ChemPlusChem

Description

ChemPlusChem is a peer-reviewed journal tailored to multidisciplinary chemistry and materials researchers from across the world. Fully comprehensive in its scope, ChemPlusChem publishes original papers covering at least two different aspects (subfields) of chemistry or one of chemistry and one of another scientific discipline (one chemistry topic plus another one, hence the title ChemPlusChem).

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  • ISSN
    2192-6506

Publications in this journal

  • [Show abstract] [Hide abstract]
    ABSTRACT: Supported phosphine ligands are auxiliaries of topical academic and industrial interest in catalysis promoted by transition metals. However, both controlled implantation and controlled conformation of ligands should be achieved to produce immobilized catalysts that are able to structurally “copy” efficient homogeneous systems. We provide herein a general synthetic strategy for assembling a new class of branched tetra- and triphosphine ligands with a unique controlled rigid conformation, and thus providing a high local density of phosphorus atoms for extended coordination to the metal center. We prepared new functionalized cyclopentadienyl (Cp) salts to design polyphosphines that were “ready for immobilization”. These protected Cp fragments might also be of synthetic utility for generating other supported metallocenes. Tetra- and triphosphines were then formed and diversely functionalized for immobilization on virtually any kind of support. As evidenced by 31P NMR spectroscopy and the strong “through-space” spin–spin TSJ(P,P) coupling observed between P atoms, these modified polyphosphines induce, when immobilized on a support, a high local concentration of phosphorus donors that are spatially very close to each other (3–5 Å). These functionalized ligands have been incorporated into polystyrene to give either soluble or insoluble polymers and on inorganic supports such as silica. We report the catalytic performance at 0.05–0.5 mol % low palladium loading of the resulting immobilized polyphosphine ligands. This study provides proof-of-concept of supported catalytic materials built from modular polyphosphines with a novel approach to structurally controlled polydentate heterogeneous catalysts.
    ChemPlusChem 08/2014;
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    ABSTRACT: Quaternary semiconductor Cu2CoSnS4 single-crystalline nanowires arrays have been prepared through a solvothermal synthetic route by using anodic aluminum oxide as a hard template. The as-prepared Cu2CoSnS4 nanowires are uniform with a [112] growth direction. An optimal solvent of diethylenetriamine is critical for the formation of single-crystalline Cu2CoSnS4 nanowires. The structure, morphology, composition, and optical absorption properties of the as-prepared Cu2CoSnS4 nanowires were characterized by using X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and UV/Vis spectroscopy. A thin film prepared from Cu2CoSnS4 single-crystalline nanowires displayed a clear photoelectric response, which suggested its potential application in photovoltaic devices.
    ChemPlusChem 08/2014;
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    ABSTRACT: A fabrication process that combines an ultrathin alumina membrane (UTAM) surface nanopatterning technique and a physical vapor deposition method has been designed for realizing well-defined Au nanoparticle arrays for sensitive, uniform, and stable surface-enhanced Raman scattering (SERS)-active substrates. High Raman signals are obtained by adjusting the structural parameters of the metallic nanoparticles when rhodamine 6G (R6G) and 4-mercaptopyridine (4-MP) are used as the probe molecules. The corresponding estimated enhancement factors (EFs) are 6.5×106 (R6G) and 6.8×105 (4-MP), respectively. The simulated distributions of the electric field of SERS substrates coincide with the experimental results. Raman measurements at randomly selected spots on a substrate show a standard EF deviation of about 5 %, which indicates a desirable SERS uniformity. An advantageous feature of our SERS substrate is its long-term stability of enhanced Raman signals. Raman measurements on a substrate after one year show almost the same magnitude of Raman signal (106 for R6G and 105 for 4-MP) as that of the original measurement. Such substrates with good SERS sensitivity, uniformity, and stability should have high potential for SERS-related applications.
