Ab initio simulations of liquid electrolytes for energy conversion and storage

Understanding physicochemical properties of liquid electrolytes is essential for predicting and optimizing device performance for a wide variety of emerging energy technologies, including photoelectrochemical water splitting, supercapacitors, and batteries. In this work, we review recent progress and open challenges in predicting structural, dynamical, and electronic properties of the liquids using first-principles approaches. We briefly summarize the basic concepts of first-principles molecular dynamics (FPMD), and we discuss how FPMD methods have enriched our understanding of a number of liquids, including aqueous solutions, organic electrolytes and ionic liquids. We also discuss technical challenges in extending FPMD simulations to the study of liquid electrolytes in more complex environments, including the interface between electrolytes and electrodes, which is a key component in many energy storage and conversion systems.     

Electrochemical and spectroelectrochemical characterization of Ru(2)(4+) and Ru(2)(3+) complexes under a CO atmosphere

Eleven different Ru(2)(4+) and Ru(2)(3+) derivatives are characterized by thin-layer FTIR and UV-visible spectroelectrochemistry under a CO atmosphere. These compounds, which were in-situ electrogenerated from substituted anilinopyridine complexes with a Ru(2)(5+) core, are represented as Ru(2)(L)(4)Cl where L = 2-CH(3)ap, ap, 2-Fap, 2,3-F(2)ap, 2,4-F(2)ap, 2,5-F(2)ap, 3,4-F(2)ap, 3,5-F(2)ap, 2,4,6-F(3)ap, or F(5)ap. The Ru(2)(5+) complexes do not axially bind CO while mono- and bis-CO axial adducts are formed for the Ru(2)(4+) and Ru(2)(3+) derivatives, respectively. Six of the eleven investigated compounds exist in a (4,0) isomeric form while five adopt a (3,1) geometric conformation. These two series of compounds thus provide a large enough number of derivatives to examine trends and differences in the spectroscopic data of the two types of isomers in their lower Ru(2)(4+) and Ru(2)(3+) oxidation states. UV-visible spectra of the Ru(2)(4+) derivatives and IR spectra of the Ru(2)(3+) complexes under CO are both isomer dependent, thus suggesting that these data can be used to reliably predict the isomeric form, i.e., (3,1) or (4,0), of diruthenium complexes containing four unsymmetrical substituted anilinopyridinate bridging ligands; this was confirmed by X-ray crystallographic data for seven compounds whose structures were available.     

A nanocomposite prepared from FeOOH and N-doped carbon nanosheets as a peroxidase mimic,and its application to enzymatic sensing of glucose in human urine

A method is described for the synthesis of a nanocomposite containing FeOOH and N-doped carbon nanosheets. The nanocomposite was synthesized by a hydrothermal method using a Fe₃O₄/chitosan nanocomposite as the precursor. The nanocomposite displays peroxidase-like activity and catalyzes the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) by H₂O₂. This results in the formation of a blue colored product with an absorption maximum at 652 nm in the UV-vis spectra. Based on these findings, colorimetric assays were worked out for both hydrogen peroxide and glucose. The H₂O₂ assay works in the 5 to 19 μM concentration range, and the limit of detection is 5 nM. The glucose assay works in the 8 μM to 0.8 mM concentration range and has a 0.2 μM detection limit. The method was successfully applied to the determination of glucose in human urine.

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Graphical abstract Schematic of the hydrothermal synthesis of a FeOOH/N-doped carbon nanocomposite. It was used to replace peroxidase enzyme for the catalytic oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in a visual colorimetric test for glucose in human urine.

     

Improved method for the determination of sulfur components in natural gas

Determination of trace concentrations of sulfur components in natural gas is a true analytical challenge. Only analytical procedures based on gas chromatography can meet the sensitivity and accuracy requirements dictated by environmental regulation institutions and modern chemical industry. In the present contribution the sample pretreatment and chromatographic separation steps have been evaluated and optimized based on the use of a flamebased sulfur chemiluminescence detector (SCD) for target compound detection. The proposed instrument consists of a programmed temperature vaporizing (PTV) injector employing a liner packed with Chromosorb 104, a 4 μm thick film apolar column and a flame-based SCD. Using a 13 mL sample loop the detection limit achievable with the new method is 3 μg S/m³. The precision of replicate measure. ments is generally in the range of 5–15% relative standard deviation. Lower detection limits can be achieved by preconcentrating larger sample volumes, e.g. 100 mL.     

