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71.
This article presents reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems and regression analyses using recently developed thermodynamic rate equations that contain electrostatic and solvent-solute terms. The isomole fraction plots for these reaction systems are linear, and previous theoretical work has shown that the electrostatic term is negligible for such systems. On the other hand, the reaction rates are dependent upon the cosolvent mole fraction, indicating that the solvent-solute term, which is modeled empirically, is significant. The results of the analyses provide the foundation for a paradigm shift away from the emphasis on electrostatic effects to more tenable explanations of kinetic behavior in solvent systems. 相似文献
72.
Arijit Ghorai Arun Kumar Mandal Susanta Banerjee 《Journal of polymer science. Part A, Polymer chemistry》2020,58(2):263-279
Sulfonated polytriazoles have drawn a great attention as high performance polymers and their good film forming ability. In the present study, a phosphorus containing new diazide monomer namely, bis-[4-(4′-aminophenoxy)phenyl]phenylphosphine was synthesized and accordingly, a series of phosphorus containing sulfonated polytriazoles (PTPBSH-XX) was synthesized by reacting equimolar amount of this diazide monomer (PAZ) in combination with another sulfonated diazide monomer (DSAZ) and a terminal bis-alkyne (BPALK) by the Cu (I) catalyzed azide–alkyne click polymerization. The polymers were characterized by nuclear magnetic resonance (1H, 13C, 31P NMR) and Fourier transform infrared spectroscopic techniques. The sulfonic acid content of the copolymers also determined from the different integral values obtained from the 1H NMR signals. The small-angle X-ray scattering results unfolded the well-separated dispersion of the hydrophilic and hydrophobic domains of the polymers. As a whole, the copolymer membranes displayed sufficient thermal, mechanical, and oxidative stabilities high with high proton conductivity and low water uptake that are essential for proton exchange membrane applications. The copolymers exhibited oxidative stability in the range of 15–24 h and had proton conductivity values were found as high as 38–110 mS cm−1 at 80 °C in completely hydrated condition. Among the all copolytriazoles, PTPBSH-90 (BPALK:DSAZ:PAZ = 100:90:10) having IECW = 2.44 mequiv g−1, showed proton conductivity as high as 119 mS cm−1 at 90 °C with an activation energy of 10.40 kJ mol−1 for the proton conduction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 263–279 相似文献
73.
Dr. Andrew Ballard Dr. Stefania Narduolo Dr. Hiwa O. Ahmed Nathaniel I. Keymer Dr. Nabil Asaad Dr. David A. Cosgrove Dr. Niklaas J. Buurma Dr. Andrew G. Leach 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3661-3687
The two enantiomers of a compound often have profoundly different biological properties and thus their liability to racemisation in aqueous solutions is an important piece of information. The authors reviewed the available data concerning the process of racemisation in vivo, in the presence of biological molecules (e.g., racemase enzymes, serum albumin, cofactors and derivatives) and under purely chemical but aqueous conditions (acid, base and other aqueous systems). Mechanistic studies are described critically in light of reported kinetic data. The types of experimental measurement that can be used to effectively determine rate constants of racemisation in various conditions are discussed and the data they provide is summarised. The proposed origins of enzymatic racemisation are presented and suggest ways to promote the process that are different from processes taking place in bulk water. Experimental and computational studies that provide understanding and quantitative predictions of racemisation risk are also presented. 相似文献
74.
Dr. Shuangyan Wu Dr. Mingchang Zhu Dr. Ying Zhang Prof. Marina Kosinova Prof. Vladimir P. Fedin Prof. Enjun Gao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(14):3137-3144
As a hot topic of global concern, the distinguishing and detecting of antibiotic pollution is crucial owing to its adverse effect on ecosystems and human health stemming from excessive use and poor management. Herein, a water-stable lanthanide coordination polymer sensor (Dy-TCPB) with multiple emitting centers is prepared. The versatile Dy-TCPB can conveniently differentiate various antibiotics, and displays a self-calibration luminescent response to nitrofurazone (NFZ) and furazolidone (FZD). Each antibiotic exhibits notable correlation to a unique combination of the two ligand-to-Dy ion emission intensity ratios, enabling two-dimensional fingerprint recognition. Furthermore, the novel self-calibration sensor demonstrates effective recognition of NFZ and FZD with excellent sensitivity and selectivity, and detection limits as low as 0.0476 and 0.0482 μm for NFZ and FZD, respectively. The synthetic approach for the fabrication of a singular coordination polymer exhibiting multiple emissions provides a promising strategy for the development of facile and effective ratiometric sensors. 相似文献
75.