    ChemPlusChem 08/2014;
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    ABSTRACT: Sodium 5-cyanotetrazolate sesquihydrate (1) is prepared from sodium azide and two equivalents of sodium cyanide under acidic conditions. 1 is then N-oxidized with Oxone to sodium 5-cyanotetrazolate monohydrate (2). Compound 2 is treated with sodium azide and a Lewis acid to form 5-(1H-tetrazolyl)-2-hydroxytetrazole monohydrate (3). Compound 3 can be deprotonated twice by various bases to give ionic derivatives such as the bis(hydroxylammonium) (4), bis(hydrazinium) (6), bis(guanidinium) (7), bis(aminoguanidinium) (8), bis(ammonium) (9), and diaminouronium (11) salt. In addition, compound 3 can only be deprotonated once, as demonstrated by the hydroxylammonium (4) and triaminoguanidinium (10) salts. Compounds 2–5 and 10–11 are structurally characterized by single-crystal X-ray diffraction. Additionally, compounds 2–11 are characterized by using NMR and vibrational (IR, Raman) spectroscopy as well as mass spectrometry and elemental analysis. Their thermal behaviors are studied from differential thermal analysis measurements, and the sensitivities of the compounds toward shock, friction, and electrostatic discharge are determined. In addition, the heats of formation are calculated (atomization method, CBS-4M enthalpies), and several detonation/propulsion parameters are computed with the EXPLO5 code.
    ChemPlusChem 08/2014;
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    ABSTRACT: A strategy to prevent and treat tooth decay, which utilises electrophoretic movement of charged, antibacterial silver nanocomposite structures to infiltrate human dentine to target bacteria contained within the dentine tubules, has been developed and evaluated. Scanning electron microscopy and energy-dispersive X-ray spectroscopy have confirmed high affinity of the nanocomposite structures for tooth tissue, and enhanced penetration of the nanostructures into the tubules under the influence of direct current. It is anticipated that this strategy could be used to sterilise dentine prior to the placement of a dental restorative material.
    ChemPlusChem 08/2014;
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    ABSTRACT: In this contribution, we report a detailed investigation of a photocatalytic system capable of producing hydrogen under aerobic conditions. This system consists of [Ru(dnbpy)(tbbpy)2](PF6)2 (1; dnbpy=4,4′-dinitrile-2,2′-bipyridine; tbbpy=4,4′-di-tert-butyl-2,2′-bipyridine) as the chromophore, [Co(dmgH)2] (dmgH=dimethylglyoximato) as the reduction catalyst, and triethylamine (TEA) as the electron donor. Most surprisingly, the system shows a higher catalytic activity under aerobic than under inert conditions. Detailed investigations of the catalytic process reveal that the nitrile groups probably convert to amides upon addition of TEA, and further intermediates are formed during the catalytic process. For further investigation of the surprising photocatalytic behavior of compound 1 in air, UV/Vis spectroscopic studies and time-dependent measurements of the oxygen concentration during the photocatalytic process, both in the headspace and the liquid phase, are performed.
    ChemPlusChem 08/2014;
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    ABSTRACT: A photoreactive ruthenium(II) complex that contains two tetraazaphenanthrene (TAP) and one phenanthroline (phen) ligands was synthesized and then tethered to (antisense) oligonucleotides (Ru–ASO) to target a destabilized GFP (dGFP). The specificity of the photoreaction of this Ru–ASO conjugate was studied in vitro by polyacrylamide gel electrophoresis (PAGE) experiments in denaturing conditions. Other nonspecific Ru–ASO conjugates were also prepared and evaluated with human keratinocytes that expressed dGFP. An illumination-dependent cytotoxicity was observed for most Ru–ASO conjugates that varied from 10 to almost 40 %, but only the specific Ru–ASO conjugate was able to significantly reduce GFP expression in illuminated cells.
    ChemPlusChem 08/2014;
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    ABSTRACT: Two soluble and stable 1,2:8,9-dibenzozethrene derivatives (3 a,b) are synthesized through a palladium-catalyzed cyclodimerization reaction. X-ray crystallographic analysis shows that these molecules are highly twisted owing to congestion at the cove region. Broken-symmetry DFT calculations predict that they have a singlet biradical ground state with a smaller biradical character and a large singlet–triplet energy gap; these predictions are supported by NMR and electronic absorption measurements. They have small energy gaps and exhibit far-red/near-infrared absorption/emission and amphoteric redox behaviors.