Solution/Ammonolysis Syntheses of Unsupported and Silica-Supported Copper(I) Nitride Nanostructures from Oxidic Precursors

Herein we describe an alternative strategy to achieve the preparation of nanoscale Cu₃N. Copper(II) oxide/hydroxide nanopowder precursors were successfully fabricated by solution methods. Ammonolysis of the oxidic precursors can be achieved essentially pseudomorphically to produce either unsupported or supported nanoparticles of the nitride. Hence, Cu₃N particles with diverse morphologies were synthesized from oxygen-containing precursors in two-step processes combining solvothermal and solid−gas ammonolysis stages. The single-phase hydroxochloride precursor, Cu₂(OH)₃Cl was prepared by solution-state synthesis from CuCl₂·2H₂O and urea, crystallising with the atacamite structure. Alternative precursors, CuO and Cu(OH)₂, were obtained after subsequent treatment of Cu₂(OH)₃Cl with NaOH solution. Cu₃N, in the form of micro- and nanorods, was the sole product formed from ammonolysis using either CuO or Cu(OH)₂. Conversely, the ammonolysis of dicopper trihydroxide chloride resulted in two-phase mixtures of Cu₃N and the monoamine, Cu(NH₃)Cl under similar experimental conditions. Importantly, this pathway is applicable to afford composite materials by incorporating substrates or matrices that are resistant to ammoniation at relatively low temperatures (ca. 300 °C). We present preliminary evidence that Cu₃N/SiO₂ nanocomposites (up to ca. 5 wt.% Cu₃N supported on SiO₂) could be prepared from CuCl₂·2H₂O and urea starting materials following similar reaction steps. Evidence suggests that in this case Cu₃N nanoparticles are confined within the porous SiO₂ matrix.     

Secondary Metabolites from the Fruiting Bodies of Coriolopsis aspera in Vietnam and their Bioactivities

Chemistry of Natural Compounds -     

用硼酸作催化剂一锅法合成双（二氢化嘧啶酮-4-基）苯

A simple effective synthesis of bis(dihydropyrimidinone-4-yl)benzene derivatives, using boric acid as catalyst,from isophthalic aldehyde or terephthalic aldehyde, 1,3-dicarbonyl compounds and urea or thiourea in glacial acetic acid was described. As the expansion of the classical Biginelli reaction, this method has the advantage of excellent yields 83%-94% and short reaction time 0.5-1.5 h.     

3-(Triethoxysilyl)propionitrile sol-gel coating

3-(Triethoxysilyl)propionitrile (TESPN) sol-gel has been prepared under different conditions. It was employed for coating the surfaces of quartz and aluminum. Infrared (IR) and Raman spectra of TESPN and TESPN sol-gels have been recorded in the study of the sol-gel process. Transmission and reflection absorption IR (RAIR) spectra of TESPN sol-gel coated quartz and aluminum have also been collected for better understanding the film formation on the substrate surfaces. Spectra collected at different temperatures indicated that the silane film on quartz decomposes at 700 degrees C. Results from thermal gravimetric analysis (TGA) supported this result. Based on the group frequencies and the spectral behavior in different states, some vibrational modes were assigned to the observed bands. The anticorrosion behavior of the sol-gel coated aluminum in comparison with the uncoated metal was evaluated by measuring the potentiodynamic polarization and electrochemical impedance spectra (EIS).     

“Printing” DNA Strand Patterns on Small Molecules with Control of Valency,Directionality, and Sequence

The incorporation of synthetic molecules as corner units in DNA structures has been of interest over the last two decades. In this work, we present a facile method for generating branched small molecule‐DNA hybrids with controllable valency, different sequences, and directionalities (5′–3′) using a “printing” process from a simple 3‐way junction structure. We also show that the DNA‐imprinted small molecule can be extended asymmetrically using polymerase chain reaction (PCR) and can be replicated chemically. This strategy provides opportunities to achieve new structural motifs in DNA nanotechnology and introduce new functionalities to DNA nanostructures.