Low‐Temperature Facile Template Synthesis of Crystalline Inorganic Composite Hollow Spheres

This report presents a facile approach for the low‐temperature synthesis of crystalline inorganic‐oxide composite hollow spheres by employing the bulk controlled synthesis of inorganic‐oxide nanocrystals with polymer spheres as templates. The sulfonated polystyrene gel layer can adsorb the target precursor and induce inorganic nanocrystals to grow on the template in situ. The crystalline phase and morphology of the composite shell is tunable. By simply adjusting the acidity of the titania sol, crystalline titania composite hollow spheres with tunable crystalline phases of anatase, rutile, or a mixture of both were achieved. The approach is general and has been extended to synthesize the representative perovskite oxide (barium and strontium titanate) composite hollow spheres. The traditional thermal treatment for crystallite transformation is not required, thus intact shells can be guaranteed. The combination of oxide properties such as high refractive index, high dielectric constant, and catalytic ability with the cavity of the hollow spheres is promising for applications such as opacifiers, photonic crystals, high‐κ‐gate dielectrics, and photocatalysis.     

Synthesis and Spectroscopic Characterization of New Lead(II) Thiosaccharinates. Molecular Structure of Bis(thiosaccharinato)tetrakis(pyridine)dilead(II) and Thiosaccharinato‐bis(1,10‐phenantroline)lead(II) Thiosaccharinate

Four new lead(II) thiosaccharinate complexes: [Pb(tsac)₂H₂O] (1) (tsac: thiosaccharinate anion), [Pb₂(tsac)₄(py)₄] (2) (py: pyridine), [Pb(tsac)(o‐phen)₂](tsac)·CH₃CN (3) (o‐phen: 1,10‐phenantroline), and [Pb(tsac)₂(bipy)] (4) (bipy: 2,2′‐bipyridine) were prepared. The infrared and electronic spectra as well as the thermal analysis of all the compounds were recorded and discussed. The thiosaccharinate anion acts in three different coordination forms, one of then reported for the first time. The crystal structures of complexes 2 and 3 have been determined by single crystal X‐ray diffractometry. In complex 2 , two monomeric moieties are joined together forming a symmetric bis‐μ‐sulphur bridged dimer by interaction of two lead(II) atoms through the exocyclic sulphur atoms of two thiosaccharinate ligands. The seven‐fold coordination sphere of each lead atom is completed by two pyridine nitrogen atoms and by another sulfur and two nitrogen atoms of the thiosaccharinate anions. In complex 3 , the lead(II) atom is coordinated by four nitrogen atoms of two 1,10‐phenantroline molecules and by the sulfur and nitrogen atoms of one thiosaccharinate ion. The second anion has an electrostatic interaction with the nucleus.     

Structural and Spectroscopic Studies of Halocuprate(I) and Haloargentate(I) Complexes [M2XnX′4−n]2−

The complexes [Cu₂Br₄]^2?, [Cu₂I₄]^2?, [Cu₂I₂Br₂]^2?, [Cu₂I₃Cl]^2?, [Ag₂Cl₄]^2? have been characterized as their isomorphous bis(triphenylphosphoranylidene)ammonium ([Ph₃PNPPh₃]⁺ = PNP⁺) salts by single crystal structural determinations. All anions show the centrosymmetric doubly halogen‐bridged forms [XM(μ‐X)₂MX]^2? with three‐coordinate metal atoms that have been observed in [M₂X₄]^2? complexes with other large organic cations. In [Cu₂I₂Br₂]^2? the iodide ligands occupy the bridging positions and the bromide the terminal positions, while in [Cu₂I₃Cl]^2?, obtained in an attempt to prepare [Cu₂I₂Cl₂]^2?, two of the iodide ligands occupy the bridging positions with the third iodide and the chloride ligand occupying two statistically disordered terminal positions. In [Ag₂Cl₄]^2? the distortion from ideal trigonal coordination of the metal atom is greater than in the copper complexes, but less than in other previously reported [Ag₂Cl₄]^2? complexes with organic cations. The ν(MX) bands have been assigned in the far‐IR spectra, and confirm previous observations regarding the unexpectedly simple IR spectra of [Cu₂X₄]^2? complexes.     

Alginic acid–silica hydrogel coatings for the protection of osmotic distillation membranes against wet-out by surface-active agents

The formulation of organic–inorganic polymer composites can be used to enhance selected properties, such as susceptibility to microbial attack, thermal stability, mechanical strength and water sorption capability. Accordingly, a series of alginic acid–silica hydrogel films was prepared for testing as protective coating materials for PTFE osmotic distillation membranes. Unprotected hydrophobic membranes are subject to wet-out when contacted by surface-active agents, such as oils and detergents. Films containing 5, 10, 15 and 20 wt.% silica, with and without the addition of glycerol for plasticisation, moisturisation and silica dispersion, were characterised using scanning electron microscopy, X-ray diffraction, differential scanning calorimetry, mechanical strength measurements, and water-swelling measurements. Composites prepared with glycerol addition had better thermal stability, mechanical strength and water sorption capability than those prepared without glycerol addition. Uncoated membranes and membranes coated with composites prepared with glycerol addition were tested for OD performance and resistance to surface-active agents using pure water, orange oil (limonene)–water mixtures, and sodium dodecylbenzene sulfonate detergent solutions. Uncoated membranes showed immediate hydrophobicity loss in the presence of orange oil and detergent. For coated membranes, no wet-out occurred over the 15 h duration of three consecutive 5 h OD trials using orange oil–water mixtures. In the case of detergent solutions, the coating afforded protection to the membrane for 4–5 h. In a separate trial, no wet-out occurred when the coated side of the membrane was placed in contact with 1.2 wt.% orange oil for 72 h.     

