A green,isocyanide-based three-component reaction approach for the synthesis of multisubstituted ureas and thioureas

A one-pot, isocyanide based multicomponent protocol was presented starting from secondary amines towards (thio)urea derivatives and utilized for the construction of a diverse 27-membered chemical library. Following a green compatible microwave assisted condition, the formed N,N′-multisubstituted (thio)ureas were obtained in up to 85% yield.     

1.25–2.5 Gb/s Simple Nyquist Transmitters for Coherent UDWDM-PON with Enhanced Spectral Efficiency

We present a coherent ultra-dense wavelength division multiplexing passive optical network (UDWDM-PON) with enhanced spectral efficiency. The benefit of using Gaussian or Nyquist pulse-shaping filters at the transmitter is evaluated through numerical simulations and experiments. The transmitters consist of directly phase modulated distributed feedback (DFB) lasers through beat signals whose duty-cycle and amplitude are digitally adjusted. The results show that transmitting a Nyquist-shaped signal achieves a 25% spectral saving allowing to place 2.5 Gb/s/user data in 6.25 GHz channels. Furthermore, the proposed transmitter tolerates differential link-losses of 15 dB at Rx sensitivity of ?44 dBm at BER=10^?3 with intradyne detection.     

De-Equivariantization of Hopf Algebras

We study the de-equivariantization of a Hopf algebra by an affine group scheme and we apply Tannakian techniques in order to realize it as the tensor category of comodules over a coquasi-bialgebra. As an application we construct a family of coquasi-Hopf algebras A(H, G, Φ) attached to a coradically-graded pointed Hopf algebra H and some extra data.     

Fast screening of perfluorooctane sulfonate in water using vortex-assisted liquid-liquid microextraction coupled to liquid chromatography-mass spectrometry

Fast screening of trace amounts of the perfluorooctane sulfonate anion (PFOS) in water samples was performed following a simple, fast and efficient sample preparation procedure based on vortex-assisted liquid-liquid microextraction (VALLME) prior to liquid chromatography-mass spectrometry. VALLME initially uses vortex agitation, a mild emulsification procedure to disperse microvolumes of octanol, a low density extractant solvent, in the aqueous sample. Microextraction under equilibrium conditions is thus achieved within few minutes. Subsequently, centrifugation separates the two phases and restores the initial microdrop shape of the octanol acceptor phase, which can be collected and used for liquid chromatography-single quadrupole mass spectrometry analysis. Several experimental parameters were controlled and the optimum conditions found were: 50 μL of octanol as the extractant phase; 20 mL aqueous donor samples (pH=2); a 2 min vortex extraction time with the vortex agitator set at a 2500 rpm rotational speed; no ionic strength adjustment. Centrifugation for 2 min at 3500 rpm yielded separation of the two phases throughout this study. Enhanced extraction efficiencies were observed at low pH which was likely due to enhanced electrostatic interaction between the negatively PFOS molecules and the positively charged octanol/water interface. The effect of pH was reduced in the presence of sodium chloride, likely due to electrical double layer compression. The linear response range for PFOS was from 5 to 500 ng L(-1) (coefficient of determination, r(2), 0.997) and the relative standard deviation for aqueous solutions containing 10 and 500 ng L(-1) PFOS were 7.4% and 6.5%, respectively. The limit of detection was 1.6 ng L(-1) with an enrichment factor of approximately 250. Analysis of spiked tap, river and well water samples revealed that matrix did not affect extraction.     

Hydrolysis and Extraction Properties of Aroylhydrazones Derived from Nicotinic Acid Hydrazide

The kinetics of hydrolysis of N′-salicylidene-3-pyridinecarbohydrazide (1) and N′-(2-hydroxy-3-methoxyphenylmethylidene)-3-pyridinecarbohydrazide (2) were investigated in the dioxane/water (1/1, volume ratio) solvent system in acidic and basic media, and the corresponding reaction mechanisms were proposed. The kinetic results suggest that in the acidic solutions the rate-determining step of the hydrolysis reaction is the attack of a water molecule on the protonated azomethine group, whereas in the basic medium it is the attack of water on the completely deprotonated hydrazone. By analyzing the temperature dependence of the reaction rates, the thermodynamic activation parameters, i.e. activation enthalpy and entropy, were also evaluated and discussed. The complexation reactions of vanadium(V) with aroylhydrazones 1 and 2 as well as the extraction of V(V) from aqueous to an organic phase were studied spectrophotometrically. The optimum conditions for complex formation and extraction of vanadium(V) into chloroform solutions of compounds 1 or 2 have been evaluated. Based on the results obtained by Job’s method and the equilibrium shift method, the stoichiometries of the complexes were determined to be 1:1. The effect of foreign ions on V(V) extraction by compound 2 has been determined as well.     

