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1.
Excess enthalpies (H
E
) for mixtures of cyclohexanone with propan-1-ol. propan-2-ol, butan-1-ol, butan-2-ol and 2-methyl propan-1-ol at 298.15 K
have been measured over the entire composition range. All mixed endothermically with the maximum values ofH
E
occurring at equimole fraction. Comments about the molecular interactions contributing to the excess enthalpies of a cyclic
ketone + an alcohol are made on the basis of these results. 相似文献
2.
3.
We report a set of material characterizations on the nematic mixture Mischung V . With these measurements, as well as previously known results, Mischung V becomes the second nematic liquid crystal possessing a complete set of known physical parameters relevant for electroconvection, enabling quantitative comparison with theoretical predictions to be made. Additionally, we have identified a stable dopant which induces in Mischung V the electrical conductivity necessary for observing the conduction regime of electroconvection. Mischung V is thus validated as a suitable substitute for materials that have traditionally been chosen for these types of experiments. However, Mischung V does not present the same experimental difficulties as traditional materials. 相似文献
4.
Symes MD Surendranath Y Lutterman DA Nocera DG 《Journal of the American Chemical Society》2011,133(14):5174-5177
The oxidation of water to molecular oxygen is a kinetically demanding reaction that requires efficient coupling of proton and electron transfer. The key proton-coupled electron transfer (PCET) event in water oxidation mediated by a cobalt-phosphate-based heterogeneous catalyst is the one-electron, one-proton conversion of Co(III)-OH to Co(IV)-O. We now isolate the kinetics of this PCET step in a molecular Co(4)O(4) cubane model compound. Detailed electrochemical, stopped-flow, and NMR studies of the Co(III)-OH to Co(IV)-O reaction reveal distinct mechanisms for the unidirectional PCET self-exchange reaction and the corresponding bidirectional PCET. A stepwise mechanism, with rate-limiting electron transfer is observed for the bidirectional PCET at an electrode surface and in solution, whereas a concerted proton-electron transfer displaying a moderate KIE (4.3 ± 0.2), is observed for the unidirectional self-exchange reaction. 相似文献
5.
P. Radhakrishnanand D. V. Subba Rao K. V. Surendranath D. Subrahmanyam V. Himabindu 《Chromatographia》2008,68(7-8):669-673
A new and accurate chiral liquid chromatographic method has been developed for the separation and quantification of (S,R,S)-enantiomer (unwanted enantiomer) and (R,R,R)-isomer (key intermediate) of aprepitant in bulk drug and formulation samples of apprepitant. The elution time was approximately 20 min using an immobilized amylose-based chiral stationary phase (Chiralpak-IA). The mobile phase was n-hexane and ethanol (90:10, v/v) and was delivered at a flow rate of 1.0 mL min?1. Detection was carried out with a wavelength set to 220 nm. The resolution factor between enantiomers was found to be greater than five. Limit of detection for both (S,R,S) enantiomer and (R,R,R) isomer of aprepitant was 0.035 µg, and limit of quantification for both (S,R,S) enantiomer and (R,R,R) isomers of aprepitant was 0.1 µg, for a 10 µL injection. The developed method showed excellent linearity (r > 0.999) for both isomers. When the method was applied to bulk drug samples and in pharmaceutical formulations recoveries were obtained ranging from 97.2 to 103.1%. Aprepitant sample solutions were found to be stable when characterized over a period of 48 h. 相似文献
6.
Delafuente DA Kosturko GW Graham PM Harman WH Myers WH Surendranath Y Klet RC Welch KD Trindle CO Sabat M Harman WD 《Journal of the American Chemical Society》2007,129(2):406-416
A series of pyridine complexes are prepared of the general form TpW(NO)(PMe3)(pyr) where pyr is either pyridine or a substituted pyridine. Depending on substitution pattern, the pyridine can be either N- or eta2-coordinated, and the role of the pyridine substituents and metal oxidation state in determining this equilibrium is explored. For eta2-pyridine complexes, the substituent pattern and solubility characteristics also determine the ratio of coordination diastereomers. Rates of both intra- and interfacial linkage isomerizations are explored along with the pyridine rotational barrier. This study is supported by DFT calculations and X-ray data and includes characterization of both eta2-pyridine and eta2-pyridinium complexes. 相似文献
7.
