A quantum chemical study on the polycondensation reaction of polyesters: The mechanism of catalysis in the polycondensation reaction

We carried out a theoretical study on the mechanism of catalysis in the poly(ethylene terephthalate) (PET) polycondensation reaction. Transesterification reaction of diethylterephthalate with ethanol is investigated as a model system by using the B3LYP level of theory, and Sb(OEt)₃, Ge(OEt)₄ and Ti(OEt)₄ are adopted as model catalysts. We found that the metal center of metal alkoxides coordinates to the carbonyl oxygen atom of the ester, and the alkoxy oxygen atom of alkoxy ligands attacks to the carbonyl carbon atom of the ester to form the four-centered transition state. The activation energy for tetraethoxy titanium catalyzed reaction in vacuo is 15.47 kcal/mol; this is comparable to the experimental result of 11.2 kcal/mol for poly(butylene terephthalate)/Ti(OBu)₄. Because the other mechanisms gave much higher activation energies, this is the most convincing mechanism of PET polycondensation catalysis by antimony, germanium and titanium alkoxides.     

A simple and fast method to disperse long single-walled carbon nanotubes introducing few defects

A simple and fast dispersion method that incorporates heating is used to disperse long (more than 10 μm) single-walled carbon nanotubes (SWCNTs) with minimal defects. The method enables a dispersed solution of SWCNTs to be produced in less than 10 min in only three steps: (1) addition of the dispersant, (2) heating, and (3) grinding. The dispersion method does not require sonication, which shortens the SWCNTs and can generate surface defects. SWCNT films were prepared from the dispersed solution, and the films exhibited a resistance of 380 Ω/sq at a transparency of 64.8%. This dispersion method can be easily scaled up, making it useful for the preparation of dispersed SWCNTs for commercial and industrial applications.     

Decomposition kinetics and recycle of binary hydrogen‐tetrahydrofuran clathrate hydrate

Decomposition kinetics and recycle of hydrogen–tetrahydrofuran (H₂–THF) clathrate hydrates were investigated with a pressure decay method at temperatures from 265.1 to 273.2 K, at initial pressures from 3.1 to 8.0 MPa, and at stoichiometric THF hydrate concentrations for particle sizes between 250 and 1000 μm. The decomposition was modeled as a two‐step process consisting of H₂ diffusion in the hydrate phase and desorption from the hydrate cage. The adsorption process occurred at roughly two to three times faster than the desorption process, whereas the diffusion process during formation was slightly higher (ca. 20%) than that during decomposition. Successive formation and decomposition cycles showed that occupancy seemed to decrease only slightly with cycling and that there were no large changes in hydrate structure due to cycling. Results provide evidence that the formation and decomposition of H₂ clathrate hydrates occur reversibly and that H₂ clathrate hydrates can be recycled with pressure. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Electrodeposition of amorphous gold alloy films

The process for electroplating amorphous gold-nickel-tungsten alloy that we developed previously based on the addition of a gold salt to a known amorphous Ni-W electroplating solution was investigated further using the X-ray diffraction (XRD) method for the purpose of quickly surveying the effects of various experimental variables on the microstructure of the alloy. In this system the gold concentration in the plating bath was found to be critical; i.e., when it is either very low or very high, the deposit becomes crystalline to XRD. The deposit composition varies linearly with the mole ratio of Au to Ni in solution, and the alloy deposit is amorphous to XRD when the atomic ratio of Au/Ni in the deposit is between 0.5 and 1.5. At suitable concentrations of the metal ions, the deposit contains essentially no tungsten. By extending the work on the Au-Ni-W system, an amorphous Au-Co alloy plating process was also developed.     

Flexible and Conductive 3D Printable Polyvinylidene Fluoride and Poly(N,N‐dimethylacrylamide) Based Gel Polymer Electrolytes

In this work, 3D printable gel polymer electrolytes (GPEs) based on N,N‐dimethylacrylamide (DMAAm) and polyvinylidene fluoride (PVDF) in lithium chloride containing ethylene glycol solution are synthesized and their physicochemical properties are investigated. 3D printing is carried out with a customized stereolithography type 3D gel printer named “Soft and Wet Intelligent Matter‐Easy Realizer” and free forming GPE samples having variable shapes and sizes are obtained. Printed PVDF/PDMAAm‐based GPEs exhibit tunable mechanical properties and favorable thermal stability. Electrochemical proprieties of the printed GPEs are carried out via impedance spectroscopy in the temperature range of 25–90 °C by varying PVDF content. Ionic conductivity as high as 6.5 × 10^?4 S cm^?1 is achieved at room temperature for GPE containing low PVDF content (5 wt%) and conductivity of the GPEs is increased as temperature rises.     

Structural Analysis of the Complex between Penta-EF-Hand ALG-2 Protein and Sec31A Peptide Reveals a Novel Target Recognition Mechanism of ALG-2

ALG-2, a 22-kDa penta-EF-hand protein, is involved in cell death, signal transduction, membrane trafficking, etc., by interacting with various proteins in mammalian cells in a Ca²⁺-dependent manner. Most known ALG-2-interacting proteins contain proline-rich regions in which either PPYPXnYP (type 1 motif) or PXPGF (type 2 motif) is commonly found. Previous X-ray crystal structural analysis of the complex between ALG-2 and an ALIX peptide revealed that the peptide binds to the two hydrophobic pockets. In the present study, we resolved the crystal structure of the complex between ALG-2 and a peptide of Sec31A (outer shell component of coat complex II, COPII; containing the type 2 motif) and found that the peptide binds to the third hydrophobic pocket (Pocket 3). While amino acid substitution of Phe⁸⁵, a Pocket 3 residue, with Ala abrogated the interaction with Sec31A, it did not affect the interaction with ALIX. On the other hand, amino acid substitution of Tyr¹⁸⁰, a Pocket 1 residue, with Ala caused loss of binding to ALIX, but maintained binding to Sec31A. We conclude that ALG-2 recognizes two types of motifs at different hydrophobic surfaces. Furthermore, based on the results of serial mutational analysis of the ALG-2-binding sites in Sec31A, the type 2 motif was newly defined.     

