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: An amino-core-substituted naphthalenediimide (NDI) derivative has been synthesized in good yield in two steps. The NDI bearing a diamine moiety undergoes a reversible protonation–deprotonation process, which results in intensity changes in the absorption and emission spectra. This derivative exhibits good photostability, good selectivity, high sensitivity, and is employed to exhibit the pH within the rough endoplasmic reticulum of living cells.
    ChemPlusChem 11/2014;
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    ABSTRACT: Size exclusion is a widespread phenomenon in supra- and macromolecular chemistry. Herein, the size exclusion properties of polyphenylene dendrimers on the surface of high fundamental frequency quartz crystal microbalances are reported. For this purpose, a new dense fifth-generation polyphenylene dendrimer, which was previously not possible owing to the high steric demand of the dendron arms, was synthesized. By increasing the volume and size of subjected analytes an affinity shift from smaller to larger dendrimers can be obtained.
    ChemPlusChem 11/2014;
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    ABSTRACT: By introducing 2,6-bis(2-benzimidazolyl)pyridyl and 2,6-di-(pyrazol-3-yl)pyridine derivatives as ligand in the reaction system, three new transition-metal coordination complexes have been successfully synthesized, namely, [Co(HL1)2] (1), [Ni(HL1)2] (2), and [Ni3(H2L2)2⋅(HL2)2]⋅(OH)3⋅(Ac)⋅H2O (3) (H2L1=2,6-bis(benzimidazol-2-yl)pyridine and H2L2=2,6-di-(5-phenyl-1H-pyrazol-3-yl)pyridine). They are all characterized by elemental analysis, IR spectroscopy, UV absorption spectroscopy, thermogravimetric analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Structural analysis shows that the structures of complexes 1 and 2 are similar. They are constructed from one metal (Co, Ni) atom and two 2,6-bis(benzimidazol-2-yl)pyridine ligands (HL1−); the HL1− ligand is in the tridentate coordination mode with N3 donors. Complex 3 is a trinuclear Ni complex with four 2,6-di-(5-phenyl-1H-pyrazol-3-yl)pyridine (H2L2) ligands, in which the H2L2 possesses two coordination fashions: terminal tridentate and bridging tetradentate. In addition, the surface photovoltage spectroscopy and photocatalytic activities of complexes 1–3 were investigated in detail. The results reveal that complex 3 possesses higher photocatalytic activity.
    ChemPlusChem 11/2014;
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    ABSTRACT: Magnesium silicate double-walled hollow nanofibers (MSHNFs) with a hierarchical nanostructure have been successfully fabricated by combining the electrospinning technique with a hydrothermal method. The as-prepared MSHNFs are composed of numerous ultrathin nanosheets with a thickness of approximately 10 nm and have a high specific surface area (632.2 m2 g−1) and large pore volume (0.92 cm3 g−1). The MSHNFs exhibit high adsorption capacity and excellent stability in a purification test with organic molecules and a solution of heavy-metal ions. Moreover, the MSHNFs can be easily separated from solution by gravitational sedimentation owing to their unique structure.
    ChemPlusChem 11/2014;
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    ABSTRACT: The Zn–Ce flow battery is a recently introduced hybrid redox flow battery (RFB) but has been extensively studied in the laboratory and at the industrial pilot scale since its introduction in 2005. The cell has the highest open-circuit cell potentials amongst aqueous RFBs, which can exceed 2.4 V at full charge. Although original patents were filed in 2004 and 2005, the history of the half-cell reactions stretches back many decades, with the CeIV/CeIII redox couple being well studied in sulfuric acid as a redox mediator in organic electrosynthesis or in nitric acid for specialist cleaning in the chemical and nuclear industries; in addition, zinc deposition and stripping in acid media are well known in hydrometallurgy and electroplating of metals as well as in other secondary batteries using zinc negative electrodes. Methanesulfonic acid electrolytes were introduced in surface finishing several decades ago but their use in flow batteries is only 20 years old. This Review considers the thermodynamics and kinetics of the electrode reactions (desired and secondary) in each half-cell, operational variables, materials for cell components, cell design and performance of the zinc–cerium flow battery. Continuing challenges are highlighted and critical research needs for the science and technological development are considered.
