光谱法研究N-烃基吖啶满和10,10''''-二烃基-9,9''''-联二吖啶烯的氧化反应

ＵＶ，ＩＲ，ＥＳＲ和荧光光谱法研究了Ｎ－烃基吖啶满和１０，１０’－二烃基－９，９’－联二吖啶烯与π－电子受体：ＤＤＱ、ＴＣＮＱ、ＴＣＮＥ、ＣＡ的氧化反应过程，提出了它们的氧化反应机理。     

合成抗孕酮新药RU-486中间体3,3-乙撑二氧-5α,10α及5β,10β-环氧-Δ~(9(11))-雌烯-17α(1-丙炔基)-17β-羟基的~1H和~(13)C NMR谱线全归属

用１Ｄ及２ＤＮＭＲ技术（ＣＯＳＹ，ＴＯＣＳＹ，ＨＭＱＣ及ＨＭＢＣ）归属了合成抗孕酮新药ＲＵ－４８６中间体３，３乙撑二氧５α，１０α及５β，１０β环氧－Δ９（１１），雌烯１７α（１－丙炔基）１７β羟基的１Ｈ和１３ＣＮＭＲ谱线．     

黄嘌呤氧化酶－乙醛－吖啶酯化学发光分析新体系

乙醛在黄嘌呤氧化酶催化作用下，被空气氧化生成乙酸和过氧化氢，酶反应生成的过氧化氢氧化新吖啶酯试剂［１０－甲基－９－（对甲酰苯基）吖啶羧酸酯氟磺酸盐］产生化学发光，化学发光强度与己醛浓度在一定范围内成线性关系．由此建立了一种化学发光分析新体系，用于测定乙醇含量．线性范围２．０×１０－７～１．２×１０－３ｍｏｌ／Ｌ，测定５．０×１０－７ｍｏｌ／Ｌ乙醛，相对标准偏差为６．８％，检测限为１．２×１０－７ｍｏｌ／Ｌ，测定环境水样中乙醇含量，取得满意结果，回收率为９５～１０６％．     

多核芳烃正离子自由基的ENDOR和EPR研究

用ＥＰＲ和ＥＮＤＯＲ方法检测傅氏烷基化反应（Ｆｒｉｅｄｅｌ－Ｃｒｕｆｔｓｒｅａｃｔｉｏｎ）中所生成的多核芳烃正离子自由基：１，４，５，８－四甲基惠、９，１０－二氘代－１，４，５，８－四甲基蒽、２，６，９，１０－四甲基蒽、２，６－二甲基－９，１０－二（对甲苯基）蒽、３，６，１１，１４－四甲基二苯并（ａ，ｃ）三亚苯正离子自由基，测定了它们的超精细偶合常数并提出了其生成机理。     

低密度聚乙烯光引发交联机理

首次用溶液高分辨￣（１３）ＣＮＭＲ研究了由二苯甲酮光引发低密度聚乙烯（ＬＤＰＥ）交联所产生的交联结构，现已观测和鉴定了Ｈ型和Ｙ型长链支化两类交联点。对于熔融态紫外光交联５－１０ｓ的ＬＤＰＥ样品，其Ｈ型和Ｙ型交联点的浓度据估测分别为一万个碳原子中有５．７－１６．９和７．６－２１．６个结构单元。     

THE MACQM CALCULATION OF THE TOTAL ENERGY CURVE OF THE BODY-CENTERED CUBIC STRUCTURE OF THE H_9~- CLUSTER

ＴＨＥＭＡＣＱＭＣＡＬＣＵＬＡＴＩＯＮＯＦＴＨＥＴＯＴＡＬＥＮＥＲＧＹＣＵＲＶＥＯＦＴＨＥＢＯＤＹ－ＣＥＮＴＥＲＥＤＣＵＢＩＣＳＴＲＵＣＴＵＲＥＯＦＴＨＥＨ－９ＣＬＵＳＴＥＲＧｏｕＱｉｎｇｑｕａｎＺｈａｎｇＪｉａｎｐｉｎｇＬｉＰｉｎｇＩｎｓｔｉｔｕ...     

敏通CCD——MTV-1881EX用于业余天文望远镜

敏通ＣＣＤ——ＭＴＶ－１８８１ＥＸ用于业余天文望远镜我们在１９９６年偿试用高解析度、高灵敏度（０．０２ｌｘ）的敏通ＣＣＤ、ＭＴＶ－１８８１ＥＸ加装在口径仅为１０ｃｍ的业余级天文望远镜上看到了清晰的月亮、木星和土星（包括它的光环）等天体。它可直接用电视...     

