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Chemical Reviews

Yulin Li, Yin Xiao, Changsheng Liu
Although the biological functions of cell and tissue can be regulated by biochemical factors (e.g., growth factors, hormones), the biophysical effects of materials on the regulation of biological activity are receiving more attention. In this Review, we systematically summarize the recent progress on how biomaterials with controllable properties (e.g., compositional/degradable dynamics, mechanical properties, 2D topography, and 3D geometry) can regulate cell behaviors (e.g., cell adhesion, spreading, proliferation, cell alignment, and the differentiation or self-maintenance of stem cells) and tissue/organ functions...
February 21, 2017: Chemical Reviews
Justin O Zoppe, Nariye Cavusoglu Ataman, Piotr Mocny, Jian Wang, John Moraes, Harm-Anton Klok
No abstract text is available yet for this article.
February 21, 2017: Chemical Reviews
Yongguang Yin, Zhiqiang Tan, Ligang Hu, Sujuan Yu, Jingfu Liu, Guibin Jiang
The rapidly growing applicability of metal-containing engineered nanoparticles (MENPs) has made their environmental fate, biouptake, and transformation important research topics. However, considering the relatively low concentration of MENPs and the high concentration of background metals in the environment and in organisms, tracking the fate of MENPs in environment-related scenarios remains a challenge. Intrinsic labeling of MENPs with radioactive or stable isotopes is a useful tool for the highly sensitive and selective detection of MENPs in the environment and organisms, thus enabling tracing of their transformation, uptake, distribution, and clearance...
February 17, 2017: Chemical Reviews
Xian Shi, Nicolás Coca-López, Julia Janik, Achim Hartschuh
Tip-enhanced near-field Raman microscopy spectroscopy is a scanning probe technique that is capable of providing vibrational spectroscopic information on single nanoobjects and surfaces at (sub-) nanometer spatial resolution and high detection sensitivity. In this review, we first illustrate the physical principle of optical nanoantennas used in tip-enhanced near-field Raman microscopy and tip-enhanced Raman scattering (TERS) to efficiently couple light to Raman excitations on nanometer length scales. Although the antennas' electric near-field distributions are commonly understood to determine the spatial resolution, recent experiments showing subnanometer-resolved optical images put this understanding into question...
February 17, 2017: Chemical Reviews
Christopher G Newton, Shou-Guo Wang, Caio C Oliveira, Nicolai Cramer
The development of new methods for the direct functionalization of unactivated C-H bonds is ushering in a paradigm shift in the field of retrosynthetic analysis. In particular, the catalytic enantioselective functionalization of C-H bonds represents a highly atom- and step-economic approach toward the generation of structural complexity. However, as a result of their ubiquity and low reactivity, controlling both the chemo- and stereoselectivity of such processes constitutes a significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with an emphasis on the nature of stereochemistry generation...
February 17, 2017: Chemical Reviews
Matthew B Stone, Sarah A Shelby, Sarah L Veatch
Lipids and the membranes they form are fundamental building blocks of cellular life, and their geometry and chemical properties distinguish membranes from other cellular environments. Collective processes occurring within membranes strongly impact cellular behavior and biochemistry, and understanding these processes presents unique challenges due to the often complex and myriad interactions between membrane components. Super-resolution microscopy offers a significant gain in resolution over traditional optical microscopy, enabling the localization of individual molecules even in densely labeled samples and in cellular and tissue environments...
February 17, 2017: Chemical Reviews
Vincent C-C Wang, Suman Maji, Peter P-Y Chen, Hung Kay Lee, Steve S-F Yu, Sunney I Chan
Methane monooxygenases (MMOs) mediate the facile conversion of methane into methanol in methanotrophic bacteria with high efficiency under ambient conditions. Because the selective oxidation of methane is extremely challenging, there is considerable interest in understanding how these enzymes carry out this difficult chemistry. The impetus of these efforts is to learn from the microbes to develop a biomimetic catalyst to accomplish the same chemical transformation. Here, we review the progress made over the past two to three decades toward delineating the structures and functions of the catalytic sites in two MMOs: soluble methane monooxygenase (sMMO) and particulate methane monooxygenase (pMMO)...
