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Chemical Society Reviews

Fernanda Oliveira Chagas, Rita de Cassia Pessotti, Andrés Mauricio Caraballo-Rodríguez, Mônica Tallarico Pupo
Microorganisms are found everywhere, and they are closely associated with plants. Because the establishment of any plant-microbe association involves chemical communication, understanding crosstalk processes is fundamental to defining the type of relationship. Although several metabolites from plants and microbes have been fully characterized, their roles in the chemical interplay between these partners are not well understood in most cases, and they require further investigation. In this review, we describe different plant-microbe associations from colonization to microbial establishment processes in plants along with future prospects, including agricultural benefits...
December 8, 2017: Chemical Society Reviews
Shengli Zhang, Shiying Guo, Zhongfang Chen, Yeliang Wang, Hongjun Gao, Julio Gómez-Herrero, Pablo Ares, Félix Zamora, Zhen Zhu, Haibo Zeng
Phosphorene, an emerging two-dimensional material, has received considerable attention due to its layer-controlled direct bandgap, high carrier mobility, negative Poisson's ratio and unique in-plane anisotropy. As cousins of phosphorene, 2D group-VA arsenene, antimonene and bismuthene have also garnered tremendous interest due to their intriguing structures and fascinating electronic properties. 2D group-VA family members are opening up brand-new opportunities for their multifunctional applications encompassing electronics, optoelectronics, topological spintronics, thermoelectrics, sensors, Li- or Na-batteries...
December 6, 2017: Chemical Society Reviews
Douglas J Kenny, Emily P Balskus
Microbes living within host-associated microbial communities (microbiotas) rely on chemical communication to interact with surrounding organisms. These interactions serve many purposes, from supplying the multicellular host with nutrients to antagonizing invading pathogens, and breakdown of chemical signaling has potentially negative consequences for both the host and microbiota. Efforts to engineer microbes to take part in chemical interactions represent a promising strategy for modulating chemical signaling within these complex communities...
December 6, 2017: Chemical Society Reviews
Hao-Yuan Wang, Stephanie A Blaszczyk, Guozhi Xiao, Weiping Tang
Carbohydrates play a significant role in numerous biological events, and the chemical synthesis of carbohydrates is vital for further studies to understand their various biological functions. Due to the structural complexity of carbohydrates, the stereoselective formation of glycosidic linkages and the site-selective modification of hydroxyl groups are very challenging and at the same time extremely important. In recent years, the rapid development of chiral reagents including both chiral auxiliaries and chiral catalysts has significantly improved the stereoselectivity for glycosylation reactions and the site-selectivity for the modification of carbohydrates...
December 5, 2017: Chemical Society Reviews
Marius M Haugland, Janet E Lovett, Edward A Anderson
EPR spectroscopy is an increasingly useful analytical tool to probe biomolecule structure, dynamic behaviour, and interactions. Nitroxide radicals are the most commonly used radical probe in EPR experiments, and many methods have been developed for their synthesis, as well as incorporation into biomolecules using site-directed spin labelling. In this Tutorial Review, we discuss the most practical methods for the synthesis of nitroxides, focusing on the tunability of their structures, the manipulation of their sidechains into spin labelling handles, and their installation into biomolecules...
December 1, 2017: Chemical Society Reviews
Robert E Continetti, Hua Guo
The dynamics of chemical reactions are often governed by transient species, including the transition state for activated bimolecular reactions. Such transient species are difficult to study experimentally, but it has proven valuable to prepare and probe transition-state dynamics by the photodetachment of anions with an equilibrium geometry similar to the neutral transition state. In this review, recent experimental advances in photoelectron and photoelectron-photofragment coincidence spectroscopy are discussed, as well as the latest progress in the calculation of multidimensional potential energy surfaces and quantum dynamics calculations that have enabled an extension of studies of transition-state dynamics to increasingly multidimensional polyatomic systems...
