The development of efficient and robust earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) is an ongoing challenge. We report metallic cobalt pyrite (cobalt disulfide, CoS2) as one such high-activity candidate material demonstrate that its specific morphology--film, microwire, or nanowire, made available through controlled synthesis--plays a crucial role in determining overall catalytic efficacy. increase effective electrode surface area accompanies CoS2 micro-...

Over the past several decades, metal-catalyzed cross-coupling has emerged as a powerful strategy to functionalize polyhedral borane clusters.

Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross-coupling. Here, for the first time, we report use of bromo-carboranes in palladium-catalyzed cross-coupling efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases outperform traditionally utilized iodo-carborane species. This marked difference reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH, -NH2, -CN) multiple...

We report the first observed Pd-catalyzed isomerization ("cage-walking") of B(9)-bromo-meta-carborane during cross-coupling, which enables formation B-O and B-N bonds at all boron vertices (B(2), B(4), B(5), B(9)) meta-carborane. Experimental theoretical studies suggest this mechanism is strongly influenced by steric crowding Pd catalyst either a biaryl phosphine ligand and/or substrate. Ultimately, "cage-walking" process provides unique pathway to preferentially introduce functional groups...

We report metallic cobalt pyrite (CoS2) nanowires (NWs) prepared directly on current collecting electrodes, e.g., carbon cloth or graphite disc, for high-performance supercapacitors. These CoS2 NWs have a variety of advantages supercapacitor applications. Because the are synthesized collector, good electrical connection enables efficient charge transfer between active materials and collector. In addition, open spaces sea urchin structure lead to large accessible surface area afford rapid...

In contrast to the plethora of metal-catalyzed cross-coupling methods available for installation functional groups on aromatic hydrocarbons, a comparable variety are currently not icosahedral carboranes, which boron-rich three-dimensional analogues aryl groups. Part this is due limited understanding elementary steps involving carboranes. Here, we report our efforts in isolating metal-boryl complexes further one these steps, oxidative addition. Structurally characterized examples group 10 M-B...

Off-cycle processes in a catalytic reaction can dramatically influence the outcome of chemical transformation and affect its yield, selectivity, rate, product distribution. While generation off-cycle intermediates complicate coordinate analyses or hamper efficiency, such species may also open new routes to unique products. We recently reported Pd-mediated functionalization carboranes with range O-, N-, C-based nucleophiles. By utilizing Pd-based system supported by biarylphosphine ligand...

High-affinity guests have been reported for the macrocyclic host cucurbit[7]uril (CB[7]), enabling widespread applications, but hindering CB[7] materials from being returned to their guest-free state reuse. Here, we present polyhedral boron clusters (carboranes) as strongly binding, yet easily removable, CB[7]. Aided by a Pd-catalyzed coupling of an azide anion, prepared boron-functionalized 9-amino-ortho-carborane that binds with Ka ≈ 1010 M–1. Upon basic treatment, ortho-carborane readily...

We report a three-dimensional (3D) mesoscale heterostructure composed of one-dimensional (1D) nanowire (NW) arrays epitaxially grown on two-dimensional (2D) nanoplates. Specifically, three facile syntheses are developed to assemble vertical ZnO NWs CuGaO2 (CGO) nanoplates in mild aqueous solution conditions. The key the successful 3D integration is preferential nucleation and heteroepitaxial growth CGO Using transmission electron microscopy, heteroepitaxy was found between basal planes NWs,...

Self-assembled monolayers (SAMs) of carborane isomers with different dipole moments passivate germanium to modulate surface work function while maintaining chemical environment and energy. To identify head groups capable monolayer formation on surfaces, we studied thiol-, hydroxyl-, carboxyl-terminated carboranes. These films were successfully formed carboxylic acid instead the archetypal thiol, suggesting that cluster significantly affects headgroup reactivity. Film characterization...

Electrochemical systems offer a versatile means for creating adaptive devices. However, the utility of electrochemical deposition is inherently limited by properties electrolyte. The development ionic liquids enables electrodeposition in high-vacuum environments and presents opportunities electrochemically regenerative spacecraft components. In this work, we developed silver-rich, boron cluster liquid (BCIL) reversible silver films. This air moisture stable electrolyte was used to deposit...

Over the past several years, a number of strategies for functionalization dicarba-closo-dodecaboranes (carboranes) have emerged. Despite these developments, B–N bond formation on carborane scaffold remains challenge due to propensity strong nucleophiles partially deboronate parent closo-carborane cluster into corresponding nido form. Here we show that azide, sulfonamide, cyanate, and phosphoramidate can be straightforwardly cross-coupled onto B(9) vertices o- m-carborane core from readily...

