Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15-tris（pentafluorophenyl）corrole Mn（V）-oxo (F₁₅CMn（V）-oxo),5,15-bis（pentafluorophenyl）-10-（phenyl）corrole Mn（V）-oxo(F₁₀CMn（V）-oxo),5,15- bis（phenyl）-10-（pentafluorophenyl）corrole Mn（V）-oxo（F₅CMn（V）-oxo） and 5,10,15-tris（phenyl）corrole Mn（V）-oxo（F₀CMn（V）-oxo） with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn（V）-oxo corrole and alkene is solvent-dependent.     

Higher alcohol synthesis over Cu-Fe composite oxides with high selectivity to C2+OH

Cu-Fe composite oxides were prepared by co-precipitation method and tested for higher alcohol synthesis from syngas. The selectivity to C2+OH and C6+OH in alcohol distribution was very high while the methane product fraction in hydrocarbon distribution was rather low, demonstrating a promising potential in higher alcohols synthesis from syngas. The distribution of alcohols and hydrocarbons approximately obeyed Anderson-Schulz-Flory distribution with similar chain growth probability, indicating alcohols and hydrocarbons derived from the same intermediates. The effects of Cu/Fe molar ratio, reaction temperature and gas hourly space velocity (GHSV) on catalytic performance were studied in detail. The sample with a Cu/Fe molar ratio of 10/1 exhibited the best catalytic performance. Higher reaction temperature accelerated water-gas-shift reaction and led to lower total alcohols selectivity. GHSV showed great effect on catalytic performance and higher GHSV increased the total alcohol selectivity, indicating there existed visible dehydration reaction of alcohol into hydrocarbon.     

硫酸酯化川芎粗多糖的半合成及其抗氧化活性

以水提醇沉法制备川芎粗多糖(1)。首次报道了1与氯磺酸-吡啶经亲核取代反应半合成硫酸酯化川芎粗多糖(2)的方法,其结构经UV和IR表征。用氯化钡-明胶比浊法测定2的取代度。考察了1和2对邻苯三酚自氧化反应产生的超氧阴离子(O2-·)和1,1-二苯基-2-苦基肼(DPPH)体外清除自由基能力。结果表明:在测定浓度范围内,1和2对O2-·清除能力极弱,但对DPPH自由基有一定的清除作用。     

Preparation of Silver Nanoparticles‐Based Sensors for the Electrochemical Detection of Thiourea in Leaching Solutions of Waste Electrical and Electronic Equipment

Waste of electrical and electronic equipment is an interesting secondary resource of base and precious metals. Particularly the use of thiourea‐leaching in acidic medium was proposed for noble metals recovery. In this work, a novel and easy‐to‐use electrochemical sensor was developed, aimed to test thiourea from leaching solutions containing significant thiourea and copper amounts. The sensor was constructed using silver nanoparticles (AgNPs) deposited on screen‐printed electrodes. Its performance was studied in a synthetic leaching solution; changes in the overall surface charge of AgNPs resulting in changes in the charge‐transfer resistance for the copper ions were evaluated by electrochemical impedance spectroscopy.     

Electrochemical Characterization of Egyptian Blue Pigment in Wall Paintings Using the Voltammetry of Microparticles Methodology

The solid state voltammetric response of Egypt blue, Han blue and ploss blue pigments upon attachment to graphite electrodes in contact with aqueous phosphate buffer at pH 7.0 is studied by voltammetry of microparticles and scanning electrochemical microscopy. Such voltammetric responses, combined with those for synthetic specimens consisting of binary mixtures of the pigment and SiO₂ or CaCO₃ as well as ternary ones of CaCO₃ and SiO₂ mixtures allow for the identification of the pigment and the support in samples from wall paintings using different electrochemical parameters, in particular upon performing the Tafel and modified Tafel analysis of voltammetric peaks. Identification of Egypt blue in microsamples of murals from a Roman archaeological site in Castulo (Jaén, Spain) is discussed.     

Isolation and determination of estrogens in water samples by solid‐phase extraction using molecularly imprinted polymers and HPLC

Advanced SPE with molecularly imprinted polymers (MIP) was used in this study. A noncovalent imprinting approach was applied to separate 17β‐estradiol, estriol, and estrone from water samples. Polymer material was prepared by bulk polymerization with methacrylic acid as a functional monomer, divinylbenzene and ethyleneglycol dimethacrylate as crosslinkers, and acetonitrile, acetonitrile/toluene (3:1, v/v) or isooctane/toluene (1:99, v/v) as a porogen. We also prepared an MIP film on a silica gel surface with methacrylic acid and ethyleneglycol dimethacrylate as monomers and acetonitrile as a solvent. Qualitative and quantitative hormone analyses were carried out by HPLC with various detection techniques, including UV/visible spectroscopic detection (diode array detection) and electrochemical detection (CoulArray). The results of the study indicate that MIP technology is an excellent method for the quality control of estrogens in environmental analyses with a low quantification limit for 17β‐estradiol of around 26 (diode array detection) and 0.25 ng/mL (electrochemical detection). The proposed method was found to be suitable for routine determinations of the analyzed compound in environmental laboratories.     

