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71.
Amanda C. Garcia Thomas Touzalin Celine Nieuwland Nickson Perini Marc T. M. Koper 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(37):13133-13137
Herein, the effect of the alkali cation (Li+, Na+, K+, and Cs+) in alkaline electrolytes with and without Fe impurities is investigated for enhancing the activity of nickel oxyhydroxide (NiOOH) for the oxygen evolution reaction (OER). Cyclic voltammograms show that Fe impurities have a significant catalytic effect on OER activity; however, both under purified and unpurified conditions, the trend in OER activity is Cs+ > Na+ > K+ > Li+, suggesting an intrinsic cation effect of the OER activity on Fe‐free Ni oxyhydroxide. In situ surface enhanced Raman spectroscopy (SERS), shows this cation dependence is related to the formation of superoxo OER intermediate (NiOO?). The electrochemically active surface area, evaluated by electrochemical impedance spectroscopy (EIS), is not influenced significantly by the cation. We postulate that the cations interact with the Ni?OO? species leading to the formation of NiOO??M+ species that is stabilized better by bigger cations (Cs+). This species would then act as the precursor to O2 evolution, explaining the higher activity. 相似文献
72.
Haraguchi SK Silva AA Vidotti GJ dos Santos PV Garcia FP Pedroso RB Nakamura CV de Oliveira CM da Silva CC 《Molecules (Basel, Switzerland)》2011,16(2):1166-1180
A series of new thiosemicarbazones derived from natural diterpene kaurenoic acid were synthesized and tested against the epimastigote forms of Trypanosoma cruzi to evaluate their antitrypanosomal potential. Seven of the synthesized thiosemicarbazones were more active than kaurenoic acid with IC?? values between 2-24.0 mM. The o-nitro-benzaldehyde-thiosemicarbazone derivative was the most active compound with IC?? of 2.0 mM. The results show that the structural modifications accomplished enhanced the antitrypanosomal activity of these compounds. Besides, the thiocyanate, thiosemicarbazide and the p- methyl, p-methoxy, p-dimethylamine, m-nitro and o-chlorobenzaldehyde-thiosemicarbazone derivatives displayed lower toxicity for LLMCK? cells than kaurenoic acid, exhibing an IC?? of 59.5 mM. 相似文献
73.
A. B. Garcia E. R. Galán J. A. S. Blázquez C. V. Calahorro 《Journal of Thermal Analysis and Calorimetry》1986,31(2):247-251
The thermal behaviour of some 2-benzylamino-2-deoxyheptonic acids obtained from 2-benzylamino-2-deoxy-D-glycero-L-gluco, 2-benzylamino-2-deoxy-D-glycero-D-ido and 2-benzylamino-2-deoxy-D-glycero-D-taloheptononitriles (reported) previously has been studied in air (static atmosphere) and N2 (dynamic atmosphere, flow rate 200 ml/min).
Zusammenfassung Das thermische Verhalten einiger aus 2-Benzylamino-2-desoxy-D-glycero-L-gluco-, 2-Benzylamino-2-desoxy-D-glycero-D-ido und 2-Benzylamino-2-desoxy-D-glycero-D-talo-heplononitril (kürzlich beschrieben) erhaltenen 2-Benzylamino-2-desoxy-heptonsäuren wurde ín Luft (statische Atmosphäre) und N2 (dynamische Atmosphäre, Strömungsgeschwindigkeit 200 ml/min) untersucht.
( 200 /) 2--2- , 2--2---uepo-L, 2-2- ---- 2-2--- -- 2--2----ma .相似文献
74.
J. M. Garcia de la Vega B. Miguel E. San Fabian 《International journal of quantum chemistry》1997,61(3):533-540
Density functional (DF) calculations of the tetrachloromethane cation and its most important competitive process, the formation of CCl+3, were carried out to explain the possible stability of CCl+4. From results obtained with B-LYP and B-P86 methods, it is possible to produce a slight Jahn-Teller (JT) effect for a Cs planar structure of the cation type CCl2(SINGLE BOND)Cl(SINGLE BOND)Cl+ compatible with the experimental data obtained by electron-spin resonance spectroscopy. A complex of C3v structure CCl+3(SINGLE BOND)Cl which is similar to the previous one found in CF+4 appears when symmetry-broken wave functions are used in HF-LYP and HF-P86 methods. Depending of the DF method employed, either one of the minima [Cs (planar) and C3v] is the most stable and competes with the dissociation of the molecular ion to give CCl+3. The JT stabilization energy is smaller when the JT active coordinates are considered. © 1997 John Wiley & Sons, Inc. 相似文献
75.
