Low-Temperature Reaction of Aurivillius Phases with Halides

Kijima et al. [T. Kijima, S. Kimura, Y. Kawahara, K. Ohe, M. Yada, and M. Machida, J. Solid State Chem. 146, 60 (1999)] recently reported a reaction between Bi₄Ti₃O₁₂ and LiI in the presence of iodine at 350°C. Their product was never obtained free of Bi₄Ti₃O₁₂, but their claim was that their product was Bi₄Ti₃O₁₂ intercalated with I and Li. We have repeated this reaction and found conditions under which the reaction goes to completion, i.e., Bi₄Ti₃O₁₂ is completely consumed. The dominant crystalline product is apparently identical to the product reported by Kijima et al. However, we conclude that no intercalation of Bi₄Ti₃O₁₂ has occurred. This dominant crystalline phase is in fact BiOI. The remainder of the product is poorly crystalline. Analogous reactions occur at low temperature using other halides such as NaCl and other Aurivillius phases such as Bi₂WO₆.     

A New Method of Synthesis of Nanosized Metal Oxide Powders

A new method of synthesis of nanosized metal oxide powders (Al₂O₃, MgO, ZnO) has been suggested. The method involves successive heat treatment at 350°С and then at 800°С of saturated solutions of the corresponding metal salts and sucrose. Physicochemical and technological properties of the synthesized materials have been determined.     

A New Class of Homogeneous Visible‐Light Photocatalysts: Molecular Cerium Vanadium Oxide Clusters

The first systematic access to molecular cerium vanadium oxides is presented. A family of structurally related, di‐cerium‐functionalized vanadium oxide clusters and their use as visible‐light‐driven photooxidation catalysts is reported. Comparative analyses show that photocatalytic activity is controlled by the cluster architecture. Increased photoreactivity of the cerium vanadium oxides in the visible range compared with nonfunctionalized vanadates is observed. Based on the recent discovery of the first molecular cerium vanadate cluster, (nBu₄N)₂[(Ce(dmso)₃)₂V₁₂O₃₃Cl] ? 2 DMSO ( 1 ), two new di‐cerium‐containing vanadium oxide clusters [(Ce(dmso)₄)₂V₁₁O₃₀Cl] ? DMSO ( 2 ) and [(Ce(nmp)₄)₂V₁₂O₃₂Cl] ? NMP ? Me₂CO ( 3 ; NMP=N‐methyl‐2‐pyrrolidone) were obtained by using a novel fragmentation and reassembly route. Pentagonal building units {(V)M₅} (M=V, Ce) reminiscent of “Müller‐type” pentagons are observed in 2 and 3 . Compounds 1 – 3 feature high visible‐light photooxidative activity, and quantum efficiencies >10 % for indigo photooxidation are observed. Photocatalytic performance increases in the order 1 < 3 < 2 . Mechanistic studies show that the irradiation wavelength and the presence of oxygen strongly affect photoreactivity. Initial findings suggest that the photooxidation mechanism proceeds by intermediate formation of hydroxyl radicals. The findings open new avenues for the bottom‐up design of sunlight‐driven photocatalysts.     

Metallomesogens: Metal Complexes in Organized Fluid Phases

Metallomesogens, metal complexes of organic ligands which exhibit liquid crystalline (mesomorphic) character, combine the variety and range of metal-based coordination chemistry with the extraordinary physical properties exhibited by liquid crystals. Thermotropic metallomesogens have been made incorporating many metals, including representatives of s-, p-, d-and even f-block elements. Both rodlike (calamitic) and disklike (discotic) thermotropic metallomesogens are known, and examples of all the main mesophase types are found. Many different varieties of ligand can be used: monodentate (4-substituted pyridines), bidentate (β-diketonates, dithiolenes, carboxylates, cyclometalated aromatic amines), or polydentate (phthalocyanines, porphyrins). As with organic mesogens, molecular shape and intermolecular forces play an important role, i.e. the ligands are important in determining mesophase character. The chief requirement for a metallomesogen is a rigid core, usually unsaturated and either rod- or disklike in shape, bearing several long hydrocarbon tails. The metal atom is usually at or near the center of gravity of the molecule. In some cases the ligands are themselves mesogenic, but this is not a requirement. The presence of one or more metals opens many exciting possibilities: new shapes, not easily generated by organic compounds, and hence new properties are then accessible. The incorporation of d-block metals brings with it features such as color and paramagnetism. Profound effects arise from the large and polarizable concentration of electron density that every metal atom possesses, since the molecular polarizability is a key factor in determining whether a molecule will form liquid crystals. Enhanced physical properties (e.g. high birefringencies), as well as new and unexpected ones, will result. A major requirement for metallomesogens to find applications in new device technology is that the metal–ligand bonds are strong and inert and the complexes stable; this can be accomplished with, for example, chelating ligands and the 5d metals.     

