Neutral poly(3,4-ethylenedioxythiophene-2,5-diyl)s: preparation by organometallic polycondensation and their unique p-doping behavior

Neutral and non-doped poly(3,4-ethylenedioxythiophene), PEDOTh(Ni), and its hexyl derivative, PEDOTh-C₆(Ni), have been prepared by organometallic dehalogenation polycondensation of 2,5-dichloro-3,4-ethylenedioxythiophene and its hexyl derivative with a zerovalent nickel complex. PEDOTh-C₆(Ni) was soluble in organic solvents and ¹H NMR data indicated that it had an M_n of 11,000. MALDI-TOF mass analysis of PEDOTh(Ni) gave M_n and M_w of about 1700 and 2400, respectively. PEDOTh-C₆(Ni) showed a UV-Vis absorption peak at 546 nm in CHCl₃. Electrochemical oxidation of PEDOTh-C₆(Ni) started at about −0.40 V vs Ag⁺/Ag and gave a peak at 0.20 V vs Ag⁺/Ag. Chemical and electrochemical oxidation (or p-doping) of PEDOTh-C₆(Ni), both in solutions and in a solid state, led to weakening of the original π-π^∗ peaks and rise of new peak(s) in a region of 800-1500 nm. The p-doping of PEDOTh-C₆(Ni) caused not only a decrease in the intensity of ¹H NMR signals of the bridging ethylene hydrogens but also a decrease in that of the hexyl side chain, suggesting a strong interaction of the p-dopant with the side chain. NMR data of poly(3-methoxythiophene-2,5-diyl) also supported an assumption that p-doping brings about a severe change in electronic state of the substituent attached to the polythiophene main chain. PEDOTh(Ni) had a density of 1.71 g cm⁻³; the molecular packing mode of PEDOTh(Ni) is discussed based on the density of the polymer and its XRD data.     

Thallium-201 myocardial SPECT in Bland-White-Garland syndrome: two adult patients with inferoposterior perfusion defect

A myocardial 201TI SPECT examination was conducted both prior to and following surgery of two adult patients with an anomalous left coronary artery originating from the pulmonary artery (Bland-White-Garland syndrome). In this syndrome, the anterior wall is usually affected first. Preoperative examination demonstrated an inferoposterior perfusion defect. In both patients, the right coronary artery was markedly dilated, and a significant left-to-right shunt formation was observed. Both patients were diagnosed as possibly having coronary steal syndrome. A prolonged inadequate blood supply to the right coronary region may cause inferoposterior cardiomyopathy. In the postoperative examination, myocardial perfusion markedly improved in one patient whose preoperative SPECT showed redistribution in a delayed scan. Thallium-201 SPECT was therefore found to be useful in assessing both the preoperative and postoperative myocardial perfusion.     

Effects of cytogenin on spontaneous arthritis in MRL/1 mice and on pristane-induced arthritis (PIA) in DBA/1J mice

Cytogenin, 8-hydroxy-3-hydroxymethyl-6-methoxyisocoumarin, has low cytotoxicity on murine and human tumour cells in vitro. It augments or suppresses phagocytosis of macrophages and lymphocyte proliferation. It has been reported that cytogenin has a potent inhibitory effect clinically on adjuvant arthritis in Lewis rats and on type II collagen-induced arthritis in DBA/1J mice. Our experimental findings provide evidence that cytogenin has beneficial effects on spontaneous polyarthritis in MRL/1 mice and pristane-induced arthritis in DBA/1J mice. The results suggest that the mode of the anti-arthritic action of cytogenin is different from those of NSAIDs; although the precise mode of action remains unclear, cytogenin may become an excellent therapeutic agent for rheumatoid arthritis.     

Parameters affecting the frequencies of transformation and co-transformation with synthetic oligonucleotides in yeast.

Factors influencing the direct transformation of the yeast Saccharomyces cerevisiae with synthetic oligonucleotides were investigated by selecting for cyc1 transformants that contained at least partially functional iso-1-cytochrome c. Approximately 3 x 10(4) transformants, constituting 0.1% of the cells, were obtained by using 1 mg of oligonucleotide in the reaction mixture. Carrier, such as heterogeneous oligonucleotides, enhanced transformation frequencies. Transformation frequencies were dramatically reduced if the oligonucleotides had a large number of mismatches or had terminally located mismatches. Transformation with oligonucleotides, but not with linearized double-strand plasmid, was efficient in a rad52- strain, suggesting that the pathway for transformation with oligonucleotides is different from that with linearized double-strand plasmid. We describe a procedure of co-transformation with two oligonucleotides, one correcting the cyc1 defect of the target allele in the host strain, and the other producing a desired amino acid alteration elsewhere in the iso-1-cytochrome c molecule; approximately 20% of the transformants obtained by co-transformation contained these desired second alterations.     

