Nitroxide‐mediated radical polymerization in miniemulsion: Bimolecular termination in monomer‐free model systems

Bimolecular termination in nitroxide‐mediated radical polymerization in miniemulsion has been investigated through the heating of a polystyrene–2,2,6,6‐tetramethylpiperidinyl‐1‐oxy macroinitiator and its 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyl‐1‐oxy analogue in an aqueous toluene dispersion with sodium dodecyl benzenesulfonate as a surfactant at 125 °C. The level of bimolecular termination by combination, evaluated from the high‐molecular‐weight shoulder, was higher in miniemulsion than in solution and increased with decreasing particle size. Quantitative analysis revealed that these results cannot be rationalized solely by nitroxide partitioning to the aqueous phase. The results are explained by an interface effect, by which nitroxide is adsorbed or located at the aqueous–organic interface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4995–5004, 2007     

Manifestation of diamagnetic chemical shifts of proton NMR signals by an anisotropic shielding effect of nitrate anions

A remarkable upfield shift of the py_α protons of complexed 2,2′-bipyridine in [cis-Pd(bpy)(NO₃)₂] is observed which is considered to originate from the anisotropic influence of suitably positioned coordinated nitrate anions around the Pd(II) centre of the molecule. A typical complexation-induced downfield shift is observed for the NH₂ protons in [cis-Pd(en)(NO₃)₂] where ‘en’ stands for ethylenediamine.     

A di-μ-oxomolybdenum(V) complex of 6-acetonylisoxanthopterin,undergoing oxygen atom transfer with dimethyl sulphoxide

The new compound, Na[(Mo₂ ^VO₄)(pte)(OMe)(MeOH)₂] (pte = anion of 6-acetonylisoxanthopterin), has been prepared using the redox non-innocent title ligand in MeOH–H₂O, and characterized by elemental analysis and physico-chemical methods including e.s.m.s., i.r., u.v.–vis. and ¹H-n.m.r. spectra. Rate constants data (1.4 × 10^–3 s^–1 at 300 K) for its oxygen atom transfer with dimethyl sulphoxide tally with those of synthetic analogue systems reported earlier by different authors. The negative activation entropy (–206.3 J mol^–1 deg^–1) is consistent with an associative mechanism for this reaction.     

Large-volume stacking in capillary electrophoresis using pH hysteresis of the electroosmotic flow in a bare fused-silica capillary

For large-volume stacking with the electroosmotic flow pump (LVSEP) in capillary electrophoresis of anionic analytes it is required that the electroosmotic mobility (EOM) should be smaller than the magnitudes of the effective mobilities of the analytes. When a fused-silica capillary is treated with an acidic solution, the silanoate group on the silica surface is neutralized to silanol and the EOM is suppressed. Due to the slow deprotonation equilibrium of the silanol group at an intermediate pH, this reduced EOM can be retained during a number of electrophoresis runs. Using a bare fused-silica capillary preconditioned with 0.01 M HCl, successful LVSEP at pH 6.0 was achieved for weakly acidic compounds with two orders of magnitude enhancements in the concentration sensitivity. The repeatability in migration times of ten analytes stacked by LVSEP in a single day was excellent with the relative standard deviation (RSD) less than 1% (n = 6). The day-to-day repeatability was also excellent with RSD less than 3% (n = 3 x 6) when the capillary was preconditioned each day.     

Development of honey hydrogel dressing for enhanced wound healing

Radiation at 25 and 50 kGy showed no effect on the acidic pH of the local honey, Gelam, and its antimicrobial property against Staphylococcus aureus but significantly reduced the viscosity. Honey stored up to 2 years at room temperature retained all the properties studied. Radiation sterilized Gelam honey significantly stimulated the rate of burn wound healing in Sprague-Dawley rats as demonstrated by the increased rate of wound contraction and gross appearance. Gelam honey attenuates wound inflammation; and re-epithelialization was well advanced compared to the treatment using silver sulphadiazine (SSD) cream. To enhance further the use of honey in wound treatment and for easy handling, Gelam honey was incorporated into our hydrogel dressing formulation, which was then cross-linked and sterilized using electron beam at 25 kGy. Hydrogel with 6% of honey was selected based on the physical appearance.     

