Reduction of Entrained Hydroxy Species in Ormosil Films for Integrated Optics

Organically modified silicates (ormosils) have been viewed as possible materials for optical signal processing devices for communications networks. One significant problem obstructing their use in this application is the absorption of infrared light by hydroxy species (present for example in silanol groups (SiOH) and water) around the communications wavelengths (1310 and 1550 nm). We have investigated several ormosil compositions, synthesised via an aqueous sol-gel method, to determine if residual hydroxy groups can be removed more effectively via reducing the connectivity of the material by increasing the number of organic groups (such as Si—CH₃). Furthermore, we have investigated the effect of different inert atmospheres on the drying process. It was found that reducing the connectivity does promote the removal of hydroxy absorption, mainly via the condensation of residual silanol groups, but also by removal of residual water, depending on the other precursors in the system. It was also found that the drying atmosphere used (nitrogen or helium) had no effect on the drying process.     

Insight into chain dimensions in PEO/water solutions

Small‐Angle Neutron Scattering has been performed from poly(ethylene oxide) in deuterated water at temperature ranging from 10 to 80 °C. A simple fitting model was used to obtain a correlation length and a Porod exponent. The correlation length L characterizes the average distance between entanglements in the semidilute region and is proportional to the individual coil sizes in the dilute region. L was found to increase with temperature in the semidilute region but it decreases with temperature in the dilute region. This decrease is the precursor to the single‐chain collapse which applies to very dilute polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2196–2200, 2007     

Current Trend in Synthesis,Post‐Synthetic Modifications and Biological Applications of Nanometal‐Organic Frameworks (NMOFs)

Since the early reports of MOFs and their interesting properties, research involving these materials has grown wide in scope and applications. Various synthetic approaches have ensued in view of obtaining materials with optimised properties, the extensive scope of application spanning from energy, gas sorption, catalysis biological applications has meant exponentially evolved over the years. The far‐reaching synthetic and PSM approaches and porosity control possibilities have continued to serve as a motivation for research on these materials. With respect to the biological applications, MOFs have shown promise as good candidates in applications involving drug delivery, BioMOFs, sensing, imaging amongst others. Despite being a while away from successful entry into the market, observed results in sensing, drug delivery, and imaging put these materials on the spot light as candidates poised to usher in a revolution in biology. In this regard, this review article focuses current approaches in synthesis, post functionalization and biological applications of these materials with particular attention on drug delivery, imaging, sensing and BioMOFs.     

AFM of adsorbed polyelectrolytes on cellulose I surfaces spin-coated on silicon wafers

Thin layers of cellulose I nanocrystals were spin-coated onto silicon wafers to give a flat model cellulose surface. A mild heat treatment was required to stabilize the cellulose layer. Interactions of this surface with polyelectrolyte layers and multilayers were probed by atomic force microscopy in water and dilute salt solutions. Deflection–distance curves for standard silicon nitride tips were measured for silicon, cellulose-coated silicon, and for polyelectrolytes adsorbed on the cellulose surface. Transfer of polymer to the tip was checked by running deflection–distance curves against clean silicon. Deflection–distance curves were relatively insensitive to adsorbed polyelectrolyte, but salt addition caused transfer of cationic polyelectrolyte to the tip, and swelling of the polyelectrolyte multilayers.     

Phosphonomethylation of 2-aminoethanethiol and thiazolidine. An unexpected product

Phosphonomethylation of 2-aminoethanethiol and thiazolidine gives the unexpected dimethylene diphosphonic acid 6.     

The synthesis and electrochemistry of CpTiCl2(OR) (R = alkyl, aryl) complexes

The syntheses of several new CpTiCl₂(OR) (R = alkyl, aryl) complexes are described. It was possible to isolate pure product when the R group is substituted such as to cause steric crowding at the metal centre; for example, particularly good yields of the phenolate complexes were obtained when there were isopropyl substituents in the 2 and 6 positions of the phenolate. Electrochemical studies of the complexes in dry THF show that the Ti^III complexes are relatively stable, but only a diol complex could be reduced further to a Ti^II species. In general, the Ti^IV complexes undergo a reversible 1e⁻ reduction reaction. The chemistry is more complex if the electrolyte contains added water: both the Ti^IV and Ti^III complexes can react with water, the OR group being replaced by OH. The reaction is particularly rapid for the Ti^III alkoxide complexes.     

Effect of included guest molecules on the normal state conductivity and superconductivity of beta''-(ET)(4)[(H(3)O)Ga(C(2)O(4))(3)].G (G = pyridine,nitrobenzene)

Normal state conductivity and superconductivity together with bulk magnetic susceptibility and magnetization measurements have been measured for two molecular charge-transfer salts: beta' '-(ET)4[(H3O)Ga(C2O4)3]G (ET = bis(ethylenedithio)tetrathiafulvalene, G = pyridine for compound I and nitrobenzene for compound II). With the exception of the included guest molecules (G) the crystal structures are almost identical. Both show minima in their electrical transport at 130 K for I and at 160 K for II, but at lower temperatures their behaviors differ markedly. The resistance of I reaches a maximum at 50 K with a further small peak at 2 K and possible superconductivity only below 2 K, whereas that of II increases continuously down to 7.5 K, where an abrupt transition to a superconducting state occurs.     

Conversion of clavulanic acid into thiadeoxa nuclear analogues

1,4-Addition of sulphur nucleophiles to the diene ($\text{12}$) derived $\text{via}$ the pen-2-em ($\text{5}$) from clavulanic acid provides the thiadeoxa analogues ($\text{14}$–$\text{15}$). X-ray analysis of the ester ($\text{14}$) shows the thermodynamically stable isomers to have the same relative stereochemistry as clavulanic acid.     

Expedient Diels-Alder assembly of 4-aryl-4-phenylsulfonyl cyclohexanones

The efficient preparation of 4-aryl-4-phenylsulfonyl cyclohexanones, containing a quaternary sulfone-bearing carbon centre, is described. Their synthesis proceeds in 38-78% overall yield by way of three steps: (i) sulfinate alkylation; (ii) methylenation; and (iii) regioselective Diels-Alder condensation with 2-trimethylsiloxybutadiene. The scope and limitations of the one-pot Mannich-type methylenation described were examined.