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We chose to understand the cyclic instability and rate instability issues in the promising class of Na+ conversion and alloying anodes with Sb2Se3 as a typical example. We employ a synthetic strategy that ensures efficient rGO (reduced graphene oxide) wrapping over Sb2Se3 material. By utilization of the minimum weight of additive (5 wt.% of rGO), we achieved a commendable performance with a reversible capacity of 550 mAh g−1 at a specific current of 100 mA g−1 and an impressive rate performance with 100 % capacity retention after high current cycling involving a 2 Ag−1 intermediate current step. The electrochemical galvanostatic intermittent titration technique (GITT) has been employed for the first time to draw a rationale between the enhanced performance and the increased mobility in the rGO wrapped composite (Sb2Se3-rGO) compared to bare Sb2Se3. GITT analysis reveals higher Na+ diffusion coefficients (approx. 30 fold higher) in the case of Sb2Se3-rGO as compared to bare Sb2Se3 throughout the operating voltage window. For Sb2Se3-rGO the diffusion coefficients in the range of 8.0×10−15 cm2 s−1 to 2.2×10−12 cm2 s−1 were observed, while in case of bare Sb2Se3 the diffusion coefficients in the range of 1.6×10−15 cm2 s−1 to 9.4×10−15 cm2 s−1 were observed.  相似文献   
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The conformational change induced by the introduction of a ketenedithioacetal moiety at C-4 of 1,7-substituted-1,6-heptadiene-3,5-diones results in favorable spatial relationships between the alkenoyl groups to effect efficient intramolecular cycloadditions: irradiation of bis(alkenoyl)ketenedithioacetals in solution leads to facile and stereospecific intramolecular [2 + 2] photocycloadditions resulting in the formation of substituted bicyclo[3.2.0]heptane-2,4-diones, the observed conformational rigidity of which is attributed to the push-pull character of the ketenedithioacetal group.  相似文献   
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[reaction: see text] Lewis acid-promoted addition of allyltri-n-butylstannane to o-quinonediimines afforded tetrahydroquinoxaline derivatives or allylated amides depending on the nature of the substituent on imine nitrogen.  相似文献   
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Rate coefficients for the reaction of Cl atoms with cycloalkenes have been determined using the relative rate method, at 298 K and atmospheric pressure of N2. Reference molecule was n‐hexane, and the concentrations of the organics were followed by gas chromatographic analysis. Cl atoms were prepared by photolysis of trichloroacetyl chloride at 254 nm. The relative rates of reactions of Cl atoms with cycloalkenes, with respect to n‐hexane, are measured as 1.12 ± 0.38, 1.31 ± 0.14, and 1.69 ± 0.18 for cyclopentene, cyclohexene, and cycloheptene, respectively. Considering the absolute value of the rate coefficient of the reaction of Cl atom with n‐hexane as 3.03 ± 0.06 × 10?10 cm3 molecule?1 s?1, the rate coefficient values for cyclopentene, cyclohexene, and cycloheptene are calculated to be (3.39 ± 1.08) × 10?10, (3.97 ± 0.43) × 10?10, and (5.12 ± 0.55) × 10?10 cm3 molecule?1 s?1, respectively. The experiments for each molecule were repeated six to eight times, and the slopes and the rate coefficients given above are the average values of these measurements, and the quoted error includes 2σ as well as all other uncertainties in the measurement and calculations. The rate coefficient increases linearly with the number of carbon atoms, with an increment per additional CH2 group being (8.7 ± 1.6) × 10?12 cm3 molecule?1 s?1. Chloroketones and chloroalcohols, along with unsaturated ketones and alcohols, were found to be the major products of Cl‐atom‐initiated oxidation of cycloalkenes in the presence of air. The atmospheric implications of these results are discussed, along with a comparison with the reported structure activity relationships. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 42: 98–105, 2010  相似文献   
6.
Electrochemical transformations provide enticing opportunities for programmable, residue-specific peptide modifications. Herein, we harness the potential of amidic side-chains as underutilized handles for late-stage modification through the development of an electroauxiliary-assisted oxidation of glutamine residues within unprotected peptides. Glutamine building blocks bearing electroactive side-chain N,S-acetals are incorporated into peptides using standard Fmoc-SPPS. Anodic oxidation of the electroauxiliary in the presence of diverse alcohol nucleophiles enables the installation of high-value N,O-acetal functionalities. Proof-of-principle for an electrochemical peptide stapling protocol, as well as the functionalization of dynorphin B, an endogenous opioid peptide, demonstrates the applicability of the method to intricate peptide systems. Finally, the site-selective and tunable electrochemical modification of a peptide bearing two discretely oxidizable sites is achieved.  相似文献   
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Journal of Fluorescence - A heterocyclic Schiff base (MPDPI)was synthesized by the condensation reaction of 1-phenylisatin with 4,5-dimethylphenylene diamine. It was characterized by using...  相似文献   
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Benzodiazepinones are privileged scaffolds with activity against multiple therapeutically relevant biological targets. In support of our ongoing studies around allosteric modulators of metabotropic glutamate receptors (mGlus) we required the multigram synthesis of a β-ketoester key intermediate. We report the continuous flow synthesis of tert-butyl 3-(2-cyanopyridin-4-yl)-3-oxopropanoate and its transformation to potent mGlu2/3 negative allosteric modulators (NAMs) in batch mode.  相似文献   
10.
Electrical and optical properties of thermally evaporated air annealed Tetra-Tert-Butyl 2,3 Naphthalocyanine (TTBNc) thin films are studied. From the Arrhenius plot, the thermal activation energy is calculated for intrinsic and extrinsic region. Different hopping conduction parameters are tabulated using the Variable Range Hopping (VRH) model in the low temperature region. The studies on the optical absorption spectra lead to the determination of optical band gap energy and Urbach’s energy of TTBNc thin films. Also the temperature dependence of steepness parameter is explained.  相似文献   
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