Trimethylsilylverbindungen der Vb-Elemente. VII. Die Kristallstrukturen von Lithium-bis(trimethylsilyl)bismutid · DME und Tetrakis(trimethylsilyl)dibismutan sowie Bemerkungen zur Kristallstruktur des Bis(4-methoxyphenyl)ditellans

Trimethylsilyl Derivatives of Vb Elements. VII. Crystal Structures of Lithium Bis(trimethylsilyl)bismuthide · DME and of Tetrakis(trimethylsilyl)dibismuthane as well as Some Comments on the Crystal Structure of Bis(4-methoxyphenyl)ditellane Colourless lithium bis(trimethylsilyl)bismuthide · DME

1 1,2-Dimethoxyethan (DME); Tetrahydrofuran (THF)

1 and green, metallic lustrous tetrakis(trimethylsilyl)dibismuthane 2 crystallize isotopic to their antimony homologues [1, 2]. As it is shown by crystal structure determinations { 1 : ?90°C; I 4 2d; a = 1017,3(4); c = 3738,0(26) pm; Z = 8; R _w = 0,065; 2 : + 20°C; P2 ₁ /c; a = 680,9(4); b = 1704,8(13); c = 1197,9 (10) pm; β = 119,46(6)°; Z = 2; R _w = 0,084} both compounds form chains which in the case of bismuthide 1 are built up as screws of alternating bismuth and lithium atoms; bonding further to two trimethylsilyl groups or to the chelating DME ligand both atoms gain coordination number 4 {Li? Bi 292(3); Bi? Si 263.3(14) pm; Bi? Li? Bi 132(1); Li? Bi? Li 148(1); φ(Li? Bi? Li? Bi) 83°}. In the case of dibismuthane 2 the centrosymmetric molecules are strung, their Bi-Bi groups forming nearly linear zigzag chains with shortened intermolecular contact distances {Bi-Bi 303.5(3); Bi …? Bi 380.4(3); Bi? Si 268 pm; Bi? Bi …? Bi 169; Bi? Bi? Si 97.4(5) and 92.0(5)°}. Structure and properties of 2 are compared with those of similar compounds; the crystal structure of brown, green metallic lustrous bis(4-methoxyphenyl)ditellane 5 already published by Ludlow and McCarthy[3] is reinvestigated with respect to very short intermolecular Te…?Te contacts.     

Melt miscibility of HDPE/UHMWPE,LDPE/UHMWPE,and LLDPE/UHMWPE blends detected by dynamic rheometer

The dynamic rheological behavior of high density polyethylene (HDPE)/ultrahigh molecular weight polyethylene (UHMWPE) blends, low density polyethylene (LDPE)/UHMWPE blends and linear low density polyethylene (LLDPE)/ UHMWPE blends was measured in parallel plate rheometer at 200°C. The analysis of log-additivity rule, Cole-Cole plots and Han curves of the three series blends indicated that the LDPE/UHMWPE blends were miscible in the melt, while the HDPE/UHMWPE blends and LLDPE/UHMWPE blends showed phase separation. The DSC results of LLDPE/UHMWPE blends and HDPE/UHMWPE blends were consistent with the rheological properties, while for the thermal properties of LDPE/UHMWPE blends, results revealed three endothermic peaks, which indicated a liquid-solid phase separation in LDPE/UHMWPE blends.     

Multiresidue Determination of Ten Nonsteroidal Anti-inflammatory Drugs in Bovine,Porcine, and Chicken Liver Tissues by HPLC-MS/MS

Nonsteroidal anti-inflammatory drugs (NSAIDs) are the group of drugs having the therapeutic efficacy of analgesic and antipyretic. To detect health-threatening residues of NSAIDs, a fast and easy multiresidue method based on liquid chromatography tandem mass spectrometry (LC-MS/MS) was described. Ten NSAIDs were extracted from the tissues using 2 mL of acetonitrile and 0.1 mL of 2 mM ammonium formate in distilled water. After clean-up using C18 sorbent, it was evaporated under nitrogen, reconstituted with 1 mL distilled water and analyzed by LC-MS/MS. The method was validated based on guideline for residue testing laboratory. Furthermore, the method has also been applied successfully to detect ten NSAIDs from bovine, porcine, and chicken liver tissues. In a total of 315 liver samples tested, acetylic salicylic acid was detected from 28 porcine and 2 chicken liver tissues at levels of 13?～?576 and 50?～?53 ng/g, respectively. Subsequently, paracetamol was detected in 15 porcine liver tissues with a detection levels of 28?～?381 ng/g. Phenylbutazone and its metabolite, oxyphenylbutazone, were detected at 247 and 15 ng/g range in one of the bovine liver tissue, respectively.     