类Be等电子序列的奇宇称高激发态结构（J=1）

应用本征通道量子亏损理论（ＥＱＤＴ），计算了类Ｂｅ原子体系（Ｂｅ－ＭｇⅨ）的高激发态结构（奇宇称，Ｊ＝１），得到了表征高激发态性质的ＥＱＤＴ参量及２ｐｎｓ，２ｐｎｄ和２ｓｎｐ组态的全部Ｒｙｄｂｅｒｇ能级位置及通道混合系数。从各种相互作用之间竞争的角度，讨论了高激发态结构沿该等电子序列的变化规律。     

碳纳米管和高取向热解石墨的拉曼光谱对比研究

同时测量了碳纳米管（Ｄ－ＣＮＴ）和高取向热解石墨（ＨＯＰＧ）的拉曼光谱，第一次分别在ＨＯＰＧ和Ｄ－ＣＮＴ中观察到了位于４２６５ｃｍ－１和４２４８ｃｍ－１的（Ｇ＋Ｄ＊）三级模的拉曼散射；拉曼谱的研究显示，Ｄ－ＣＮＴ的结构比ＨＯＰＧ的无序，同时也进一步表明此无序程度主要来源于结构的缺陷，而非石墨层卷曲成筒状之故     

二维核磁共振谱解析及其应用

２ＤＮＭＲ在波谱学的化学应用中占据首要位置。本文简述了ＣＯＳＹ，ＬＲＣＯＳＹ，ＣＯＳＹＤＥＣ，ＳＥＣＳＹ，ＤＱＣ－ＣＯＳＹ，ＲＣＴ，ＩＮＡＤＩＱＵＡＴＥ，ＲＥＬＡＹ，ＩＮＶＥＲＳＥ，ＮＯＥＳＹ，ＨＯＥＳＹ，ＯＨＡＨＡ，ＲＯＥＳＹ，ＨＭＱＣ，ＨＭＢＣ等谱的形状，指认步骤及其应用。     

6种不同取代基的双吖啶类探针的化学发光性质及其构效关系的研究

研究了10，10’-二甲基-9，9’-双吖啶二硝酸盐(DMBAI)N)；10，10’-二甲基-3，3’-二磺酸基-9，9’-双吖啶(I)MDSBA)；3，3’-二磺酸基-9，9’-双吖啶二硝酸盐(DSBADN)；10，10’-二乙羧基-9，9’-双吖啶硝酸盐(DEBADN)；10，10’一二甲基-3，3’-二氨基-9，9’-双吖啶(DMDABA)和10，10’-二(4-氨基丁基)-9，9’-双吖啶硝酸盐(DABADN)等6种9，9’-双吖啶类探针的化学发光性质，获得了9，9’-双吖啶类探针的结构与化学发光性质之间的某些关系，为设计合成新型用于化学发光免疫分析的高发光效率的9，9’-双吖啶类探针提供了一定的理论和实验依据。     

Energetics and electronic structures of encapsulated C60 in a carbon nanotube

We report total-energy electronic structure calculations that provide energetics of encapsulation of C60 in the carbon nanotube and electronic structures of the resulting carbon peapods. We find that the encapsulating process is exothermic for the (10,10) nanotube, whereas the processes are endothermic for the (8,8) and (9,9) nanotubes, indicative that the minimum radius of the nanotube for the encapsulation is 6.4 A. We also find that the C(60)@(10,10) is a metal with multicarriers each of which distributes either along the nanotube or on the C60 chain. This unusual feature is due to the nearly free electron state that is inherent to hierarchical solids with sufficient space inside.     

Effect of cyclodextrin solutions on chemiluminescence of 10,10′-dimethyl- 9,9′biacridinium nitrate

Solutions of alpha, beta, and gamma cyclodextrin have been shown to enhance the chemiluminescence of the reaction between hydrogen peroxide and 10,10'-dimethyl-9,9'biacridinium nitrate. A 20-fold increase in chemiluminescence intensity is observed in 10^-2 M beta cyclodextrin. The enhancement is attributed to an increase in the excitation efficiency and the rate of the reaction through the inclusion of a reaction intermediate in the cyclodextrin cavity.     

测定癌胚抗原的化学发光免疫分析新方法

使用自制的双吖啶发光示标识别１０,１０′－二甲基－３,３′－二磺酸基－９,９′－双吖啶（简称ＤＭＤＳＢＡ）标识抗癌胚抗原（ＣＥＡ）抗体,标识率达１．１５－１．３２。研究了标识反应、双抗夹心免疫反应和化学发光反应的条件,建立了一种测定ＣＥＡ的双抗夹心免疫分析新方法,测定ＣＥＡ的线性范围为１．０－１５０．０ｎｇ．ｍＬ＾－１,最小检测浓度为０．５３ｎｇ．ｍＬ＾－１。应用于人血清中ＣＥＡ含量的测定,结果与放射免疫法相关性良好。     

Emitting layer analysis of blue thermally activated delayed fluorescence devices using capacitance–voltage method

In this paper, blue thermally activated delayed fluorescence (TADF) organic light-emitting diodes (OLEDs) have been elucidated, with a focus on the degradation characteristics of the emission layer (EML). The operational stability against electrical stress was investigated for two host materials and four doping concentrations, which were used as the EML. The operating stability of the devices was confirmed by comparing the peak capacitance before and after degradation. Devices using bis [2-(diphenyl-phosphino) phenyl] ether oxide (DPEPO) as a host exhibited poor degradation characteristics. However, high stability was confirmed when 3,3-di (9H-carba-zol-9-yl)-biphenyl (mCBP) was used. DPEPO host devices are most resistant against performance degradation when they are doped with 10 wt% 10,10'-(4,4′-sulfonylbis(4,1-phenylene))bis(9,9-dimethyl-9,10-dihydroacridine (DMAC-DPS). We successfully determined the electroluminescence characteristics of the device depending on the host material, as well as the doping concentration, using the capacitance–voltage method.     