    ChemPlusChem 11/2014;
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    ABSTRACT: A facile, eco-friendly method for the synthesis of gold/platinum catalysts through electrodeposition of platinum nanoparticles, followed by the deposition of solutions of HAuCl4 onto the surface of pre-prepared platinum for a galvanic replacement reaction, is reported. Different molar ratios of bimetallic structures of platinum and gold could be easily achieved and characterized by energy-dispersive X-ray spectroscopy, SEM, and XRD. Electrochemical measurements reveal that the electrocatalytic activities of these series of gold/platinum catalysts towards formic acid oxidation reaction are superior to that of pure platinum. In addition, the formic acid oxidation route is related to the molar ratio of gold to platinum, which can be ascribed to the influence of gold. The gold/platinum catalyst with a platinum to gold atomic ratio of 2.51:1 exhibits maximum activity. Moreover, this optimized molar ratio shows a highly stable electrocatalytic activity for CO antipoisoning effects. These experimental results suggest that the prepared gold/platinum catalysts have great potential for applications in fuel cells.
    ChemPlusChem 11/2014;
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    ABSTRACT: Various α-Fe2O3 hollow structures, such as wormlike shapes, ellipsoids, and quasicubes, were synthesized successfully by a halide-ion-assisted solvothermal method. The self-assembly assisted by selective absorption of halide ions and Ostwald ripening speeded up by acidic etching commonly determine the final unique structures. The electrochemical performance of the α-Fe2O3 with different structures in reversible lithium-ion storage was investigated, and showed that the hollow Fe2O3 quasicubes exhibit the best cycling performance with a charge capacity of 401.6 mAh g−1 after 100 cycles at 0.2 C. The superior cycling stability and high specific capacity can be ascribed to the higher specific surface area, lower charge-transfer resistance, and adequate alleviation of volume variation.
    ChemPlusChem 11/2014;
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    ABSTRACT: Folic acid has emerged as an interesting cell-targeting moiety and a number of drugs have been conjugated to folate. In this context, new conjugates of β-cyclodextrins with folate have been synthesised as drug carriers to improve their selectivity for cells overexpressing the folic acid receptor. In particular, both 3- and 6-functionalised β-cyclodextrins, linked to the α- or γ-carboxylic group of folic acid, have been synthesised and fully characterised. As a proof of concept, the antitumour platinum(IV) complex cis–trans–cis-[PtCl2(CH3CO2)2(adamantylamine)(NH3)] (LA-12) has been used as a guest drug. The LA-12–cyclodextrin inclusion complexes have been tested on tumour cells. In the presence of cyclodextrin–folate conjugates, LA-12 exhibited IC50 values four times smaller than those of LA-12 alone in MDA-MB-231 cells, which overexpress folic acid receptors on their membrane. No improvement of LA-12 cytotoxicity was found in control tumour cells that do not overexpress the folate receptor. Thus, the non-covalent approach, based on inclusion complexes with functionalised cyclodextrins, looks very promising for drug targeting.
    ChemPlusChem 11/2014;
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    ABSTRACT: The individual and competitive adsorption of PbII, NiII, and SrII on graphene oxides (GOs) was investigated by experimental and density functional theory (DFT) studies. Experimental results indicate that 1) in all the single, binary, and ternary metal-ion adsorption systems, the sequence of maximum adsorption capacities is PbII>NiII>SrII on GOs; 2) the desorption hysteresis of metal ions from GOs shows the adsorption affinity in the same sequence: PbII>NiII>SrII. For the first time, DFT calculations indicate that 1) PbII and NiII prefer to interact with the COH group, whereas SrII interacts with COH and COC comparably, and 2) PbII can easily abstract the OH group from the GOs to form the much more stable Pb(OH)–GO complex. These findings are very important and useful for understanding the mechanisms of heavy-metal-ion adsorption on GOs and assessing the adsorption of coexisting heavy-metal ions on GOs.
    ChemPlusChem 11/2014;
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    ABSTRACT: The electropolymerisation of poly(3,4-ethylenedioxythiopene) (PEDOT) from an ionic liquid, butyl-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (C4mpyrTFSI), onto flexible carbon cloth electrodes is reported. A continuous, homogeneous and well-adhered coating of the individual cloth fibres is achieved by employing a sandwich cell arrangement in which the carbon cloth, which is soaked with electrolyte, is placed between two indium tin oxide electrodes isolated from each other by a battery separator. The resultant PEDOT-modified carbon cloth electrode demonstrates excellent activity for the oxygen reduction reaction, which results from the doping level, conductivity and morphology of the PEDOT layer, and is also tolerant to the presence of methanol in the electrolyte. This simple approach therefore offers a route to fabricate flexible polymer electrodes that could be used in various electronic applications.