Highly sensitive carbon paste electrode with silver-filled carbon nanotubes as a sensing element for determination of free cyanide ion in aqueous solutions

We report on newly synthesized Ag(I)-filled multiwall carbon nanotubes as a potential sensing element in ion-selective carbon paste electrodes for the determination of free cyanide in aqueous solution. The electrode was obtained by entrapping the silver-filled nanotubes into a carbon paste and displays a Nernstian response with a slope of 59.8?±?0.3?mV decade^?1, a very wide linear range (from 21.0?nM to 0.1?M of cyanide), a lower detection limit of 13.0?nM, and a response time of <2?min. The operational lifetime is up to 3?months without significant deviation in normal function.

Low Temperature Heat Capacities and Thermodynamic Properties of Zinc L-Threonate Zn（C4H7O5）2（s） by Adiabatic Calorimetry

Low-temperature heat capacities of the solid compound Zn（C4H7O5）2（s） were measured in a temperature range from 78 to 374 K, with an automated adiabatic calorimeter. A solid-to-solid phase transition occurred in the temperature range of 295？322 K. The peak temperature, the enthalpy, and entropy of the phase transition were determined to be （316.269±1.039） K, （11.194±0.335） kJ？mol-1, and （35.391±0.654） J？K-1？mol-1, respectively. The experimental values of the molar heat capacities in the temperature regions of 78？295 K and 322？374 K were fitted to two polynomial equations of heat capacities（Cp,m） with reduced temperatures（X） and [X = f（T）], with the help of the least squares method, respectively. The smoothed molar heat capacities and thermodynamic functions of the compound, relative to that of the standard reference temperature 293.15 K, were calculated on the basis of the fitted polynomials and tabulated with an interval of 5 K. In addition, the possible mechanism of thermal decomposition of the compound was inferred by the result of TG-DTG analysis.     

Alkylidinphosphane und -arsane. II. Über die Oxydation des Lithoxy-methylidinphosphans PC?O?Li mit Schwefeldioxid und Iod

Alkylidynephosphanes and -arsanes. II. Oxydation of Lithoxy-methylidynephosphane P?C? O? Li with Sulphur Dioxide and Iodine At ?50°C bis(1,2-dimethoxyethane-O,O′)lithoxymethylidynephosphane P?C? O? Li(dme)₂^1,2) ( 1 a ) [2] reacts almost quantitatively with sulphur dioxide or iodine in 1,2-dimethoxyethane solution to give bis(1,2-dimethoxyethane-O,O′)bis(tetrahydrofuran-O)(μ-1,2,4-triphospholo[1,2-a]-1,2,4-triphosphol-1,3,5,7-tetraonato(2?)-O¹,O⁷:O³,O⁵)dilithium ( 2 a ) and lithium dithionite or iodide respectively. From the reaction with sulphur dioxide the crystalline, pale yellow compound is obtained in 40% yield. The formation of the unusual anionic heterocycle, built up of four PCO units, may be explained by an oxydation of two [P?C? O]^? species first, followed by a nucleophilic attack of two other [P?C? O]^? anions and coupled ?intramolecular”? cycloaddition reactions. In the ³¹P{¹H} nmr spectrum two phosphorus atoms each of coordination number two and three give rise to two triplets with chemical shift values of 81.4 and 36.9 ppm and a ²J(PP) coupling constant of 31.7 Hz; the ¹³C{¹H} resonances of the [(PCO)₄]^2? anion come from an ABMM′X spin system, the X part being discussed in detail. An X-ray structure determination {Cmcm; a = 1 277.14(11); b = 1 487.7(2); c = 1 556.94(11) pm at ?100 ± 3°C; Z = 4 molecules; R₁ = 0.061; wR₂ = 0.150} shows compound 2 a to crystallize as a neutral complex of symmetry mm2. The anionic part of the molecule consists of two anellated 1,2-dihydro-5-oxo-1,2,4-triphosphol-3-olate rings which share the central P? P unit (P1? P1′ 215.3; P1–C1 189.1; C1 P2 178.4; C1 O1 123.9pm; C1? P1? P1′ 98.4; Cl? P1? C1″ 91.2; C1 P2 C1′ 98.7°). Thus compound 2a may be assigned to the group of P? P heterocycles with a butterfly structure [71–75] as well as to the well-known diacylphosphanides taking into account, however, the unusual E,E configuration of both O?C? P?C? O^? units. The lithium cations are square pyramidally coordinate (Li? O 193.5 to 209.1 pm), each additionally binding an 1,2-dimethoxyethane and a tetrahydrofuran molecule.     