An Enzyme-Linked Immunosorbent Assay (Elisa) for the Detection of Acetochlor

Competitive enzyme-linked immunosorbent assays (ELISAs) were developed in hapten-homologous and hapten-heterologous formats for the detection of the chloroacetanilide herbicide acetochlor. ELISA systems were devised using antibodies generated against acetochlor conjugated to carrier proteins through a thioether moiety replacing the chlorine atom in the parent structure, while haptens modified both on the chloroacetyl moiety and on the ethoxymethyl group of acetochlor have been used for coating antigens. The optimized ELISA systems allowed the detection of acetochlor 0.2-65 µg/L, and cross-reactivity studies revealed high specificity of the immunoassay: only four (propisochlor, butachlor, alachlor and metolachlor) among 18 structurally related acetanilide herbicides, fungicides and intermediates showed significant (> 1%) cross-reactivity, with even the highest value (propisochlor) being below 10%. Assay performance was not affected detrimentally by methanol up to 10% (v/v) and ethanol up to 5% (v/v). Assay performance was tested by measuring acetochlor concentration in water samples and compared favorably ( r 2 = 0.976) with those detected by gas chromatographic method coupled with mass spectrometry (GC-MS) using solid-phase microextraction (SPME) for sample preparation.     

Molecular Weight and Functionality Determination of Polyisobutylenes Containing Tertiary Chlorine Chain Ends by Thermal Dehydrochlorination

A sensitive thermal dehvdrochlorination method has been used to determine quantitatively the HCl arising from -CH₂C(CH₃)₂Cl endgroups in polyisobutylenes synthesized by BCb as the co-initiator. Quantitative endgroup analyses provided number-average molecular weights, M _n and functionality, F _n. Select M _n data obtained by this endgroup analysis is in agreement with those obtained by osmometry, GPC, and NMR techniques; indeed, M _n's obtained by this dehydrochlorination technique appears to be more accurate (2-3% error) than conventional methods (～5-10% error). The rate of HCl loss from -CH₂C(CH₃)₂Cl termini is first order in HCl with an ΔE_a of 19.1 kcal/mol in the 170-200°C range. This relatively low activation energy is most likely due to internal strain in the -CH₂C(CH₃)₂CH₂C(CH₃)₂Cl endgroup. These studies quantitatively substantiate earlier conclusions in regard to the mechanism of endgroup formation in BC13 coinitiated isobutylene polymerization.     

Basicity and Electrolyte Composition Dependent Stability of Ni-Fe-S and Ni-Mo Electrodes during Water Splitting

Non-noble metal electro-catalysts for water splitting are highly desired when we are moving towards a society where green electrons are becoming abundantly available, offering clear prospects to make our society more sustainable. In this work, Ni−Fe−S is reported as a high performing anode material for the water splitting reaction, operating at low overpotentials and showing high apparent stability. Furthermore, Ni−Mo electrodes are developed on metallic foam substrates and optimized in terms of their performance. The Ni−Fe−S material as anode, combined and integrated with Ni−Mo as cathode in a cell configuration, splits water at 10 mA cm⁻² and a potential of 1.55 V. Similar to previous reports, we confirm that Mo leaches from Ni−Mo/Ni foam electrodes. Cycling tests and ICP-AES measurements show that the stability of Ni−Fe−S is apparent, and that in reality S is leaching from the material as was already suggested in literature. We expand on this knowledge and show that the leaching of S is dependent on both pH and the cation used during electrocatalysis. Furthermore, we find that applying an oxidative potential is in truth stabilizing towards S and that the alkalinity causes leaching. S was furthermore mobile and found to segregate towards the surface. Finally, using too low pH values (11 and lower) result in the passivating hydroxide metal layers being destroyed and the Ni−Fe−S dissolving completely.     

General Catalytic Methylation of Amines with Formic Acid under Mild Reaction Conditions

A general catalytic protocol for the methylation of amines has been developed applying, for the first time, formic acid as the C₁ building block and silanes as reducing agents. A broad range of aromatic and aliphatic, both primary and secondary, amines has been converted to the corresponding tertiary amines including [N‐¹³C]‐labelled drugs in good to excellent yields under mild conditions.