The effects of melt annealing and counterpart's molecular weight on the thermal properties and phase morphology of poly(L‐lactide)‐based blends

The thermal properties and phase morphology of poly(L ‐lactide) (PLLA)‐based blends have been studied. Two poly(ethylene glycol)s (PEGs) with molecular weight (MW) of about 1,500 (1.5k) g/mol and 2,000,000 (2M) g/mol, respectively, were used as counterparts. The blends were annealed at a preselected temperature of 200 °C for either 2 min or 30 min before the characterizations. Both PEGs were determined to enhance the crystallizability of PLLA. After a 2‐min process of annealing, the PEG(1.5k)'s crystallization efficiency on PLLA has been noted to increase with the increase of its content. Conversely, PEG(2M)'s crystallization efficiency declined with the increase of its content. Extending the annealing time has evidently changed the PEGs' crystallization effect on PLLA. Moreover, the PEG(1.5k) has, to a greater extent, brought about the depression of PLLA's melting temperature by increasing its content, and this depression increased with the annealing time. The blends exhibited lower thermal stability than those of the parent components, particularly for the PEG(1.5k)‐included system with a higher PEG content. Regardless of the annealing time, the PEG(1.5k)‐included blends have shown homogeneous melt morphology under light microscope, whereas the PEG(2M)‐included blends have displayed phase‐separated melt morphology. In addition to the composition, PEG's MW and annealing time influence the crystalline morphology of the blends. The ringed PLLA spherulites have appeared mostly in the 2‐min annealed PEG(1.5k)‐included blends. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1497–1510, 2009     

Phenanthrene removal in unsaturated soils treated by electrokinetics with different surfactants—Triton X-100 and rhamnolipid

In this study, the remediation performance of electrokinetic (EK) technology integrated with different surfactants for removing phenanthrene from unsaturated soils was investigated. A synthetic surfactant (Triton X-100) and a biosurfactant (rhamnolipid) were used to enhance phenanthrene solubility and removal efficiency during EK process. Results indicate that the electro-osmotic flow (EOF) rate in the rhamnolipid system is higher than that in Triton X-100. Using the EK technology for the removal of phenanthrene in the presence of rhamnolipid was more efficient than in the presence of Triton X-100. In addition to the transport mechanism of phenanthrene in EK system, the presence of rhamnolipid may promote microbial growth in the soil–water system and bring about biodegradation of phenanthrene. A diffusion–advection–sorption (DAS) model was solved by MATLAB, based on the linear sorption isotherm at the non-equilibrium condition, which is feasible to simulate the movement of phenanthrene during the EK + Triton X-100 treatment.     

Thermochemistry of thermal plasma chemical reactions. Part II. A survey of synthesis routes for silicon nitride production

Feasibility routes for thermal plasma production of silicon nitride powders are explored. First, a collation of the various proposed systems from the extant literature is examined. Reactant systems investigated include free silicon, silicon monoxide, silicon dioxide, silicon tetrachloride, silane, and other organosilicon precursors, along with various nitriding and reducing species. The reaction yields of these systems are brought to a common denominator by thermodynamic analysis and a first-step introduction of nucleation kinetics including comparisons against published experiments and the authors' own research. In particular, it is observed that the formation of liquid-phase free silicon in the neighborhood of 2500 K is quite detrimental to silicon nitride yield, and furthermore, a high supersaturation of silicon should always be avoided.     

3D imager using dual color-balanced lights

A novel method for grabbing 3D shape of an object is proposed. It uses a pair of color-coded light sources to create a 3D-coordinated illumination space. The intensities of two modulation colors are complementally balanced, which makes the sum of the intensities of the colors a constant. This method demonstrates the abilities of uniquely representing any point in the 3D-coordinated illumination space, reducing the measuring problems in blind area, and compensating the effect caused by changes of surface color and reflection. In addition, this method has the ability of acquiring the 3D shape information in parallel and the algorithm is fairly simple, so the 3D imaging speed is basically restricted by the frame rate of the color CCD camera.     

Study on Chromium‐Containing Aluminophosphate CrAPO‐5 via Density Functional Theory

Various structures of CrAPO‐5 clusters are studied via density functional B3LYP exchange‐correlation method. The optimized structures are compared with data from X‐ray absorption. Their total energies and atomic net charges are also analyzed. Results indicate that the substitution of the aluminum site of an AFI framework by chromium is in general not feasible. The chromium ion is more likely docked in between two neighboring 12‐membered rings of the framework of AFI. To further verify our claim, the excitation energies of the representative chromium structures of CrAPO‐5 clusters are calculated via the TDDFT method. The results for excitation energies further support that Cr³⁺ is not incorporated into the framework.     