Electrochemical DNA biosensor for the detection of Trichoderma harzianum based on a gold electrode modified with a composite membrane made from an ionic liquid, ZnO nanoparticles and chitosan, and by using acridine orange as a redox indicator

An electrochemical DNA biosensor was developed that is based on a gold electrode modified with a nanocomposite membrane made from an ionic liquid, ZnO nanoparticles and chitosan. A single-stranded DNA probe was immobilized on this electrode. Acridine orange was used as the hybridization probe for monitoring the hybridization of the target DNA. The biosensor was capable of detecting target DNA in the concentration range from 1.0?×?10?C14 to 1.8?×?10?C4?mol?L-1, with a detection limit of 1.0?×?10?C15?mol?L-1. The approach towards constructing a DNA biosensor allows studies on the hybridization even with crude DNA fragments and also to analyze sample obtained from real samples. The results show that the DNA biosensor has the potential for sensitive detection of a specific sequence of the Trichoderma harzianum gene and provides a quick, sensitive and convenient method for the study of microorganisms.

Magnetic nanoparticles modified with polydimethylsiloxane and multi-walled carbon nanotubes for solid-phase extraction of fluoroquinolones

We have surface-functionalized magnetic particles (MPs) with polydimethylsiloxane and multi-walled carbon nanotubes in a two-step reaction. The MPs were applied to solid-phase extraction of the fluoroquinolones ofloxacin, norfloxacin, ciprofloxacin, enrofloxacin prior to their determination by capillary liquid chromatography. The effects of sample pH, adsorption time, type of eluent, desorption time and desorption temperature were investigated. Under the optimum conditions, the extraction efficiencies are in the range from 81.5?% to 94.1?%, with relative standard deviations (RSDs) of <7.6?%. The detection limits vary from 0.24 to 0.48?ng?mL^?1. The method was applied to the analysis of spiked mineral water and honey. The recoveries for the fluoroquinolones in the real samples range from 84.0?% to 112?%, with RSDs ranging from 2.9?% to 7.8?%.

Performance of Co/MgO catalyst for C02 reforming of toluene as a model compound of tar derived from biomass gasification

Catalytic performances of the CO2 reforming of toluene on Co/MgO catalysts with different cobalt loadings were evaluated in a fluidized-bed reactor. The results showed that the conversion of toluene and the stability of Co/MgO increased, but the apparent reaction rate decreased at the initial stage with increasing the amount of metallic Co formed from the reduction of Co/MgO catalysts at 700 ~C. The deactivation of Co/MgO catalysts was mainly resulted from that a part of the metallic Co was oxidized by CO2 and could not be re-reduced by H2 at reaction temperature. Therefore, the excess metallic Co on the higher Co loading catalysts was beneficial to the catalyst stability.     

Influence of the anion on stabilization and Coordination of Cu(II) and Cu(I) Complexes with Bis-[2-(4,6-Dimethylpyrimidyl)] Disulphide

Complexes of the type Cu(L? S? S? L)X₂ (X = Cl, Br) and Cu(L? S? S? L)₂X (X = ClO₄, BF₄) were prepared in CHCl₃? MeOH solution from CuX₂ · 6 H₂O (X = Cl, Br, ClO₄, BF₄) and bis-[2-(4, 6-dimethylpyrimidyl)]disulphide (L? S? S? L), and examined in the mid-(4000–250 cm^?1) and far-i.r. (5000–60 cm^?1) regions. Assignments for metal-ligand and metalhalogen vibrations were made. On the basis of these assignments, conductivity measurements and from magnetic moments and visible absorption data, the stereochemistry of the compounds was tentatively inferred. For Cu(L? S? S? L)X₂ (X = Cl, Br) species may be proposed an essentially [CuN₂X₂] in-plane microsymmetry achieved through two pyrimidyl nitrogen atoms of a ligand molecule, to form a seven-membered chelate ring and two halide ions, with probable interaction along the z axis with adjacent molecules. The Cu(L? S? S? L)₂X (X = ClO₄, BF₄) species, may be considered to contain isolated complexes cations, Cu(L? S? S? L) , or polynuclear cationic polymers, Cu_n(L? S? S? L), in which Cu(I) is, probably via N₃S, tetrahedraly coordinated.     