Qualitative and quantitative analysis of poly(amidoamine) dendrimers in an aqueous matrix by liquid chromatography–electrospray ionization-hybrid quadrupole/time-of-flight mass spectrometry (LC-ESI-QTOF-MS)

This work introduces a liquid chromatography–electrospray ionization-hybrid quadrupole/time-of-flight mass spectrometry (LC-ESI-QTOF-MS)-based method for qualitative and quantitative analysis of poly(amidoamine) (PAMAM) dendrimers of generations 0 to 3 in an aqueous matrix. The multiple charging of PAMAM dendrimers generated by means of ESI has provided key advantages in dendrimer identification by assignation of charge state through high resolution of isotopic clusters. Isotopic distribution in function of abundance of isotopes ¹²C and ¹³C yielded valuable and complementarity data for confident characterization. A mass accuracy below 3.8 ppm for the most abundant isotopes (diagnostic ions) provided unambiguous identification of PAMAM dendrimers. Validation of the LC-ESI-QTOF-MS method and matrix effect evaluation enabled reliable and reproducible quantification. The validation parameters, limits of quantification in the range of 0.012 to 1.73 μM, depending on the generation, good linear range (R?>?0.996), repeatability (RSD?<?13.4 %), and reproducibility (RSD?<?10.9 %) demonstrated the suitability of the method for the quantification of dendrimers in aqueous matrices (water and wastewater). The added selectivity, achieved by multicharge phenomena, represents a clear advantage in screening aqueous mixtures due to the fact that the matrix had no significant effect on ionization, with what is evidenced by an absence of sensitivity loss in most generations of PAMAM dendrimers.

Strategy of Cr detoxification by Callitriche cophocarpa

The present work focused on the qualitative and quantitative analysis of Cr detoxification strategy of aquatic cosmopolitan plant Callitriche cophocarpa. This plant species has just been described in the context of its unusual accumulation potential of Cr. The emphasis of the work was placed on the redox reaction Cr(VI)→Cr(III) which is considered to be remediation mechanism of highly reactive and mobile Cr(VI) ions. Plants were immersed for 5 days in 1 mM of Cr(VI) (potassium dichromate) or 1 mM of Cr(III) (chromium sulphate) solutions in semi-natural conditions. Cr was effectively removed from the solution up to the extent of ca.58% or 35% of the starting amount, in the case of Cr(III) and Cr(VI), respectively. No plant-induced Cr(VI) reduction accompanying Cr accumulation was observed in Cr(VI) solutions except from the apparent one, noticed at the fourth day of incubation. On the contrary to these results, according to the method of electron paramagnetic resonance spectroscopy (L-band EPR), biphasic signal of Cr(V) attending Cr(VI) to Cr(III) reduction was detected inside the plant tissue every day of investigations. Our results show that phytoextraction but not phytostabilization is the main strategy of Cr detoxification by C. cophocarpa in aquatic systems.      

Voltammetric methods of reboxetine analysis and the mechanism of its electrode reactions

Reboxetine (RBX) electrochemical redox behavior at hanging mercury drop (HMDE) and glassy carbon electrodes (GCE) was studied in various pH Britton-Robinson universal buffers using cyclic voltammetry and square-wave voltammetry. RBX was reduced at the HMDE and oxidized at the GCE with reversible adsorption controlled and irreversible diffusion controlled processes respectively. The anodic peak is due to the amine and the cathodic peak may correspond to oxygen protonation. An oxidation reaction mechanism is proposed. The linear relation between peak currents and RBX concentration allowed simple, sensitive, precise and inexpensive voltammetric procedures to be developed. The limit of detection was 0.04 µM RBX. The procedures were successfully applied to human urine and RBX tablet assay. Therapeutic RBX concentrations in human serum were not detected due to strong drug-protein binding. Using bovine serum albumin, the methods were used to investigate the effect of serum protein binding on RBX determination.      

The zwitterionic structure of 2‐hydroxy‐4‐[(2‐hydroxybenzylidene)amino]benzoic acid

The title compound, C₁₄H₁₁NO₄, exists in the solid phase in the zwitterionic form, 2‐{[(4‐carboxy‐3‐hydroxyphenyl)iminiumyl]methyl}phenolate, with the H atom from the phenol group on the 2‐hydroxybenzylidene ring transferred to the imine N atom, resulting in a strong intramolecular N—H...O hydrogen bond between the iminium H atom and the phenolate O atom, forming a six‐membered hydrogen‐bonded ring. In addition, there is an intramolecular O—H...O hydrogen bond between the carboxylic acid group and the adjacent hydroxy group of the other ring, and an intermolecular C—H...O contact involving the phenol group and the C—H group adjacent to the imine bond, connecting the molecules into a two‐dimensional network in the (10) plane. π–π stacking interactions result in a three‐dimensional network. This study is important because it provides crystallographic evidence, supported by IR data, for the iminium zwitterionic form of Schiff bases.<!?tpb=12pt>