February 16, 2017: Chemical Reviews
Amit Kumar Chattopadhyay, Stephen Hanessian
Daphniphyllum is an evergreen species known since 1826. After initial systematic investigations, more than 320 members of this family have been isolated, which comprise complex and fascinating structures. Unique azapolycyclic architectures containing one or more quaternary stereocenters render these alkaloids synthetically challenging. This review covers efforts toward the synthesis of Daphniphyllum alkaloids spanning the period from 2005 to the beginning of 2016, including reported biological activities as well as the isolation of new members of this genus...
February 16, 2017: Chemical Reviews
Abhik Ghosh
Presented herein is a comprehensive account of the electronic structure of corrole derivatives. Our knowledge in this area derives from a broad range of methods, including UV-vis-NIR absorption and MCD spectroscopies, single-crystal X-ray structure determination, vibrational spectroscopy, NMR and EPR spectroscopies, electrochemistry, X-ray absorption spectroscopy, and quantum chemical calculations, the latter including both density functional theory and ab initio multiconfigurational methods. The review is organized according to the Periodic Table, describing free-base and main-group element corrole derivatives, then transition-metal corroles, and finally f-block element corroles...
February 13, 2017: Chemical Reviews
Sylwia Otocka, Małgorzata Kwiatkowska, Lidia Madalińska, Piotr Kiełbasiński
Asymmetric synthesis, in which chiral organocatalysts or metal complexes with chiral ligands are used, has become the most valuable methodology for the preparation of enantiomerically pure organic compounds. Among such catalysts/ligands, a growing number constitute various organosulfur compounds. This Review provides comprehensive and critical information on the plethora of sulfur-based chiral ligands and organocatalysts used in asymmetric synthesis, which have been published within the last 15 years. However, it is confined to the presentation of only those chiral catalysts/ligands that possess a stereogenic sulfur atom and includes sulfoxides, sulfinamides, N-sulfinyl ureas, sulfoximines, and some related S-chiral derivatives...
February 13, 2017: Chemical Reviews
Dongshi Zhang, Bilal Gökce, Stephan Barcikowski
Driven by functionality and purity demand for applications of inorganic nanoparticle colloids in optics, biology, and energy, their surface chemistry has become a topic of intensive research interest. Consequently, ligand-free colloids are ideal reference materials for evaluating the effects of surface adsorbates from the initial state for application-oriented nanointegration purposes. After two decades of development, laser synthesis and processing of colloids (LSPC) has emerged as a convenient and scalable technique for the synthesis of ligand-free nanomaterials in sealed environments...
February 13, 2017: Chemical Reviews
Ilia G Denisov, Stephen G Sligar
Membrane proteins play a most important part in metabolism, signaling, cell motility, transport, development, and many other biochemical and biophysical processes which constitute fundamentals of life on the molecular level. Detailed understanding of these processes is necessary for the progress of life sciences and biomedical applications. Nanodiscs provide a new and powerful tool for a broad spectrum of biochemical and biophysical studies of membrane proteins and are commonly acknowledged as an optimal membrane mimetic system that provides control over size, composition, and specific functional modifications on the nanometer scale...
February 8, 2017: Chemical Reviews
Marzena Dzida, Edward Zorębski, Michał Zorębski, Monika Żarska, Monika Geppert-Rybczyńska, Mirosław Chorążewski, Johan Jacquemin, Ivan Cibulka
A complete review of the literature data on the speed of sound and ultrasound absorption in pure ionic liquids (ILs) is presented. Apart of the analysis of data published to date, the significance of the speed of sound in ILs is regarded. An analysis of experimental methods described in the literature to determine the speed of sound in ILs as a function of temperature and pressure is reported, and the relevance of ultrasound absorption in acoustic investigations is discussed. Careful attention was paid to highlight possible artifacts, and side phenomena related to the absorption and relaxation present in such measurements...