    ChemPlusChem 08/2014;
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    ABSTRACT: Cardo-poly(etherketone)-based anion-exchange membranes (AEMs) were prepared and employed as separators in a vanadium–cerium redox flow battery (V-Ce RFB). V-Ce RFBs with AEM separators yielded energy efficiencies (EEs) ranging from 67 to 84 % at current densities between 20 and 80 mA cm−2. V-Ce RFBs using Nafion 212 as the separator had EEs ranging from 50 to 84 % and displayed a capacity and efficiency loss as a result of cation intermixing. Over 20 charge/discharge cycles, the RFB with the AEM separator yielded unchanged efficiencies and capacity, whereas the loss of capacity was 50 % with the Nafion separator. There was no substantial change in the ionic conductivity, ultimate tensile strength, and Young’s modulus of AEMs after 50 charge/discharge cycles. This suggests that AEMs are promising candidates as V-Ce RFB separators that: 1) are chemically and mechanically stable during cycling, and 2) act as efficient barriers that preclude the intermixing of vanadium and cerium cations.
    ChemPlusChem 08/2014;
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    ABSTRACT: By combining nitrile-tethered pyridinium-based ionic liquid dication with the polyoxometalate anion of Keggin H5PMo10V2O40 (PMoV2) through precipitation in aqueous solution, an organic–inorganic hybrid catalyst 1,1′-(butane-1,4-diyl)-bis(3-cyanopyridine)–PMoV2 was prepared for heterogeneous hydroxylation of benzene to phenol with O2 and ascorbic acid as the oxidant and reductant, respectively. The hybrid catalyst not only gave the high phenol yield of 13.0 % under the optimized reaction conditions, but also exhibited high potential for reusability. The catalyst and its analogue samples were characterized by elemental analysis, Fourier transform infrared spectroscopy, electron spin resonance spectroscopy, X-ray diffraction, scanning electron microscopy, and nitrogen adsorption–desorption analysis. The structure–activity relationship is discussed according to the characterization and density functional theory calculation results.
    ChemPlusChem 08/2014;
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    ABSTRACT: The shape-controlled synthesis of monodispersed CaGd3F11 nanocrystals by means of a solvothermal method is reported for the first time. Their morphologies can be controlled to spherical nanoparticles and one-dimensional (1D) nanorods by tuning the volumes of oleic acid and octylamine in the reaction solution. Powder X-ray diffraction demonstrated their hexagonal crystalline structure. Transmission electron microscopy showed their ultrasmall sizes (sub-10 nm) and good monodispersity. The organic capping ligands on the CaGd3F11 surfaces were analyzed through infrared spectra and X-ray photoelectron spectroscopy. Also investigated is the influence of oleic acid and octylamine on the morphology of CaGd3F11 nanocrystals. Upconversion (UC) luminescence and magnetic resonance imaging (MRI) performance that depend on the shapes of as-prepared CaGd3F11 were studied further. CaGd3F11 nanoparticles and nanorods exhibited UC luminescence with green monochrome after doping with Yb3+ and Er3+ ions. The CaGd3F11 nanorods emitted a much higher UC intensity than the nanoparticles. The MRI relaxivity of CaGd3F11 nanorods was enhanced relative to that of nanoparticles.
    ChemPlusChem 08/2014;
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    ABSTRACT: The influence of (visible) light on the performance of laccase mediator systems (LMS) was investigated. As a model reaction, LMS-mediated nicotinamide adenine dinucleotide (NAD+) regeneration to promote alcohol dehydrogenase catalyzed oxidation reactions was examined.
    ChemPlusChem 08/2014;
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    ABSTRACT: Silica and graphene oxide (GO) were synthesized by modified Stöber and Hummer’s methods, respectively. Silica/GO composite powders of different compositions were obtained by introduction of GO sheets in between silica particles through a hydrothermal synthesis. Composites were characterized by Fourier transform infrared spectroscopy, X-ray diffraction analysis, and scanning and transmission electron microscopy. Density measurements were performed with a pycnometer and chemical analyses of powders were performed by energy-dispersive X-ray and X-ray photoelectron spectroscopies. Composite powders showed an improvement in the Cu2+ ion adsorption property relative to pure silica. Composite powders were further consolidated at 1200 °C under 50 MPa pressure in vacuum by pulsed electric current sintering. Transparency in the UV/Vis region, the electrical conductivity, and the toughness of consolidated samples were altered by varying the GO content in the starting materials. Studies suggest that the use of GO as a reinforcing agent not only improves the mechanical properties of transparent silica ceramic, but also improves the electrical conductivity and adsorption properties of silica.