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) graft copolymers and their application as carriers for drug delivery system

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) [P(NIPAM‐co‐HEMA)] copolymer was synthesized by controlled radical polymerization from respective N‐isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) monomers with a predetermined ratio. To prepare the thermosensitive and biodegradable nanoparticles, new thermosensitive graft copolymer, poly(L ‐lactide)‐graft‐poly(N‐isoporylacrylamide‐co‐hydroxyethyl methacrylate) [PLLA‐g‐P(NIPAM‐co‐HEMA)], with the lower critical solution temperature (LCST) near the normal body temperature, was synthesized by ring opening polymerization of L ‐lactide in the presence of P(NIPAM‐co‐HEMA). The amphiphilic property of the graft copolymers was formed by the grafting of the PLLA hydrophobic chains onto the PNIPAM based hydrophilic backbone. Therefore, the graft copolymers can self‐assemble into uniformly spherical micelles ò about 150–240 nm in diameter as observed by the field emission scanning electron microscope and dynamic light scattering. Dexamethasone can be loaded into these nanostructures during dialysis with a relative high loading capacity and its in vitro release depends on temperature. Above the LCST, most of the drugs were released from the drug‐loaded micelles, whereas a large amount of drugs still remains in the micelles after 48 h below the LCST. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of organic groups on hydrogen adsorption properties of periodic mesoporous organosilicas

We investigate the hydrogen adsorption properties of periodic mesoporous organosilicas (PMOs) and focus, in particular, on how these properties are affected by diverse organic groups embedded in the walls. PMOs with π electrons on the pore surface adsorb more hydrogen molecules per unit area and have a higher isosteric heat of hydrogen adsorption (Q_st). The number of adsorbed hydrogen molecules per unit area correlates well with the density of organic groups on the pore surface. We attribute the high Q_st to the high polarizability of organic groups with π electrons, which enhances the dispersion force. The molecular order of organic groups affects the adsorption-site affinity to hydrogen molecules as well as the location of adsorption sites. For phenylene-bridged PMOs with crystal-like pore walls, Q_st decreases rapidly with increasing hydrogen loading, which indicates two types of adsorption sites with different affinities to hydrogen molecules: one is an exposed CH bond and the other is a siloxane bond. However, Q_st for phenylene-bridged PMOs with amorphous pore walls exhibits a moderate slope, which might be caused by the random order of organic groups; this results in several types of adsorption sites with various affinities.     

Gelation mechanism of agarose and κ-carrageenan solutions estimated in terms of concentration fluctuation

The gelation mechanism of agarose and κ-carrageenan aqueous solutions was investigated by using polarized light scattering and X-ray diffraction techniques in terms of the liquid-liquid phase separation. When an incident beam of He-Ne gas laser was directed to the gel prepared by quenching the agarose solution, the logarithm of scattered intensity increased linearly in the initial stage and tended to deviate from this linear relationship in the latter stage. If the linear increase in the initial stage could be analyzed within the framework of the linear theory of spinodal decomposition proposed by Cahn, the phase diagram indicated that the gelation is attributed to the phase separation due to the concentration fluctuation of solution. Furthermore, in the later stage showing the deviation of the linear relationship, light scattering under Hv polarization condition showed a X-type pattern indicating the existence of optically anisotropic rods, the optical axes being parallel or perpendicular with respect to the rod axis. In spite of the existence of the rods, no crystallites were confirmed by the corresponding X-ray diffraction and DSC measurements. For κ-carrageenan solutions, the logarithm of scattered intensity against time showed a constant value. This indicated that the gelation of κ-carrageenan solutions is independent of liquid-liquid phase separation but is due to the rapid formation of cross-linking points. Accordingly it turns out that the small difference of chemical structure between agarose and κ-carrageenan causes quite different gelation mechanism.     

Marked particle size and support effect of Pd catalysts upon the direct decomposition of nitric oxide

The catalytic behavior of beryllia-supported Pd catalyst for the direct decomposition of NO was compared with that of silica supported one. The TOF of NO decomposition was one order of magnitude larger in the case of Pd/BeO. Over Pd/SiO₂, the TOF was increased with the increase of the Pd particle size. On the contrary, over Pd/BeO smaller Pd particles exhibited higher TOF for NO decomposition suggesting some strong electronic or structural interaction between Pd and beryllia. TPD spectra of NO(a) over reduced catalysts indicated that NO was adsorbed on Pd/SiO₂ more strongly than on Pd/BeO, and dissociation of NO(a) was easier on the former catalyst. FT-IR spectra of adsorbed NO at room temperature followed by the evacuation at elevated temperatures confirmed this. TPD spectra of O₂ desorbed from oxidized surface indicated that adsorption strength of O(a) is one of the most important factors to determine the catalytic activity of NO decomposition over supported Pd catalysts.