Preparation of high molecular weight polyurethane particles by nonaqueous emulsion polyaddition

A versatile nonaqueous emulsion polyaddition process for the one-step fabrication of spherical polyurethane nanoparticles is presented. Three different emulsion systems were used consisting of N,N′-dimethylformamide (DMF) dispersed in n-hexane, acetonitrile dispersed in cyclohexane, and acetonitrile dispersed in tetradecane. After successful stabilization of the emulsion systems by using a poly(isoprene)-poly(methylmethacrylate) block copolymer, the fabrication of the polyurethanes was carried out within the dispersed polar phase. The polyurethane particles showed average diameters as small as 35 nm. Additionally, infrared (IR) characterization revealed that the formation of any urea, which decreases the mechanical properties of the polyurethanes, was prevented during the polyaddition. This was attributed to the anhydrous reaction conditions. Gel permeation chromatography (GPC) analysis demonstrated the average molecular weights (M _n) of the polyurethanes to be as high as 16,500 g/mol, corresponding to conversions of 0.98. Comparable molecular weights and conversions have not previously been achieved without the formation of urea.     

The synthesis and characterization of a new (<Emphasis Type="Italic">E,E</Emphasis>)-dioxime containing 13-membered dithiadiazamacrocyclic moieties and its mononuclear complexes

A new (E,E)-dioxime, (6Z,7Z)-15,16-dihydro-14H-dibenzo[b,h][1,10,4, 7]dithiadiazacyclotride-cine-6,7(5H,8H)-dionedioxime (H ₂ L) has been synthesized by reacting cyanogen-di-N-oxide (2) with 2,2′-[propane-1,3-diylbis(thio)]dianiline (1). Mononuclear complexes (4) and (5) of this ligand have been synthesized by reacting the vic-dioxime (H₂L) with NiCl₂ · 6H₂O and CoCl₂ · 6H₂O, respectively. The BF ₂ ⁺ capped Ni(II) and Co(III) complexes (6) and (7) of the dioxime have been synthesized from (4) and (5). The new compounds were characterized by a combination of elemental analysis, ¹H- and ¹³C-n.m.r, i.r. and m.s. spectral data.     

Polymer dispersions from catalytic polymerization in aqueous systems

By contrast to traditional free radical emulsion polymerization, catalytic polymerization allows for polymer microstructure control. In terms of polymerizable monomers, both techniques are largely complementary. Since the beginning of this decade, an increasing number of reports on polyolefin, polybutadiene, polyalkenamer, polynorbornene, polyketone, and polyacetylene dispersions prepared by catalytic polymerization in disperse aqueous systems has appeared. This contribution reviews the preparation of these dispersions, their colloidal properties, particle formation mechanisms, particle morphologies, and polymer microstructures.     

Thermal behavior of polyacrylonitrile polymers synthesized under different conditions and comonomer compositions

Polyacrylonitrile (PAN) polymers are used as precursors for carbon fiber production. This process requires an oxidative stabilization step, which can be studied by differential scanning calorimetry (DSC). In this sense, thermal behavior of PAN based terpolymers by different polymerization processes, compositions and itaconic acid concentrations in the reaction media were investigated. The obtained results showed that the addition of itaconic acid and methyl acrylate as comonomers resulted a lower heat flow during the process comparing to the PAN homopolymer. It suggested that these comonomers aid the oxidative stabilization stage for all studied process. The redox system polymerization at 40°C resulted in a lower heat flow. Itaconic acid decreases slightly initial and peak temperatures of the terpolymer and heat flow until concentration of 3y. The cyclization temperature decreases when MAis incorporated into the terpolymer compared to the MMA terpolymer and increases when MAA is the acidic monomer. Among terpolymers the AN/MA/AA polymer showed the best thermal behavior for carbon fiber producing.     

Site-selective RNA cleavage by DNA bearing a base pair-mimic nucleoside

We have synthesized the deoxyadenosine derivative tethering a phenyl group (X), which mimics the Watson-Crick A/T base pair. The RNA/DNA hybrid duplexes containing X in the middle of the DNA sequence showed a similar thermal stability regardless of the ribonucleotide species (A, G, C, or U) opposite to X, probably because of the phenyl group stacking inside of the duplex accompanied by the opposite ribonucleotide base flipped in an extrahelical position. The RNA strand hybridized with the DNA strand bearing X was cleaved on the 3'-side of the ribonucleotide opposite to X in the presence of MgCl2, and the RNA sequence to be cleaved was not restricted. The site-specific RNA hydrolysis suggests that the DNA strand bearing X has the advantage of the site-selective base flipping in the target sequence and the development of a "universal deoxyribozyme" to exclusively cleave a target RNA sequence.     

Thermodynamic analysis of duplex formation of the heterochiral DNA with L-deoxyadenosine.

