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891.
皂类液膜振荡器 总被引:2,自引:0,他引:2
实验发现了一类新型液膜振荡器,在油水两相之间进行成皂反应的过程中,界面附近出现了长时间规则的大幅度pH振荡,将W/O两相体系换成W1/O/W2三相体系,振幅从0.50 pH明显提高到2.88 pH.其中水相组成为CTAB溶液及NaOH溶液,油相组成为油酸的煤油溶液.同时,此类液膜振荡体系中亦存在明显的电势振荡和电导率振荡.为深入了解机理,进行了浓度影响测定,电极位置和种类的变化以及辅助实验等,提出了普遍化的机理,并进行了实验振荡曲线的拟合对比.这个机理指出,在膜反应批量进行的条件下,当反应速率与扩散成比例时,便会产生规则的周期现象.在一价皂液膜振荡器的基础上,通过替换或添加各种金属盐,形成了各类高价皂液膜振荡器,测定了反应过程中pH、电势及电导率的变化.经过同类化学振荡器的比较研究,结合金属离子与酸根之间的络合作用,得出了其中的一些规律. 相似文献
892.
893.
Dr. J. Kegel 《Analytical and bioanalytical chemistry》1972,276(1):45-50
The direct determination of CO2 is often faulty because of certain contents of the natural water. Due to this reason a specific method was worked out. The water to be analysed and distilled water are placed side by side in a gas-tight vessel with an atmosphere free of CO2, whereby mixing is avoided but gas-exchange is possible. After adjustment to the gas-equilibration the CO2 content of the distilled water is determined e.g. by titration, measuring of conductivity or other methods, from where the CO2 content in the natural water is calculated. 相似文献
894.
Xu W. B. Zhou Z. F. He P. S. Pan W.-P. 《Journal of Thermal Analysis and Calorimetry》2004,78(1):113-124
The Flory's gelation theory, non-equilibrium thermodynamic fluctuation theory and Avrami equation have been used to predict
the gel time t
g and the cure behavior of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposites at various temperatures
and organo-montmorillonite loadings. The theoretical prediction is in good agreement with the experimental results obtained
by dynamic torsional vibration method, and the results show that the addition of organo-montmorillonite reduces the gelation
time t
gand increases the rate of curing reaction, the value of k, and half-time of cure after gelation point t1/2 decreases with the increasing of cure temperature, and the value of n is ~2 at the lower temperatures (<60°C) and decreases to ~1.5 as the temperature increases, and the addition of organo-montmorillonite
decreases the apparent activation energy of the cure reaction before gelation point, but has no apparent effect on the apparent
activation energy of the cure reaction after gelation point. There is no special curing process required for the formation
of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposite.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
895.
A rapid and simple method using capillary electrophoresis (CE) with chemiluminescence (CL) detection was developed for the determination of levodopa. This method was based on enhance effect of levodopa on the CL reaction between luminol and potassium hexacyanoferrate(III) (K3[Fe(CN)6]) in alkaline aqueous solution. CL detection employed a lab-built reaction flow cell and a photon counter. The optimized conditions for the CL detection were 1.0 × 10−5 M luminol added to the CE running buffer and 5.0 × 10−5 M K3[Fe(CN)6] in 0.6 M NaOH solution introduced postcolumn. Under the optimal conditions, a linear range from 5.0 × 10−8 to 2.5 × 10−6 M (r = 9991), and a detection limit of 2.0 × 10−8 M (signal/noise = 3) for levodopa were achieved. The precision (R.S.D.) on peak area (at 5.0 × 10−7 M of levodopa, n = 11) was 4.1%. The applicability of the method for the analysis of pharmaceutical and human plasma samples was examined. 相似文献
896.
Qiang Xu Prof. Dr. Nobuko Tsumori Prof. Dr. Ling Jiang Masanobu Kondo Ryuichi Arakawa Prof. Dr. 《化学:亚洲杂志》2007,2(5):599-608
Carbonyldinitrosyltris(fluorosulfato)tungstate(II) and ‐molybdate‐(II) anions, [fac‐M(CO)(NO)2(SO3F)3]? (M=W, Mo), which are novel weakly coordinating anions that contain a metal carbonyl/nitrosyl moiety, have been generated in fluorosulfonic acid and completely characterized by multinuclear NMR, IR, and Raman spectroscopy as well as ESI mass spectrometry. ESI MS measurements performed for the first time on a superacidic solution system unambiguously reveal the formation of the monoanionic, mononuclear W and Mo complexes formulated as [M(CO)(NO)2(SO3F)3]? (M=W, Mo). Multinuclear NMR spectroscopic studies at natural abundance and 13C and 15N enrichment clearly indicate the presence of one CO ligand, two equivalent NO ligands, and two types of nonequivalent SO3F? groups in a 2:1 ratio. The IR and Raman spectra reveal that the two equivalent NO ligands have a cis conformation, thus indicating a fac structure. Density functional calculations at the B3LYP level of theory predict that these anions have a singlet ground state (1A′) with a Cs symmetry along with C–O and N–O vibrational frequencies that are in agreement with the experimental observations. Mulliken population analysis shows that the monovalent negative charge is dispersed on the bulky sphere, the surface of which is covered by all the negatively charged O and F atoms with charge densities much lower than SO3F?, suggesting that [fac‐M(CO)(NO)2(SO3F)3]? (M=W, Mo) are weakly nucleophilic and poorly coordinating anions. 相似文献
897.