Ravi Kiran Kaja K. V. Surendranath P. Radhakrishnanand J. Satish P. V. V. Satyanarayana 《Chromatographia》2009,69(9-10):1007-1012
A novel, sensitive, stability-indicating gradient RP-LC method has been developed for quantitative analysis of balsalazide disodium and its related impurities both in the bulk drug and in pharmaceutical dosage forms. Efficient chromatographic separation was achieved on a C18 stationary phase with a simple mobile-phase gradient prepared from methanol and phosphate buffer (10 mm potassium dihydrogen orthophosphate monohydrate, adjusted to pH 2.5 by addition of orthophosphoric acid). The mobile-phase flow rate was 1.0 mL min?1. Quantification was achieved by use of ultraviolet detection at 240 nm. Under these conditions resolution of balsalazide disodium from its three potential impurities was greater than 2.0. Regression analysis resulted in a correlation coefficient greater than 0.99 for balsalazide disodium and all three impurities. This method was capable of detecting the three impurities at 0.003% of the test concentration of 0.3 mg mL?1, using an injection volume of 10 μL. Inter-day and intra-day precision for all three impurities and for balsalazide disodium was within 2.0% RSD. Recovery of balsalazide disodium from the bulk drug (99.2–101.5%) and from pharmaceutical dosage forms (99.8–101.3%), and recovery of the three impurities (99.1–102.1%) was consistently good. The test solution was found to be stable in 70:30 (v/v) methanol–water for 48 h. When the drug was subjected to hydrolytic, oxidative, photolytic, and thermal stress, acidic and alkaline hydrolysis and oxidizing conditions led to substantial degradation. The RP-LC method was validated for linearity, accuracy, precision, and robustness. 相似文献
8.
Satheesh Kumar Shetty K. V. Surendranath P. Radhakrishnanand J. Satish Johnson Jogul Upendra Mani Tripathi 《Chromatographia》2009,69(11-12):1189-1199
A new, sensitive, stability indicating gradient RP-LC related substances and assay method has been developed for the quantitative determination of entacapone in bulk drugs. Efficient chromatographic separation was achieved on a C18 stationary phase with simple mobile phase combination of buffer and acetonitrile. Buffer consisted of 0.1% orthophosphoric acid, delivered in a gradient mode and quantitation was carried out using ultraviolet detection at 220 nm with a flow rate of 1.5 mL min?1. In the developed LC method the resolution (R s ) between entacapone and its three potential process impurities were found to be >2.0. Regression analysis showed an r 2 value (correlation coefficient) >0.99 for entacapone and its three potential impurities. This method was capable to detect all three process impurities of entacapone at a level of 0.003% with respect to test concentration of 0.5 mg mL?1 for a 20 μL injection volume. The inter- and intra-day precision values for all three impurities and for entacapone was found to be within 2.0% RSD. The method has shown good and consistent recoveries for entacapone in bulk drugs (99.2–101.5%) and its three impurities (99.5–102.2%). The test solution was found to be stable in diluent for 48 h. The drug substances were subjected to stress conditions of hydrolysis, oxidation, photolysis and thermal degradation. Considerable degradation was found to occur in acid stress, base stress and oxidative conditions. The stressed test solutions were assayed against the qualified working standard of entacapone and the mass balance in each case was close to 99.7% indicating that the developed method was stability-indicating. The developed RP-LC method was validated with respect to linearity, accuracy, precision and robustness. 相似文献
9.
JH Engel Y Surendranath AP Alivisatos 《Journal of the American Chemical Society》2012,134(32):13200-13203
Semiconductor nanocrystal solids are attractive materials for active layers in next-generation optoelectronic devices; however, their efficient implementation has been impeded by the lack of precise control over dopant concentrations. Herein we demonstrate a chemical strategy for the controlled doping of nanocrystal solids under equilibrium conditions. Exposing lead selenide nanocrystal thin films to solutions containing varying proportions of decamethylferrocene and decamethylferrocenium incrementally and reversibly increased the carrier concentration in the solid by 2 orders of magnitude from their native values. This application of redox buffers for controlled doping provides a new method for the precise control of the majority carrier concentration in porous semiconductor thin films. 相似文献
10.
Competition between H and CO for Active Sites Governs Copper‐Mediated Electrosynthesis of Hydrocarbon Fuels
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Dr. Marcel Schreier Dr. Youngmin Yoon Megan N. Jackson Prof. Yogesh Surendranath 《Angewandte Chemie (International ed. in English)》2018,57(32):10221-10225
The dynamics of carbon monoxide on Cu surfaces was investigated during CO reduction, providing insight into the mechanism leading to the formation of hydrogen, methane, and ethylene, the three key products in the electrochemical reduction of CO2. Reaction order experiments were conducted at low temperature in an ethanol medium affording high solubility and surface‐affinity for carbon monoxide. Surprisingly, the methane production rate is suppressed by increasing the pressure of CO, whereas ethylene production remains largely unaffected. The data show that CH4 and H2 production are linked through a common H intermediate and that methane is formed through reactions among adsorbed H and CO, which are in direct competition with each other for surface sites. The data exclude the participation of solution species in rate‐limiting steps, highlighting the importance of increasing surface recombination rates for efficient fuel synthesis. 相似文献