Quadruplex-Templated and Catalyzed Ligation of Nucleic Acids

Template-guided chemical reactions between nucleic acid strands are an important process in biomedical research. However, almost all of these reactions employ an oligonucleotide-templated approach that is based on the double-helix alignment. The moderate stability of the double helix makes this approach unsuitable for many chemical reactions, so alternative nucleic acid alignment mechanisms, demonstrating higher thermal and chemical stability, are desirable. Earlier, we described a noncovalent coupling mechanism between DNA strands through a quadruplex-and-Mg²⁺ connection (QMC). QMC is based on G-quadruplexes and allows unusually stable and specific interactions. Herein, a novel catalytic nucleic acid reaction, based on QMC, is described. This approach uses G-tetrads as a structural and recognition element without employing Watson-Crick complementarity rules at any stage of substrate/catalyst formation or interaction between them. Quadruplex-templated ligation can be achieved through the self-ligation of two nucleic acid strands, or through a quadruplex catalyst, which forms a G-triplex and specifically connects the strands. The process is extraordinarily robust and efficient. For instance, the ligation of carbodiimide-activated substrates can proceed in boiling solutions, and complete ligation is demonstrated within a minute. The quadruplex-templated and catalyzed reactions will create new opportunities for chemical reactions requiring harsh experimental conditions.     

State-of-the-art technology: Recent investigations on laser-mediated synthesis of nanocomposites for environmental remediation

In both developing and industrialized/developed countries, various hazardous/toxic environmental pollutants are entering water bodies from organic and inorganic compounds (heavy metals and specifically dyes). The global population is growing whereas the accessibility of clean, potable and safe drinking water is decreasing, leading to world deterioration in human health and limitation of agricultural and/or economic development. Treatment of water/wastewater (mainly industrial water) via catalytic reduction/degradation of environmental pollutants is extremely critical and is a major concern/issue for public health. Light and/or laser ablation induced photocatalytic processes have attracted much attention during recent years for water treatment due to their good (photo)catalytic efficiencies in the reduction/degradation of organic/inorganic pollutants. Pulsed laser ablation (PLA) is a rather novel catalyst fabrication approach for the generation of nanostructures with special morphologies (nanoparticles (NPs), nanocrystals, nanocomposites, nanowires, etc.) and different compositions (metals, alloys, oxides, core-shell, etc.). Laser ablation in liquid (LAL) is generally considered a quickly growing approach for the synthesis and modification of nanomaterials for practical applications in diverse fields. LAL-synthesized nanomaterials have been identified as attractive nanocatalysts or valuable photocatalysts in (photo)catalytic reduction/degradation reactions. In this review, the laser ablation/irradiation strategies based on LAL are systematically described and the applications of LAL synthesized metal/metal oxide nanocatalysts with highly controlled nanostructures in the degradation/reduction of organic/inorganic water pollutants are highlighted along with their degradation/reduction mechanisms.     

Improvement of Ni-Cermet performance of protonic ceramic fuel cells by catalyst

Generally, the NiO composite anode becomes porous after reduction. To infiltrate additional catalysts such as Pd into the NiO-composite anode before reducing NiO to Ni, a porous NiO composite anode for protonic ceramic fuel cells (PCFCs) was fabricated in this study. The porous NiO composite was fabricated by adding graphite as a pore former along with CuO as a sintering agent. The addition of graphite increased the porosity of the NiO composite anode but resulted in poor sinterability, which was addressed by adding CuO as a sintering agent to the NiO composite anode. The Pd catalyst was added to the NiO-composite anode before reducing NiO to Ni. The composite anode for PCFC with three components, namely Ni, protonic ceramics, and a Pd catalyst, was obtained by reducing NiO to Ni during the measurement. The addition of the Pd catalyst improved the anode performance in methane fuel and hydrogen fuel by enhancing the catalytic activity for the electrochemical reaction on the surface.     

Synthesis and Characterization of Co Nanocomposite Based on Poly(benzimidazole-amide) Matrix and Their Behavior as Catalyst in Oxidation Reaction

2,6-Bis(5-amino-1H-benzimidazol-2-yl)pyridine was prepared and characterized by Fourier transform infrared spectroscopy, elemental analysis, ¹H-NMR, and ¹³C-NMR spectroscopic methods. Then a new poly(benzimidazole-amide) was synthesized by polymerization of the corresponding diamine and isophthalic acid. The obtained poly(benzimidazole-amide) exhibited good yield and high thermal stability. Due to the existence of benzimidazole moieties in polymer’s structure, it has the tendency to form complexes with metal ions. So, a new poly(benzimidazole-amide)/Co nanocomposite was prepared. Morphological studies revealed that metal nanoparticles were dispersed in the polymer matrix without any aggregation. poly(benzimidazole-amide)/Co nanocomposite was used as a catalyst in the oxidation of ethyl benzene to acetophenone with tert-butyl hydroperoxide.     

