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61.
Summary The lead ion selective electrode (ISE) consisting of PbS-Ag2S is normally used with a membrane surface of outer layer areaA
o) and inner layer area (A
i) at unity (A
o=A
i). Partial covering of one surface area with an insulating material and keeping the other surface layer intact resulted in different ratios of membrane surface areas exposed to lead solutions. The potential linearly increased with increasing theA
o/A
i ratio and decreased with decreasing theA
o/A
i ratio. The lead ISE potential increased linearly with increasing the membrane thickness, but which required much longer time for a stable potential.
Wirkung von Oberflächenverhältnis und Dicke der Elektrodenmembran auf das Potential einer Bleielektrode
Zusammenfassung Die aus PbS-Ag2S bestehende spezifische Bleiionen-Elektrode wird üblicherweise mit einem Oberflächenverhältnis der Außenfläche (A o) und der Innenfläche (A i) mitA o=A i verwendet. Durch teilweise Abdeckung einer Oberfläche mit isolierendem Material, ohne daß die andere Oberfläche verändert wird, ergaben sich verschiedene Verhältnisse der mit der Bleilösung in Berührung stehenden Oberflächen. Mit dem VerhältnisA o/A i stieg das Potential linear an bzw. es fiel mit diesem Verhältnis ab. Das Potential der spezifischen Bleielektrode stieg mit der Dicke der Membran, stabilisierte sich aber wesentlich langsamer.相似文献
62.
Sarkar S Sarkar B Chanda N Kar S Mobin SM Fiedler J Kaim W Lahiri GK 《Inorganic chemistry》2005,44(17):6092-6099
The complex framework [Ru(tpy)(dpk)]2+ has been used to study the generation and reactivity of the nitrosyl complex [Ru(tpy)(dpk)(NO)]3+ ([4]3+). Stepwise conversion of the chloro complex [Ru(tpy)(dpk)(Cl)]+ ([1]+) via [Ru(tpy)(dpk)(CH3CN)]2+ ([2]2+) and the nitro compound [Ru(tpy)(dpk)(NO2)]+ ([3]+) yielded [4]3+; all four complexes were structurally characterized as perchlorates. Electrochemical oxidation and reduction was investigated as a function of the monodentate ligand as was the IR and UV-vis spectroscopic response (absorption/emission). The kinetics of the conversion [4]3+/[3]+ in aqueous environment were also studied. Two-step reduction of [4]3+ was monitored via EPR, UV-vis, and IR (nu(NO), nu(CO)) spectroelectrochemistry to confirm the {RuNO}7 configuration of [4]2+ and to exhibit a relatively intense band at 505 nm for [4]+, attributed to a ligand-to-ligand transition originating from bound NO-. 相似文献
63.
Elevated Catalytic Activity of Ruthenium(II)–Porphyrin‐Catalyzed Carbene/Nitrene Transfer and Insertion Reactions with N‐Heterocyclic Carbene Ligands 下载免费PDF全文
Ka‐Ho Chan Dr. Xiangguo Guan Dr. Vanessa Kar‐Yan Lo Prof. Dr. Chi‐Ming Che 《Angewandte Chemie (International ed. in English)》2014,53(11):2982-2987
Bis(NHC)ruthenium(II)–porphyrin complexes were designed, synthesized, and characterized. Owing to the strong donor strength of axial NHC ligands in stabilizing the trans M?CRR′/M?NR moiety, these complexes showed unprecedently high catalytic activity towards alkene cyclopropanation, carbene C? H, N? H, S? H, and O? H insertion, alkene aziridination, and nitrene C? H insertion with turnover frequencies up to 1950 min?1. The use of chiral [Ru(D4‐Por)(BIMe)2] ( 1 g ) as a catalyst led to highly enantioselective carbene/nitrene transfer and insertion reactions with up to 98 % ee. Carbene modification of the N terminus of peptides at 37 °C was possible. DFT calculations revealed that the trans axial NHC ligand facilitates the decomposition of diazo compounds by stabilizing the metal–carbene reaction intermediate. 相似文献
64.
Cyclam-based enediynes 1-3 have been synthesized for the first time either by direct bis- or tetra-alkylation of the cyclam or via double alkylation of the 1,8-bis-sulfonyl derivative. The enediyne 1 readily forms a complex with Ni(II), which also lowered the onset temperature for Bergman cyclization of the parent enediyne by 60 °C. In the presence of a co-oxidant, MMPP, the Ni-complex can cleave ds-DNA into the nicked relaxed form at micromolar concentrations. 相似文献
65.
