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201.
Substituent effects on the ring‐opening mechanism of gem‐dibromospiropentanes to related allenes: a theoretical study 下载免费PDF全文
Density functional theory computations at B3LYP and X3LYP levels were performed for ring openings of substituted gem‐dibromospiropentanes (R = ―H, ―Cl, ―Br, ―CH3, ―SiH3, ―OH, ―OCH3, ―CF3, ―BF2, and ―SH) to related allenes. The conversion of spiropentanoids 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h , 5i , 5j to the corresponding allenes 7a , 7b , 7c , 7d , 7e , 7f , 7g , 7h , 7i , 7j can proceed in both concerted and stepwise mechanism except for R = ―H. Both ring‐opening mechanisms have similar activation energy barriers to open the spiropentanylidene ring and generate the structure of allene at all theoretical levels used herein. Generally the π electron‐donating group (―OH or ―SH) decreases the activation barrier for the follow‐up reaction of 1‐bromo‐1‐lithiospiropentanoid and free spiropentanylidene. Hence, both bearing electron‐donating substituents are more reactive than those with electron‐withdrawing group, and the first one to open the ring to the LiBr–allene complex does so more readily than the second. The sEDA index used to measure sigma‐electron excess/deficiency of the cyclopropylidene ring is mutually correlated for the studied systems. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
202.
Reactivities of mixed organozinc and mixed organocopper reagents. Part 13 Kinetic study for phosphine‐catalyzed acylation of alkylarylzincs and effect of residual group on the transfer rate of alkyl group 下载免费PDF全文
Özgen Ömür Pekel 《Journal of Physical Organic Chemistry》2016,29(4):190-195
Kinetics of reactions of di‐n‐butylzinc, n‐Bu2Zn, and mixed n‐butyl(substituted phenyl)zinc reagents and n‐Bu(functional group (FG)?C6H4)Zn with benzoyl chloride in the presence of tri‐n‐butylphosphine have been investigated. Reaction rates of transferable n‐butyl group have been determined in tetrahydrofuran at 0 °C to compare the transfer rate of n‐butyl group in homo and mixed diorganozincs. Rate law is consistent with a third‐order reaction, which is first order in diorganozinc, benzoyl chloride, and n‐Bu3P, and a mechanism was proposed. The lower reaction rate of n‐BuPhZn than that of n‐Bu2Zn and negative reaction constant in Hammett plot are in accordance with the carbanionic charge of transferable n‐butyl group in the acylation reaction. These findings support the hypothesis that the reaction rate of transferable group, RT, changes depending upon the residual group, RR, in RRRTZn reagents. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
203.
Multi‐crystalline silicon solar cells with metal‐assisted nano‐texturing using HNO3 as hole injection agent 下载免费PDF全文
In this study, metal‐assisted etching (MAE) with nitric acid (HNO3) as a hole injecting agent has been employed to texture multi‐crystalline silicon wafers. It was previously proven that addition of HNO3 enabled control of surface texturing so as to form nano‐cone shaped structures rather than nanowires. The process parameters optimized for optically efficient texturing have been applied to multi‐crystalline wafers. Fabrication of p‐type Al:BSF cells have been carried out on textured samples with thermal SiO2/PECVD‐SiNx stack passivation and screen printed metallization. Firing process has been optimized in order to obtain the best contact formation. Finally, jsc enhancement of 0.9 mA/cm2 and 0.6% absolute increase in the efficiency have been achieved. This proves that the optimized MAE texture process can be successfully used in multi‐crystalline wafer texturing with standard passivation methods.
204.
Oleg Lebedev Hans Peter Nilles Stuart Raby Saúl Ramos-Sánchez Michael Ratz Patrick K.S. Vaudrevange Akın Wingerter 《Physics letters. [Part B]》2007
We explore a “fertile patch” of the heterotic landscape based on a Z6-II orbifold with SO(10) and E6 local GUT structures. We search for models allowing for the exact MSSM spectrum. Our result is that of order 100 out of a total 3×104 inequivalent models satisfy this requirement. 相似文献
205.