Review on synthesis of porous TiO2-based catalysts for energy conversion systems

Porous TiO₂-based catalysts have recently received remarkable attention in the field of energy conversion systems, including hydrogen/oxygen evolution reaction, oxygen/nitrogen reduction reaction, and photodegradation of pollutants owing to their unique structure, large surface area, and good chemical stability. In this report, we review existing research on porous TiO₂-based catalysts for energy conversion systems during the past four years. First, the advantages of porous TiO₂-based catalysts are introduced. Next, the synthetic approaches in developing porous TiO₂-based catalysts are summarized. The different types of energy conversion systems based on porous TiO₂-based catalysts are then presented. Finally, the challenges and future perspectives in synthesizing porous TiO₂-based catalysts are discussed.     

Highly stable nanocarbon supported Pt catalyst for fuel cell via a molten salt graphitization strategy

Proton exchange membrane fuel cells (PEMFCs) durability has been severely hindered by carbon support poor stability in the cathodic Pt-based catalyst. Herein, a high-surface-area nitrogen-doped graphitic nanocarbon (N-G-CA) with mesopores is developed as Pt support to address PEMFCs durability challenge. Resorcinol-formaldehyde aerogel pyrolyzed carbon aerogel is selected as N-G-CA raw material. Nitrogen atoms are introduced into carbon aerogel via NH₃ heat treatment. Then, nitrogen-doped carbon aerogel is transferred into N-G-CA via heating together with transition-metal salts (one of FeCl₃, FeCl₂, CoCl₂, or MnCl₂, etc.) at 1200 °C. As ORR catalyst, Pt/N-G-CA half-wave potential only lost 10 mV, after 30, 000 cycles accelerated aging test in the rotating-desk-electrode. Only 12 mV voltage loss at 1.5 A/cm2 is observed, after 5, 000 cycles for membrane electrode. Pt/N-G-CA exhibits superior durability and activity than commercial Pt/C. High durability of Pt/N-G-CA is due to N-G-CA high graphitization extent, as well as the interactions between doping nitrogen and Pt. N-G-CA is promising as stable support for durable Pt-based catalysts in PEMFCs, thanks to enhanced carbon corrosion resistance, uniformly dispersed Pt, and strong support-metals interaction.     

作为城市触媒的公共文化设施及其设计

首先阐述了城市触媒的概念和内涵,然后从城市触媒的角度对公共文化设施及其设计进行了思考,分析了国内外公共文化设施的最新实例以及设计趋向和建设模式,最后指出了对当前我国公共文化设施建设的启示和指导意义.     

La0.8Sr0.2Cr0.95Ru0.05O3−x and Sm0.8Ba0.2Cr0.95Ru0.05O3−x as partial oxidation catalysts for diesel

La_0.8Sr_0.2Cr_0.95Ru_0.05O_3−x (LSCR) and Sm_0.8Ba_0.2Cr_0.95Ru_0.05O_3−x (SBCR), Ru-substituted perovskite catalysts, are investigated for the partial oxidation (POX) of diesel to produce hydrogen-rich gases for fuel cell applications. Metal-substituted perovskite materials have been investigated as reforming catalysts because the metal atoms are well-dispersed in the perovskite structure. However, Ru de-mixing and a secondary phase of LSCR and SBCR are observed after reduction at high temperature. The thermal stability, sulfur tolerance and aromatic decomposition over LSCR and SBCR are compared to those over Ru on Ce_0.9Gd_0.1O_2−x (CGO). During the thermal stability test, the catalytic activities of LSCR and SBCR improve after operating at 1000 °C. The sulfur tolerance and aromatic decomposition activity of LSCR and SBCR improve when the temperature increases to 950 °C. The improvements are attributed to the de-mixed Ru from the perovskite structure at high temperatures under a reductive atmosphere.     

Development of new high-throughput screening method to compare and to detect efficient catalysts for adhesive materials

Organotin compounds particularly dibutyltin dilaurate, are commonly used as catalysts in coatings or adhesive materials to crosslink silyl modified polymers. However, environmental concerns should lead before 2020 to ban organotin compounds due to their high toxicity. Thus new catalysts must be developed. According to the different types of catalytic systems, i.e. acid, basic or metal containing catalysts, a large variety of candidates should be tested. Thus a high-throughput screening (HTS) method could be an interesting tool for the detection of new efficient catalysts to substitute organotin compounds. We report a global HTS method, compatible with organic amino or acid catalysts libraries, as well as with metal-containing libraries.     

Direct thermochemical liquefaction of microcrystalline cellulose by sub- and supercritical organic solvents

Direct thermochemical liquefaction of microcrystalline cellulose was carried out using sub- and supercritical solvents in a batch reactor. The decomposition efficiency of dodecane and m-xylene widely used in petrochemical industries was compared to that of methanol and 1,4-dioxane. At 400 °C, the conversion in methanol was the highest (92 wt% including gaseous products), but the operating pressure was too high. m-Xylene at the same temperature showed the conversion of 71.5 wt% with a lower number of products and milder pressure. Hydrogen contributed to the increase of the total conversion by 3–8% in m-xylene and methanol, compared with the results without adding any additional gas or with nitrogen pressurization. An acid-modified silica catalyst led to a significant increase of conversion in the supercritical methanol, but its effect was negligible in the aprotic solvents. The product compounds and property of solid residue depended on the supercritical solvents applied. The thermal-treated char after liquefaction in m-xylene, dodecane and 1,4-dioxane was an effective adsorbent for CO₂ adsorption, showing the level comparable with activated carbons.