Synthesis, thermal properties, and biodegradability of propyl-etherified starch

High amylose corn starch (HACS) was etherified with 1-bromopropane in dimethyl sulfoxide. The structure of the products was characterized by infra-red and ¹H-NMR spectroscopy. The degree of substitution (DS) on glucose unit calculated from ¹H-NMR spectrum was varied from 0.9 to 2.7 by changing feed ratio of 1-bromopropane to HACS. Thermogravimetric analysis reveals that the etherified HACS has a higher decomposition temperature than unmodified HACS. Differential scanning calorimetry analysis reveals that the etherified starch has a clear glass transition temperature which decreased with increasing DS, and that no melting point is observed. This result demonstrates that the etherified HACS mainly consists of amorphous region. The biodegradation rate decreases with increasing degree of etherification.     

Molecular structure of some [1.1 ]ferrocenylruthenocenophanium (n = 1,2 polyiodides salts

Oxidation of [1.1]ferrocenylruthenocenophane with a large excess and 1.5 equivalents of iodine gives dicationic iodo[1.1]ferrocenylruthenocenophanium²⁺I₃⁻ · 0.5I₂2 (1) and monocationic [1.1]ferrocenylruthenocenophanium⁺I₃⁻ (2) salts respectively. The structures of 1 and 2 were analyzed by single-crystal X-ray diffraction studies. The crystal form of 1 is monoclinic space group C2/c, A = 21.35](5), B = 20.594(5), C = 17.397(4) Å, β = 124.17(1)°, Z = 8, and the final R = 0.068 and R_w = 0.070. The cation formulated as [Fe^III(C₅H₄CH₂C₅H₄)₂Ru^IVI]²⁺ exists in a syn-conformation as in the cases of the neutral compound. The distance between the Ru^IV and Fe^II is 4.656(4) Å, which is much shorter than the value of the neutral compound (4.792(2) Å), and the bond angle of I---Ru^IV,Fe^III is 81.26°. The dihedral angle between the two η⁵-C₅H₄ (fulvenide) rings on the Ru^IV moiety is 37.56° due to the Ru^IV---I bond (2.758(3) Å). These two rings of Fe^III and Ru^IV moieties are essentially eclipsed. The unit cell has three kinds of I₃⁻ (I_3a⁻, I_3b⁻ and I_3c⁻) and one I₂, and the formula of 1 is given as [Fe^III(C₅H₄CH₂CSH₄)₂Ru^IVI]²⁺I₃⁻ · 0.5(I₃⁻)₂ · 0.5I₂. The crystal of 2 formulated as [Fe^III(C₅H₄CH₂C₅H₄)₂Ru^II]⁺I₃⁻ is triclinic space group

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, and the final R = 0.067 and R_w = 0.068. The unit cell has two independent molecules (unit A and B); i.e. two kinds of distance between the Ru^II and Fe^III, are observed; one (A) is 4.615(3) and the other (B) is 4.647(3) α. The two η⁵-C₅H₄ rings of both Fe^III and Ru^II are essentially staggered and the dihedral angles between the rings of FcH and RcH moieties are less than 5.8°. Typical ferrocenium-type broad singlet ⁵⁷Fe-Mössbauer lines are observed for both salts (1, 2) at all temperatures.     

Racemization behavior of l,l-lactide during heating

To control the depolymerization process of poly(l-lactic acid) into l,l-lactide for feedstock recycling, the racemization of l,l-lactide as a post-depolymerization reaction was investigated. In the absence of a catalyst, the conversion to meso-lactide increased with increase in the heating temperature and time at a higher rate than the conversion into oligomers. The resulting high composition of meso-lactide suggests that the direct racemization of l,l-lactide had occurred in addition to the known racemization mechanism that occurs on the oligomer chains. In the presence of MgO, the oligomerization rapidly proceeded to reach an equilibrium state between monomers and oligomers. The equilibrium among l,l-, meso-, and d,d-lactides was found to be a convergent composition ratio l,l-:meso-:d,d-lactides = 1:1.22:0.99 (wt/wt/wt) after 120 min at 300 °C. This composition ratio also indicates that in addition to the known racemization reaction on the oligomer chains, direct racemization among the lactides is also a frequent occurrence.     

