Photocatalytic Reduction of Cr (VI) over g-C3N4 Photocatalysts Synthesized by Different Precursors

Graphitic carbon nitride (g-C₃N₄) photocatalysts were synthesized via a one-step pyrolysis process using melamine, dicyandiamide, thiourea, and urea as precursors. The obtained g-C₃N₄ materials exhibited a significantly different performance for the photocatalytic reduction of Cr(VI) under white light irradiation, which is attributed to the altered structure and occupancies surface groups. The urea-derived g-C₃N₄ with nanosheet morphology, large specific surface area, and high occupancies of surface amine groups exhibited superior photocatalytic activity. The nanosheet morphology and large surface area facilitated the separation and transmission of charge, while the high occupancies of surface amine groups promoted the formation of hydrogen adsorption atomic centers which were beneficial to Cr(VI) reduction. Moreover, the possible reduction pathway of Cr(VI) to Cr(III) over the urea-derived g-C₃N₄ was proposed and the reduction process was mainly initiated by a direct reduction of photogenerated electrons.     

Electronic effects of the functional groups in ortho-Nitrobenzenesulfonic acids on the results of NBO analysis

An NBO analysis of electronic density distribution is performed for gaseous benzenesulfonic acid and its mono- and trinitro-substituted molecules (B3LYP, MP2, HF /cc-pVTZ). The energy of orbital inter-actions of nitro and sulfonic groups with benzene ring orbitals is calculated for the most stable acid conformers, and the contributions of inductive and resonance effects of substituents are determined. The dependences of these contributions on the positions and number of nitro groups in an aromatic ring and the possibility of intramolecular hydrogen bond formation are revealed. The nitro group in nitrobenzene exhibits a stronger electron-acceptor effect than the sulfonic group in benzenesulfonic acid. Under the influence of the strong electron-acceptor properties of the nitrogroups, the sulfonic group has a donating effect in ortho-nitrosubstituted benzenesulfonic acids.     

Synthesis of beta-lactams from a N-rhenaimine: effect of the transition metal on the energetic profile of the Staudinger reaction

As depicted in the scheme, the alkylidenamido complex 1, a N-rhenaimine, reacts with ketenes to afford the beta-lactams 2-4, which possess a {Re(CO)3(bpy)} fragment as substituent at nitrogen. Clean demetalations using HOTf or MeOTf yield the free beta-lactams or N-methyl-beta-lactams along with [Re(OTf)(CO)3(bpy)]. DFT calculations help to rationalize why the reaction is faster than those of non transition metal N-substituted imines.     

Binding of protein to polystyrene particles in the presence of polyvinylpyrrolidone in the surface layer

Adsorption and chemisorption of bovine serum albumin on polystyrene particles obtained by dispersion polymerization and containing graft polystyrene/polyvinylpyrrolidone copolymers and carboxy groups of the initiator in the surface layer were studied.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 12, 2004, pp. 2036–2041.Original Russian Text Copyright © 2004 by Menshikova, Skurkis, Evseeva, Shkarubskaya, Tennikova, Ivanchev.     

Seasonal variations of the composition,structural features,and antitumor properties of polysaccharides from <Emphasis Type=Italic>Padina pavonica</Emphasis> (Lebanon) as a function of composition

The variation of the polysaccharide composition of the brown alga Padina pavonica from the Mediterranean Sea was studied as a function of the collection season (April–July). It was shown that the principal polysaccharide (8.0-13.3% of dry alga weight) was alginic acid. Its content did not undergo significant changes from April to July. The content of water-soluble polysaccharides (laminarans and fucoidans) was low (<0.3% of dry alga weight). Water-soluble polysaccharides of the studied alga were practically pure fucoidan. The amount of laminarans was insignificant (<0.01% of dry alga weight). The content of fucoidans increased in alga samples from May through July. It was shown that P. pavonica is a promising source of alginic acids, which have a high capacity for gelation, and fucoidans, which exhibit antitumor action against RPMI-7951 human melanoma cells.     

A facile and efficient synthetic method for 4-phenylethynylphthalic anhydride

A novel approach to the synthesis of 4-phenylethynylphthalic anhydride has been described.The target compound was synthesized by Pd/Cu catalyzed Sonogashira coupling reaction between phenylacetylene and 4-bromophthalic acid which was for the first time employed as start material,followed by dehydration of 4-phenylethynylphthalic acid.Compared with traditional synthetic routes,this method provides several advantages such as readily available raw materials,convenient manipulation and high yield.The product...     

A Facile Method for Preparation of Superhydrophobic Surfaces with Poly(furfuryl Alcohol)/PTFE Composites

A stable superhydrophobic surface have been fabricated with poly(furfuryl alcohol) (PFA)/polytetrafluoroethylene (PTFE) composite coatings on steel substrates by using a facile method. The observation of field emission scanning electron microscopy revealed that the hierarchical microstructures formed on the surfaces are controlled by varying the curing temperature. This method can be easily operated on substrates of steel, therefore is readily developed to other engineering metal substrates such as aluminum, copper, etc.     

Thermodynamics of alpha-Cyclodextrin-p-Nitrophenyl Glycoside Complexes. A Simple System To Understand the Energetics of Carbohydrate Interactions in Water

Thermodynamic studies of the binding of a series of p-nitrophenyl glycosides (PNPGly) of varying stereochemistry to alpha-cyclodextrin (alpha-CD) were performed at three different temperatures (25, 35, and 42 degrees C) using a microcalorimetric technique. The system p-nitrophenol (PNP) at pH = 3 and alpha-CD was also studied for the sake of comparison. All these complexes were found to be enthalpy driven with a favorable enthalpic term clearly dominant over an unfavorable entropic term. A clear enthalpy-entropy compensation effect was observed at all the temperatures, with a slope close to unity (alpha = 1.02) and an intercept TDeltaS degrees (o) = 2.91 kcal mol(-)(1). This thermodynamic pattern is in agreement with those usually found for lectin-carbohydrate associations and for the binding processes of several host-guest systems. This pattern is explained in terms of the contribution of primarily two driving forces: the van der Waals interactions between the host and the guest, and the solvation/desolvation processes which accompany the association reaction. The presence of the carbohydrate molecule in the PNP ring causes a slight destabilization of the complex at 25 degrees C with respect to the alpha-CD-PNP (pH = 3) complex, although a different behavior has been observed depending on the axial/equatorial configuration of the glycoside and the temperature. This behavior is modulated by the stereochemistry of the glycoside. Differences were observed between the deoxy-derivatives (LAra and LFuc) and those derivatives with a hydroxymethyl group (Glc, Gal, Man). DeltaC(p) degrees values were obtained from the dependency of DeltaH degrees on temperature (=( partial differentialDeltaH degrees / partial differentialT)(p)). These values are small and negative except for alphaMan complex. For the latter complex, discrepancy between the calorimetric and the calculated van't Hoff enthalpies was observed. Parallels are drawn between the thermodynamics of our model and those proposed for carbohydrate-protein associations.     

Synthesis and photophysical properties of silica nanoparticles based on europium(iii) complexes

Monodisperse 280?C480 nm silica particles doped with europium complexes with thenoyltrifluoroacetylacetone and adducts with some phosphine oxides as luminophores were prepared for the first time by the optimized Stober procedure using surfactants. The size and the polydispersity of the obtained particles depend on the luminophore incorporated in the polymer template. The photophysical properties of aqueous dispersions of the europium(iii)-doped silica particles were studied by the luminescence method.