Preferential oxidation of CO in excess H2 over the CeO2/CuO catalyst： Effect of initial support

Three series of CeO2/CuO samples were prepared by impregnation method and characterized by XRD, N2adsorption-desorption, temperatureprogrammed reduction(TPR), XPS and TEM techniques. In comparison with the samples prepared with CuO as initial support, the samples with Cu(OH)2as initial support have higher reducibilities and smaller relative TPR peak areas, and also larger specific surface areas at calcination temperatures of 400℃–600℃. As a result, Cu(OH)2is better than CuO as initial support for preferential oxidation of CO in excess H2(CO-PROX). The best catalytic performance was achieved on the sample calcined at 600℃ and with an atomic ratio of Ce/Cu at 40%. XPS analyses indicate that more interface linkages Ce-O-Cu could be formed when it was calcined at 600℃. And the atomic ratio of Ce/Cu at 40%led to a proper reducibility for the sample as illustrated by the TPR measurements.     

One-pot synthesis of porous nickel–manganese sulfides with tuneable compositions for high-performance energy storage

Mixed-metal compounds, especially for the sulfides, have been investigated as a very attractive type of electroactive materials for supercapacitors. In this work, we demonstrate nickel?manganese (Ni?Mn) sulfides are very attractive for supercapacitors with promising electrochemical performance. The Ni?Mn sulfides with different Ni to Mn ratios have been synthesized via a facile one-pot hydrothermal method, which show a similar structure of interconnected particles and are very porous in microstructure. And then, the Ni?Mn sulfides are investigated by three-electrode measurements and demonstrate strong synergy between Ni and Mn. The Ni?Mn sulfide with a Ni to Mn ratio of 2:1 demonstrates superior performance of 1068?F?g^?1 at 1?A?g^?1. Lastly, The Ni?Mn sulfide with a Ni to Mn ratio of 2:1 are used as positive electrode for two-electrode test, and the asymmetric supercapacitor shows both high energy and power densities combined with excellent cycling stability. Our work demonstrates that the Ni?Mn sulfides are also very electrochemical active for supercapacitors and their performance can be tuned by changing the Ni to Mn ratio.

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Boron-Nitrogen Compounds 83 [1]. Experimental and Theoretical Studies on Monomeric Iminoboranes

Nuclear magnetic resonance and vibrational spectroscopic data support the existence of liner C?N? B skeleton in monomeric iminoboranes of the type R₂C?N? BR. This allene-like arrangement of the central moiety of the compounds does not seem to enhance the N? B bond strength by interaction of this bond with the vicinal C?N bond. Rather, in the case of R′ being a hydrocarbon group, the nature of the N? B bond is similar to that found in (monoamino) diorganyl-boranes, R₂N? Br. Similarly, (CF₃)₂C?N? B[N(CH₃)₂]₂ may ve viewed as a trisaminoborane. However, the rigid C?N? BN₂ unit makes this compound colored and the electronic structure of the species was studied; theoretical and experimental data are in good agreement.     

Determination Rapide de la Configuration Cis Trans des Alcenes CH?CHCH? Utilisation des Complexes de Terres Rares

In Z? CH? CH?CH? Y compounds (Z or Y being an alkyl group) the ethylenic part of the spectra is often very complex and the ³J(H? C?C? H) coupling constant which is a good tool for determining the configuration, is not easily determined. We have studied such allylic derivatives and many configurations have been assigned through stereospecific synthesis. Except a very few cases, δ CH(Z) of the cis isomer is larger than δ CHZ of the trans isomer. In alcohols RCH?CH? CHOHR′ the stereoisomers behave differently in solutions with europium, praseodymium, holmium and dysprosium complexes. The spectra of the trans isomers remain strongly coupled but ³J(H? C?C? H) becomes easy to measure in the cis compounds.     

Incorporation of Lysine-Containing Copolymer with Polyurethane Affording Biomaterial with Specific Adsorption of Plasminogen

A novel biomaterial based on polyurethane (PU) was prepared through physical incorporation of lysine-containing copolymer to improve its hemocompatibility and surface recognition of plasminogen.The lysine-containing copolymer was synthesized via the copolymerization of 2-ethylhexyl methacrylate (EHMA),oligo (ethylene glycol)methyl ether methacrylate (OEGMA) and 6-tert-butoxycarbonyl amino-2-(2-methyl-acryloylamino)-hexanoic acid tert-butyl ester (Lys(P)MA),followed by the deprotection of COOH and ε-NH2 groups on lysine residues in the copolymer.The composition of the copolymer can be adjusted by varying the monomer feed ratio.The three components contribute to improving the compatibility with PU,resistance to nonspecific protein adsorption and specific binding of plasminogen,respectively.The binding capacity towards plasminogen increased with the lysine content in the copolymer.This approach illustrates a simple way for the generation of novel biomaterials with improved hemocompatibility and surface recognition of specific biomolecules.     