November 30, 2017: Chemical Society Reviews
Samuel J Thompson, Marshall R Brennan, Siu Yin Lee, Guangbin Dong
Organotransition metal complexes capable of forming metalloradicals have been an intriguing subject of study for the past fifty years. Of these, rhodium porphyrin complexes have proven particularly interesting due to their straightforward synthesis and unique reactivity; indeed, these complexes are responsible for some highly influential transformations of organic compounds, including rare C-H and C-C bond activations. The complexity and selectivity of rhodium porphyrins has been attractive for catalytic transformations, with specific interest in their usage for selective carbon monoxide reduction for fuel cell applications...
November 30, 2017: Chemical Society Reviews
Chengliang Wang, Huanli Dong, Lang Jiang, Wenping Hu
Organic semiconductors have attracted a lot of attention since the discovery of highly doped conductive polymers, due to the potential application in field-effect transistors (OFETs), light-emitting diodes (OLEDs) and photovoltaic cells (OPVs). Single crystals of organic semiconductors are particularly intriguing because they are free of grain boundaries and have long-range periodic order as well as minimal traps and defects. Hence, organic semiconductor crystals provide a powerful tool for revealing the intrinsic properties, examining the structure-property relationships, demonstrating the important factors for high performance devices and uncovering fundamental physics in organic semiconductors...
November 29, 2017: Chemical Society Reviews
A Zieleniewska, F Lodermeyer, A Roth, D M Guldi
In this review article, we highlight over 25 years of fullerene research in charge transfer chemistry. The major thrust of this work is to illustrate interfacial interactions between fullerenes and porphyrins in electron donor-acceptor conjugates as well as self-assembled associates and co-crystallites all the way to organic photovoltaics. Hereby, the analysis of the fundamental proceses, namely, energy transfer, charge shift, charge separation as well as charge recombination stand at the forefront. Our examples, illustrate on how fine-tuning the structure leads to substantial alteration of interfacial interactions...
November 29, 2017: Chemical Society Reviews
Wei-Hui Fang, Lei Zhang, Jian Zhang
As one of the most prosperous classes of cluster-based materials reported to date, polyoxo-titanium clusters (PTCs) have been closely related to many photo-activities that broadly impact not only chemical but also energy and environmental sciences. In contrast to the well-developed polyoxometalates like polyoxotungstates and polyoxomolybdates, there is still large room for the development of PTCs. The exploration of crystalline PTC materials originates from the molecular model of technically important TiO2 materials but has been greatly hindered by their daunting and challenging synthesis...
November 27, 2017: Chemical Society Reviews
Xueming Yang, David C Clary, Daniel M Neumark
No abstract text is available yet for this article.
November 27, 2017: Chemical Society Reviews
Weipeng Li, Wentao Xu, Jin Xie, Shouyun Yu, Chengjian Zhu
The remote radical migration strategy has gained considerable momentum. During the past three years, we have witnessed the rapid development of sustainable and practical C-C and C-H bond functionalization by means of long-distance 1,n-radical migration (n = 4, 5, 6) events. Its advent brings our chemical community a new platform to deal with the challenging migration transformations and thus complements the existing ionic-type migration protocols. In this review, the recent achievements in distal radical migration triggered C-C and C-H bond functionalization are summarized...
November 27, 2017: Chemical Society Reviews
Fergus E Poynton, Sandra A Bright, Salvador Blasco, D Clive Williams, John M Kelly, Thorfinnur Gunnlaugsson
Ruthenium(ii) [Ru(ii)] polypyridyl complexes have been the focus of intense investigations since work began exploring their supramolecular interactions with DNA. In recent years, there have been considerable efforts to translate this solution-based research into a biological environment with the intention of developing new classes of probes, luminescent imaging agents, therapeutics and theranostics. In only 10 years the field has expanded with diverse applications for these complexes as imaging agents and promising candidates for therapeutics...
November 27, 2017: Chemical Society Reviews
Samuel M Meier-Menches, Christopher Gerner, Walter Berger, Christian G Hartinger, Bernhard K Keppler
Anticancer metallodrugs based on ruthenium and osmium are among the most investigated and advanced non-platinum metallodrugs. Inorganic drug discovery with these agents has undergone considerable advances over the past two decades and has currently two representatives in active clinical trials. As many ruthenium and osmium metallodrugs are prodrugs, a key question to be addressed is how the molecular reactivity of such metal-based therapeutics dictates the selectivity and the type of interaction with molecular targets...
