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81.
Alan M. Bond Roger J. OHalloran Ivica Ruzic Donald E. Smith 《Journal of Electroanalytical Chemistry》1978,90(3):381-388
Rate laws presented to date for analysis of a.c. cyclic voltammetric data have invoked the so-called “slow scan limit approximation” which requires that ΔEω ? v, where Δ E and ω are the applied a.c. potential amplitude and angular frequency, respectively, and v is the d.c. potential scan rate. To provide a more useful guideline for the experimentalist than this qualitative condition, a pure digital simulation approach has been used to compute the a.c. cyclic time domain waveform for a reversible process under small amplitude conditions. The a.c. content of this waveform is extracted by the digital FFT alogirthm. Results of this study are presented here. Among the conclusions reached are more quantitative limitations for the slow scan limit rate laws describing the fundamental and second harmonic responses (approximately 128 a.c. cycles/d.c. cyclic sweep and 512 a.c. cycles/d.c. cyclic sweep, respectively) and an interesting prediction that the latter limitations can be relaxed further by a current waveform subtraction strategy, to as low as about 16 a.c. cycles/d.c. cyclic sweep for the fundamental and second harmonics. The cycles/sweep values assume one triangular wave potential scan of ±200 mV is encompassed. 相似文献
82.
Excess enthalpies and excess volumes were determined at 298.15 K for: dimethoxymethane+heptane, diethoxymethane+heptane, 1,1-dimethoxyethane+heptane, 1,1-diethoxyethane+heptane, 2,2-dimethoxypropane+heptane and 1,1-diethoxypropane+heptane. 相似文献
83.
Work which has recently appeared on the structures of Celastraceae alkaloids in addition to physical and chemical evidence adduced with respect to cathidine D permits formulation of structure 7a or 7b for this component of Catha edulis. 相似文献
84.
Tomás Moya-Pizarro Roger Salmon Léopold Fournes Gilles Le Flem Barbara Wanklyn Paul Hagenmuller 《Journal of solid state chemistry》1984,53(3):387-397
Single crystals of the high-temperature form of NaFeP2O7 have been grown by a flux technique. II-NaFeP2O7 crystallizes in the monoclinic space group with lattice parameters: a = 7.298(2) Å, b = 7.874(2) Å, c = 9.536(3) Å, β = 111.85(2)°. The structure refined from 1481 independent reflections leads to R = 0.044 and confirms the work previously published by M. Gabelica-Robert, M. Goreaud, P. Labbe, and B. Raveau (J. Solid State Chem.45, 389, 1982). Magnetic Mössbauer resonance studies have shown the existence of antiferromagnetic ordering with a weak ferromagnetic component below 30 K. The FeO bond is markedly ionic in character due to the highly polarizing power of phosphorus in tetrahedral site. 相似文献
85.
The products of hydrolysis of C60F48 (which contains six isolated double bonds) by either aq. acetone or aq. THF show that no more than twelve fluorines are replaced through nucleophilic substitution, as predicted by the recently identified S(N)2' mechanism. Subsequent HF elimination gives fragments containing a maximum of six epoxide oxygens. Calculated heats of formation of models for the possible initial hydroxy derivatives indicate that there is little energetic discrimination between them, so that a complex mixture is likely to be formed. Overall the data show that hydrolytic degradation of fluorofullerenes is less severe than believed previously, requires a specific motif, and explains the low susceptibility of C60F18 towards hydrolysis and the high stability of trannulenes. 相似文献
86.
Barnes JH Schilling GD Stone SF Sperline RP Denton MB Young ET Barinaga CJ Koppenaal DW Hieftje GM 《Analytical and bioanalytical chemistry》2004,380(2):227-234
The use of a separation step, such as liquid chromatography, prior to inductively coupled plasma mass spectrometry (ICP–MS) has become a common tool for highly selective and sensitive analyses. This type of coupling has several benefits including the ability to perform speciation analysis or to remove isobaric interferences. Several limitations of conventional instruments result from the necessity to scan or pulse the mass spectrometer to obtain a complete mass spectrum. When the instrument is operated in such a non-continuous manner, duty cycle is reduced, resulting in poorer absolute limits of detection. Additionally, with scanning instruments, spectral skew can be introduced into the measurement, limiting quantitation accuracy. To address these shortcomings, a high-performance liquid chromatograph has been coupled to an ICP–MS capable of continuous sample introduction and simultaneous multimass detection. These features have been realized with a novel detector array, the focal plane camera. Instrument performance has been tested for both speciation analysis and for the elimination of isobaric interferences. Absolute limits of detection in the sub picogram to tens of picograms regime are obtainable, while the added mass dimension introduced by simultaneous detection dramatically increases chromatographic peak capacity. 相似文献
87.