February 8, 2017: Chemical Reviews
Ayelet Vilan, Dinesh Aswal, David Cahen
We review charge transport across molecular monolayers, which is central to molecular electronics (MolEl), using large-area junctions (NmJ). We strive to provide a wide conceptual overview of three main subtopics. First, a broad introduction places NmJ in perspective to related fields of research and to single-molecule junctions (1mJ) in addition to a brief historical account. As charge transport presents an ultrasensitive probe for the electronic perfection of interfaces, in the second part ways to form both the monolayer and the contacts are described to construct reliable, defect-free interfaces...
February 8, 2017: Chemical Reviews
Vikram Bhat, Eric R Welin, Xuelei Guo, Brian M Stoltz
Stereoconvergent catalysis is an important subset of asymmetric synthesis that encompasses stereoablative transformations, dynamic kinetic resolutions, and dynamic kinetic asymmetric transformations. Initially, only enzymes were known to catalyze dynamic kinetic processes, but recently various synthetic catalysts have been developed. This Review summarizes major advances in nonenzymatic, transition-metal-promoted dynamic asymmetric transformations reported between 2005 and 2015.
February 6, 2017: Chemical Reviews
Kamilla Norregaard, Ralf Metzler, Christine M Ritter, Kirstine Berg-Sørensen, Lene B Oddershede
The biomolecule is among the most important building blocks of biological systems, and a full understanding of its function forms the scaffold for describing the mechanisms of higher order structures as organelles and cells. Force is a fundamental regulatory mechanism of biomolecular interactions driving many cellular processes. The forces on a molecular scale are exactly in the range that can be manipulated and probed with single molecule force spectroscopy. The natural environment of a biomolecule is inside a living cell, hence, this is the most relevant environment for probing their function...
February 3, 2017: Chemical Reviews
Sónia P M Ventura, Francisca A E Silva, Maria V Quental, Dibyendu Mondal, Mara G Freire, João A P Coutinho
Ionic liquids (ILs) have been proposed as promising media for the extraction and separation of bioactive compounds from the most diverse origins. This critical review offers a compilation on the main results achieved by the use of ionic-liquid-based processes in the extraction and separation/purification of a large range of bioactive compounds (including small organic extractable compounds from biomass, lipids, and other hydrophobic compounds, proteins, amino acids, nucleic acids, and pharmaceuticals). ILs have been studied as solvents, cosolvents, cosurfactants, electrolytes, and adjuvants, as well as used in the creation of IL-supported materials for separation purposes...
February 2, 2017: Chemical Reviews
Alex von Diezmann, Yoav Shechtman, W E Moerner
Single-molecule super-resolution fluorescence microscopy and single-particle tracking are two imaging modalities that illuminate the properties of cells and materials on spatial scales down to tens of nanometers or with dynamical information about nanoscale particle motion in the millisecond range, respectively. These methods generally use wide-field microscopes and two-dimensional camera detectors to localize molecules to much higher precision than the diffraction limit. Given the limited total photons available from each single-molecule label, both modalities require careful mathematical analysis and image processing...
February 2, 2017: Chemical Reviews
Eduardo Peris
It is well-recognized that N-heterocyclic carbene (NHC) ligands have provided a new dimension to the design of homogeneous catalysts. Part of the success of this type of ligands resides in the limitless access to a variety of topologies with tuned electronic properties, but also in the ability of a family of NHCs that are able to adapt their properties to the specific requirements of individual catalytic transformations. The term "smart" is used here to refer to switchable, multifunctional, adaptable, or tunable ligands and, in general, to all those ligands that are able to modify their steric or electronic properties to fulfill the requirements of a defined catalytic reaction...
February 2, 2017: Chemical Reviews
Preethanuj Preethalayam, K Syam Krishnan, Sreeja Thulasi, S Sarath Chand, Jomy Joseph, Vijay Nair, Florian Jaroschik, K V Radhakrishnan
Pentafulvenes are a unique class of compounds that originally attracted attention due to their propensity to display nonbenzenoid aromaticity. Subsequently, they were recognized as valuable synthons for the construction of a wide range of compounds by virtue of their ability to display multiple cycloaddition profiles. Naturally, this area of organic chemistry has experienced rapid growth over the last five decades, fueled by elegant work showcasing the unique reactivity of pentafulvenes in a plethora of cycloaddition reactions...
February 2, 2017: Chemical Reviews
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