Ayten Behçet Aydın Aktaş Yetkin Gök Rüya Kaya Parham Taslimi İlhami Gülçin 《Journal of heterocyclic chemistry》2021,58(2):603-611
Herein, novel silver-based N-heterocyclic carbene (NHC) complexes bearing 2-(4-hydroxyphenyl)ethyl group were synthesized. Novel Ag(I)NHC complexes were synthesized from the 2-(4-hydroxyphenyl)ethyl-substituted benzimidazolium salts and silver oxide via in situ deprotonation method. The successful formation of all Ag(I)NHC complexes was proved by using 1H NMR, 13C NMR, FTIR spectroscopy, and elemental analysis techniques. In addition, their inhibitory effects have been investigated of these substances on acetylcholinesterase (AChE), α-glycosidase (α-Gly), human carbonic anhydrase I (hCA I), and human carbonic anhydrase II (hCA II) enzymes. It has been seen that all compounds have a better ability to inhibit compared with existing tried inhibitors. Among these, the best inhibitor against AChE enzyme is 1g (Ki : 9.54 ± 0.98 μM and IC50 : 17.40), and against α-Gly, 1c showed the highest effect (Ki 3.09 ± 0.36 μM and IC50 7.91). The best inhibitor against hCA I and hCA II enzymes are 1c and 1g compounds. For hCA I and hCA II, IC50 values were calculated as 17.85 and 9.06 μM and Ki values were measured as 5.45 ± 2.02 and 8.99 ± 2.02 μM, respectively. 相似文献
206.
Avcıbaşı Uğur Türkyarar Taner Karadağ Ayşegül Bakan Buket Yavaşoğlu Nefise Ülkü Karabay Kuşat Kevser Akgöl Sinan Gülcemal Derya Tekin Volkan Müftüler Fazilet Zümrüt Biber Topal Gökcen Parlak Yasemin Gümüşer Fikriye Gül 《Journal of Radioanalytical and Nuclear Chemistry》2021,329(2):511-525
Journal of Radioanalytical and Nuclear Chemistry - The aim of this study is the synthesis of a novel 99mTc-labeld graft polymer and the biological evaluation of its in vitro and in vivo properties.... 相似文献
207.
Kaloğlu Murat Kaloğlu Nazan Özdemir Namık Özdemir İsmail 《Research on Chemical Intermediates》2021,47(7):2821-2843
Research on Chemical Intermediates - N-Heterocyclic carbene (NHC)-linked PEPPSI-type palladium complexes have recently been used in the direct C-H bond arylation of heteroarenes. However, in most... 相似文献
208.
Stefan Dieckhöfer Dr. Denis Öhl João R. C. Junqueira Thomas Quast Prof. Dr. Thomas Turek Prof. Dr. Wolfgang Schuhmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):5906-5912
Discerning the influence of electrochemical reactions on the electrode microenvironment is an unavoidable topic for electrochemical reactions that involve the production of OH− and the consumption of water. That is particularly true for the carbon dioxide reduction reaction (CO2RR), which together with the competing hydrogen evolution reaction (HER) exert changes in the local OH− and H2O activity that in turn can possibly affect activity, stability, and selectivity of the CO2RR. We determine the local OH− and H2O activity in close proximity to a CO2-converting Ag-based gas diffusion electrode (GDE) with product analysis using gas chromatography. A Pt nanosensor is positioned in the vicinity of the working GDE using shear-force-based scanning electrochemical microscopy (SECM) approach curves, which allows monitoring changes invoked by reactions proceeding within an otherwise inaccessible porous GDE by potentiodynamic measurements at the Pt-tip nanosensor. We show that high turnover HER/CO2RR at a GDE lead to modulations of the alkalinity of the local electrolyte, that resemble a 16 m KOH solution, variations that are in turn linked to the reaction selectivity. 相似文献
209.
A q‐ary code of length n, size M, and minimum distance d is called an code. An code with is said to be maximum distance separable (MDS). Here one‐error‐correcting () MDS codes are classified for small alphabets. In particular, it is shown that there are unique (5, 53, 3)5 and (5, 73, 3)7 codes and equivalence classes of (5, 83, 3)8 codes. The codes are equivalent to certain pairs of mutually orthogonal Latin cubes of order q, called Graeco‐Latin cubes. 相似文献
210.
Synergistic Effect of Lithium Perchlorate and Sodium Hydroxide in the Preparation of Electrochemically Treated Pencil Graphite Electrodes for Selective and Sensitive Bisphenol A Detection in Water Samples 下载免费PDF全文
Ali Özcan 《Electroanalysis》2014,26(7):1631-1639
In this study, pencil graphite electrodes were activated electrochemically in the presence of different supporting electrolytes and used for the selective and sensitive determination of bisphenol A (BPA) in water samples. Synergistic effects of both LiClO4 and NaOH supporting electrolytes on the performance of the electrochemically treated pencil graphite electrode (ETPGE) were demonstrated in the oxidation of BPA. The electrochemical behavior of BPA on the ETPGE showed two irreversible oxidation peaks at 0.744 V and 0.877 V (vs. SCE). The detection limit was determined to be 3.1 nM. This single‐use electrode is a very promising candidate to overcome the passivation problems arising from the oxidation of BPA. The analytical application of the ETPGE was performed in tap and river water samples. 相似文献