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71.
Double [2,3] sigmatropic rearrangements of bis(propargyl sulfenates) to bis(allenic sulfoxides) and of bis(propargyl sulfinates) to bis(allenic sulfones) are shown to be a convenient and effective method for the preparation of conjugated diallene systems bearing two electron withdrawing trihalomethyl sulfoxide or sulfone substituents either on C-1 and C-6, or on C-3 and C-4. Such substituents are further shown to facilitate cyclization to bis(methylene)cyclobutenes, and to stabilize the latter. The electron withdrawing group substitution on the exocyclic methylene extremities proved more effective than similar substitution on the endocyclic double bond. 相似文献
72.
Eric W. Bohannan Xuerong Gao Kimberly R. Gaston Christopher D. Doss Chariklia Sotiriou-Leventis Nicholas Leventis 《Journal of Sol-Gel Science and Technology》2002,23(3):235-245
This study shows that conventional photolithography can be applied for patterning native or organic dye-doped silica films (0.5 m thick) obtained via a base-catalyzed sol-gel process. Photoresist was spin-coated onto high optical quality xerogel films, soft-baked, exposed to UV irradiation through a photomask, and developed with a commercial photoresist developing solution. Etching away of the photoresist-unprotected areas of the silica films was carried out with a dilute HF solution, while the remaining unexposed photoresist was removed with acetone. Interdigitated array patterns with features as small as 0.5 mm show a smooth surface and extremely sharp interfaces. Densification of the films at 550°C for 2 h decreases the film thickness by 11%, increases the refractive index from 1.420 to 1.456, and allows for well-defined patterning down to length scales of 10 m. Since the densification conditions are incompatible with organic dopants, it is demonstrated that sol-gel films can be doped after pattering (post-doping) by adsorption of cationic dyes from solution. Scanning electron microscopy reveals that the microstructure of patterned sol-gel films is similar to that of bulk monoliths, indicating that the photolithographic procedure is not harmful to the film quality. All patterned films demonstrate highly regular light diffraction patterns. 相似文献
73.
A new type of inorganic biosensor is introduced. The sensor comprises glucose oxidase enzymes encapsulated in a sol-gel-derived
Prussian blue-silicate hybrid network. Glucose is detected by the biocatalytic reduction of oxygen followed by catalytic reduction
of hydrogen peroxide by the Prusian blue catalyst. The sol-gel silicate entails a rigid encapsulating matrix, the Prussian
blue provides chemical catalysis and charge mediation from the reduction site to the supporting electrode, and the enzyme
is responsible for the biocatalysis. The feasibility of a dual optical/electrochemical mode of analysis is also demonstrated. 相似文献
74.
工业氨基三甲叉膦酸中副产物的核磁共振分析 总被引:1,自引:0,他引:1
采用多种核磁共振(NMR)技术测定了工业氨基三甲叉膦酸(ATMP)产品中副产物的分子结构,发现该物质为甲氨基二甲叉膦酸(MADMP),它是甲醛歧化反应导致的副产物;给出了可能的反应方程式;测出了MADMP的相对含量,MADMP与ATMP摩尔比约为2。 相似文献
75.
Zhi Qiang LIU Qi FANG* Wen Tao YU Gang XUE Du Xia CAO Dong WANG Guang Ming XIA Min Hua JIANG State Key Laboratory of Crystal Materials Shandong University Jinan 《中国化学快报》2002,13(10)
In common fluorescence process, molecular excitation is caused by the absorption of at least a single photon with shorter wavelength. When certain laser is used as the pump source, some compounds can be excited by simultaneous absorption of at least two photons and then the emission of up-converted fluorescence may occur. This process is called two-photon excited fluorescence (TPEF)1,2. Because of several advantages of TPEF, including intrinsic high three-dimensional resolution and the p… 相似文献
76.
Three highly sensitive spectrophotometric methods for the determination of platinum(IV) have been developed, based on its colour reactions with molybdate and basic dyes (BD) in aqueous solution in the presence of poly(vinyl alcohol). Platinum(IV) reacts with molybdate and BD to form ion — association complexes of composition (BD)2[Pt (MoO4)3]. The molar absorptivities are between 6.83 × 105 and 9.51 × 105 dm3mol–1cm–1, the highest value being found with nile blue. Suitable conditions for the reactions and the effects of foreign ions were investigated. The methods can be applied to the spectrophotometric determination of trace amounts of platinum(IV) in some catalysts and ores. 相似文献
77.