Two novel polysiloxane-based polymers, which contain metal complexes, have been prepared. To prepare the Co(TACN)3+(2) (TACN= 1,4,7-triazacyclononane) based polymers, an orthoamide derivative of TACN was added to bromobutane-substituted methylpolysiloxane and hydrolyzed with base. Co(II) was then coordinated to the TACN, followed by cobalt oxidation to make polymer A or followed by N-octyl TACN coordination and cobalt oxidation to make polymer B. In both materials, TACN forms thermodynamically and kinetically stable Co(TACN)3+(2) complexes in which the six coordination sites of the Co(III) are occupied by nitrogens from the TACN. The polymers were coated on fused-silica capillary columns and spherical silica particles, which were used for capillary electrophoresis and capillary electrochromatography, respectively. The open and packed columns showed strong and pH-independent reversed electroosmotic flow. 相似文献
88.
Beaudoin E Gourier C Hiorns RC François J 《Journal of colloid and interface science》2002,251(2):398-408
Hydrophobically modified poly(ethylene oxide), HMPEO, was studied in concentrated salt solutions. The influence of salts was compared to the effect of temperature on poly(ethylene oxide), PEO. As expected, the addition of monovalent cations (Na(+), K(+)) has the same effect as an increase in temperature in agreement with the thermodynamic properties of PEO: a decrease in solubility, micelle size, and viscosity was observed. Moreover, the intensity of neutron scattering peaks (characteristic of the semi-dilute solutions of these associative polymers) increases due to the collapse of PEO coronae in micelles. Very peculiar behavior was observed in the presence of divalent cations (Ca(2+), Mg(2+)): larger micelle aggregates and higher viscosities, relaxation times, and activation energies were observed by dynamic rheology. This behavior is attributed to interactions between divalent cations and oxygen in PEO backbones close to the micelle core, which may reinforce intermicellar bridges. 相似文献
89.
Schott D Sleigh CJ Lowe JP Duckett SB Mawby RJ Partridge MG 《Inorganic chemistry》2002,41(11):2960-2970
NMR studies reveal that complexes Ru(CO)(2)(H)(2)L(2) (L = PMe(3), PMe(2)Ph, and AsMe(2)Ph) can have three geometries, ccc, cct-L, and cct-CO, with equilibrium ratios that are highly dependent on the electronic properties of L; the cct-L form is favored, because the sigma-only hydride donor is located trans to CO rather than L. When L = PMe(3), the ccc form is only visible when p-H(2) is used to amplify its spectral features. In contrast, when L = AsMe(2)Ph, the ccc and cct-L forms are present in similar quantities and, hence, must have similar free energies; for this complex, however, the cct-CO isomer is also detectable. These complexes undergo a number of dynamic processes. For L(2) = dppe, an interchange of the hydride positions within the ccc form is shown to be accompanied by synchronized CO exchange and interchange of the two phosphorus atoms. This process is believed to involve the formation of a trigonal bipyramidal transition state containing an eta(2)-H(2) ligand; in view of the fact that k(HH)/k(DD) is 1.04 and the synchronized rotation when L(2) = dppe, this transition state must contain little H-H bonding character. Pathways leading to isomer interconversion are suggested to involve related structures containing eta(2)-H(2) ligands. The inverse kinetic isotope effect, k(HH)/k(DD) = 0.5, observed for the reductive elimination of dihydrogen from Ru(CO)(2)(H)(2)dppe suggests that substantial H-H bond formation occurs before the H(2) is actually released from the complex. Evidence for a substantial steric influence on the entropy of activation explains why Ru(CO)(2)(H)(2)dppe undergoes the most rapid hydride exchange. Our studies also indicate that the species [Ru(CO)(2)L(2)], involved in the addition of H(2) to form Ru(CO)(2)(H)(2)L(2), must have singlet electron configurations. 相似文献
90.
Roger L. Snowden 《Tetrahedron letters》1984,25(35):3835-3836
An efficient synthesis of dienediester 3, a key intermediate for drimane-related sesquiterpenes, is described starting from enal 4. 相似文献