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Chemical Reviews

Damián Alvarez-Paggi, Luciana Hannibal, María A Castro, Santiago Oviedo-Rouco, Veronica Demicheli, Veronica Tórtora, Florencia Tomasina, Rafael Radi, Daniel H Murgida
Cytochrome c (cyt c) is a small soluble heme protein characterized by a relatively flexible structure, particularly in the ferric form, such that it is able to sample a broad conformational space. Depending on the specific conditions, interactions, and cellular localization, different conformations may be stabilized, which differ in structure, redox properties, binding affinities, and enzymatic activity. The primary function is electron shuttling in oxidative phosphorylation, and is exerted by the so-called native cyt c in the intermembrane mitochondrial space of healthy cells...
October 13, 2017: Chemical Reviews
Cedric Belair, Soyeong Sim, Sandra L Wolin
Numerous surveillance pathways sculpt eukaryotic transcriptomes by degrading unneeded, defective, and potentially harmful noncoding RNAs (ncRNAs). Because aberrant and excess ncRNAs are largely degraded by exoribonucleases, a key characteristic of these RNAs is an accessible, protein-free 5' or 3' end. Most exoribonucleases function with cofactors that recognize ncRNAs with accessible 5' or 3' ends and/or increase the availability of these ends. Noncoding RNA surveillance pathways were first described in budding yeast, and there are now high-resolution structures of many components of the yeast pathways and significant mechanistic understanding as to how they function...
October 12, 2017: Chemical Reviews
Alexander P Demchenko, Vladimir I Tomin, Pi-Tai Chou
This paper provides a systematic review and analysis of different phenomena that violate a basic principle, Kasha's rule, when applied to photochemical reactions. In contrast to the classical route of ultrafast transition to the lowest energy excited state and photochemical reaction starting therein, in some cases, these reactions proceed directly from high-energy excited states. Nowadays, this phenomenon can be observed for a number of major types of excited-state reactions: harvesting product via intersystem crossing; photoisomerizations; bond-breaking; and electron, proton, and energy transfers...
October 9, 2017: Chemical Reviews
Guoyou Huang, Fei Li, Xin Zhao, Yufei Ma, Yuhui Li, Min Lin, Guorui Jin, Tian Jian Lu, Guy M Genin, Feng Xu
The cell microenvironment has emerged as a key determinant of cell behavior and function in development, physiology, and pathophysiology. The extracellular matrix (ECM) within the cell microenvironment serves not only as a structural foundation for cells but also as a source of three-dimensional (3D) biochemical and biophysical cues that trigger and regulate cell behaviors. Increasing evidence suggests that the 3D character of the microenvironment is required for development of many critical cell responses observed in vivo, fueling a surge in the development of functional and biomimetic materials for engineering the 3D cell microenvironment...
October 9, 2017: Chemical Reviews
Ming Yan, Yu Kawamata, Phil S Baran
Electrochemistry represents one of the most intimate ways of interacting with molecules. This review discusses advances in synthetic organic electrochemistry since 2000. Enabling methods and synthetic applications are analyzed alongside innate advantages as well as future challenges of electroorganic chemistry.
October 9, 2017: Chemical Reviews
Regina A Baglia, Jan Paulo T Zaragoza, David P Goldberg
Heme proteins utilize the heme cofactor, an iron porphyrin, to perform a diverse range of reactions including dioxygen binding and transport, electron transfer, and oxidation/oxygenations. These reactions share several key metalloporphyrin intermediates, typically derived from dioxygen and its congeners such as hydrogen peroxide. These species are composed of metal-dioxygen, metal-superoxo, metal-peroxo, and metal-oxo adducts. A wide variety of synthetic metalloporphyrinoid complexes have been synthesized to generate and stabilize these intermediates...
October 9, 2017: Chemical Reviews
Yaqing Liu, Ke He, Geng Chen, Wan Ru Leow, Xiaodong Chen
Exciting advancements have been made in the field of flexible electronic devices in the last two decades and will certainly lead to a revolution in peoples' lives in the future. However, because of the poor sustainability of the active materials in complex stress environments, new requirements have been adopted for the construction of flexible devices. Thus, hierarchical architectures in natural materials, which have developed various environment-adapted structures and materials through natural selection, can serve as guides to solve the limitations of materials and engineering techniques...