The structure of [(CF3N2NMe)Mo(CH2SiMe3)2] (in which (CF3N2NMe)2? is [(3‐CF3C6H4NCH2CH2)2NMe]2?) is approximately trigonal bipyramidal with one axial and one equatorial alkyl ligand. Heating of solutions of [(CF3N2NMe)Mo(CH2SiMe3)2] in [D6]benzene in the presence of five equivalents of 2‐butyne led to diamagnetic [(CF3N2NMe)Mo(CHSiMe3)(η2‐MeC?CMe)], whose structure is approximately square pyramidal with the alkyne occupying the axial site. Addition of one equivalent of cyclohexene sulfide to [(CF3N2NMe)Mo(CH2SiMe3)2] at room temperature produced the diamagnetic, dimeric molybdenum(IV) sulfido complex, [{(CF3N2NMe)MoS}2]. This complex is composed of two approximately trigonal bipyramidal centers, each containing one axial and one equatorial sulfur atom. Oxidation of [(CF3N2NMe)Mo(CH2SiMe3)2] with hexachloroethane resulted in formation of tetramethylsilane, HCl, and the sparingly soluble, red alkylidyne complex, [{(CF3N2NMe)Mo(CSiMe3)Cl}2]. This complex forms a dimer through bridging chlorides. The oxidation reactions of [(CF3N2NMe)Mo(CH2SiMe3)2] with 2‐butyne, cyclohexene sulfide, or C2Cl6 are all proposed to proceed by α‐hydrogen abstraction in the MoVI species to yield (initially) the Mo?CHSiMe3 species and tetramethylsilane. 相似文献
898.
New copper(II) complexes of the hydrazone ligands H2salhyhb, H2salhyhp, and H2salhyhh, derived from salicylaldehyde and ω‐hydroxy carbonic acid hydrazides, have been synthesized and physically characterized. Two fundamental structures were found in solid state depending on the pH‐value of the reaction solution. Acidic conditions lead to the formation of the di‐μ‐phenoxo‐bridged dicationic complex dimers [{Cu(Hsalhyhb)}2]2+ ( 1a ), [{Cu(Hsalhyhp)}2]2+ ( 2a ), and [{Cu(Hsalhyhh)}2]2+ ( 3a ), isolated as perchlorate salts. The dimeric complexes show strong antiferromagnetic coupling with J = ?399 ( 1a ), ?410 ( 2a ), and ?311 cm?1 ( 3a ). Higher pH‐values resulted in the aggregation of neutral copper ligand fragments to the one‐dimensional coordination polymers [{Cu(salhyhb)}n] ( 1b ), [{Cu(salhyhp)}n] ( 2b ), and [{Cu(salhyhh)}n] ( 3b ). 3b has been examined by means of X‐ray crystallography and represents the first example of a structurally characterized neutral copper(II) N‐salicylidenehydrazide complex without additional ligands. The magnetic interactions in the polymers are also antiferromagnetic with J = ?125 ( 1b ), ?136 ( 2b ), and ?148 cm?1 ( 3b ), but strongly reduced compared to the corresponding dimeric complexes. The two basic structure types can be reversibly interconverted simply by pH‐control. 相似文献
899.
Wang‐Ting Wu Feng‐Ying Chen Shui‐Yang He Huai‐Ming Hu Meng‐Lin Yang Yao‐Yu Wang 《中国化学》2006,24(5):711-713
The binuclear praseodymium(III) complex with N‐(1‐carboxyethylidene)‐salicylhydrazide (C10H10N2O4, H2L) was prepared in H2O‐C2H5OH mixed solution, and the crystal structure of [Pr2L2(HL)2(H2O)4]·3H2O·C6H6 was determined by X‐ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P‐1, and in the structure each Pr atom is 9‐coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five‐membered rings sharing one side in keto‐mode and two water molecules. The coordination polyhedron around Pr3+ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via μ2‐bridging mode. 相似文献
900.
An electrochemical DNA hybridization detection assay based on a silver nanoparticle label 总被引:3,自引:0,他引:3
A novel, sensitive electrochemical DNA hybridization detection assay, using silver nanoparticles as the oligonucleotide labeling tag, is described. The assay relies on the hybridization of the target DNA with the silver nanoparticle-oligonucleotide DNA probe, followed by the release of the silver metal atoms anchored on the hybrids by oxidative metal dissolution and the indirect determination of the solubilized Ag(I) ions by anodic stripping voltammetry (ASV) at a carbon fiber ultramicroelectrode. The influence of the relevant experimental variables, including the surface coverage of the target oligonucleotide, the duration of the silver dissolution steps and the parameters of the electrochemical stripping measurement of the silver(I) ions, is examined and optimized. The combination of the remarkable sensitivity of the stripping metal analysis at the microelectrode with the large number of silver(I) ions released from each DNA hybrid allows detection at levels as low as 0.5 pmol L(-1) of the target oligonucleotides. 相似文献