Voltammetric determination of cadmium (II) based on a composite film of a thiol-functionalized mesoporous molecular sieve and an ionic liquid

A composite film made from a thiol-functionalized mesoporous molecular sieve and an ionic liquid is introduced for use in a voltammetric sensor for Cd(II). The electrode exhibits excellent sensitivity towards Cd(II) in showing a markedly increased stripping peak current. Following the optimization of the experimental parameters, a linear response is obtained in the concentration range from 29?nM to 0.87?mM of Cd(II). The detection limit is as low as 1.0?nM (at S/N?=?3) after an accumulation at ?1.1?V for 4?min. The method was successfully applied to determine Cd(II) in water samples. Features such as large electroactive area, fast electron transfer and low background current make this electrode a promising platform for fabricating reliable electrochemical sensors for various species, such as heavy metals and environmental pollutants.

Miscibility between PS and PSAN Affected by Solvent and Temperature of the System

The influence of solvent on the miscibility of polystyrene（PS） and poly（styrene-co-acrylonitrile）（PSAN） blends has been investigated viscometrically. The miscibility of different PS/PSAN blend（30/70, 50/50 and 70/30） compositions in acetone and benzene at 20, 30, and 40 °C was investigated on the basis of the sign of Chee（ΔB and ）, and Sun’s（α） criteria. The values of these parameters were evaluated from the analyses of reduced viscosity data of binary（solvent/polymer） and ternary（solvent/polymer1/polymer2） polymer systems. These investigations indicated partial miscibility for both the blend systems. However, PS/PSAN/acetone blend system showed somewhat higher partial miscibility than the PS/PSAN/Benzene blend system highlighting the impact of solvent over the polymer-polymer interactions and hence their miscibility. The results obtained through viscometry were also corroborated by the refractive index and density results for the blends under study. The effect of temperature on miscibility in both the cases was almost negligible.     

Square wave anodic stripping voltammetric determination of lead(II) using a glassy carbon electrode modified with a lead ionophore and multiwalled carbon nanotubes

We report on a glassy carbon electrode (GCE) modified with a lead ionophore and multiwalled carbon nanotubes. It can be applied to square wave anodic stripping voltammetric determination of Pb(II) ion after preconcentration of Pb(II) at ?1.0?V (vs. SCE) for 300?s in pH?4.5 acetate buffer containing 400?μg?L^?1 of Bi(III). The ionophore-MWCNTs film on the GCE possesses strong and highly selective affinity for Pb(II) as confirmed by quartz crystal microbalance experiments. Under the optimum conditions, a linear response was observed for Pb(II) ion in the range from 0.3 to 50?μg?L^?1. The limit of detection (at S/N?=?3) is 0.1?μg?L^?1. The method was applied to the determination of Pb(II) in water samples with acceptable recovery.

Preparation of cassava starch-based superabsorbent polymer using a twin-roll mixer as reactor

Cassava starch-based superabsorbent polymer was successfully synthesized using a new technology that based on modification of a Haake twin-roll mixer as reactor. The cassava starch was first gelatinized then modified by grafting under external shear stress in the reactor. The torque and temperature curves as a function of time can reflect the variations in the reactor and also offer some information about the copolymerization reaction. The advantages of this system include starch modification can be carried out(1) with high starch concentration,(2) under controlled time and(3) smaller amount of sample(60 g) required. The technology provides useful guides for reactive extrusion. The starch grafted composites were characterized by Fourier transform infrared spectroscopy(FTIR), nuclear magnetic resonance(NMR) and thermal gravimetric analysis(TGA). The TGA was also used for determining the percentage of grafting ratio. The results show that the cassava starch has been successfully grafted with acrylamide then crosslinked by N,N′-methylene-bisacrylamide using this reactor. The ultimate water absorbent capacity of the cassava-based superabsorbent polymer impacted by various pH values illustrated that the acid and basic solutions inhibit the ability of imbibing water. Additionally, gel properties of the cassava-based superabsorbent polymer were investigated. It can be concluded that the structure of cassava gel is stable, while the three dimensional network of cassava-based superabsorbent polymer is rigid but its structure could not resist external force effectively and everlastingly since G′ was decreased with increasing amplitude.