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Chemical Reviews

F Peter Guengerich, Francis K Yoshimoto
Many oxidation-reduction (redox) enzymes, particularly oxygenases, have roles in reactions that make and break C-C bonds. The list includes cytochrome P450 and other heme-based monooxygenases, heme-based dioxygenases, nonheme iron mono- and dioxygenases, flavoproteins, radical S-adenosylmethionine enzymes, copper enzymes, and peroxidases. Reactions involve steroids, intermediary metabolism, secondary natural products, drugs, and industrial and agricultural chemicals. Many C-C bonds are formed via either (i) coupling of diradicals or (ii) generation of unstable products that rearrange...
June 22, 2018: Chemical Reviews
Ye Chen, Zhanxi Fan, Zhicheng Zhang, Wenxin Niu, Cuiling Li, Nailiang Yang, Bo Chen, Hua Zhang
As one unique group of two-dimensional (2D) nanomaterials, 2D metal nanomaterials have drawn increasing attention owing to their intriguing physiochemical properties and broad range of promising applications. In this Review, we briefly introduce the general synthetic strategies applied to 2D metal nanomaterials, followed by describing in detail the various synthetic methods classified in two categories, i.e. bottom-up methods and top-down methods. After introducing the unique physical and chemical properties of 2D metal nanomaterials, the potential applications of 2D metal nanomaterials in catalysis, surface enhanced Raman scattering, sensing, bioimaging, solar cells, and photothermal therapy are discussed in detail...
June 21, 2018: Chemical Reviews
Minkui Luo
Protein lysine methylation is a distinct posttranslational modification that causes minimal changes in the size and electrostatic status of lysine residues. Lysine methylation plays essential roles in regulating fates and functions of target proteins in an epigenetic manner. As a result, substrates and degrees (free versus mono/di/tri) of protein lysine methylation are orchestrated within cells by balanced activities of protein lysine methyltransferases (PKMTs) and demethylases (KDMs). Their dysregulation is often associated with neurological disorders, developmental abnormalities, or cancer...
June 21, 2018: Chemical Reviews
Parthiv Kant Chaudhuri, Boon Chuan Low, Chwee Teck Lim
Over the past decade, researchers have highlighted the importance of mechanical cues of the metastatic niche such as matrix stiffness, topography, mechanical stresses, and deformation on cells in influencing tumor growth and proliferation. Understanding the cellular and molecular basis and fine-tuning the mechano-response of cancer cells to this niche could lead to new and novel therapeutic interventions. In this review, we discuss the importance of mechanical cues surrounding tumor microenvironment that govern the growth and progression of cancer...
June 21, 2018: Chemical Reviews
Jae Hyo Han, Minkyoung Kwak, Youngsoo Kim, Jinwoo Cheon
The precise control in size/thickness, composition, crystal phases, doping, defects, and surface properties of two-dimensional (2D) layered transition metal chalcogenide (TMC) is important for the investigation of interwoven relationship between structures, functions, and practical applications. Of the multiple synthetic routes, solution-based top-down and bottom-up chemical methods have been uniquely important for their potential to control the size and composition at the molecular level in addition to their scalability, competitive production cost, and solution processability...
June 21, 2018: Chemical Reviews
Renhao Dong, Tao Zhang, Xinliang Feng
The discovery of graphene one decade ago has triggered enormous interest in developing two-dimensional materials (2DMs)-that is 2D allotropes of various elements or compounds (consisting of two or more covalently bonded elements) or molecular frameworks with periodic structures. At present, various synthesis strategies have been exploited to produce 2DMs, such as top-down exfoliation and bottom-up chemical vapor deposition and solution synthesis methods. In this review article, we will highlight the interfacial roles toward the controlled synthesis of inorganic and organic 2DMs with varied structural features...