Synthesis,self‐assembly and recognition properties of biomimetic star‐shaped poly(ε‐caprolactone)‐b‐glycopolymer block copolymers

Biomimetic star‐shaped poly(ε‐caprolactone)‐b‐poly(gluconamidoethyl methacrylate) block copolymers (SPCL‐PGAMA) were synthesized from the atom transfer radical polymerization (ATRP) of unprotected GAMA glycomonomer using a tetra(2‐bromo‐2‐methylpropionyl)‐terminated star‐shaped poly(ε‐caprolactone) (SPCL‐Br) as a macroinitiator in NMP solution at room temperature. The block length of PGAMA glycopolymer within as‐synthesized SPCL‐PGAMA copolymers could be adjusted linearly by controlling the molar ratio of GAMA glycomonomer to SPCL‐Br macroinitiator, and the molecular weight distribution was reasonably narrow. The degree of crystallization of PCL block within copolymers decreased with the increasing block length ratio of outer PGAMA to inner PCL. Moreover, the self‐assembly properties of the SPCL‐PGAMA copolymers were investigated by NMR, UV‐vis, DLS, and TEM, respectively. The self‐assembled glucose‐installed aggregates changed from spherical micelles to worm‐like aggregates, then to vesicles with the decreasing weight fraction of hydrophilic PGAMA block. Furthermore, the biomolecular binding of SPCL‐PGAMA with Concanavalin A (Con A) was studied by means of UV‐vis, fluorescence spectroscopy, and DLS, which demonstrated that these SPCL‐PGAMA copolymers had specific recognition with Con A. Consequently, this will not only provide biomimetic star‐shaped SPCL‐PGAMA block copolymers for targeted drug delivery, but also improve the compatibility and drug release properties of PCL‐based biomaterials for hydrophilic peptide drugs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 817–829, 2008     

Saccharomyces cerevisiae oxidosqualene‐lanosterol cyclase: A chemistry–biology interdisciplinary study of the protein's structure–function–reaction mechanism relationships

The oxidosqualene cyclases (EC 5.4.99‐) constitute a family of enzymes that catalyze diverse cyclization/rearrangement reactions of (3S)‐2,3‐oxidosqualene into a distinct array of sterols and triterpenes. The relationship between the cyclization mechanism and the enzymatic structure is extremely complex and compelling. This review covers the historical achievements of biomimetic studies and current progress in structural biology, molecular genetics, and bioinformatics studies to elucidate the mechanistic and structure–function relationships of the Saccharomyces cerevisiae oxidosqualene‐lanosterol cyclase‐catalyzed cyclization/rearrangement reaction. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 302–325; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20157     

Influence of substituents in the salicylaldehyde‐derived Schiff bases on vanadium‐catalyzed asymmetric oxidation of sulfides

A series of chiral Schiff bases ( L ¹ – L ⁵ ) with different substituents in the salicylidenyl unit were prepared from condensation of 3‐aryl‐5‐ tert ‐butylsalicylaldehyde derivatives and optically active amino alcohols. Bromination of 3‐phenyl‐5‐ tert ‐butylsalicylaldehyde gave an unexpected product 3‐(4‐bromophenyl)‐5‐bromosalicylaldehyde, from which the corresponding Schiff base ligands L ⁶ and L ⁷ , derived from (S)‐valinol and (S)‐ tert ‐leucinol, respectively, were prepared. Ligands L ¹ – L ⁷ were applied to the vanadium‐catalyzed asymmetric oxidation of aryl methyl sulfides. Under the optimal conditions, the oxidation of the thioanisole with H₂O₂ as oxidant in CH₂Cl₂ catalyzed by VO(acac)₂‐ L ¹ – L ⁷ gives good yields (74–83%) with moderate enantioselectivity (58–77% ee). Ligand L ⁷ , containing a 4‐bromophenyl group on the 3‐position and a Br atom on the 5‐position of the salicylidenyl moiety, displays an 80–90% ee for vanadium‐catalyzed oxidation of methyl 4‐bromophenyl sulfide and methyl 2‐naphthyl sulfide. Copyright © 2008 John Wiley & Sons, Ltd.     

Electrochemical properties of niosomes‐modified Au electrode and its interaction with 1‐anilino‐8‐naphthalene‐sulfonate

The gold electrode was modified by noisomes, prepared by sonicating the mixed solution of PEG 6000/Tween 80/Span 80/H₂O. Electrochemical cyclic voltammetry (CV) and impedance spectroscopy (EIS) were performed for characterizing the modification. The construction of multilayer films of octadecanethiol (ODT)‐niosomes had almost no pinholes, which elicited that niosomes‐coated electrode through ODT assembly was more effective immobilization compared to direct modification method. A large semicircle formation in the entire range of frequency indicated the complete electron‐transfer control for the redox reaction, implying a perfect blocking behavior. The Nyquist plot was consisting of two depressed semicircles after storage for 36 h in air, which implied a progressive and uniform construction manner, as expected for porous coatings. The modified electrode was used to investigate the interaction between 1‐anilino‐8‐naphthalene‐sulfonate (ANS) and noisomes. It was found that the low‐frequency semicircular arcs increase in diameter, indicating that the increase in the resistance R_p attributed mainly to the niosomes/solution interface. It was due to the binding of ANS to the niosomes‐modified electrode surface, exhibited against diffusing species through the pores. Copyright © 2009 John Wiley & Sons, Ltd.