The synthesis of two bis(carboranyl) ( bc ) magnesium reagents is described. Treatment 1,1′‐bis( o ‐carborane) H 2 ‐bc or 8,8′,9,9′,10,10′,12,12′‐octamethyl‐1,1′‐bis( ‐Mebc with Mg( n Bu) in 1,2‐dimethoxyethane (DME) affords )Mg(DME) 1a , b as crystalline solids. compounds, which have been characterized by NMR spectroscopy and single‐crystal X‐ray crystallography the case serve competent Grignard‐type to generate ‐containing species tin from Me SnCl 2a ). type substitution bis( ‐carboranyl)...

The synthesis of fully alkylated closo-hexaborate dianions is reported. reaction [NBu4][B6H6Hfac], benzyl bromide, and triethylamine under microwave heating conditions affords persubstituted [NBu4][B6(CH2Ar)6Hfac] (Ar = C6H5, 4–Br-C6H4), which have been isolated characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, other spectroscopic techniques. Electrochemical studies these clusters reveal an irreversible one-electron oxidation, likely indicating...

A perhydroxylated dodecaborate cluster acts as an inorganic polyol to produce cross-linked polyurethanes, which confers a porous structure and enhanced thermal stability compared analogous polymers produced from carbon-based polyols.

ADVERTISEMENT RETURN TO ISSUEPREVFirst ReactionsNEXTAn Inorganic Twist in Nanomaterials: Making an Atomically Precise Double HelixBringing a common biological motif to the world of inorganic materials (from Advanced Materials).Liban M. A. Saleh†, Rafal Dziedzic†, and Alexander Spokoyny†‡View Author Information† Department Chemistry Biochemistry, University California, Los Angeles, 607 Charles E. Young Drive East, California 90095, United States‡ NanoSystems Institute (CNSI), 570 Westwood...

In this hands-on, inquiry-based lab, high school and undergraduate students learn about nanotechnology by synthesizing their own nanoparticles in a single class period. This simple synthesis of zinc oxide nanorods hydroxy sulfate nanoplates can be done 15 min using household microwave oven. Reagent concentration, reaction temperature, time all affect the size shape particles synthesized, allowing to explore how materials scientists control conditions achieve desired results.

Abstract The chloride gradient plays an important role in regulating cell volume, membrane potential, pH, secretion, and the reversal potential of inhibitory glycine GABA A receptors. Measurement intracellular activity, $${{\boldsymbol{a}}}_{{\boldsymbol{Cl}}}^{{\boldsymbol{i}}}$$ <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msubsup><mml:mrow><mml:mi>a</mml:mi></mml:mrow><mml:mrow><mml:mi>Cl</mml:mi></mml:mrow><mml:mrow><mml:mi>i</mml:mi></mml:mrow></mml:msubsup></mml:math>...

Here we show that azide, sulfonamide, cyanate, and phosphoramidate nucleophiles can be straightforwardly cross-coupled onto the B(9) vertices of o- m-carborane core from readily accessible precursors without significant deboronation by-products, laying groundwork for further study into utility properties these new B-aminated carborane species.

ABSTRACT The chloride gradient plays an important role in regulating cell volume, membrane potential, pH, secretion, and the reversal potential of inhibitory GABA A receptors. Measurement intracellular activity, , using liquid ion-selective microelectrodes (ISM), however, has been limited by physiochemical properties Cl ionophores which have caused poor stability, drift, sluggish response times, interference from other biologically relevant anions. Most importantly, HCO 3 − may be up to 4...

Here we show that azide, sulfonamide, cyanate, and phosphoramidate nucleophiles can be straightforwardly cross-coupled onto the B(9) vertices of o- m-carborane core from readily accessible precursors without significant deboronation by-products, laying groundwork for further study into utility properties these new B-aminated carborane species.

Biofilms are complex three-dimensional structures formed by microorganisms. protect microorganisms (for example, pathogenic bacteria) against antimicrobial compounds, therefore posing a threat to human, animal, and plant health. Despite numerous biofilm formation studies, details of factors influencing bacterial cell-to-cell cell-surface interaction mechanisms often unclear. We have been observing the unique association disciplines new techniques dedicated examining how living non-living...

Journal Article The use of Microcontact Printing Thiols to Evaluate Attachment Xylella fastidiosa Under Distinct Conditions Calcium Availability Get access Breno Leite, Leite JEOL USA, Inc., Peabody, MA, USA Search for other works by this author on: Oxford Academic Google Scholar Rafal Dziedzic, Dziedzic University Wisconsin, MRSEC Education Group, Madison, WI, L F Cruz, Cruz Auburn University, Department Entomology & Plant Pathology, Auburn, AL, (bleite@jeol.com) A Gillian-Daniel,...