Dr. Karl P. J. Gustafson Arnar Guðmundsson Dr. Éva G. Bajnóczi Dr. Ning Yuan Prof. Xiaodong Zou Prof. Ingmar Persson Prof. Jan-E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3411-3419
The activation process of a known Ru-catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X-ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert-butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1-phenylethanol a fast-dynamic equilibrium was observed. 相似文献
76.
Dr. Lidia A. Maslovskaya Dr. Andrei I. Savchenko Prof. Elizabeth H. Krenske Dr. Sharon Chow Tina Holt Dr. Victoria A. Gordon Dr. Paul W. Reddell Carly J. Pierce Prof. Peter G. Parsons Prof. Glen M. Boyle Prof. Andrei G. Kutateladze Prof. Craig M. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11862-11867
Structurally unique halimanes EBC-232 and EBC-323, isolated from the Australian rainforest plant Croton insularis, proved considerably difficult to elucidate. The two diastereomers, which consist an unusual oxo-6,7-spiro ring system fused to a dihydrofuran, were solved by unification and consultation of five in silico NMR elucidation and prediction methods [i.e., ACDLabs, olefin strain energy (OSE), DP4, DU8+ and TD DFT CD]. Structure elucidation challenges of this nature are prime test case examples for empowering future AI learning in structure elucidation. 相似文献
77.
Prof. Dr. Shina Caroline Lynn Kamerlin Prof. Dr. Pernilla Wittung-Stafshede 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(38):8319-8323
Despite slow ongoing progress in increasing the representation of women in academia, women remain significantly under-represented at senior levels, in particular in the natural sciences and engineering. Not infrequently, this is downplayed by bringing forth arguments such as inherent biological differences between genders, that current policies are adequate to address the issue, or by deflecting this as being “not my problem” among other examples. In this piece we present scientific evidence that counters these claims, as well as a best-practice example, Genie, from Chalmers University of Technology, where one of the authors is currently employed. We also highlight particular challenges caused by the current COVID-19 pandemic. Finally, we conclude by proposing some possible solutions to the situation and emphasize that we need to all do our part, to ensure that the next generation of academics experience a more diverse, inclusive, and equitable working environment. 相似文献
78.
79.
80.
The looming global energy crisis and ever-increasing energy demands have catalyzed the development of renewable energy storage systems. In this regard, supercapacitors (SCs) have attracted widespread attention because of their advantageous attributes such as high power density, excellent cycle stability, and environmental friendliness. However, SCs exhibit low energy density and it is important to optimize electrode materials to improve the overall performance of these devices. Among the various electrode materials available, spinel nickel cobaltate (NiCo2O4) is particularly interesting because of its excellent theoretical capacitance. Based on the understanding that the performances of the electrode materials strongly depend on their morphologies and structures, in this study, we successfully synthesized NiCo2O4 nanosheets on Ni foam via a simple hydrothermal route followed by calcination. The structures and morphologies of the as-synthesized products were characterized by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller (BET) surface area analysis, and the results showed that they were uniformly distributed on the Ni foam support. The surface chemical states of the elements in the samples were identified by X-ray photoelectron spectroscopy. The as-synthesized NiCo2O4 products were then tested as cathode materials for supercapacitors in a traditional three-electrode system. The electrochemical performances of the NiCo2O4 electrode materials were studied and the area capacitance was found to be 1.26 C·cm-2 at a current density of 1 mA·cm-2. Furthermore, outstanding cycling stability with 97.6% retention of the initial discharge capacitance after 10000 cycles and excellent rate performance (67.5% capacitance retention with the current density from 1 to 14 mA·cm-2) were achieved. It was found that the Ni foam supporting the NiCo2O4 nanosheets increased the conductivity of the electrode materials. However, it is worth noting that the contribution of nickel foam to the areal capacitance of the electrode materials was almost zero during the charge and discharge processes. To further investigate the practical application of the as-synthesized NiCo2O4 nanosheets-based electrode, a device was assembled with the as-prepared samples as the positive electrode and active carbon (AC) as the negative electrode. The assembled supercapacitor showed energy densities of 0.14 and 0.09 Wh·cm-3 at 1.56 and 4.5 W·cm-3, respectively. Furthermore, it was able to maintain 95% of its initial specific capacitance after 10000 cycles. The excellent electrochemical performance of the NiCo2O4 nanosheets could be ascribed to their unique spatial structure composed of interconnected ultrathin nanosheets, which facilitated electron transportation and ion penetration, suggesting their potential applications as electrode materials for high performance supercapacitors. The present synthetic route can be extended to other ternary transition metal oxides/sulfides for future energy storage devices and systems. 相似文献