October 9, 2017: Chemical Reviews
Dmitrii S Bolotin, Nadezhda A Bokach, Marina Ya Demakova, Vadim Yu Kukushkin
This review classifies and summarizes the past 10-15 years of advancements in the field of metal-involving (i.e., metal-mediated and metal-catalyzed) reactions of oximes. These reactions are diverse in nature and have been employed for syntheses of oxime-based metal complexes and cage-compounds, oxime functionalizations, and the preparation of new classes of organic species, in particular, a wide variety of heterocyclic systems spanning small 3-membered ring systems to macroheterocycles. This consideration gives a general outlook of reaction routes, mechanisms, and driving forces and underlines the potential of metal-involving conversions of oxime species for application in various fields of chemistry and draws attention to the emerging putative targets...
October 9, 2017: Chemical Reviews
Katerina Sordakis, Conghui Tang, Lydia K Vogt, Henrik Junge, Paul J Dyson, Matthias Beller, Gábor Laurenczy
Hydrogen gas is a storable form of chemical energy that could complement intermittent renewable energy conversion. One of the main disadvantages of hydrogen gas arises from its low density, and therefore, efficient handling and storage methods are key factors that need to be addressed to realize a hydrogen-based economy. Storage systems based on liquids, in particular, formic acid and alcohols, are highly attractive hydrogen carriers as they can be made from CO2 or other renewable materials, they can be used in stationary power storage units such as hydrogen filling stations, and they can be used directly as transportation fuels...
October 6, 2017: Chemical Reviews
Bin Yuan, Abigail R Koss, Carsten Warneke, Matthew Coggon, Kanako Sekimoto, Joost A de Gouw
Proton-transfer-reaction mass spectrometry (PTR-MS) has been widely used to study the emissions, distributions, and chemical evolution of volatile organic compounds (VOCs) in the atmosphere. The applications of PTR-MS have greatly promoted understanding of VOC sources and their roles in air-quality issues. In the past two decades, many new mass spectrometric techniques have been applied in PTR-MS instruments, and the performance of PTR-MS has improved significantly. This Review summarizes these developments and recent applications of PTR-MS in the atmospheric sciences...
October 4, 2017: Chemical Reviews
Dian Wang, Adam B Weinstein, Paul B White, Shannon S Stahl
Palladium-catalyzed aerobic oxidation reactions have been the focus of industrial application and extensive research efforts for nearly 60 years. A significant transition occurred in this field approximately 20 years ago, with the introduction of catalysts supported by ancillary ligands. The ligands play crucial roles in the reactions, including promotion of direct oxidation of palladium(0) by O2, bypassing the typical requirement for Cu salts or related redox cocatalysts to facilitate oxidation of the reduced Pd catalyst; facilitation of key bond-breaking and bond-forming steps during substrate oxidation; and modulation of chemo-, regio-, or stereoselectivity of a reaction...
October 4, 2017: Chemical Reviews
Feng Lin, Yijin Liu, Xiqian Yu, Lei Cheng, Andrej Singer, Oleg G Shpyrko, Huolin L Xin, Nobumichi Tamura, Chixia Tian, Tsu-Chien Weng, Xiao-Qing Yang, Ying Shirley Meng, Dennis Nordlund, Wanli Yang, Marca M Doeff
Rechargeable battery technologies have ignited major breakthroughs in contemporary society, including but not limited to revolutions in transportation, electronics, and grid energy storage. The remarkable development of rechargeable batteries is largely attributed to in-depth efforts to improve battery electrode and electrolyte materials. There are, however, still intimidating challenges of lower cost, longer cycle and calendar life, higher energy density, and better safety for large scale energy storage and vehicular applications...
September 29, 2017: Chemical Reviews
Nina Jiang, Xiaolu Zhuo, Jianfang Wang
Active plasmonics is a burgeoning and challenging subfield of plasmonics. It exploits the active control of surface plasmon resonance. In this review, a first-ever in-depth description of the theoretical relationship between surface plasmon resonance and its affecting factors, which forms the basis for active plasmon control, will be presented. Three categories of active plasmonic structures, consisting of plasmonic structures in tunable dielectric surroundings, plasmonic structures with tunable gap distances, and self-tunable plasmonic structures, will be proposed in terms of the modulation mechanism...
