Determination of hexavalent chromium by on-line dialysis ion chromatography in a matrix of strong colourants and trivalent chromium

Hexavalent chromium detection in the presence of a high load of colourants without any false positive and in-procedure oxidation of Cr(III) is an important area of study. Colourants are a class of interfering substances in many spectroscopic analyses and chromatographic separations and detection. A purification method using an on-line dialysis technique for ion chromatography (IC) has been developed to remove water-soluble anionic dyes and particulate colourants and other substances to facilitate Cr(VI) quantification and the method is discussed. The dialysis was optimized with Cr(VI) standard solutions for quantification. The efficacy of the procedure for the removal of anionic dyes and detection of Cr(VI) was checked with a Cr(VI) spiked synthetic preparation containing a water-soluble dye and trivalent chromium. Soluble Cr(VI) extracted with organic dyes from environmental samples was analyzed. The method has a detection limit of 5 microg/l, recovery rate of 100% and analysis time less than 20 min.     

NMR Crystallography Reveals Carbonate Induced Al-Ordering in ZnAl Layered Double Hydroxide

Layered double hydroxides (LDHs) serve a score of applications in catalysis, drug delivery, and environmental remediation. Smarter crystallography, combining X-ray diffraction and NMR spectroscopy revealed how interplay between carbonate and pH determines the LDH structure and Al ordering in ZnAl LDH. Carbonate intercalated ZnAl LDHs were synthesized at different pH (pH 8.5, pH 10.0, pH 12.5) with a Zn/Al ratio of 2, without subsequent hydrothermal treatment to avoid extensive recrystallisation. In ideal configuration, all Al cations should be part of the LDH and be coordinated with 6 Zn atoms, but NMR revealed two different Al local environments were present in all samples in a ratio dependent on synthesis pH. NMR-crystallography, integrating NMR spectroscopy and X-ray diffraction, succeeded to identify them as Al residing in the highly ordered crystalline phase, next to Al in disordered material. With increasing synthesis pH, crystallinity increased, and the side phase fraction decreased. Using ¹H−¹³C, ¹³C−²⁷Al HETCOR NMR in combination with ²⁷Al MQMAS, ²⁷Al-DQ-SQ measurements and Rietveld refinement on high-resolution PXRD data, the extreme anion exchange selectivity of these LDHs for CO₃²⁻ over HCO₃⁻ was linked to strict Al and CO₃²⁻ordering in the crystalline LDH. Even upon equilibration of the LDH in pure NaHCO₃ solutions, only CO₃²⁻ was adsorbed by the LDH. This reveals the structure directing role of bivalent cations such as CO₃²⁻ during crystallization of [M²⁺₄M³⁺₂(OH)₂]²⁺[A²⁻]₁⋅yH₂O LDH phases.     

Underwater adhesive using solid–liquid polymer mixes

Instantaneous adhesion between different materials is a requirement for several applications ranging from electronics to biomedicine. Approaches such as surface patterning, chemical cross-linking, surface modification, and chemical synthesis have been adopted to generate temporary adhesion between various materials and surfaces. Because of the lack of curing times, temporary adhesives are instantaneous, a useful property for specific applications that need quick bonding. However, to this day, temporary adhesives have been mainly demonstrated under dry conditions and do not work well in submerged or humid environments. Furthermore, most rely on chemical bonds resulting from strong interactions with the substrate such as acrylate based. This work demonstrates the synthesis of a universal amphibious adhesive solely by combining solid polytetrafluoroethylene (PTFE) and liquid polydimethylsiloxane (PDMS) polymers. While the dipole-dipole interactions are induced by a large electronegativity difference between fluorine atoms in PTFE and hydrogen atoms in PDMS, strong surface wetting allows the proposed adhesive to fully coat both substrates and PTFE particles, thereby maximizing the interfacial chemistry. The two-phase solid–liquid polymer system displays adhesive characteristics applicable both in air and water, and enables joining of a wide range of similar and dissimilar materials (glasses, metals, ceramics, papers, and biomaterials). The adhesive exhibits excellent mechanical properties for the joints between various surfaces as observed in lap shear testing, T-peel testing, and tensile testing. The proposed biocompatible adhesive can also be reused multiple times in different dry and wet environments. Additionally, we have developed a new reactive force field parameterization and used it in our molecular dynamics simulations to validate the adhesive nature of the mixed polymer system with different surfaces. This simple amphibious adhesive could meet the need for a universal glue that performs well with a number of materials for a wide range of conditions.     