June 18, 2018: Chemical Reviews
Xing Wang, Arun Richard Chandrasekaran, Zhiyong Shen, Yoel P Ohayon, Tong Wang, Megan E Kizer, Ruojie Sha, Chengde Mao, Hao Yan, Xiaoping Zhang, Shiping Liao, Baoquan Ding, Banani Chakraborty, Natasha Jonoska, Dong Niu, Hongzhou Gu, Jie Chao, Xiang Gao, Yuhang Li, Tanashaya Ciengshin, Nadrian C Seeman
Over the past 35 years, DNA has been used to produce various nanometer-scale constructs, nanomechanical devices, and walkers. Construction of complex DNA nanostructures relies on the creation of rigid DNA motifs. Paranemic crossover (PX) DNA is one such motif that has played many roles in DNA nanotechnology. Specifically, PX cohesion has been used to connect topologically closed molecules, to assemble a three-dimensional object, and to create two-dimensional DNA crystals. Additionally, a sequence-dependent nanodevice based on conformational change between PX and its topoisomer, JX2 , has been used in robust nanoscale assembly lines, as a key component in a DNA transducer, and to dictate polymer assembly...
June 18, 2018: Chemical Reviews
Michael Holmes, Leyah A Schwartz, Michael J Krische
Metal-catalyzed reductive coupling has emerged as an alternative to the use of stoichiometric organometallic reagents in an increasingly diverse range of carbonyl and imine additions. In this review, the use of diene, allene, and enyne pronucleophiles in intermolecular carbonyl and imine reductive couplings are surveyed, along with related hydrogen autotransfer processes.
June 13, 2018: Chemical Reviews
Patrick Norman, Andreas Dreuw
During the past decade, the research field of computational X-ray spectroscopy has witnessed an advancement triggered by the development of advanced synchrotron light sources and X-ray free electron lasers that in turn has enabled new sophisticated experiments with needs for supporting theoretical investigations. Following a discussion about fundamental conceptual aspects of the physical nature of core excitations and the concomitant requirements on theoretical methods, an overview is given of the major developments made in electronic-structure theory for the purpose of simulating advanced X-ray spectroscopies, covering methods based on density-functional theory as well as wave function theory...
June 12, 2018: Chemical Reviews
Melanie M Cooper, Ryan L Stowe
This Review of Chemistry Education Research (CER) provides an overview of the development of research in chemistry education from the early days, when ideas about how to teach chemistry and help students learn were guided by practitioner wisdom, to current research that is based on theories of learning and provides evidence from which to make arguments about improving teaching and learning. We introduce the dominant learning theories that have guided CER over the years and attempt to show how they have been integrated into modern research in chemistry education...
June 12, 2018: Chemical Reviews
Christopher Engelhard, Igor Chizhov, Friedrich Siebert, Martin Engelhard
Early research on the four microbial rhodopsins discovered in the archaeal Halobacterium salinarum revealed a structural template that served as a scaffold for two different functions: light-driven ion transport and phototaxis. Bacteriorhodopsin and halorhodopsin are proton and chloride pumps, respectively, while sensory rhodopsin I and II are responsible for phototactic behavior of the archaea. Halorhodopsins have been identified in various other species. Besides this group of archaeal halorhodopsins distinct chloride transporting rhodopsins groups have recently been identified in other organism like Flavobacteria or Cyanobacteria...
June 8, 2018: Chemical Reviews
Ivan Tochitsky, Michael A Kienzler, Ehud Isacoff, Richard H Kramer
Degenerative retinal diseases such as retinitis pigmentosa (RP) and age-related macular degeneration (AMD) affect millions of people around the world and lead to irreversible vision loss if left untreated. A number of therapeutic strategies have been developed over the years to treat these diseases or restore vision to already blind patients. In this Review, we describe the development and translational application of light-sensitive chemical photoswitches to restore visual function to the blind retina and compare the translational potential of photoswitches with other vision-restoring therapies...
June 6, 2018: Chemical Reviews
Suvarn S Kulkarni, Cheng-Chung Wang, Narayana Murthy Sabbavarapu, Ananda Rao Podilapu, Pin-Hsuan Liao, Shang-Cheng Hung
Carbohydrates, which are ubiquitously distributed throughout the three domains of life, play significant roles in a variety of vital biological processes. Access to unique and homogeneous carbohydrate materials is important to understand their physical properties, biological functions, and disease-related features. It is difficult to isolate carbohydrates in acceptable purity and amounts from natural sources. Therefore, complex saccharides with well-defined structures are often most conviently accessed through chemical syntheses...
June 5, 2018: Chemical Reviews
Austin T Raper, Andrew J Reed, Zucai Suo
Faithful transmission and maintenance of genetic material is primarily fulfilled by DNA polymerases. During DNA replication, these enzymes catalyze incorporation of deoxynucleotides into a DNA primer strand based on Watson-Crick complementarity to the DNA template strand. Through the years, research on DNA polymerases from every family and reverse transcriptases has revealed structural and functional similarities, including a conserved domain architecture and purported two-metal-ion mechanism for nucleotidyltransfer...
