生成的载流子引起的电偶极矩和极化强度增强，在混合膜中，则是电荷转移所生成的络合物起主要作用。     

5—Br—PADAP测定地下水中钒

本文研究了ＨＣｌ－ＫＣｌ缓冲体系中钒（Ｖ）与５－Ｂｒ－ＰＡＤＡＰ形成配合物的条件及配合物的带电性质。提出一个灵敏、简便、快速测定钒的分光光度法。配合物的表观摩尔吸光系数为３．８×１０＾４，最大吸收波长为５８８ｎｍ，钒（Ｖ）与５－Ｂｒ－ＰＡＤＡＰ的配合比为１：１。含钒量在０－２０μｇ／２５ｍＬ范围内符合比尔定律。分析季地下水中钒，结果满意。     

新型物理喷束淀积技术制备富勒烯薄膜

建立了一套新型物理喷束淀积装置，并且成功地进行了薄膜制备工作，所制备的薄膜包括Ｃ６０，Ｃ７０，ＰＶＫ，ＰＶＫ／Ｃ６０等薄膜，并测量了物理喷束淀积技术制备得的Ｃ６０薄膜，ＰＶＫ／Ｃ６０混合膜的吸收光谱，荧光光谱，时间分辨率荧光光谱，与Ｃ６０等薄膜的高真空蒸发膜的相应光谱进行了比较，结果表明，物理喷束淀积可以制备具有很好质量的高抗光损伤薄膜，薄膜的荧光衰减特性与蒸发膜有很大差别。采用该法制备的ＰＶＫ／     

聚乙烯咔唑超分子膜／p－Si体系的表面光电压谱研究

利用ＬＢ技术，以二十碳酸作辅助成膜材料，在疏水处理的Ｐ－Ｓｉ上分别制备了２、４、６、１０和２０层聚乙烯咔唑（ＰＶＫ）超分子膜。对这种体系的表面光电压谱（ＳＰＳ）研究结果表明，表面光电压随ＰＶＫ膜层数的增加而增强，在紫外区增强较为明显。随着膜层数的增加，表面光电压有趋于饱和的趋势。膜对基底的敏化主要是由于ＰＶＫ的光导电性引起的。     

非离子水溶性膦铑配合物催化剂的XPS表征

用Ｘ射线光电子能谱（ＸＰＳ）的分析方法，对非离子水溶性膦铑配合物ＲｈＣｌ３／ＴＰＰＰ的组成，结构进行表征，并且用曲线拟合分峰技术对配体ＴＰＰＰ，配合物ＲｈＣｌ３／ＴＰＰＰ催化剂中各元素的峰进行数据处理，结果表明配体ＴＰＰＰ与配合物ＲｈＣｌ３／ＴＰＰＰ比较，配合物中存在Ｒｈ－ＣＯ配位和Ｒｈ－Ｐ配位，通过ＸＰＳ分析测试结果推断，原位合成的ＲｈＣｌ３／ＴＰＰＰ配合物催化剂其结构表示为ＣｌＲｈ（ＣＯ）ｎ（     

VO￣（2＋）—谷氨酸—π受体三元混配配合物的结构与波谱研究

测定了ＶＯＳＯ＿４－谷氨酸（Ｇｌｕ）－邻菲啉（ｐｈｅｎ）及ＶＯＳＯ＿４－谷氨酸－联吡啶（ｂｉｐｙ）三元混配配合物在不同酸度下（ｐＨ＝１～１４）的乙二醇／水（１：１）溶液中的低温（１７３Ｋ）ＥＳＲ谱．发现随ｐＨ的变化形成各种结构和组成的配合物，利用Ｊｏｈｎｓｏｎ的加合规则、结合配合物的ＩＲ光谱推测了各种配合物的可能结构；利用电子光谱数据计算了配合物的晶体场多数；讨论了谷氨酸、π受体配合物的成配规律。     

簇合物[Co6S8（PEt3）6]^n的电子结构及组装机理研究

动用Ｇ９４Ｗ量子化学程序包,采用ＬａｎＬ２ＫＺ基组,对簇合物「Ｃo６Ｓ８（ＰＥt３）６」＾n（n＝－１,０,＋１,＋２）的电子结构及组装机理进行从头计算研究,探讨这些簇合物的稳定性、Ｓ和Ｐ原子在成簇中的作用以及从三钴簇状碎片「Ｃo３（u２－Ｓ）３（u３－Ｓ）（ＰＨ３）３」＾n（n＝＋１,０）出发而提出的成簇机理等。计算结果表明 ,簇合物模型」Ｃo６Ｓ８（ＰＨ３）６「＾n的负离子构型「Ｃo６Ｓ８（ＰＨ３）６」＾     

聚合物共混过程中的小角激光光散射在线分析(英文)

利用激光小角背散射法对不相容聚合物体系聚苯乙烯／顺丁橡胶（ＰＳ／ＰｃＢＲ）共混过程中结构变化进行了在线分析。分散相颗粒尺寸由Ｄｅｂｙｅ散射理论中相关距离（αｃ）及平均直径（Ｄ描述）。由相关距离随组成比变化显示,在ＰＳ／ＰｃＢＲ共混质量比为５０／５０时出现相反转,即当ＰＳ含量小于５０％时ＰＳ为分散相,当ＰＳ含量大于５０％时ＰＳ为连续相,ＰＳ含量为５０％时体系为双连续相。分散相平均直径随共混时间延长而降低,其变化过程满足颗粒粉碎理论：ｄｔ＝－ｂＤ－ｎｄＤ,系数ｎ和ｂ与共混条件、共混材料特征及共混物两相含量等有关。共混物经不同共混时间后试样由扫描电子显微镜分析结果与激光小角背散射分析结果一致。     