Antimicrobial Treatment of Different Metal Oxide Nanoparticles: A Critical Review

Many nanomaterials can be used as metal oxides (Ti, Ag, Zn, Cu, Mg, Ca, Ce, Yt, Al). Metal oxide nanoparticles have strong antimicrobial properties. The oxides that play a large role as antimicrobial agents can be divided into two major groups based on their mechanism of action i.e., those that involve oxidation and those that inhibit the production of Reactive Oxygen Species (ROS). Previous studies have shown that, toxic metals like silver and titanium, and their metals oxides, employ the ROS‐mediated mechanism that leads to oxidative stress‐related cytotoxicity, cancer, and heart diseases. Oxidative stress further leads to increased ROS production and also delays the cellular processes involved in wound heal‐ ing. Other metal oxide nanoparticles, like Y₂O₃, CeO₂ and Al₂O₃ act as free radical scavengers. Out of these, aluminium oxide nanoparticles are more effective antimicrobial agents, than the other metal oxide nanoparticles. A combination of Al₂O₃ and other antimicrobial agents such as TiO₂ may act as ideal antimicrobial agents, along with possessing free radical scavenging activity. This critical review aims to study the antimicrobial properties of different metal oxide nanoparticles and the mechanism of action in‐ volved, besides comparing their efficacy to eliminate bacteria.     

A New Class of Organocatalysts: Sulfenate Anions

Sulfenate anions are known to act as highly reactive species in the organic arena. Now they premiere as organocatalysts. Proof of concept is offered by the sulfoxide/sulfenate‐catalyzed (1–10 mol %) coupling of benzyl halides in the presence of base to generate trans‐stilbenes in good to excellent yields (up to 99 %). Mechanistic studies support the intermediacy of sulfenate anions, and the deprotonated sulfoxide was determined to be the resting state of the catalyst.     

Diamidopyrazoles: A New Class of Anion Receptors

The synthesis of a series of 3,5-diamidopyrazoles is reported. The anion binding properties of these systems were examined via ¹H NMR, UV/Vis and ITC titration techniques. Target compound 2a acts as a selective receptor for phosphate and sulfate anions in DMSO, whereas N-methylated 2b and the unmethylated species 4d show no appreciable binding affinity. Insights into the binding events occurring in solution came from the solid state structures of compounds 2a and 4a, 4b, and 4d, which were deduced from single crystal X-ray diffraction analyses.     

Aurivillius Phases in the Bi4Ti3O12/BiFeO3 System: Thermal Behaviour and Crystal Structure

Four compounds of the Bi₄Ti₃O₁₂/BiFeO₃ system with the formula Bi₂Bi_n?1(Ti,Fe)_nO_3n+3, n = 3, 4, 4.5 and 6 were studied using high‐temperature X‐ray powder diffraction and differential thermoanalysis methods. The crystal structure of the n = 6 phase was refined by the Rietveld method. An unusual behaviour of thermal expansion attributed to an orthorhombic‐to‐tetragonal transformation was revealed. For all the compounds, the lattice parameter c vs temperature T dependence has three regions in the range of T = 20 –750 °C interpreted as (1) expansion of the initial orthorhombic phase, (2) a pronounced structure reconstruction to the tetragonal phase, (3) an expansion of the tetragonal phase. The crystal structure of Bi₇Ti₃Fe₃O₂₁ based on 6‐layer‐perovskite blocks is proposed from X‐ray powder diffraction data. The Rietveld refinement of the structure in the orthorhombic space group F2mm with lattice parameters a = 5.4699(3), b = 5.4924(3), c = 57.551(3) Å (R_p = 9.4, R_wp = 11.9, R_exp = 4.7, R_B = 4.4 %) shows that a distorted 6‐layer model fits the data of Bi₇Ti₃Fe₃O₂₁.     