Asymptotic properties on codeword lengths of an optimal FV code for general sources

This correspondence is concerned with asymptotic properties on the codeword length of a fixed-to-variable length code (FV code) for a general source {X/sup n/}/sub n=1//sup /spl infin// with a finite or countably infinite alphabet. Suppose that for each n /spl ges/ 1 X/sup n/ is encoded to a binary codeword /spl phi//sub n/(X/sup n/) of length l(/spl phi//sub n/(X/sup n/)). Letting /spl epsiv//sub n/ denote the decoding error probability, we consider the following two criteria on FV codes: i) /spl epsiv//sub n/ = 0 for all n /spl ges/ 1 and ii) lim sup/sub n/spl rarr//spl infin///spl epsiv//sub n/ /spl les/ /spl epsiv/ for an arbitrarily given /spl epsiv/ /spl isin/ [0,1). Under criterion i), we show that, if X/sup n/ is encoded by an arbitrary prefix-free FV code asymptotically achieving the entropy, 1/nl(/spl phi//sub n/(X/sup n/)) - 1/nlog/sub 2/ 1/PX/sup n/(X/sup n/) /spl rarr/ 0 in probability as n /spl rarr/ /spl infin/ under a certain condition, where P/sub X//sup n/ denotes the probability distribution of X/sup n/. Under criterion ii), we first determine the minimum rate achieved by FV codes. Next, we show that 1/nl(/spl phi//sub n/(X/sup n/)) of an arbitrary FV code achieving the minimum rate in a certain sense has a property similar to the lossless case.     

Synthesis of polymeric microspheres employing SPG emulsification technique

Relatively uniform polymeric microspheres, the coefficients of variation being close to 10%, were obtained by the BPO-initiated suspension polymerization of styrenic monomers. Unlike the conventional stirred-tank system, a particular microporous glass membrane (SPG) provided uniform monomer droplets continuously when monomer was allowed to permeate through the micropores. The monomer droplets were suspended in an aqueous solution containing the stabilizing agents, transferred to a stirred vessel, and polymerized. Up to 10μm spheres, of a far narrower size distribution than those obtained by conventional microsuspension polymerization spheres, were obtained. The initial droplet size and distribution were retained with the successful suppression of secondary particle nucleation by the addition of hydroquinone in the aueous phase. Crosslinked polystyrene spheres were also synthesized in the presence of various low-molecular-weight diluents. While a good solvent, toluene, was not so effective; poor solvents, n-heptane and n-heptane, easily yielded the microporous structure, the specific surface area being as high as 160 m²/g. © 1994 John Wiley & Sons, Inc.     

The characteristics and measuring technique of refractory dissolved organic substances in urban runoff.

It is considered that refractory dissolved organic substances have caused an increase in the COD concentration in Lake Biwa in recent years. We investigated the organic matter in the first flush of stormwater runoff from a road in the watershed area of the lake, and studied the possibility of improvement in the water environment from that aspect. After percolating the stormwater through soil, we analyzed organic substances fractionated by using GPC-TC. And we examined the effect of removal of organic substances by comparing the peak height before and after percolation. In the result of the experiments, we found that soil infiltration reduced the refractory dissolved organic substance and we successfully designed a system for a simple and easy experimental facility to treat urban runoff.     

Effects of weak shear on hyperswollen lyotropic smectic liquid crystals

We have developed a Zimm-type viscometer specially designed for the simultaneous measurements of the structure factor and the viscosity of hyperswollen lyotropic liquid crystals under a very weak shear. We have investigated the shear effects on the layer undulation fluctuation in the lamellar structure and the transition from the anisotropic lamellar to the isotropic sponge phase. We have found a significant difference in the rheological properties between the lamellar and the sponge phase: The former exhibits non-Newtonian flow behavior, while the latter exhibits Newtonian behavior.Paper presented at the Twelfth Symposium on Thermophysical Properties, June 19–24, 1994, Boulder, Colorado, U.S.A.     

The first specific antibody against cytotoxic polyacetylenic alcohol, panaxynol

Antitumor polyacetylenic alcohol, panaxynol, was isolated and purified from a powder of the root of Panax ginseng C.A. Meyer. Panaxynol inhibited the growth of various kinds of cultured tumor cell lines in a dose-dependent manner. In this paper we demonstrated the first specific antibody production against panaxynol. Anti-panaxynol antibody was elicited in rabbits by immunization with panaxynol hemisuccinate-bovine serum albumin conjugate (panaxynol hemisuccinate-BSA conjugate). An enzyme immunoassay (EIA) for the determination of panaxynol was established using a double-antibody technique. The EIA was highly specific against panaxynol although the antibody showed a minimal cross-reactivity with other types of polyacetylenic alcohol, i.e. panaxydol (12.0%) and panaxytriol (0.77%). Panaxynol at a concentration as low as 6.4 ng/ml can be detected. Using this assay we reconfirmed the rapid consumption of panaxynol by target tumor cells in an in vitro-culture system. The anti-panaxynol antibody may be a valuable tool for studies of the biological properties of polyacetylenic compounds.