November 24, 2017: Chemical Society Reviews
Helen H Fielding, Graham A Worth
Time-resolved photoelectron spectroscopy measurements combined with quantum chemistry and dynamics calculations allow unprecedented insight into the electronic relaxation mechanisms of photoexcited molecules in the gas-phase. In this Tutorial Review, we explain the essential concepts linking photoelectron spectroscopy measurements with electronic structure and how key features on the potential energy landscape are identified using quantum chemistry and quantum dynamics calculations. We illustrate how time-resolved photoelectron spectroscopy and theory work together using examples ranging in complexity from the prototypical organic molecule benzene to a pyrrole dimer bound by a weak N-Hπ interaction and the green fluorescent protein chromophore...
November 23, 2017: Chemical Society Reviews
Huilin Pan, Kopin Liu, Adriana Caracciolo, Piergiorgio Casavecchia
Over the past ten years or so, great advances in our understanding of the dynamics of elementary (bimolecular) polyatomic reactions in the gas-phase have occurred. This has been made possible by critical improvements (a) in crossed molecular beam (CMB) instruments with rotating mass spectrometric detection and time-of-flight analysis, especially following the implementation of soft ionization (by tunable low energy electrons or vacuum-ultraviolet synchrotron radiation) for product detection with increased sensitivity and universal detection power, and (b) in REMPI-slice velocity map ion imaging (VMI) detection techniques in pulsed CMB experiments for obtaining product pair-correlated information through high-resolution measurements directly in the center of mass system...
November 23, 2017: Chemical Society Reviews
Soham Dutta, Andrew J Gellman
Research on surface chirality is motivated by the need to develop functional chiral surfaces for enantiospecific applications. While molecular chirality in 3D has been the subject of study for almost two centuries, many aspects of 2D chiral surface chemistry have yet to be addressed. In 3D, racemic mixtures of chiral molecules tend to aggregate into racemate (molecularly heterochiral) crystals much more frequently than conglomerate (molecularly homochiral) crystals. Whether chiral adsorbates on surfaces preferentially aggregate into heterochiral rather than homochiral domains (2D crystals or clusters) is not known...
November 22, 2017: Chemical Society Reviews
Junwei Lucas Bao, Donald G Truhlar
This article reviews the fundamentals of variational transition state theory (VTST), its recent theoretical development, and some modern applications. The theoretical methods reviewed here include multidimensional quantum mechanical tunneling, multistructural VTST (MS-VTST), multi-path VTST (MP-VTST), both reaction-path VTST (RP-VTST) and variable reaction coordinate VTST (VRC-VTST), system-specific quantum Rice-Ramsperger-Kassel theory (SS-QRRK) for predicting pressure-dependent rate constants, and VTST in the solid phase, liquid phase, and enzymes...
November 22, 2017: Chemical Society Reviews
Iñigo Bretos, Ricardo Jiménez, Jesús Ricote, M Lourdes Calzada
Over the last few years the efforts devoted to the research on low-temperature processing of metal oxide thin films have increased notably. This has enabled the direct integration of metal oxide layers (amorphous semiconductors) on low-melting-point polymeric substrates for flexible electronic systems, which adds to the economic and environmental benefits of the use of these processes with reduced energy consumption. More challenging is the preparation of crystalline complex oxide films at temperatures compatible with their direct integration in flexible devices...
November 22, 2017: Chemical Society Reviews
You-Quan Zou, Fabian M Hörmann, Thorsten Bach
Although enantioselective catalysis under thermal conditions has been well established over the last few decades, the enantioselective catalysis of photochemical reactions is still a challenging task resulting from the complex enantiotopic face differentiation in the photoexcited state. Recently, remarkable achievements have been reported by a synergistic combination of organocatalysis and photocatalysis, which have led to the expedient construction of a diverse range of enantioenriched molecules which are generally not easily accessible under thermal conditions...
November 20, 2017: Chemical Society Reviews
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