    ChemPlusChem 11/2014;
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    ABSTRACT: Based on specific reactivity of the vinyloxy group to Hg2+ ions, a new ratiometric phenanthroimidazole-based fluorescent sensor, 2-(2-(vinyloxy)phenyl)-1 H-phenanthro[9,10-d]imidazole, is prepared. The selectivity of the probe toward Hg2+ ions is very high, and shows minimal interference from other commonly coexistent metal ions. The reactive stoichiometry of the probe with Hg2+ ion is 2:1. Its detection limit is evaluated and Hg2+ ions can be detected down to a lower limit of 2.5×10−8 M. Moreover, the Hg2+-promoted selective hydrolysis of a vinyloxy group of the probe is further confirmed by 1H NMR spectroscopy and mass spectrometry.
    ChemPlusChem 10/2014;
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    ABSTRACT: The trans-activator of transcription (TAT) peptide is regarded as the “gold standard” for cell-penetrating peptides, capable of traversing a mammalian membrane passively into the cytosolic space. This characteristic has been exploited through conjugation of TAT for applications such as drug delivery. However, the process by which TAT achieves membrane penetration remains ambiguous and unresolved. Mechanistic details of TAT peptide action are revealed herein by using three complementary methods: quartz crystal microbalance with dissipation (QCM-D), scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM). When combined, these three scales of measurement define that the membrane uptake of the TAT peptide is by trans-membrane insertion using a “worm-hole” pore that leads to ion permeability across the membrane layer. AFM data provided nanometre-scale visualisation of TAT punctuation using a mammalian-mimetic membrane bilayer. The TAT peptide does not show the same specificity towards a bacterial mimetic membrane and QCM-D and SECM showed that the TAT peptide demonstrates a disruptive action towards these membranes. This investigation supports the energy-independent uptake of the cationic TAT peptide and provides empirical data that clarify the mechanism by which the TAT peptide achieves its membrane activity. The novel use of these three biophysical techniques provides valuable insight into the mechanism for TAT peptide translocation, which is essential for improvements in the cellular delivery of TAT-conjugated cargoes including therapeutic agents required to target specific intracellular locations.
    ChemPlusChem 10/2014;
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    ABSTRACT: In an electrochemical alloying reaction, the electroactive particles become mechanically unstable owing to large volume changes occurring as a result of high amounts of lithium intake. This is detrimental for long-term battery performance. Herein, a novel synthesis approach to minimize such mechanical instabilities in tin particles is presented. An optimal one-dimensional assembly of crystalline single-phase tin–antimony (SnSb) alloy nanoparticles inside porous carbon fibers (abbreviated SnSb–C) is synthesized for the first time by using the electrospinning technique (employing non-oxide precursors) in combination with a sintering protocol. The ability of antimony to alloy independently with lithium is beneficial as it buffers the unfavorable volume changes occurring during successive alloying/dealloying cycles in Sn. The SnSb–C assembly provides nontortuous (tortuosity coefficient, τ=1) fast conducting pathways for both electrons and ions. The presence of carbon in SnSb–C completely nullifies the conventional requirement of other carbon forms during cell electrode assembly. The SnSb–C exhibited remarkably high electrochemical lithium stability and high specific capacities over a wide range of currents (0.2–5 A g−1). In addition to lithium-ion batteries, it is envisaged that SnSb–C also has potential as a noncarbonaceous anode for other battery chemistries, such as sodium-ion batteries.
    ChemPlusChem 10/2014;
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    ABSTRACT: Electrochromic symmetric and non-symmetric disubstituted oxo-bipyridinium ionic liquids are developed in high purities and yields. Detailed spectroscopic (NMR, FTIR and elemental analysis), thermal (DSC for melting point and glass transition temperatures, Tg determination) and electrochemical (cyclic and square wave voltammetry for determination of redox potential and evaluation of reversibility behaviour) analyses are performed. The most promising electrochromic oxo-bipyridinium ionic liquids in combination with transparent electrolytes are tested as reversible electrochromic devices. More efficient and sustainable electrochromic devices inspired by bipyridinium ionic liquids can be conceived for industrial applications such as electrochromic car rear-view mirrors and smart windows.
