Aryl Boronic Acid Catalysed Dehydrative Substitution of Benzylic Alcohols for C−O Bond Formation

A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C−O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.     

Cascaded Plasma–Ozone Injection System: A Novel Approach for Controlling Total Hydrocarbon Emission in Diesel Exhaust

Plasma Chemistry and Plasma Processing - The hydrocarbons present in diesel exhaust, although treated as minor pollutants, are equivalent to some of the major pollutants in terms of toxicity,...     

Comparison of fast field-cycling magnetic resonance imaging methods and future perspectives

ABSTRACT

Fast field-cycling (FFC) nuclear magnetic resonance relaxometry is a well-established method to determine the relaxation rates as a function of magnetic field strength. This so-called nuclear magnetic relaxation dispersion gives insight into the underlying molecular dynamics of a wide range of complex systems and has gained interest especially in the characterisation of biological tissues and diseases. The combination of FFC techniques with magnetic resonance imaging (MRI) offers a high potential for new types of image contrast more specific to pathological molecular dynamics. This article reviews the progress in FFC-MRI over the last decade and gives an overview of the hardware systems currently in operation. We discuss limitations and error correction strategies specific to FFC-MRI such as field stability and homogeneity, signal-to-noise ratio, eddy currents and acquisition time. We also report potential applications with impact in biology and medicine. Finally, we discuss the challenges and future applications in transferring the underlying molecular dynamics into novel types of image contrast by exploiting the dispersive properties of biological tissue or MRI contrast agents.     

Intramolecular Hydroamination of Selenoalkynes to 2-Selenylindoles in the Absence of Catalyst

In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles.     

Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light

Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl₄^?_(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O₂ through the transfer of SPR‐excited hot electrons to O₂ molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O₂ molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O₂ charge‐transfer process.     

Diastereoselective Cyclobutenol Synthesis: A Heterogeneous Palladium-Catalyzed Oxidative Carbocyclization-Borylation of Enallenols

A highly selective and efficient oxidative carbocyclization/borylation of enallenols catalyzed by palladium immobilized on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was developed for diastereoselective cyclobutenol synthesis. The heterogeneous palladium catalyst can be recovered and recycled without any observed loss of activity or selectivity. The high diastereoselectivity of the reaction is proposed to originate from a directing effect of the enallenol hydroxyl group. Optically pure cyclobutenol synthesis was achieved by the heterogeneous strategy by using chiral enallenol obtained from kinetic resolution.     

Stereochemistry of the citrate anion in compounds containing guanidinium and citrate ions

Journal of Structural Chemistry - An analysis is presented for the results obtained in the studies initiated by A. E. Shvelashivili, Corresponding Member, Academy of Sciences of Georgia, and...     

A note on Hadwiger’s conjecture for W5-free graphs with independence number two

The Hadwiger number of a graph $G$, denoted $h\left(G\right)$, is the largest integer $t$ such that $G$ contains $K_t$ as a minor. A famous conjecture due to Hadwiger in 1943 states that for every graph $G$, $h\left(G\right)\ge \chi \left(G\right)$, where $\chi \left(G\right)$ denotes the chromatic number of $G$. Let $\alpha \left(G\right)$ denote the independence number of $G$. A graph is $H$-free if it does not contain the graph $H$ as an induced subgraph. In 2003, Plummer, Stiebitz and Toft proved that $h\left(G\right)\ge \chi \left(G\right)$ for all $H$-free graphs $G$ with $\alpha \left(G\right)\le 2$, where $H$ is any graph on four vertices with $\alpha \left(H\right)\le 2$, $H=C_5$, or $H$ is a particular graph on seven vertices. In 2010, Kriesell subsequently generalized the statement to include all forbidden subgraphs $H$ on five vertices with $\alpha \left(H\right)\le 2$. In this note, we prove that $h\left(G\right)\ge \chi \left(G\right)$ for all $W_5$-free graphs $G$ with $\alpha \left(G\right)\le 2$, where $W_5$ denotes the wheel on six vertices.