Kinetics of the oxidation of 1-phenyl ethanols with phase-transferred monochromate in organic solvents

Kinetic studies on the oxidation of 1-phenyl ethanol and its para-methyl, para-methoxy and para chloro derivatives have been carried out using phase transferred chromate as oxidant in pure organic solvents. The inorganic oxidant was transferred to the non polar media using the phase transfer catalyst, tetrabutyl phosphonium bromide (TB PB). The electronic effects of the substituents, effect of varying the temperature on the rate, as well as the effect of varying the dielectric constant of the medium on the rate have been investigated. The rate data fitted well with the Hammett equation.     

Palladium-catalyzed highly chemo- and regioselective formal [2+2+2] sequential cycloaddition of alkynes: a renaissance of the well known trimerization reaction?

A new concept of highly chemo- and regioselective formation of the benzene ring by a palladium-catalyzed formal [2 + 2 + 2] sequential intermolecular trimerization of alkynes is proposed. Homodimerization of terminal alkynes and subsequent [4 + 2] benzannulation with diynes gives tetrasubstituted benzenes in moderate to good yields. The introduction of two different alkynes (terminal and internal) in the first step of the sequence allows for construction of pentasubstituted benzenes from three different acyclic acetylenic units. In all cases the tetra- and pentasubstituted benzenes are formed as a single reaction product without being accompanied by any of regio- or chemoisomers. A significant acceleration of the sequential trimerization reaction in the presence of Lewis acid/phosphine combined system was observed. Mechanistic studies reveal that the Lewis acid assisted isomerization of the E-enyne formed in the first step of the sequence to the more reactive Z-isomer is responsible for the observed acceleration effect. The proposed methodology provides a conceptually new and synthetically useful route to multifunctional aromatic compounds.     

Characterization of a hybrid Li-ion anode system from pulsed laser deposited silicon on CVD-grown multilayer graphene

A hybrid anode system for lithium (Li) ion battery applications based on pulsed laser deposited silicon films on chemical vapor deposited multilayer graphene (MLG) layers on a nickel foam substrate was electrochemically characterized. The as-grown material was directly fabricated into an anode without a binder, and tested in a half-cell configuration. There is evidence of the participation of both the multilayer graphene and the Si in the transport of Li ions. Even when cycled under stressful voltage limits that accelerate degradation, the MLG–Si films displayed higher stability than Si-only anodes, especially at higher cycling rates. Unlike the Si cells that display capacity fade even within the first few cycles, the MLG–Si cells show a very narrow spread in capacity, indicative of the role of the graphene layers in improving adhesion of the Si and acting as a compliant buffer for its volume expansion. Stable average specific capacities of ~1,200 mAh/g per total weight of MLG + Si, over 80 cycles at C/5 rate, were obtained for the MLG–Si anode. Pre- and post-cycling characterization of the anode materials revealed the differences between the two systems.     

Oscillatory free convection heat transfer along a semi-infinite vertical plate

Summary The fluctuating free convection flow along a semi-infinite vertical plate is considered when the plate temperature is of the form T _p –T =(T ₀ –T ) where 0 < 1, denotes the frequency of oscillation and the mean temperature T ₀–T is proportional to ⁿ (0 n < 1). Flow and temperature fields have been obtained by means of two asymptotic expansions. For small values of the frequency parameter , a regular expansion is obtained while for large the method of matched asymptotic expansion is used. It is found that the skin friction and the rate of heat transfer obtained from two expansions overlap satisfactorily for a certain value of . For n=1 the flow governing equations to a semisimilar form, and have been solved by finite difference method. The results obtained from the series and the finite difference methods are in good agreement.

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Oszillierender Wärmeübergang an einer halbunendlichen senkrechten Platte bei freier Konvektion

Übersicht Betrachtet wird die fluktuierende freie Konvektionsströmung längs einer halbunendlichen senkrechten Platte, deren Temperatur dem Gesetz T _p –T =(T ₀–T ) [1+ sin {ie1-03}] folgt, wobei 0 < 1 gelte, {ie1-04} die Frequenz ist und der Temperatur-Mittelwert T ₀–T proportional zu ⁿ (0 n < 1) ist. Mit Hilfe zweier asymptotischer Entwicklungen werden die Strömungs- und Temperaturfelder gewonnen. Für kleine Werte des Frequenzparameters wird eine gewöhnliche Entwicklung benutzt, für große die Methode angepaßter asymptotischer Entwicklungen. Es stellt sich heraus, daß die Oberflächenreibung und die Wärmeübergangsrate aus zwei Entwicklungen für ein bestimmtes zufriedenstellend aufeinander fallen. Für n=1 werden die Grundgleichungen zueinander ähnlich und werden nach der Finite-Differenzen-Methode gelöst. Die Ergebnisse nach den Reihenentwicklungen und der Finite-Differenzen-Methode stimmen gut überein.