《Electroanalysis》2005,17(3):210-222
Presented in this work is the first step towards an enzymeless/mediatorless glucose sensor. We first observed remarkable electrocatalytic oxidation of glucose using combinative ruthenium oxide (RuOx)‐Prussian blue (PB) analogues (designated as mvRuOx‐RuCN, mv: mixed valent) at ca. 1.1 V (vs. Ag/AgCl) in acidic media (pH 2 Na2SO4/H2SO4). Individual RuOx and PB analogs failed to give any such catalytic response. A high ruthenium oxidation state (i.e., oxy/hydroxy‐RuVII, E°≈1.4 V vs. RHE), normally occurring in strong alkaline conditions at RuOx‐based electrodes, was electrogenerated and stabilized (without any conventional disproportionation reaction) in the mvRuOx‐RuCN matrix for glucose catalysis. Detail X‐ray photoelectron spectroscopic studies can fully support the observation. The catalyst was chemically modified onto a disposable screen‐printed carbon electrode and employed for the amperometric detection of glucose via flow injection analysis (FIA). This system has a linear detection range of 0.3–20 mM with a detection limit and sensitivity of 40 μM (S/N=3) and 6.2 μA/(mM cm2), respectively, for glucose. Further steps towards the elimination of interference and the extendibility to neutral pHs were addressed. 相似文献
78.
Reaction of an alkyne‐bridged dicobalt complex, [Co2(CO)6(μ‐Me3SiC=Cpy)] 4 , with bis(diphenylphosphino)methylene (DPPM) or bis(diphenylphosphino)ethylene (DPPE) in THF at 55 °C yielded a DPPM or DPPE doubly bridged dicobalt compound, [{μ‐P,P‐PPh2CH2PPh2}Co2(CO)4(μ‐Me3SiC=Cpy)] 5 or [{μ‐P,P‐PPh2CH2CH2PPh2}Co2(CO)4(μ‐Me3SiC≡Cpy)] 6 . Compound 5 and 6 were characterized by spectroscopic means as well as X‐ray crystal structure determination. 相似文献
79.
将含有1.0%普鲁士蓝的碳黑与固体石蜡按2.5∶1(质量比)混合后装入φ0.2mm的石英毛细管中,在其上端插入一铂丝并抛光后即制成普鲁士蓝修饰碳黑微电极.对多巴胺(DA)及抗坏血酸(VC)在此电极上的电化学行为及应用此电极测定两组分的最佳条件进行了研究,在定量测定中采用二次微分线性扫描伏安法.在最佳条件下,DA与VC的峰电流(i″p)分别与各自的浓度保持如下线性关系DA为4.0×10-6~8.0×10-4mol·L-1,VC为6.0×10-5~1.0×10-3mol·L-1;检出限(3σ)依次为2.0×10-6mol·L-1及1.0×10-5mol·L-1.应用此方法分析了3种含DA及VC的混合溶液,测得结果的相对标准偏差(n=8)依次小于2.0%及3.0%,回收率范围依次为96.5%~101.0%及95.0%~102.5%. 相似文献
80.
Ying Liu Wenqing Liu Haiyang Li Yong Yang Shuang Cheng 《International journal of quantum chemistry》2007,107(2):396-402
Ab initio molecular orbital and density functional theory (DFT) in conjunction with different basis sets calculations were performed to study the N? H…O and S? H…O blue‐shifted H‐bonds in the HNO…HFSO2 complex. The geometric structures, vibrational frequencies, and interaction energies were calculated by both standard and CP‐corrected methods. Natural bond orbital (NBO) analysis was used to investigate the origin of blue‐shifted H‐bonds, showing that the decrease in the σ*(N? H) and σ*(S? H) is due to the electron density redistribution effect. The structure reorganization effect on the blue‐shifted hydrogen bonds was discussed in detail. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献