Nickel-Doped Decatungstate as a Robust Photocatalyst for Violet Light-Triggered Redox Coupling Conversion of Alcohol and Water to Aldehyde/Ketone and Hydrogen.

The effective coupling of photoinduced alcohol oxidation and water reduction may economically produce hydrogen (H2) from water, which is of great significance in solving the current energy crisis. This study discloses that decatungstate (DT) and especially Ni2+ions-doped DTs are active for the photoreaction of benzyl alcohol with H2O, and under 48 h of violet light illumination, the best 1%Ni-DT yields ca. 86.1% benzoic acid and a 4.65 h-1 H2 generation efficiency (turnover frequency, TOF). Also, 1%Ni-DT is efficient for the photoredox coupling reaction of aliphatic and especially aromatic primary/secondary alcohols with water. A series of characterizations support that the doubled-reduced H2DT produced from the photoreaction plays a key role in water reduction to H2, which is accelerated by the doped Ni2+. In particular, it and the derived Ni3+ may construct a Z-type catalyst for water overall splitting, thereby hoisting the acid yield and H2 amount in the later stage of the photoreaction.

Hybridizing Engineering Strategy of Decatungstate. 2. Regulated Effect of Doping Transition Metal Ions on Photocatalytic Oxidation Performance of (nBu4N)4W10O32.

This paper discloses a simple and productive hybridizing engineering (HE) strategy for the 3d transition-metal-ion (Mn+ = Fe3+, Fe2+, Co2+, Ni2+)-doped (nBu4N)4W10O32 (Mn+-TBADT) compounds as highly efficient visible-light catalysts. Ultraviolet visible (UV-vis), Fourier transform infrared (FT-IR) and photoluminescence (PL) spectra, and cyclic voltammetry (CV) characterizations indicate that the synthetic quality, redox capacity, and visible light harvesting efficiency of TBADT, especially the separation efficiency of its photogenerated electron-hole pairs, are regulated by the metal ion dopants and gradually improved with a change of the dopant from Fe3+, Fe2+, and Co2+ to Ni2+, along with a continuous and significant enhancement of its photocatalytic efficiency in the visible-light-triggered selective oxidation of ethylbenzene with dioxygens in acetonitrile. The best 0.5 mol % Ni2+-doped TBADT can achieve a ca. 55% conversion under optimal reaction conditions and also exhibits much higher photocatalytic activity for the photo-oxidation of toluene, cyclohexane, and benzyl alcohol compared to pure TBADT. This HE strategy showcases great potential in improving the photocatalysis performance of TBADT.

Visible-Light-Triggered Quantitative Oxidation of 9,10-Dihydroanthracene to Anthraquinone by O2 under Mild Conditions.

The development of mild and efficient processes for the selective oxygenation of organic compounds by molecular oxygen (O2 ) is key for the synthesis of oxygenates. This paper discloses an atom-efficient synthesis protocol for the photo-oxygenation of 9,10-dihydroanthracene (DHA) by O2 to anthraquinone (AQ), which could achieve quantitative AQ yield (100 %) without any extra catalysts or additives under ambient temperature and pressure. A yield of 86.4 % AQ was obtained even in an air atmosphere. Furthermore, this protocol showed good compatibility for the photo-oxidation of several other compounds with similar structures to DHA. From a series of control experiments, free-radical quenching, and electron paramagnetic resonance spin-trapping results, the photo-oxygenation of DHA was probably initiated by its photoexcited state DHA*, and the latter could activate O2 to a superoxide anion radical (O2 .- ) through the transfer of its electron. Subsequently, this photo-oxidation was gradually dominated by the oxygenated product AQ as an active photocatalyst obtained from the oxidation of DHA by O2 .- , and was accelerated with the rapid accumulation of AQ. The present photo-oxidation protocol is a good example of selective oxygenation based on the photoexcited substrate self-activated O2 , which complies well with green chemistry ideals.

An efficient calcium phosphate nanoparticle-based nonviral vector for gene delivery.

BACKGROUND: Smaller nanoparticles facilitate the delivery of DNA into cells through endocytosis and improve transfection efficiency. The aim of this study was to determine whether protamine sulfate-coated calcium phosphate (PS-CaP) could stabilize particle size and enhance transfection efficiency. METHODS: pEGFP-C1 green fluorescence protein was employed as an indicator of transfection efficiency. Atomic force microscopy was used to evaluate the morphology and the size of the particles, and an MTT assay was introduced to detect cell viability and inhibition. The classical calcium phosphate method was used as the control. RESULTS: Atomic force microscopy images showed that the PS-CaP were much smaller than classical calcium phosphate particles. In 293 FT, HEK 293, and NIH 3T3 cells, the transfection efficiency of PS-CaP was higher than for the classical calcium phosphate particles. The difference in efficiencies implies that the smaller nanoparticles may promote the delivery of DNA into cells through endocytosis and could improve transfection efficiency. In addition, PS-CaP could be used to transfect HEK 293 cells after one week of storage at 4°C with a lesser extent of efficiency loss compared with classical calcium phosphate, indicating that protamine sulfate may increase the stability of calcium phosphate nanoparticles. The cell viability inhibition assay indicated that both nanoparticles show similar low cell toxicity. CONCLUSION: PS-CaP can be used as a better nonviral transfection vector compared with classical calcium phosphate.

DNA solution of a graph coloring problem.

The graph-theoretic parameter that has probably received the most attention over the years is the chromatic number. As is well-known, the coloring problem is an NP-Complete problem. In this paper, it has been solved by means of molecular biology techniques. The algorithm is highly parallel and has satisfactory fidelity. This work shows further evidence for the ability of DNA computing to solve NP-Complete problems.

Some notes on 2-D graphical representation of DNA sequence.

Some 2-D and 3-D graphical representations of DNA sequences have been given by Nandy, Leong and Mogenthaler, and Randic et al., which give visual characterizations of DNA sequences. In this paper, we presented a novel graphical representation of DNA sequences by taking four special vectors in 2-D Cartesian coordinate system to represent the four nucleic acid bases in DNA sequences, so that a DNA sequence is denoted on a plane by a directed walk. It is shown that the new graphical representation of DNA sequences has lower or nondegeneracy.