Metal Functionalized Diketopyrrolopyrroles: A Promising Class of Materials for Optoelectronic Applications

After first report on diketopyrrolopyrrole in 1974 by Farnum et al., a wide variety of its derivatives have been reported for material and biological applications. In this review we discuss various design strategies used for the synthesis of metal functionalized diketopyrrolopyrrole derivatives along with their photophysical and electrochemical studies with respect to material and biological applications. Some exciting applications of ferrocenyl functionalized diketopyrrolopyrrole derivatives such as non‐linear optics, organic solar cells and photothermal therapy were recently reported, which are also discussed in this review.     

New Inexpensive and Selective Sorbent Phases for Rapid Thin Layer Chromatographic Analysis of Metal Ions

Abstract

New sorbent phases have been developed by impregnating silica gel G with different inorganic salts for the analysis of metal ions by thin layer chroma to graphy in carboxylic acids media. Thin layers prepared from silica gel G impregnated with ammonium chloride or barium nitrate show the unusual selectivity towards metal ions in comparison to the thin layers prepared from plain silica gel G or silica gel impregnated with silver nitrate or aluminium nitrate. Many qualitative separations     

纳米氧化钴－氧化钌复合型超级电容器的研究

A novel type of composite electrode based on sheet like cobalt oxide particles has been used in supercapacitors. Cobalt oxide cathodically deposited from Co（NO3）2 solution with carbon nanotubes as matrix exhibited large pseudo-capacitance of 322 F·g^-1 in 6 mol·L^-1 KOH. A sol-gel process for the preparation of ultrafine RuO2 particles was developed to design electrodes with large surface area. The composite electrodes were developed by the deposition of RuO： on the surface of carbon nanotubes. A specific capacitance of 785 F·g^-1 can be achieved with the 20% carbon nanotubes loaded. To characterize the metal oxide nanocomposite electrode, a cyclic voltammetry and AC impedance test are executed. This study also reports a hybrid capacitor, which consists of cobalt oxide composite as a cathode and ruthenium oxide composite as an anode. The electrochemical performance of the hybrid capacitor is characterized by a dc charge/discharge test and cyclic voltammograms. The hybrid capacitor shows capacitor behavior with an extended operating voltage of 1.4 V. The maximum energy density and specific power density of the cell reach the value of 23.7 and 8.1 kW·g^-1 respectively. The hybrid capacitor exhibits high-energy density and stable power characteristics.     

The Crystal Chemistry of High-Temperature Oxide Superconductors and Materials with Related Structures

Never before in human history has a chemical substance been the object of collaborative research by so many scientists of different disciplines as in the case of the first high-temperature (HT_c) oxide superconductor La_2?xSr_xCuO₄. If the importance of a class of materials is measured by the number of papers published in a given period, the new superconductors hold the all-time record; moreover, this flood of publications also reflects the high expectations that are held worldwide for this class of substances. Every day seems to bring further surprises. From the two phases of HT_c oxide superconductors that were recognized at the outset there have developed within a period of scarcely two years a series of new materials which all show superconductivity at temperatures above the boiling point of liquid nitrogen; this property is undoubtedly closely related to the crystal chemistry of the individual phases and compounds. This article will report and discuss the resemblances and differences between the HT_c superconductors and materials with related structures.     

Silanediols: A New Class of Potent Protease Inhibitors

Transition state analogues of the peptide hydrolysis intermediate can take the form of complex silanediols such as 1 , which inhibits angiotensin-converting enzyme (ACE) at nanomolar concentrations. In contrast, earlier investigation of enzyme inhibition with simple silanediols and silanetriols showed them to be inactive.