Development and application of a new electrochemical cell allowing EPR/ENDOR and NIR measurements

A new kind of electrochemical cell facilitates the bulk generation of anions and cations by almost “in situ” potential controlled electrolysis and their spectroscopic characterization. The application of the cell is demonstrated with [60]fullerene and 1-(9′-anthryl)-pyrene, for the reduction processes and 10,10′-(m-phenylene)diphenothiazine for the oxidation. In the case of [60]fullerene the reduction up to the trianion was performed and monitored by means of UV/Vis and EPR spectroscopy. The dianion clearly remains paramagnetic with a dominating EPR signal in liquid solution and zero field splitting characteristic for aS=1 state in frozen solution at 135 K, while further reduction leads to the monoradical trianion. 1-(9′-anthryl)-pyrene was reduced to the monoanion and a well resolved ENDOR spectrum was recorded. The ENDOR spectrum confirms that the spin density is unambiguously localized on the anthracene subunit. For the oxidation, 10,10′-(m-phenylene)diphenothiazine was used with a first redox potential of 0.6 V vs. the reference electrode, where the UV/Vis spectra show aλ _max at 514 nm. Further oxidation at 0.8 V leads to a biradical which exhibits zero field splittings and a δm _s=2 transition in frozen solution at 135 K.     

Influence of solvent polarity and temperature on dual fluorescence of 10,10′-dibromo, 9,9′-bianthryl

Fluorescence of 10,10′-dibromo, 9,9′-bianthryl (DBrBA) in solvents of different polarities (n-hexane, dibutyl ether, tetrahydrofuran, and acetone) has been investigated as a function of temperature. Changing of the solvent and variation of temperature modifies the ratio of local (LE) and charge transfer (CT) fluorescence quantum yields. From the basic fluorescence data (quantum yields, lifetimes, ratio of CT to LE fluorescence quantum yields) the temperature-dependent equilibrium constants for the charge transfer process in the excited singlet state were calculated and discussed on the basis of the modern electron transfer theories. It has been found that the intersystem crossing in DBrBA in nonpolar n-hexane, leading to the population of the lowest triplet state, proceeds via the third triplet state. It has been confirmed by the fluorescence measurements and quantum mechanical calculations. Surprisingly, the experimentally obtained intersystem crossing rate constants are very weakly dependent on temperature. Thus, the electron transfer reaction leading to the population of the molecular triplet state is probably an adiabatic reaction with a rate constant controlled by the dielectric relaxation of the solvent.     

The vibrational energy pattern in ethylene (12C2H4)

All known vibrational energies in ¹²C₂H₄([Xtilde]¹ A_g ) are collected. A block-diagonalized vibrational matrix Hamiltonian is set up, combining a Dunham expansion with the 2/10,10, 11/2,12, and the 5,5/9,9, 1,1/11,11,1,9/5,11 and 1,11/5,9 anharmonic resonances, with the normal modes numbered according to the most usual conventions in the previous literature. A step by step fitting procedure is applied. Vibrational constants are obtained, and vibrational assignments are provided and discussed. A slightly modified ensemble of vibrational constants is also produced by taking care of a more extended set of resonances between the CH-type vibrations. A new constant of the motion N = 3ν₁ + 3ν₅ + 3ν₉ + 3ν₁₁ + 2ν₂ + ν₁₀ + ν₁₂ is demonstrated to support the latter vibrational energy pattern.     

Effects of UV-ozone treatment on the electronic structures of F8BT and PFO polymeric thin films

The property changes of polymeric films upon degradation are important to develop strategies to prolong the device lifetimes. In this regard, we investigated the effects of ultraviolet-ozone (UVO) treatment on the electronic structures of poly (9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) and poly (9,9-di-n-octylfluorenyl-2,7-diyl) (PFO) films. We found that as the UVO treatment time increased, the intensities of the UV–vis and photoluminescence spectra of both F8BT and PFO films exponentially decayed owing to the destruction of the conjugated system of the films. As per the X-ray photoelectron spectra, both the F8BT and PFO films showed significant oxidation and p-doping effects upon UVO treatment. In addition, UVO treatment caused the etching of the polymeric films, and their thickness gradually decreased; the etching rate with UVO treatment was faster for PFO than for F8BT. These results indicate that the functionalization of polymers with UVO treatment requires the careful consideration of the resulting changes in their electronic structure.