Effects of MgO catalyst on depolymerization of poly-l-lactic acid to l,l-lactide

To control the depolymerization of poly-l-lactic acid (PLLA) into l,l-lactide, effects of altering the physical and chemical properties of magnesium oxide (MgO) on its ability as a catalyst were investigated. Four kinds of MgO particles: MgO-heavy, 0.2, 0.05, and 0.01 μm, having primary particles of different dimensions, surface areas, and chemical structures/species were used. Thermo-gravimetric profiles of PLLA/MgO composites shifted into a lower temperature range due to an increase in the catalytic surface area resulting from a decrease in the dimensions of the MgO particles. However, decreasing the dimensions caused frequent side reactions with unfavorable products: cyclic oligomers and meso-lactide, due to the presence of different chemical structures/species. Heat treatment of the MgO particles not only effectively suppressed the oligomer production and enhanced the l,l-lactide production, but also accelerated the meso-lactide production at lower temperatures. These results indicate that the surface properties of MgO considerably influence the depolymerization of PLLA, with the catalytic behavior of MgO controllable by heat treatment and selection of the depolymerization conditions.     

Microreactor utilizing a vertically-aligned carbon nanotube array grown inside the channels

We have fabricated a microreactor incorporating vertically-aligned carbon nanotubes supporting Pt nanoparticles and found that the presence of aligned nanotubes significantly enhances the catalytic reaction and extends the catalyst lifetime as compared with conventional microreactors using a Pt metal film or Pt nanoparticles directly deposited on the channel walls.     

Improvement of pharmaceutical properties of insulin through conjugation with glucuronylglucosyl-β-cyclodextrin

Recently, a large number of peptides and proteins have been utilized as active pharmaceutical ingredients in the clinical field. However, the stability of peptide and protein drugs is often low. In addition, some peptides and proteins adsorb onto glass or polypropylene tube. In the present study, to improve these pharmaceutical properties of peptides and proteins, we newly prepared glucuronylglucosyl-β-cyclodextrin (GUG-β-CyD) conjugate with insulin, a model protein drug, and evaluated its enzymatic or thermal stability and adsorption onto glass or polypropylene tube. The insulin conjugate with GUG-β-CyD was successfully prepared by condensation of amine group of insulin and carboxyl group of GUG-β-CyD. Circular dichroism spectra showed that the secondary structure of insulin in this conjugate was retained. Adsorption of insulin onto glass or polypropylene tube was decreased by the conjugation with GUG-β-CyD. Moreover, enzymatic and thermal stabilities of the conjugate were higher than those of insulin and the mixture of insulin and GUG-β-CyD. These results suggest that insulin conjugation with GUG-β-CyD could improve the pharmaceutical properties of insulin.     

POLYMERIZATION-INDUCED PHASE SEPARATION OF POLYMER-DISPERSED LIQUID CRYSTAL

Abstract

Polymerization-induced phase separation in polymer-dispersed liquid crystal is studied by computer simulations in two dimensions. The domain morphology resulting from phase separation is investigated by solving the couple set of equations for the local volume fraction and the nematic order parameter, taking into account the viscoelastic effects and gelation due to polymerization. Comparing the morphology of phase separation by temperature quench, it is shown that the viscoelastic effects and gelation enable the polymer-rich phase to form a stable interconnected domain even when the polymer component is minority.     

Chemoselective hydrogenation of nitroarenes with carbon nanofiber-supported platinum and palladium nanoparticles

Platinum and palladium nanoparticles supported on three types of carbon nanofibers (CNFs) are synthesized and used as catalysts in the hydrogenation of nitroarenes. Nanosized platinum particles dispersed on platelet-type CNF efficiently catalyze the reduction of functionalized nitroarenes to the corresponding substituted anilines in high turnover numbers with other functional groups remaining intact.