Synthesis of (−)-mellein, (+)-ramulosin, and related natural products

(−)-Mellein, (+)-ramulosin, (−)-O-methylmellein, (−)-6-hydroxymellein, (−)-6-methoxymellein, and (+)-6-hydroxyramulosin were synthesized as optically active forms using one-pot esterification-Michael addition-aldol reaction of δ-hydroxy-α,β-unsaturated aldehyde and diketene as a key step.     

Synthesis and structural characterisation of a novel tris-methylene bridged compound (NO) 4Fe2 Se(μ-CH2)3

The tris-methylene bridged compound (NO)₄Fe₂Se(μ-CH₂)₃ has been isolated. It has been characterised by IR and ¹H, ¹³C, and ⁷⁷Se NMR spectroscopy. Its structure has been determined by single-crystal X-ray diffraction methods. The structure consists of a heavy atom triangle consisting of one Se and two Fe atoms. The Fe-Fe and the two Fe-Se edges are bridged by methylene groups.     

Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn3(CO)6(mu-eta2-SCH2CH2CH2S)3

Treatment of Mn(2)(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO.2H(2)O in CH(2)Cl(2) at room temperature afforded the dinuclear complexes Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (1), and Mn(2)(CO)(6)(mu-eta(4)-SCH(2)CH(2)S-SCH(2)CH(2)S) (2), respectively. Similar reactions of Re(2)(CO)(10) with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (3), Re(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S) (4), and Re(2)(CO)(6)(SCH(2)CH(2)S-SCH(2)CH(2)S) (5), respectively. In contrast, treatment of Mn(2)(CO)(10) with 1,3-propanedithiol afforded the trimanganese compound Mn(3)(CO)(6)(mu-eta(2)-SCH(2)CH(2)CH(2)S)(3) (6), whereas Re(2)(CO)(10) gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques.     

A novel hyperbranched polyester acrylate used for microfabrications

A novel hyperbranched polyester acrylate (HPEA) was synthesized based upon ethylenediamine tetraacetic acid as a “core” molecule, 5‐hydroxyisophthalic acid as an AB₂ monomer, and 2‐hydroxyethyl acrylate as an endcapping reagent. The obtained oligomer has an unsaturation concentration of 4.10 mmol_C?C g^?1 measured by nuclear magnetic resonance and a wide molecular weight distribution of 1.64 measured by gel permeation chromatography. The two‐photon absorption (TPA) photopolymerization of HPEA under the exposure of a Ti : sapphire femtosecond laser with a wavelength of 800 nm was investigated through laser exposure dose‐dependant spatial resolutions of its resins. The TPA photopolymerization thresholds at the range 1.6–4.3 × 10⁷ mJ cm^?2, and exposure dose windows at the range 3.4–4.3 for three formulations were determined. A spatial resolution of 0.85 μm was obtained through the TPA photopolymerization of the formulation containing 1 wt% photoinitiator and 0.3 wt% photoinhibitor. A diffraction grating and real three‐dimensional coupled gear wheel created by TPA photopolymerization were described to demonstrate the unique capability of HPEA in microfabrications. Copyright © 2004 John Wiley & Sons, Ltd.     

Amino acid recognition of pyridine bis(oxazoline)-copper(II) complex in aqueous solvent

Enantioselective recognition of amino acids has been studied with C₂-symmetric chiral pyridine bis(oxazoline)-copper(II) complexes at physiological pH condition. UV-visible titration revealed strong binding of submillimolar dissociation constant between pyridine bis(oxazoline)-copper(II) complex and amino acids in aqueous solution. Moderate selectivity of up to 2:1 between d- and l-amino acids was achieved. The enantiomers were baseline resolved by capillary electrophoresis, using the bis(l-lysine)-copper(II) complex as a chiral selector.