Novel sequence for generating glycopolymer tethered on a membrane surface

Cell surface carbohydrates, usually binding with other biomacromolecules (such as lipids and proteins), are involved in numerous biological functions, including cellular recognition, adhesion, cell growth regulation, and inflammation. Synthetic carbohydrate-based polymers, so-called glycopolymers, are emerging as important well-defined tools for investigating carbohydrate-based biological processes and for simulating various functions of carbohydrates. In this study, a novel two-step sequence for the generation of a glycopolymer layer tethered on a polypropylene microporous membrane is described. First, a UV-induced graft polymerization of 2-aminoethyl methacrylate hydrochloride (AEMA) was carried out on the membrane to generate an amino-functionalized surface, and the effects of polymerization factors (monomer/initiator concentration and UV irradiation time) on the grafting density were studied. Second, sugar moieties were bound with the grafted functional layer to form glycopolymer by the reaction between the amino groups on the membrane surface and carbohydrate lactones. Chemical analysis by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy combined with surface morphology observation by scanning electron microscopy confirmed the graft polymerization of AEMA and the formation of glycopolymer. The decreases of water contact angle and protein adsorption on the membrane revealed the enhancement of hydrophilicity and protein resistance due to the typical characteristics of the glycopolymer tethered on the surface. These results indicated that the novel sequence reported in this work is a facile process to form glycopolymer-modified surfaces.     

Recent Advances in Fullerene‐free Polymer Solar Cells: Materials and Devices

What is the most favorite and original chemistry developed in your research group? We focus on developing new organic photovoltaic materials and exploring their applications in photovoltaic devices. Based on the new materials, we can figure out the correlations among chemical strictures, optoelectronic properties, and photovoltaic behaviors. Our group originally demonstrated quite a few build blocks for making conjugated polymers for photovoltaic applications, some of them have been broadly used by the researchers in the field. How do you get into this specific field? Could you please share some experiences with our readers? I got into this field when I was a graduate student in 2002, just because my supervisor gave me a research topic for synthesis of new conjugated polymers. At that moment, as a fresh graduate student, I had no chance to say yes or no, but to do it. The field of organic solar cells is oriented by the new organic photovoltaic materials. In the past decades, the materials have been updated for a few generations, which promoted the device performance to be higher and closer to practical applications. We have to concentrate on the fundamental problems but also need to follow the pace of the filed. How do you supervise your students? In my opinion, the students need more specific projects to get into the field so as to be well trained at the beginning. In the later stage, I prefer to encourage them to find and creatively figure out the real fundamental problems. I used to give them a few questions: Why do you need to do this project? How to make a clear definition for the problem? Can you suggest a new and better approach to solve it? What is the most important personality for scientific research? Passion, perseverance and sense of innovation. What is your favorite journal(s)? The journals publishing the latest and/or systematic research works in chemistry and material science.     

Ion chromatographic separation of hydrogen ion and other common mono- and divalent cations

We introduced an approach to the ion chromatographic determination of common mono- and divalent cations including hydrogen ion and demonstrated the ability of a C30 column dynamically coated first with dodecylsulfate and then with 18-crown-6 ether to separate the cations by ion-exchange mechanism. Using an ethylenediamine solution containing a small concentration of 18-crown-6 ether and lithium dodecylsulfate at pH 6.2 as eluent, the cations were eluted in the order Li < Na+ < NH4+ < H+ < K+ < Mg2+ < Ca2+ with symmetrical peaks. The conductivity vs. concentration plots were linear about three orders of magnitude, from millimolar to micromolar; and the detection limits were all < 0.6 microM. Rainwater was analyzed directly using this ion chromatographic system with satisfactory results.     

{Pt

Prolonged evacuation of [{Pt(CO)(3)}(2)](2+) (1), the first homoleptic, dinuclear, cationic platinum(I) carbonyl complex, results in reversible disproportionation. Complex 1 was formed by dissolution of PtO(2) in concentrated H(2)SO(4) under an atmosphere of CO [Eq. (a)], and completely characterized by NMR ((13)C, (195)Pt), IR, and Raman spectroscopy.     

Structures of Organo Alkali Metal Complexes and Related Compounds

The investigation of the reactivity and structure of organometallic compounds of alkali metals has experienced a blustering development in the last decades. This class includes compounds that are especially important for our understanding of chemical bonding and also quite simple, for example methyl alkali metal complexes, whose structures have been unequivocally determined. Organometallic compounds of alkali metals (and also magnesium) generally exist as ion aggregates whose properties can be significantly modified through solvation by, for example, ether or amines. Important advances in the synthesis of new compounds, especially those of the heavier alkali metals, have been based on these results. It was long believed that the alkali metals had little tendency to undergo coordination and that their coordination chemistry would offer few surprises. This picture has now changed completely. Results from crystal structure investigations have revealed a variety of often surprising structure types (rings, heterocubanes, chains, layers, etc.) not only with the organometallic compounds but also with the amides, imides, alkoxides, phenoxides, enolates, and even halides. A comparison reveals interesting similarities between compounds that appear to be so different and leads to a general classification of the structure types possible with C, N, O, and halo ligands.