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71.
Evan S. O'Brien Brian Fuglestad Henry J. Lessen Matthew A. Stetz Danny W. Lin Bryan S. Marques Kushol Gupta Karen G. Fleming A. Joshua Wand 《Angewandte Chemie (International ed. in English)》2020,59(27):11108-11114
The internal motions of integral membrane proteins have largely eluded comprehensive experimental characterization. Here the fast side‐chain dynamics of the α‐helical sensory rhodopsin II and the β‐barrel outer membrane protein W have been investigated in lipid bilayers and detergent micelles by solution NMR relaxation techniques. Despite their differing topologies, both proteins have a similar distribution of methyl‐bearing side‐chain motion that is largely independent of membrane mimetic. The methyl‐bearing side chains of both proteins are, on average, more dynamic in the ps–ns timescale than any soluble protein characterized to date. Accordingly, both proteins retain an extraordinary residual conformational entropy in the folded state, which provides a counterbalance to the absence of the hydrophobic effect. Furthermore, the high conformational entropy could greatly influence the thermodynamics underlying membrane‐protein functions, including ligand binding, allostery, and signaling. 相似文献
72.
Rafael M. de Almeida Victoria C. Ferrari Dr. Juliana dos S. Souza Dr. Flavio L. Souza Wendel A. Alves 《Chemphyschem》2020,21(6):476-483
Herein, a detailed investigation of the surface modification of a zinc oxide (ZnO) nanorod electrode with FeOOH nanoparticles dispersed in glycine was conducted to improve the water oxidation reaction assisted by sunlight. The results were systematically analysed in terms of the general parameters (light absorption, charge separation, and surface for catalysis) that govern the photocurrent density response of metal oxide as photoanode in a photoelectrochemical (PEC) cell. ZnO electrodes surface were modified with different concentration of FeOOH nanoparticles using the spin-coating deposition method, and it was found that 6-layer deposition of glycine-FeOOH nanoparticles is the optimum condition. The glycine plays an important role decreasing the agglomeration of FeOOH nanoparticles over the ZnO electrode surface and increasing the overall performance. Comparing bare ZnO electrodes with the ones modified with glycine-FeOOH nanoparticles an enhanced photocurrent density can be observed from 0.27 to 0.57 mA/cm2 at 1.23 VRHE under sunlight irradiation. The impedance spectroscopy data aid us to conclude that the higher photocurrent density is an effect associated with more efficient surface for chemical reaction instead of electronic improvement. Nevertheless, the charge separation efficiency remains low for this system. The present discovery shows that the combination of glycine-FeOOH nanoparticle is suitable and environmentally-friend cocatalyst to enhance the ZnO nanorod electrode activity for the oxygen evolution reaction assisted by sunlight irradiation. 相似文献
73.
Dr. Juliana Arriel Torres Dr. Gelson T. S. T. Da Silva Dr. Fernando Barbosa de Freitas Silva Dr. Caue Ribeiro 《Chemphyschem》2020,21(21):2392-2396
Tin dioxide (SnO2) has intrinsic characteristics that do not favor its photocatalytic activity. However, we evidenced that surface modification can positively influence its performance for CO2 photoreduction in the gas phase. The hydroxylation of the SnO2 surface played a role in the CO2 affinity decreasing its reduction potential. The results showed that a certain selectivity for methane (CH4), carbon monoxide (CO), and ethylene (C2H4) is related to different SnO2 hydrothermal annealing. The best performance was seen for SnO2 annealed at 150 °C, with a production of 20.4 μmol g−1 for CH4 and 16.45 μmol g−1 for CO, while for SnO2 at 200 °C the system produced more C2H4, probably due to a decrease of surface −OH groups. 相似文献
74.
Ana Ediléia Barbosa Pereira Leal Ana Paula de Oliveira Raira Feitosa dos Santos Juliana Mikaelly Dias Soares Erica Martins de Lavor Michelle Cruz Pontes 《Natural product research》2020,34(7):995-1001
AbstractEthanol extracts of different parts of Passiflora cincinnata were obtained by maceration. The total phenolic and flavonoid contents were evaluated. The antioxidant activities were determined by β-carotene-linoleic acid bleaching test, 2,2-diphenyl-1-picrylhydrazil (DPPH), and 2,2’-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) radical scavenging. The crude ethanol stem extract showed the highest amount of total polyphenols (45.53?mg gallic acid equivalent/g) while the highest total flavonoid contents (1.42?mg of quercetin equivalent/g) were observed in the leaf extract. The lowest IC50 (25.65?μg/ml) by the DPPH method was observed for the stem extract. The ABTS method showed a significant antioxidant activity for all investigated extracts. The secondary metabolite composition of ethanol extracts was assessed by HPLC-DAD-MS/MS analysis, leading to the identification of fourteen secondary metabolites in P. cincinnata extracts. These results showed the potentiality of this species as a source of phenolic compounds and antioxidants. 相似文献
75.
