Evaluation of mass transfer rate during Ziegler-Natta propylene polymerization

Mass transfer which affects the rate of propylene polymerization with titanium trichloride–triethylaluminum, has been evaluated by use of a new method developed for this heterogeneous reaction. The polymerization was carried out with the usual flask reactor equipped with a paddle stirrer; the rate of gas absorption into the polymerization slurry was proportional to stirring speed and the reciprocal of the total amount of polymers produced. It has been confirmed that the polymerization rate separated from the absorption rate is purely kinetic (propagation), and an effective physical process, such as monomer transfer through a polymer film covering the catalyst surface, no longer exists.     

Efficient deanilidation of phosphoranilidates by the use of nitrites and acetic anhydride

Reagent systems of sodium– and tetrabutylammonium nitrite–acetic anhydride were proved to be extremely efficient for the deanilidation of nucleoside 3′-phosphoranilidates, whose reactions were rapid with the former and instant with the latter. It was further found that the reagent system is applicable to oligonucleotide synthesis provided that the exocyclic amino groups of 2′-deoxyadenosine, 2′-deoxyguanosine, and 2′-deoxycytidine were protected by succinylation.     

XAFS spectra from X-ray fluorescence Kβ line using conventional energy-discriminating detector

X-ray fluorescence spectra of copper (Cu) metal, copper monoxide (CuO), and potassium chromate (K₂CrO₄) were recorded as a function of incident X-ray energy near the Cu K-edge and chromium (Cr) K-edge, respectively, using a conventional silicon drift detector. The spectra contained components due to elastic, inelastic, and multiple scattering, in addition to the Kα and Kβ lines. Cu and Cr K-edge X-ray absorption fine structure (XAFS) spectra of Cu, CuO, and K₂CrO₄ were obtained by an intensity analysis of the Kα and Kβ lines. The intensity of the Kβ line for the different incident photon energies was obtained by numerically removing the additional scattering components using the MUSCAT program. These spectra exhibited a jump near the K absorption edges, which reproduced the spectral features obtained in transmission mode for both Cu, CuO, and K₂CrO₄. A chemical shift was also clearly identified in the X-ray absorption near edges structure using the X-ray fluorescence Kβ line. In addition, the Cr K-edge extended XAFS spectrum of K₂CrO₄ was clearly observed using the Cr Kβ fluorescent line. The XAFS measurements on the Kα and Kβ lines are possible, and they carry equally valuable information.     

TEMPO/NaIO4-SiO2: a catalytic oxidative rearrangement of tertiary allylic alcohols to beta-substituted alpha,beta-unsaturated ketones

The novel catalytic method for the oxidative rearrangement of tertiary allylic alcohols to beta-substituted alpha,beta-unsaturated ketones is described. TEMPO/NaIO4-SiO2 causes facile and efficient oxidative rearrangement of various acyclic substrates as well as medium-sized and macrocyclic substrates.     

In vitro and in vivo evaluation of microparticulate drug delivery systems composed of macromolecular prodrugs

Macromolecular prodrugs are very useful systems for achieving controlled drug release and drug targeting. In particular, various macromolecule-antitumor drug conjugates enhance the effectiveness and improve the toxic side effects. Also, polymeric micro- and nanoparticles have been actively examined and their in vivo behaviors elucidated, and it has been realized that their particle characteristics are very useful to control drug behavior. Recently, researches based on the combination of the concepts of macromolecular prodrugs and micro- or nanoparticles have been reported, although they are limited. Macromolecular prodrugs enable drugs to be released at a certain controlled release rate based on the features of the macromolecule-drug linkage. Micro- and nanoparticles can control in vivo behavior based on their size, surface charge and surface structure. These merits are expected for systems produced by the combination of each concept. In this review, several micro- or nanoparticles composed of macromolecule-drug conjugates are described for their preparation, in vitro properties and/or in vivo behavior.     