    ChemPlusChem 10/2014;
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    ABSTRACT: The effect of bromine complexing agents, N-ethyl-N-methyl-morpholinium bromide (MEM) and N-ethyl-N-methyl-pyrrolidinium bromide (MEP) on the performance of different perfluorinated cation exchange membranes, ChiNaf and VF11, is assessed in the G2 vanadium bromide battery (V/Br). It is noted that in the absence of MEM and MEP, the thicker ChiNaf (50 μm) membrane shows a higher energy efficiency at a current density of 20 mA cm−2. A preliminary test of ChiNaf at two different concentration ratios of MEM and MEP evaluated at 4 mA cm−2 shows that a mixture of 0.19 M MEM and 0.56 M MEP provides a slightly higher cell efficiency than the other tested compositions. However, better cell performance is obtained with the VF11 (25 μm) membrane at 4 mA cm−2 using 0.19 M MEM and 0.56 M MEP. Further studies using VF11 with a mixture of 0.19 M MEM and 0.56 M MEP at 20 mA cm−2 provide direct evidence that the addition of MEM+MEP lowers the cell performance through a reduction in voltage efficiency. The increased membrane resistance after the introduction of MEM and MEP marks the formation of an organic layer after bromine reacts with MEM and MEP and is deposited onto the membrane.
    ChemPlusChem 10/2014;
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    ABSTRACT: Li1.16Mn1.84O4 nanoparticles (50–90 nm) with cubic spinel structure are synthesized by combining a microemulsion process to produce ultrafine Mn(OH)2 nanocrystals (3–8 nm) with a solid-state lithiation step. The nanostructured lithium-rich Li1.16Mn1.84O4 shows stable cycling performance and superior rate capabilities as compared with the corresponding bulk material, for example, the nano-sized Li1.16Mn1.84O4 electrode shows stable reversible capacities of 74 mAh g−1 during the 1000th cycle at a high rate of 40 C between 3.0 and 4.5 V. In addition, Li1.16Mn1.84O4 nanoparticles also show high Li storage properties over an enlarged voltage window of 2.0–4.5 V with high capacities and stable cyclability, for example, delivering discharge capacities of 209 and 114 mAh g−1 at rates of 1 and 20 C, respectively.
    ChemPlusChem 10/2014;
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    ABSTRACT: A seleniumselenium σ-bond (SeSe) cleavage of a diaryl diselenide radical anion (ArSeSeAr.−) was investigated by absorption measurements during the γ radiolysis and pulse radiolysis in 2-methyltetrahydrofuran. A di-α-naphthyl diselenide radical anion (αNpSeSeαNp.−) in which an unpaired electron is localized in the SeSe σ* orbital between both Se atoms with an elongated SeSe bond showed an absorption band at 440 nm at 77 K. Upon increasing temperature, the absorption band at 440 nm shifted to 540 nm, thus suggesting that an unpaired electron is delocalized over two naphthalene rings and the SeSe bond. The disappearance of the absorption band at 540 nm and formation of absorption bands at 420, 620, and 690 nm assigned to the α-naphthylselenyl radical were observed during the pulse radiolysis of αNpSeSeαNp, thus indicating that the SeSe bond cleavage occurred in αNpSeSeαNp.−. The relationship between the SeSe bond cleavage and delocalization of the unpaired electron in ArSeSeAr.− is discussed.
    ChemPlusChem 10/2014;
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    ABSTRACT: The development of highly efficient catalysts for the selective oxidation of styrene to benzaldehyde has attracted great attention in recent years because of its significance in synthetic chemistry. In this study, two different kinds of copper-based metal oxide nanoparticles (NPs), namely, CuO and CuO/Co3O4 NPs, were synthesized by a simple and scalable method, and these nanoparticles demonstrated efficient catalytic abilities for the selective oxidation of styrene and its derivatives to the corresponding aldehydes in the presence of tert-butyl hydroperoxide (TBHP) under mild reaction conditions in excellent yields. Importantly, both of the heterogeneous catalysts can be recycled up to five runs while still maintaining their high catalytic activity.
    ChemPlusChem 10/2014;
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    ABSTRACT: Morphology evolution dependence on reaction time has been investigated to find a way to overcome polydispersity of the chalcopyrite CuInSe2 nanocrystals (NCs). A building–crumbling process is presented to understand the formation of small NCs. By carefully controlling magnetic stirring, ligand content, and duration, the polydispersity is fundamentally improved; thus solid and hollow spherical NCs and quantum dots can be easily obtained with tunable sizes. It is proposed that the NCs undergo Ostwald ripening induced morphology evolution from solid to hollow NCs. The photoelectric properties and photocatalytic activity have been investigated with TiO2 nanotube array based photoelectrodes. A maximum saturation photocurrent of 12.6 mA cm−2 has been achieved, and a structure-dependent photocatalytic property has also been confirmed by using methyl orange as a model pollutant.
    ChemPlusChem 10/2014;