5－Br－PADAP测定地下水中钒

本文研究了ＨＣｌ－ＫＣｌ缓冲体系中钒（Ⅴ）与５－Ｂｒ－ＰＡＤＡＰ形成配合物的条件及配合物的带电性质。提出一个灵敏、简便、快速测定钒的分光光度法。配合物的表观摩尔吸光系数为３．８×１０~４，最大吸收波长为５８８ｎｍ，钒（Ⅴ）与５－Ｂｒ－ＰＡＤＡＰ的配合比为１：１。含钒量在０—２０μｇ／２５ｍＬ范围内符合比尔定律。分析了地下水中钒，结果满意。     

Preparation and photoluminescence properties of electrospun nanofibers of C60/PVK

Ultrafine fullerene (C60)/poly(N-vinylcarbazole) (PVK) composite fibers with 1 μm diameter were prepared by electrospinning C60/PVK blend solutions in solvent mixtures of N,N-dimethylformamide (DMF)/toluene. The UV absorption spectra of nanofibers have a similar behavior as observed in the thin films for the same doping condition. It is interesting to observe that the PVK nanofibers have a very strong blue-violet luminescence, while ‘bright spots’ due to C60 can be observed on the C60/PVK fibers under UV irradiation in a fluorescence optical microscope. Compared to the emission spectra of PVK thin films, the photoluminescence of the PVK nanofibers shows a new emission peak at 437 nm. Efficient energy transfer was observed in C60/PVK thin films, as well as in blend nanofibers.     

Hole-transporting property of a chemically hybridized poly(vinylcarbazole)-fullerene

We synthesized a star copolymer of poly(vinylcarbazole) (PVK) branched from a fullerene (C₆₀) center, and investigated its optical absorption and photoluminescence properties. The chemically hybridized PVK-C₆₀ was then employed as a hole-transporting layer of the electroluminescent device with a poly(9,9^′-dihexylfluorene-2,7-divinylene-m-phenylenevinylene-stat-p-phenylenevinylene) (CPDHFPV) emitting layer. The ITO/PVK-C₆₀/CPDHFPV/LiF/Al device showed a strong electroluminescence quenching due to a direct contact of the PVK-C₆₀ and the CPDHFPV layers. In contrast, when an additional PVK layer was introduced between the two layers, the electroluminescence was largely enhanced. The emitted light power of the ITO/PVK-C₆₀/PVK/CPDHFPV/LiF/Al device was improved by 3 times compared with the device without the PVK-C₆₀ layer.     

Dynamic topology of fullerene coalescence

Atomic rearrangements leading to the coalescence of fullerene cages are revealed by topological analysis. Paths found for nanotubes and C(60) consist exclusively of Stone-Wales bond rotations. Computed intermediate states show gradual evolution from separate clusters to completely fused coherent units. Molecular dynamics simulations follow the predicted routes, overcome the nucleation barrier, and reach a final annealed state. While the overall behavior resembles macroscopic sintering, the nanoscale neck undergoes quantized changes in diameter and crystalline order.     

Effects of fullerene coalescence on the thermal conductivity of carbon nanopeapods

The heat conduction and its dependence on fullerene coalescence in carbon nanopeapods (CNPs) have been investigated by equilibrium molecular dynamics simulations. The effects of fullerene coalescence on the thermal conductivity of CNPs were discussed under different temperatures. It is shown that the thermal conductivity of the CNPs decreases with the coalescence of encapsulated fullerene molecules. The thermal transmission mechanism of the effect of fullerene coalescence was analysed by the mass transfer contribution, the relative contributions of phonon oscillation frequencies to total heat current and the phonon vibrational density of states (VDOS). The mass transfer in CNPs is mainly attributed to the motion of encapsulated fullerene molecule and it gets more restricted with the coalescence of the fullerene. It shows that the low-frequency phonon modes below 20 THz contribute mostly to thermal conductivity in CNPs. The analysis of VDOS demonstrates that the dominating contribution to heat transfer is from the inner fullerene chain. With the coalescence of fullerene, the interfacial heat transfer between the CNT and fullerene chain is strengthened; however, the heat conduction of the fullerene chain decreases more rapidly at the same time.     

Synthesis of a water-soluble fullerene [C60] under ultrasonication

A water-soluble fullerene [C60] is prepared with fullerene [C60] and a mixture of strong inorganic acids at the ratio (v/v) of 3:1 under ultrasonic condition at 25-43 degrees C. The MALDI-TOF MS and 13C-NMR spectra confirmed that the product of a water-soluble fullerene compound was C60.     

Gas-phase aggregation of fullerenes by laser ablation of fullerenes in reactive and nonreactive matrices

60 molecules, whereas little or no coalescence was found in the nonreactive mixture. In the negative ion TOF channel the maximum peak of twice C₆₀ coalescence by laser desorption was always located at masses greater than 120 carbon mass units, which is different from all previous reports. We suggest that the formation mechanism was due to strong interactions between the C₆₀ molecules and silica particles or surface species such as the H or OH group existing in the matrix. Received: 6 May 1996/Revised version: 22 July 1996     

Ultrafast processes of photoinduced charge and energy transfer in nanostructural fullerene-metal films

The primary stages of photoinduced processes in tin-doped C₆₀ fullerene films have been studied using a femtosecond pump-probe technique with 150-fs laser excitation pulses (λ = 400 nm) and differential transmission and reflection probing in the 1100–1700 nm range. The relaxation dynamics strongly depends both on the metal-to-fullerene ratio in the film and on the mutual distribution (packing) of components in the nanocomposite material. The observed response signal dynamics is related to features in the charge carrier generation, energy transfer between fullerene molecules, and charge transport between metal and fullerene.