Pradeep R. Varadwaj Arpita Varadwaj Helder M. Marques Koichi Yamashita 《Molecules (Basel, Switzerland)》2022,27(5)
The phosphorus bond in chemical systems, which is an inter- or intramolecular noncovalent interaction, occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a covalently or coordinately bonded phosphorus atom in a molecular entity and a nucleophile in another, or the same, molecular entity. It is the second member of the family of pnictogen bonds, formed by the second member of the pnictogen family of the periodic table. In this overview, we provide the reader with a snapshot of the nature, and possible occurrences, of phosphorus-centered pnictogen bonding in illustrative chemical crystal systems drawn from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases, some of which date back to the latter part of the last century. The illustrative systems discussed are expected to assist as a guide to researchers in rationalizing phosphorus-centered pnictogen bonding in the rational design of molecular complexes, crystals, and materials and their subsequent characterization. 相似文献
76.
A. L. Stepanov C. Marques E. Alves R. C. da Silva M. R. Silva R. A. Ganeev A. I. Ryasnyansky T. Usmanov 《Technical Physics》2006,51(11):1474-1481
Single-crystal Al2O3(0001) and Al2O3(1120) substrates are implanted by 160-keV Au+ ions with doses from 1015 to 1017 cm?2. Some of the implanted samples are air-annealed at 800–1200°C. The properties of the synthesized composite layers are studied by Rutherford backscattering and linear optical reflection measurements, and their nonlinear optical characteristics are examined by RZ-scanning using a picosecond Nd: YAG laser operating at a wavelength of 1064 nm. The Rutherford backscattering spectra indicate that the implanted impurity concentrates near the surface of the Al2O3. The formation of gold nanoparticles in the Al2O3 can be judged from the characteristic optical plasmon resonance band in the reflectance spectra of the samples irradiated to a dose higher than 6.0 × 1016 cm?2. The synthesized particles are shown to be responsible for nonlinear optical refraction in the samples. The nonlinear refractive index, n 2, and the real part of the third-order susceptibility, Rex(3), of the composite layers are determined. 相似文献
77.
Bouhali Nesrine Azzam-Laouir Dalila Monteiro Marques Manuel D. P. 《Journal of Optimization Theory and Applications》2022,194(1):59-91
Journal of Optimization Theory and Applications - We consider a control problem in a finite-dimensional setting, which consists in finding a minimizer for a standard functional defined by way of... 相似文献
78.
Ederley Vélez Jairo Quijano Rafael Notario Elizabeth Pabón Juliana Murillo Julieth Leal Edilma Zapata Gustavo Alarcón 《Journal of Physical Organic Chemistry》2009,22(10):971-977
This paper reports a theoretical study, at the B3LYP/6–31 + G(d,p) and M05‐2X/6–31G + (d,p) levels, on the thermal decomposition of menthyl benzoate (2‐isopropyl‐5‐methylcyclohexyl benzoate). It undergoes a unimolecular first‐order elimination to give 3‐menthene (1‐isopropyl‐4‐methylcyclohexene), 2‐menthene (3‐isopropyl‐6‐methylcyclohexene), and benzoic acid. We studied two possible mechanisms trying to explain the formation of 2‐ and 3‐menthene, via six‐membered or four‐membered cyclic transition states. Rate constants were calculated at two temperatures, 587.1 and 598.6 K, and they agree well with the experimentally determined values. We verify that 3‐menthene is the product mainly formed at both temperatures. The progress of the reactions has been followed by means of the Wiberg bond indices. Intrinsic reaction coordinate (IRC) calculations have been carried out to verify that the localized transition state structures connect with the reactants and products and also to verify that the parent compound, menthyl benzoate, is taking the cis‐configuration needed in the reaction. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
79.
M. Amélia Santos Sérgio M. Marques Sílvia Chaves 《Coordination chemistry reviews》2012,256(1-2):240-259
Hydroxypyridinones (HPs) are a family of N-heterocyclic core chelators which, based on their specific metal-coordination, easy manipulation/derivatization and biocompatibility, have been an attractive target for the development of new pharmaceutical drugs with manifold uses. Herein we describe the most recent advances reported in the literature on HPs, with a special focus on the metal chelating properties of the 3-hydroxy-4-pyridinone (3,4-HP) derivatives, and the different approaches used to functionalize these chelators to improve their biological properties, namely in terms of bioavailability and specific bio-targeting abilities. Representative examples of HPs are included, mostly for applications as chelating drugs for sequestration or passivation of metal overload or deregulated biometals, but also as metallodrugs for potential diagnostic/therapeutic purposes. These examples are discussed in terms of the chelating properties and structure–activity relationships. 相似文献
80.
Dr. Flávio Figueira Igor Marques Dr. Andreia S. F. Farinha Prof. Dr. Augusto C. Tomé Prof. Dr. José A. S. Cavaleiro Prof. Dr. Artur M. S. Silva Prof. Dr. Jonathan Sessler Prof. Dr. Vítor Félix Prof. Dr. João P. C. Tomé 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14349-14355
A novel sapphyrin derivative was obtained from the reaction between a free‐base sapphyrin and dimethyl acetylenedicarboxylate (DMAD). The formation of the new compound involved a double aza‐Michael addition of two pyrrolic NH groups to a DMAD molecule, with the formation of a disubstituted ethano bridge. The NMR spectral data reveal a product with an unsymmetrical structure; DFT calculations provided support for a structure in which the ethano bridge links two adjacent pyrrole units. The present study provides a seemingly unprecedented example of an N,N′‐dinucleophile reacting with DMAD to form a heterocyclic compound in which the two N‐atoms are linked to the two sp3 carbon atoms derived from a substituted acetylene. 相似文献