An L-DNA, the mirror-image isomer of natural DNA, has extraordinary nuclease resistance, and thus the molecules should be promising reagents for many applications, such as antisense technology. However, little is known about the structural and thermodynamic properties of DNAs with this modified nucleotide. In this study, we prepared the L-nucleotide (L-dA) and introduced it into oligodeoxyribonucleotides to assess the ability of the L-nucleotide as a functional molecule for many applications based on the DNA hybridization. Two decamers with an L-dA at the center were synthesized and duplexes with the complementary DNA strand were applied to structural and thermodynamic analyses. The structural study by CD spectra showed that the structures of both modified "L/D-D" duplexes were the typical B-form. This result suggests that the global structure of DNA was not collapsed by the introduction of an L-DNA. Thermodynamic parameters (deltaH degrees, deltaS degrees, and deltaG degrees 37) of the duplex formation, determined by UV melting experiments, indicated that the both duplexes were destabilized at about 2.5 to 3.0 kcal mol(-1) by the introduced L-dA, mainly due to an unfavorable enthalpic effect. In conjunction with information by other researchers, these results suggest that the L-DNA affect on the duplex structure and the stability vary locally; thus, the thermodynamic stability of modified L/D-D duplexes should be predictable by the nearest-neighbor thermodynamic parameters.     

Assessment of corrosion resistance of surface-coated galvanized steel by analysis of the AC impedance spectra measured on the salt-spray-tested specimen

In the present work, corrosion resistance of surface-coated galvanized steel was quantitatively determined by an analysis of the alternating current (AC) impedance spectra measured on the salt-spray-tested specimen. To evaluate the corrosion resistance of the surface-coated galvanized steel, AC impedance spectroscopy was performed on the salt-spray-tested specimen previously exposed to salt-sprayed corrosive environment. From the analysis of the impedance spectra, the area fraction transient of white rust θ ₂(t) was theoretically derived from the equivalent circuit equation by using two fitting parameters. The values of the two fitting parameters were determined by fitting the empirical transient equations to the area fraction of the resin coating layer and to the total resistance obtained from the impedance spectra measured, respectively. From the analyses of θ ₂(t) for four kinds of surface-coated galvanized steels with various resin coating layers, it is indicated that as the values of the two fitting parameters decrease in the order of CP, GI, OD and OM (commercial trade names) specimens, the corrosion resistance increases in that order as well. Furthermore, from the quantitative comparison of the two fitting parameters with the polarization resistance of the upper resin coating layer R _p determined from the potentiodynamic polarization curve, it is suggested that the two fitting parameters decrease in value as well with increasing R _p.     

Second Dissociation Constant of H<Subscript>2</Subscript>Te and the Absorption Spectra of HTe<Superscript>–</Superscript>, Te<Superscript>2–</Superscript> and Te<Subscript>2</Subscript><Superscript>2–</Superscript> in Aqueous Solution

We have measured the second acid dissociation constant, K _2a , at several ionic strengths for hydrogen telluride (H₂Te) using the Charge Transfer to Solvent (CTTS) uv spectra of its anions HTe⁻ and Te²⁻. Since it is produced in our solutions, we have also determined the spectra of Te₂ ²⁻ both in the uv and in the visible regions. At 25 ^∘C, K _2a = (1.28 ± 0.02) × 10⁻¹² by extrapolation to zero ionic strength. Its value at an ionic strength equal to 0.5 mol.dm^-3 was estimated to be (8.7 ± 0.2) × 10⁻¹². The solution thermodynamics of these species are also discussed and comparisons are made to related acids.     

Improvement of culture conditions forl-proline production by a recombinant strain ofSerratia marcescens

Serratia marcescens SP511 was previously reported to be anl-proline-producing strain that harbors a recombinant plasmid carrying the mutant type of the proline operon. This strain produced 65 g/L ofl-proline in a medium containing 22% sucrose and urea after 5 d of incubation under the conventional culture conditions. We searched for more suitable culture conditions for more abundantl-proline production by SP511. To improve the supply of a nitrogen source to cells, ammonium was used instead of urea and fed to a culture under control of the pH of the medium. The concentrations of MgSO₄ and K₂HPO₄ were increased, and in addition, sucrose was continuously added to the culture at a final concentration of 32%. Under these conditions, the cell amount was increased twofold over that under the previous conditions andl-proline production reached a maximum of more than 100 g/L after 4 d of incubation.     

Polymerization of (o-methylphenyl)acetylene and polymer characterization

(o-Methylphenyl)acetylene polymerized with high yields in the presence of W and Mo catalysts. W catalysts were more active than the corresponding Mo catalysts. The weight-average molecular weight of the polymer formed with W(CO)₆–CCl₄–hv reached 8 × 10⁵, being higher than the maximum value (ca. 2 × 10⁵) for poly(phenylacetylene). The polymer had the structure $\rlap{--} [{\rm CH} \hbox{=\hskip-1pt=} {\rm C}(o - {\rm CH}_3 {\rm C}_6 {\rm H}_4 )\rlap{--} ]_n $. The stereochemical structure of the main chain could be determined by ¹³C-NMR; the cis content varied in a range of 41–61% depending on the polymerization conditions. The present polymer was thermally more stable than poly(phenylacetylene) according to thermogravimetric analysis. Interestingly, this polymer possessed deeper color than poly(phenylacetylene), and showed a fairly strong absorption in the visible region.