Fluorescence studies on phenylene moieties embedded in a framework of periodic mesoporous organosilica

The excited state characteristics of phenylene (Ph)-bridged periodic mesoporous organosilica (PMO) powders with crystal-like and amorphous wall structures are investigated. Crystal-like Ph-PMO has a molecular ordering of the bridging organic moieties with intervals of 0.76 and 0.44 nm parallel and perpendicular to the mesochannel direction, respectively, whereas amorphous Ph-PMO has no molecular-level periodicity in the wall. Fluorescence from the exciton and excimer of the Ph moieties and the defect center in the silicate network were detected at room temperature, but fluorescence from the excimer and the defect center were not detected at 77 K for crystal-like Ph-PMO dispersed in a methanol/ethanol mixed solvent. The decay curve of the exciton fluorescence of crystal-like Ph-PMO at room temperature was analyzed successfully using a one-dimensional diffusion model quenched by the defect center and the excimer site. The results were discussed in comparison with those for the crystal-like biphenylene-bridged PMO reported in the preceding paper (Yamanaka et al., Phys. Chem. Chem. Phys., 2010, 12, 11688-11696). The existence of excited states with various conformations including ground state dimers or aggregates of the Ph moieties was suggested for amorphous Ph-PMO. It was clearly apparent that the differences in the excited state dynamics reflected the differences in the molecular-level structure in the wall.     

Synthesis and mechanochemical properties of biobased ABCBA-type pentablock copolymers comprising poly-d-lactide (A), poly-l-lactide (B) and poly(1,2-propylene succinate) (C)

The ABCBA pentablock copolymers (p-d -l -PPS) comprising poly(d -lactide) (PDLA: A), poly(l -lactide) (PLLA: B) and poly(propylene succinate) (PPS: C) were successfully synthesized by two-step ring-opening polymerization (ROP) of d - and l -lactide using a dihydroxy-terminated PPS as a macro-initiator. The pentablock copolymers revealed the high stereocomplex (sc) crystallinity, thermal stability and elastomeric property in their solution-cast films. It was found that the T_g was found to be proportional to the PPS content, whereas the T_m was proportional to their average block length. The thermal resistivity of the copolymer films was found to be as high as 202°C owing to their sc formation. The copolymers also showed improved stereocomplexibility compared to the enantiomeric mixtures of triblock copolymers (PLLA-PPS-PLLA and PDLA-PPS-PDLA) having similar PLLA and PDLA chain lengths. These pentablock copolymers can afford thermoplastic elastomers or flexible plastic materials having a 100% bio-based content, showing high heat-resistive property.     

Novel ring transformation of thiazolidine to oxazolidine: acyl halide-promoted intramolecular rearrangement of 4(R)-hydroxymethyl-3-methyl-1,3-thiazolidine

An interesting transformation occurs during acylation of 4(R)-hydroxymethyl-3-methyl-1,3-thiazolidine when 4(R)-acylthiomethyl-3-methyl-1,3-oxazolidines are yielded: the reaction competing with O-acylation is controlled by the bulkiness of the acyl group.     

Isolation and cationic ring-opening polymerization of 2,3,5,6-tetrahydroimidazo[2,1-b][1,3]oxazole to produce a thermally stable polyurea

A bicyclic pseudourea, 2,3,5,6-tetrahydroimidazo[2,1-b][1,3]oxazole ( 1 ), was isolated for the first time, and its cationic and spontaneous polymerizations were examined. Both polymerizations gave poly(1,3-imidazolidin-2-one-1,3-diylethylene) ( 2 ) in high yields. The polymer is a crystalline solid with glass transition and melting temperature of 51°C and 286°C, respectively. Thermogravimetry showed that it is stable up to 450°C under nitrogen.     

Biodegradation of chitin with enzymes and vital components

Chitin from squid pen was effectively degraded by the chitinase from Bacillus sp. PI-7S, while the degradation of chitin with lysozyme proceeded very slowly. Among the various vital components studied, the degradation of chitin from squid pen was performed not by canine serum, canine tela subcutanea, canine tela liver, and equine serum but by bovine serum and caprine serum. Noteworthy is the fact that chitin sponge subcutaneously implanted in dog reported not to have chitinase was degraded in ca. 14 days.