September 29, 2017: Chemical Reviews
Sirimuvva Tadepalli, Joseph M Slocik, Maneesh K Gupta, Rajesh R Naik, Srikanth Singamaneni
Through the use of the limited materials palette, optimally designed micro- and nanostructures, and tightly regulated processes, nature demonstrates exquisite control of light-matter interactions at various length scales. In fact, control of light-matter interactions is an important element in the evolutionary arms race and has led to highly engineered optical materials and systems. In this review, we present a detailed summary of various optical effects found in nature with a particular emphasis on the materials and optical design aspects responsible for their optical functionality...
September 22, 2017: Chemical Reviews
Nicolas Mano, Anne de Poulpiquet
Catalytic four-electron reduction of O2 to water is one of the most extensively studied electrochemical reactions due to O2 exceptional availability and high O2/H2O redox potential, which may in particular allow highly energetic reactions in fuel cells. To circumvent the use of expensive and inefficient Pt catalysts, multicopper oxidases (MCOs) have been envisioned because they provide efficient O2 reduction with almost no overpotential. MCOs have been used to elaborate enzymatic biofuel cells (EBFCs), a subclass of fuel cells in which enzymes replace the conventional catalysts...
September 20, 2017: Chemical Reviews
Derek Pletcher, Robert A Green, Richard C D Brown
Electrosynthesis has much to offer to the synthetic organic chemist. But in order to be widely accepted as a routine procedure in an organic synthesis laboratory, electrosynthesis needs to be presented in a much more user-friendly way. The literature is largely based on electrolysis in a glass beaker or H-cells that often give poor performance for synthesis with a very slow rate of conversion and, often, low selectivity and reproducibility. Flow cells can lead to much improved performance. Electrolysis is participating in the trend toward continuous flow synthesis, and this has led to a number of innovations in flow cell design that make possible selective syntheses with high conversion of reactant to product with a single passage of the reactant solution through the cell...
September 18, 2017: Chemical Reviews
Shuaidi Zhang, Ren Geryak, Jeffrey Geldmeier, Sunghan Kim, Vladimir V Tsukruk
The robust, sensitive, and selective detection of targeted biomolecules in their native environment by prospective nanostructures holds much promise for real-time, accurate, and high throughput biosensing. However, in order to be competitive, current biosensor nanotechnologies need significant improvements, especially in specificity, integration, throughput rate, and long-term stability in complex bioenvironments. Advancing biosensing nanotechnologies in chemically "noisy" bioenvironments require careful engineering of nanoscale components that are highly sensitive, biorecognition ligands that are capable of exquisite selective binding, and seamless integration at a level current devices have yet to achieve...
September 13, 2017: Chemical Reviews
Mahito Atobe, Hiroyuki Tateno, Yoshimasa Matsumura
The fundamental advantages and potential benefits of flow microreactor technology include extremely large surface-to-volume ratios, precise control over temperature and residence time, extremely fast molecular diffusion, and increased safety during reactive processes. These advantages and benefits can be applied to a wide range of electrosynthetic techniques, and so the integration of flow microreactors with electrosynthesis has received significant research interest from both academia and industry. This review presents an up-to-date overview of electrosynthetic processes in continuous-flow microreactors...
September 8, 2017: Chemical Reviews
Roger A Sheldon, John M Woodley
Based on the principles and metrics of green chemistry and sustainable development, biocatalysis is both a green and sustainable technology. This is largely a result of the spectacular advances in molecular biology and biotechnology achieved in the past two decades. Protein engineering has enabled the optimization of existing enzymes and the invention of entirely new biocatalytic reactions that were previously unknown in Nature. It is now eminently feasible to develop enzymatic transformations to fit predefined parameters, resulting in processes that are truly sustainable by design...
September 6, 2017: Chemical Reviews
Tiffany R Walsh, Marc R Knecht
Peptide sequences are known to recognize and bind different nanomaterial surfaces, which has resulted in the screening and identification of hundreds of peptides with the ability to bind to a wide range of metallic, metal oxide, mineral, and polymer substrates. These biomolecules are able to bind to materials with relatively high affinity, resulting in the generation of a complex biointerface between the biotic and abiotic components. While the number of material-binding sequences is large, at present, quantitative materials-binding characterization of these peptides has been accomplished only for a relatively small number of sequences...
August 29, 2017: Chemical Reviews
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