    ChemPlusChem 07/2014;
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    ABSTRACT: Perfluoroalkyl compounds are known to exhibit a hydrophobic character on the surface of the material, although the CF bond has a large dipole, which should make the molecular surface polar and hydrophilic. This inconsistency has long been a chemical matter to be solved. Herein, a stratified dipole-arrays model is proposed: the molecular polar surface can be fully hidden by forming a two-dimensional aggregate of perfluoroalkyl (Rf) groups; this aggregate is spontaneously induced by dipole–dipole interaction arrays owing to the helical structure of the Rf group. In this model, a ‘short’ Rf group should play the role of a single Rf group with a hydrophilic character, whereas a ‘long’ Rf group should spontaneously form a hexagonal aggregate. To examine this model, Rf-containing myristic acids with various Rf lengths have been synthesized and their aggregation properties are analyzed by using the Langmuir monolayer technique aided by precise IR spectroscopic analysis.
    ChemPlusChem 07/2014;
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    ABSTRACT: In complex, multicomponent systems, polymers often undergo phase transitions between distinct conformations. This paper reports a millimeter-scale granular model of coil-to-globule transitions: one “polymer” chain—a cylinders-on-a-string “pearl necklace”—and many spheres, all shaken on a horizontal surface. It is possible to describe the behavior of this granular system by using formalisms generally used in statistical physics of polymers. Two sets of experiments allowed the observation of first- and second-order coil-to-globule transitions. The model shows that the competition between long- and short-range interactions leads to a first-order transition. Well-designed granular system represents another kind of approach to the study of polymer phase transitions and might inspire future designs of polymer-like mesoscale systems.
    ChemPlusChem 07/2014;
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    ABSTRACT: In this study, a “membrane-less and spill-less” gas-sensing device has been evaluated for the electrochemical detection of oxygen. Iron oxide magnetic nanoparticles were prepared by chemical co-precipitation and used to prepare an aqueous ferrofluid. The iron oxide nanoparticles were subsequently stabilised and passivated with a cationic polymer, namely, poly(diallyldimethyl ammonium chloride). The resulting ferrofluid was evaluated as an electrolyte for the analytical quantification of oxygen on screen-printed carbon electrodes. An applied magnetic field immobilised the ferrofluid electrolyte in place to result in a “membrane-less and spill-less” ferrofluid-based gas sensor. The polymer poly(diallyldimethyl ammonium chloride) was found to result in an apparent enhancement in the electrocatalysis of the system towards the oxygen reduction reaction. Furthermore, as the strength of the applied magnetic field was increased, the oxygen reduction current also increased owing to the response of the polymer-coated nanoparticles. The oxygen reduction current was linear from 0 to 100 % oxygen content.
    ChemPlusChem 07/2014;
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    ABSTRACT: Herein is presented a simple, attractive, and reusable methodology for one-pot resolution/separation of free sec-alcohols with enantiomeric excess (ee) values over 90 % by the combination of sustainable acylating agents/solvents (polyethylene glycol derivatives) and an easily available and common biocatalyst (Candida antarctica lipase B, or CAL B) under irreversible conditions, along with a separation process by extraction or distillation. A scale-up reaction was carried out with the Fluoxetine precursor with ee values close to 90 % for the R enantiomer.
    ChemPlusChem 07/2014;
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    ABSTRACT: A lithium–air battery based on the concept of an “oxygen shuttle” with a calcium-stabilized ZrO2 electrolyte is described. The observed open-circuit voltage and discharge capacity are 1.81 V and 2179 mAh per gram of lithium, respectively, at 1073 K. When considering the transport number of an oxide ion at P in an anode chamber, the observed open-circuit voltage is reasonable. The internal resistance of the lithium–air battery has been analyzed with complex impedance, and the main internal resistance is anodic overpotential because of the platinum electrode used. After discharge, a much larger diffusion resistance, which may suggest surface oxidation of lithium, is observed. However, the observed anodic overpotential is similar to that in a magnesium–air cell reported previously, and much smaller than that of the H2–air fuel cell.
    ChemPlusChem 07/2014;

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