Thermolysis of a 2'-[(16)O]-O-benzoyl-[(17)O]-5'-O-(tert-butyldimethylsilyl)-O(2),3'-cyclouridine derivative gave the more stable 3'-[(17)O]-O-benzoyl-[(16)O]- 5'-O-(tert-butyldimethylsilyl)-O(2),2'-cyclouridine isomer, which was converted into 3'-[(17)O]-2'-azido-2'-deoxyuridine by deprotection and nucleophilic ring opening at C2' with lithium azide. The 5'-diphosphate was prepared by nucleophilic displacement of the 5'-O-tosyl group with tris(tetrabutylammonium) hydrogen pyrophosphate. Model reactions gave (16)O and (18)O isotopomers, and base-promoted hydrolysis of an O(2),2'-cyclonucleoside gave stereodefined access to 3'-[(18)O]-1-(beta-D-arabinofuranosyl)uracil. Inactivation of ribonucleoside diphosphate reductase with 2'-azido-2'-deoxynucleotides results in appearance of EPR signals for a nitrogen-centered radical derived from azide, and 3'-[(17)O]-2'-azido-2'-deoxyuridine 5'-diphosphate provides an isotopomer to perturb EPR spectra in a predictable manner. 相似文献
76.
Klimova-Berestneva T. Martinez Garcia M. Meleshonkova N. N. Klimova E. I. 《Russian Journal of General Chemistry》2001,71(10):1626-1631
The asymmetric induction in the synthesis of 3,4,5-trisubstituted 4,5-dihydropyrazoles with ferrocenyl substituents, starting from the E and Z isomers of ,-unsaturated ketones was studied. A high diastereoselectivity was revealed at the 1,2 chiral center chiral center induction, which is independent of the configuration of the starting chalcones. 相似文献
77.
de Oliveira Elcio Cruz de Santana Maia Lúcio Abdala da Costa Lívio Garcia Lourenço Túlio Campos 《Accreditation and quality assurance》2018,23(6):365-369
Accreditation and Quality Assurance - In any commercial transaction, the presence of tolerances from specification limits is essential to ensure that the true value of the property of interest is... 相似文献
78.
This review summarizes the physical approaches towards enhancement of the photocatalytic activity of titanium dioxide by controlling this semiconductor in a certain length scale from subnanometric to submillimetric distances and provides examples in which the photocatalytic activity of TiO2 is not promoted by doping or changes in the chemical composition, but rather by application of physical concepts and spatial structuring of the semiconductor. Thus, encapsulation inside the micropores and cavities of zeolites (about 1 nm) renders small titanium oxide clusters with harnessed photocatalytic activity. On the other hand, nanometric titanium particles can be ordered forming structured periodic mesoporous materials with high specific surface area and well defined porosity. Titiania nanotubes of micrometric length, either independent or forming a membrane, also exhibit unique photocatalytic activity as consequence of the long diffusion length of charge carriers along the nanotube axis. Finally, photonic crystals with an inverse opal structure and the even more powerful concept of photonic sponges can serve to slow down visible light photons inside the material, increasing the effective optical path in such a way that light absorption near the absorption onset of the material is enhanced considerably. All these physical-based approaches have shown their potential in enhancing the photocatalytic activity of titania, paving the way for a new generation of novel structured photocatalysts in which physical and chemical concepts are combined. 相似文献
79.
Weiss NG Hayes MA Garcia AA Ansari RR 《Langmuir : the ACS journal of surfaces and colloids》2011,27(1):494-498
A novel approach to molecular separations is investigated using a technique termed droplet-based isoelectric focusing. Drops are manipulated discretely on a superhydrophobic surface, subjected to low voltages for isoelectric focusing, and split-resulting in a preparative separation. A universal indicator dye demonstrates the generation of stable, reversible pH gradients (3-10) in ampholyte buffers, and these gradients lead to protein focusing within the drop length. Focusing was visually characterized, spectroscopically verified, and assessed quantitatively by noninvasive light scattering measurements. It was found to correlate with a quantitative model based on 1D steady-state theory. This work illustrates that molecular separations can be deployed within a single open drop, and the differential fractions can be separated into new discrete liquid elements. 相似文献
80.