June 4, 2018: Chemical Reviews
V G Kravets, A V Kabashin, W L Barnes, A N Grigorenko
When metal nanoparticles are arranged in an ordered array, they may scatter light to produce diffracted waves. If one of the diffracted waves then propagates in the plane of the array, it may couple the localized plasmon resonances associated with individual nanoparticles together, leading to an exciting phenomenon, the drastic narrowing of plasmon resonances, down to 1-2 nm in spectral width. This presents a dramatic improvement compared to a typical single particle resonance line width of >80 nm. The very high quality factors of these diffractively coupled plasmon resonances, often referred to as plasmonic surface lattice resonances, and related effects have made this topic a very active and exciting field for fundamental research, and increasingly, these resonances have been investigated for their potential in the development of practical devices for communications, optoelectronics, photovoltaics, data storage, biosensing, and other applications...
June 4, 2018: Chemical Reviews
Wenlong Wang, Lifeng Cui, Peng Sun, Lijun Shi, Chengtao Yue, Fuwei Li
With the continuous development of N-heterocyclic carbene (NHC) chemistry during the past decade, NHC metal complexes have gained wide applications in the research field of organometallic catalysis. The recycling and reuse of NHC metal complexes, which have undergone continuous expansion and diversification, can enhance their catalytic performance, extend their range of application, and afford new routes to green chemistry. Taking NHC metal complex catalysts as the main topic, this review intends to present a comprehensive study of recycling strategies of organometallic catalysts...
May 31, 2018: Chemical Reviews
David A Dik, Jed F Fisher, Shahriar Mobashery
The importance of the cell wall to the viability of the bacterium is underscored by the breadth of antibiotic structures that act by blocking key enzymes that are tasked with cell-wall creation, preservation, and regulation. The interplay between cell-wall integrity, and the summoning forth of resistance mechanisms to deactivate cell-wall-targeting antibiotics, involves exquisite orchestration among cell-wall synthesis and remodeling and the detection of and response to the antibiotics through modulation of gene regulation by specific effectors...
May 30, 2018: Chemical Reviews
Jan Freudenberg, Daniel Jänsch, Felix Hinkel, Uwe H F Bunz
This Review details synthetic routes toward and properties of insoluble polymeric organic semiconductors obtained through desolubilization strategies. Typical applications include fixation of donor-acceptor bulk-heterojunction morphologies in organic photovoltaic cells, cross-linking of charge transport materials and active emitters in light emitting diodes or similar devices, and immobilization of morphologies in field effect transistors. A second important application is the structuring of organic semiconductors, using them as photoresists...
May 30, 2018: Chemical Reviews
Philip Ouma Adero, Harsha Amarasekara, Peng Wen, Luis Bohé, David Crich
A critical review of the state-of-the-art evidence in support of the mechanisms of glycosylation reactions is provided. Factors affecting the stability of putative oxocarbenium ions as intermediates at the SN 1 end of the mechanistic continuum are first surveyed before the evidence, spectroscopic and indirect, for the existence of such species on the time scale of glycosylation reactions is presented. Current models for diastereoselectivity in nucleophilic attack on oxocarbenium ions are then described. Evidence in support of the intermediacy of activated covalent glycosyl donors is reviewed, before the influences of the structure of the nucleophile, of the solvent, of temperature, and of donor-acceptor hydrogen bonding on the mechanism of glycosylation reactions are surveyed...
May 30, 2018: Chemical Reviews
Puru Jena, Qiang Sun
Atomic clusters, consisting of a few to a few thousand atoms, have emerged over the past 40 years as the ultimate nanoparticles, whose structure and properties can be controlled one atom at a time. One of the early motivations in studying clusters was to understand how the properties of matter evolve as a function of size, shape, and composition. Over the past few decades, more than 200 000 papers have been published in this field. These studies have not only led to a considerable understanding of this evolution from clusters to crystals, but also have revealed many unusual size-specific properties that make cluster science an interdisciplinary field on its own, bridging physics, chemistry, materials science, biology, and medicine...
May 29, 2018: Chemical Reviews
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