Mechanical properties and degradation studies of poly(D,L‐lactide‐co‐glycolide) 50:50/graphene oxide nanocomposite films

Poly(D,L‐lactide‐co‐glycolide) 50:50 (PLGA)/graphene oxide (GO) nanocomposite films were prepared with various GO weight fractions. A significant enhancement of mechanical properties of the PLGA/GO nanocomposite films was obtained with GO weight fractions. The incorporation of only 5 wt% of GO resulted in an ~2.5‐fold and ~4.7‐fold increase in the tensile strength and Young's modulus of PLGA, respectively. The thermomechanical behaviors of composite films were investigated by dynamic mechanical analysis. Results indicated that the values of T_g and storage moduli of the PLGA/GO composites were higher than those of the pristine PLGA. The improvement in oxygen barrier properties of composites was presumably attributed to the filler effect of the randomly dispersed GO throughout the PLGA matrix. In this work, we also studied in vitro biodegradation behavior. PLGA/GO composite films were hydrolyzed at 37°C for periods up to 49 days. Because of the presence of GO nanosheets, degradation of composite films took place more slowly with increasing GO amounts. Copyright © 2013 John Wiley & Sons, Ltd.     

Biocatalytic Photosynthesis with Water as an Electron Donor

Efficient harvesting of unlimited solar energy and its conversion into valuable chemicals is one of the ultimate goals of scientists. With the ever‐increasing concerns about sustainable growth and environmental issues, numerous efforts have been made to develop artificial photosynthetic process for the production of fuels and fine chemicals, thus mimicking natural photosynthesis. Despite the research progress made over the decades, the technology is still in its infancy because of the difficulties in kinetic coupling of whole photocatalytic cycles. Herein, we report a new type of artificial photosynthesis system that can avoid such problems by integrally coupling biocatalytic redox reactions with photocatalytic water splitting. We found that photocatalytic water splitting can be efficiently coupled with biocatalytic redox reactions by using tetracobalt polyoxometalate and Rh‐based organometallic compound as hole and electron scavengers, respectively, for photoexcited [Ru(bpy)₃]²⁺. Based on these results, we could successfully photosynthesize a model chiral compound (L ‐glutamate) using a model redox enzyme (glutamate dehydrogenase) upon in situ photoregeneration of cofactors.     

Geometry‐Assisted Three‐Dimensional Superlocalization Imaging of Single‐Molecule Catalysis on Modular Multilayer Nanocatalysts

To establish the structure–catalytic property relationships of heterogeneous catalysts, a detailed characterization of the three‐dimensional (3D) distribution of active sites on a single catalyst is essential. Single‐particle catalysis of a modular multilayer catalytic platform that consists of a solid silica core, a mesoporous silica shell, and uniformly distributed Pt nanoparticles sandwiched in between these layers is presented. The first 3D high‐resolution super‐localization imaging of single fluorescent molecules produced at active sites on the core‐shell model nanocatalysts is demonstrated. The 3D mapping is aided by the well‐defined geometry and a correlation study in scanning electron microscopy and total internal reflection fluorescence and scattering microscopy. This approach can be generalized to study other nano‐ and mesoscale structures.     

Identification of Novel Rab27a/Melanophilin Blockers by Pharmacophore-Based Virtual Screening

Melanocytes are unique cells that produce specific melanin-containing intracellular organelles called melanosomes. Melanosomes are transported from the perinuclear area of melanocytes toward the plasma membrane as they become more melanized in order to increase skin pigmentation. In this vesicular trafficking of melanosomes, Rab27a, melanophilin, and myosin Va play crucial roles in linking melanosomes to actin-based motors. To identify novel compounds to inhibit binding interface between Rab27a and melanophilin, a pharmacophore model was built based on a modeled 3D structure of the protein complex that describes the essential binding residues in the intermolecular interaction. A pharmacophore model was employed to screen a chemical library database. Finally, 25 virtual hits were selected for biological evaluations. The biological activities of 11 analogues were evaluated in a second assay. Two compounds were identified as having concentration-dependent inhibitory activity. By analyzing structure–activity relationships of derivatives of BMD-20, two hydroxyl functional groups were found to be critical for blocking the intermolecular binding between Rab27a and melanophilin.     

The Scent of Maibowle – π Electron Localization in Coumarin from Its Microwave-Determined Structure

The microwave spectra of the natural substance coumarin, a planar aromatic molecule with the specific scent of maibowle, a popular fruit punch served in spring and early summer, were recorded using a molecular jet Fourier transform microwave spectrometer working in the frequency range from 4.0 to 26.5 GHz. The rotational constants and centrifugal distortion constants were determined with high precision, reproducing the spectra to experimental accuracy. The spectra of all singly-substituted ¹³C and ¹⁸O isotopologues were observed in their natural abundances to determine the experimental heavy atom substitution r_s and semi-experimental equilibrium r_e^SE structures. The experimental bond lengths and bond angles were compared to those obtained from quantum chemical calculations and those of related molecules reported in the literature with benzene as the prototype. The alternation of the C−C bond lengths to the value of 1.39 Å found for benzene reflects the localization of π electrons in coumarin, where the benzene ring and the lactone-like chain −CH=CH−(C=O)−O− are fused. The large, negative inertial defect of coumarin is consistent with out-of-plane vibrations of the fused rings.     

Emission Control by Molecular Manipulation of Double‐Paddled Binuclear PtII Complexes at the Air‐Water Interface

Molecular functions depend on conformations and motions of the corresponding molecular species. An air–water interface is a suitable asymmetric field for the control of molecular conformations and motions under a small applied force. In this work, double‐paddled binuclear Pt^II complexes containing pyrazole rings linked by alkyl spacers were synthesized and their orientations and emission properties dynamically manipulated at the air–water interface. The complexes emerge from water with concurrent variation of interface orientation of the planes of the Pt^II complexes from perpendicular to parallel during mechanical compression suggesting a unique ‘submarine emission‘. Phosphorescence of the complexes is quenched at the air–water interface prior to monolayer formation with intensities subsequently rapidly increasing during monolayer compression. These results indicate that asymmetric reactions and motions might be controlled by applying mechanical force at the air–water interface.     

Stereocontrolled Iodolactonization of Acyclic Olefinic Amides

Acyclic olefinic amides were iodolactonized in the mixed solvent of CH₃CN and H₂O (90:10₂ v/v) under reflux to give products with trans configuration of the newly formed iodomethyl to the inherent alkyl group in high yield.     

Ab initio calculation of the spin-orbit coupling constant from gaussian lobe SCF molecular wavefunctions

The spin-orbit coupling constants of BH⁺ and CH have been calculated using ab initio molecular SCF wavefunctions with the gaussian lobe function basis set. It is demonstrated that fair agreement with experimental values can be achieved even with a relatively small basis set, provided that no terms are neglected in calculating the matrix elements.     

Comparison of elemental contents of Korean space foods using instrumental neutron activation analysis

The analysis of mineral contents in space foods is needed to obtain an information on a comprehensive elemental composition as well as the investigation on the effects of human nutrition and health based on the dietary intake of mineral elements. Recently, six items of new Korean space foods (KSFs) such as kimchi, bibimbap, bulgogi, a ramen, a mulberry beverage and a fruit punch which was developed by the KAERI, and the contents of more than 15 elements in the samples were examined by using instrumental neutron activation analysis (INAA). Five biological certified reference materials, NIST SRM were used for analytical quality control. The results were compared with those of common Korean foods reported, and these results will be applied toward the identification of irradiated foods.