The ferroelectric ceramics Ba5RTi3V7O30 (R=Ho, Gd, La) have been synthesized by solid-state reaction technique. Preliminary X-ray structural analysis confirmed a single-phase formation of the compound in orthorhombic structure. Surface morphology of the compounds was studied by scanning electron microscopy (SEM). Detailed studies of electrical properties (i.e., dielectric constant, loss tangent, ac conductivity) as a function of temperature (RT-773 K) and at four different frequencies (1 kHz, 10 kHz, 100 kHz and 1 MHz) show ferroelectric–paraelectric phase transition of the compounds of diffuse-type. The activation energy has been evaluated from ac conductivity following Arrhenius equation. The conductivity pattern shows that it is strongly frequency dependent and obeys Jonscher's power relation. 相似文献
66.
67.
Arindam Roy Manas Kumar Maiti Samarjit Kar Manoranjan Maiti 《Mathematical and Computer Modelling》2007,46(11-12):1419-1433
An inventory model for a deteriorating item with stock dependent demand is developed under two storage facilities over a random planning horizon, which is assumed to follow exponential distribution with known parameter. For crisp deterioration rate, the expected profit is derived and maximized via genetic algorithm (GA). On the other hand, when deterioration rate is imprecise then optimistic/pessimistic equivalent of fuzzy objective function is obtained using possibility/necessity measure of fuzzy event. Fuzzy simulation process is proposed to maximize the optimistic/pessimistic return and finally fuzzy simulation-based GA is developed to solve the model. The models are illustrated with some numerical data. Sensitivity analyses on expected profit function with respect to distribution parameter λ and confidence levels α1 and α2 are also presented. 相似文献
68.
In this paper the nonlinear response of a base-excited slender beam carrying an attached mass is investigated with 1:3:9 internal resonances for principal and combinationparametric resonances. Here the method of normal forms is used to reduce the second order nonlinear temporal differential equation of motion of the system to a set offirst order nonlinear differential equations which are used to find the fixed-point, periodic, quasi-periodic and chaotic responses of the system.Stability and bifurcation analysis of the responses are carried out and bifurcation sets are plotted. Many chaotic phenomena are reported in this paper. 相似文献
69.
Lanthanide‐Doped Nanocrystals: Strategies for Improving the Efficiency of Upconversion Emission and Their Physical Understanding 下载免费PDF全文
The fundamental understanding of lanthanide‐doped upconverted nanocrystals remains a frontier area of research because of potential applications in photonics and biophotonics. Recent studies have revealed that upconversion luminescence dynamics depend on host crystal structure, size of the nanocrystals, dopant concentration, and core–shell structures, which influence site symmetry and the distribution and energy migration of the dopant ions. In this review, we bring to light the influences of doping/co‐doping concentration, crystal phase, crystal size of the host, and core–shell structure on the efficiency of upconversion emission. Furthermore, the lattice strain, due to a change in the crystal phase and by the core–shell structure, strongly influences the upconversion emission intensity. Analysis suggests that the local environment of the ion plays the most significant role in modification of radiative and nonradiative relaxation mechanisms of overall upconversion emission properties. Finally, an outlook on the prospects of this research field is given. 相似文献
70.
Dr. Arik Kar Sumanta Sain Dr. Simanta Kundu Arka Bhattacharyya Dr. Swapan Kumar Pradhan Prof. Amitava Patra 《Chemphyschem》2015,16(5):1017-1025
Tuning the functional properties of nanocrystals is an important issue in nanoscience. Here, we are able to tune the photocatalytic properties of SnO2 nanocrystals by controlling their size and shape. A structural analysis was carried out by using X‐ray diffraction (XRD)/Rietveld and transmission electron microscopy (TEM). The results reveal that the number of oxygen‐related defects varies upon changing the size and shape of the nanocrystals, which eventually influences their photocatalytic properties. Time‐resolved spectroscopic studies of the carrier relaxation dynamics of the SnO2 nanocrystals further confirm that the electron–hole recombination process is controlled by oxygen/defect states, which can be tuned by changing the shape and size of the materials. The degradation of dyes (90 %) in the presence of SnO2 nanoparticles under UV light is comparable to that (88 %) in the presence of standard TiO2 Degussa P‐25 (P25) powders. The photocatalytic activity of the nanoparticles is significantly higher than those of nanorods and nanospheres because the effective charge separation in the SnO2 nanoparticles is controlled by defect states leading to enhanced photocatalytic properties. The size‐ and shape‐dependent photocatalytic properties of SnO2 nanocrystals make these materials interesting candidates for photocatalytic applications. 相似文献