Preparation and structure of poly(vinyl alcohol)–poly(vinyl acetate) composite porous membrane

The preparation of poly(vinyl alcohol) (PVA)–poly(vinyl acetate) (PVAc) composite porous membrane was investigated by extracting PVAc with solvent from films of PVAc lattices which were obtained by the emulsion polymerization of vinyl acetate (VAc) in the presence of PVA. The formation of the porous membrane depended upon whether or not PVAc in the latex film was easily extracted with solvent. In the case of using hydrogen peroxide (HPO)–tartaric acid (TA) as an initiator, in the film of the latex which was produced from the batch method in which all ingredients of the batch were put into the reaction vessel before starting polymerization, PVAc could be extracted over 90% of total PVAc with common organic solvents. In the film of the latex which was produced from the dropwise addition method of VAc and initiator, the PVAc extraction was about 20-30%. On the other hand, in the case of using ammonium persulfate as an initiator, the desired porous membrane was not obtained. The structure of the porous membrane obtained from the latex of the batch method by using HPO—TA consisted of spherical cells which were made up of PVA and grafted PVAc or insoluble PVAc like microgels, which were not extracted with organic solvent and were connected by small pores. The PVA—PVAc composite porous membrane is permeated by n-hexane with 5.58 × 10² mL/cm²·s at 0.5 kg/cm², by benzene with only 1.33 × 10^?3mL/cm²·s even at 60 kg/cm².     

Effect of polymer density on polyethylene hollow fiber membrane formation via thermally induced phase separation

Microporous high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) hollow fiber membranes were prepared from polyethylene–diisodecyl phthalate solution via thermally induced phase separation. Effect of the polyethylene density on the membrane structure and performance was investigated. The HDPE membrane showed about five times higher water permeability than the LDPE membrane because it had the larger pore and the higher porosity at the outer membrane surface. The formation of the larger pore was owing to both the initial larger structure formed by spinodal decomposition and the suppression of the diluent evaporation from the outer membrane surface due to the higher solution viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 471–474, 2004     

Antitumor activity of synthetic alkylphospholipids with or without PAF activity

1-O-Octadecyl-2-O-methyl-sn-glycero-3-phosphocholine (ET-18-OMe) has been reported to possess definite antitumor activity in vivo. Twenty-two alkyl lysophospholipid analogs were chemically synthesized, and their antitumor activity against mouse experimental tumors (Sarcoma 180, MM46, P388) was examined. Among them, 1-O-octadecyl-2-O-acetoacetyl-rac-glycerol-3-phosphocholine was found to show antitumor activity similar to ET-18-OMe with less acute toxicity. Intravenous injection of the ET-18-OMe withsn-3 configuration retarded the subcutaneous growth of Sarcoma 180 cells effectively, while the growth inhibition by thesn-1 isomer was much less effective. This stereospecificity was similar to that observed in their activities as platelet-activating factor (PAF) agonists. The acetoacetyl compound, another PAF agonist, showed similar stereospecific antitumor action in vivo. These findings suggest that some alkyl lysophospholipids may activate host cells to a cytostatic stage against tumor cells in vivo through binding to a PAF receptor. Our preliminary results indicated that the responsible cells under these conditions might be primarily immature macrophages present in the bone marrow. No appreciable or even adverse stereospecificity was observed in the different sets of experiments where the activity of ET-18-OMe against MM46 tumor cells in vivo or the direct cytotoxicity against human promyelocytic leukemia HL-60 cells in vitro was examined. Under, some conditions, the antitumor activity of ET-18-OMe in vivo may be revealed through direct cytotoxicity and/or modulation of the host defense system by “nonspecific” mechanisms. Some alkylphospholipids without PAF activity may also show antitumor activity through similar, “nonspecific” mechanisms.     

Synthesis and electrode performance of layered nickel dioxide containing alkaline ions

Several polymorphs of layered nickel dioxide were prepared by using the chemical insertion of alkaline ions into Li_0.10NiO₂. We used aqueous AOH (A = Li, Na, K) solutions as reducing agents. Sodium and potassium insertion resulted in hydrated layered compounds that can be classified as γ-NiOOH with high crystallinity, while lithium insertion occurred without hydration. We discuss the coordination environment around the A⁺ ions for these inserted compounds. The thermal behavior, analyzed using high temperature (HT) X-ray diffraction (XRD) and thermogravimetric (TG) measurements, indicated that heating the hydrate at 150 °C yielded its dehydrate. The electrode performance of the nickelate was studied in lithium cells. We discuss the effect of interlayer water on cell rechargeability and the similarity between these nickelate and hydrated manganese dioxide (birnessite).     

A negative resist for KrF excimer laser lithography

The design and preparation of a series of negative resists for KrF excimer laser lithography are described. Each resist is composed of poly(hydroxystyrene) and an aromatic azide. The base resin shows high transmittance of 62%/μm at 248 nm, when p-ethylphenyl p-azidophenylsulfonate. 4-azido-4α-methoxy-chalcone, 1-(4 azidobenzylidene)-3-(α-hydroxy-4-azidobenzyl)-indene, 4,4α-diazido-3,3α-dimethoxybiphenyl, or 1-(4-azidostyryl)-5, 5-dimethyl-2-cyclohexen-1-one is employed as a sensitizer. These azides are obtained by red-shifting the absorption maxima to lower energy regions than the exposing wavelength of 248 nm. Transmittance of resists can be controlled from 10 to 30%. The resist is exposed with a KrF excimer laser stepper and developed in an alkaline solution. Sensitivities of about 15 mJ/cm² are observed. A good, subhalf-micron resist profile is achieved. The photochemical reaction mechanisms of poly(hydroxystyrene) and 4,4α-diazido-3,3α-dimethoxybiphenyl were studied at 248 nm and 313 nm exposure. Quantum yield for photodecomposition at 248 nm is seven times larger than that at 313 nm, but dissolution-inhibition effects are larger at 313 nm exposure. Consequently, the resist shows higher sensitivity at 313 nm than at 248 nm.     

Ketones from carboxylic acids over supported magnesium oxide and related catalysts

Silica-supported alkaline earth oxides revealed excellent activity to convert acetic acid selectively into acetone in a vapor-phase fixed-bed flow system. Acetone was obtained through the cyclic formation of alkaline earth acetate followed by decomposition. Magnesium oxide should be supported on the silica surface without formation of magnesium silicate, which was inactive for the present reaction. Attempted syntheses of benzophenone and acetophenone are also described.     

Ozone Generator with Cylindrical Type of Rotating Electrode

An ozone generator using a rotating electrode to improve ozone generation efficiency is proposed. The ozone generator electrode unit consists of a rotating electrode and fixed electrode. The rotating electrode has the grounded 36 pieces of tungsten wires fixed in parallel to the rotation axis on the rotating cylinder surface. A dielectric electrode is used as a fixed electrode located on the inside of the tube of the electrode unit. The width of the apparent discharge gap is 1mm. Alternating current with a frequency of 50 Hz is applied to the electrode unit. The rotation speed can be adjusted from 0 rpm to 1200 rpm by a variable speed motor. Oxygen gas is used as the material gas. Higher ozone concentration and higher ozone generation efficiency are obtained compared with that when the rotation speed is 0 rpm. The gas temperature is measured at the inlet and outlet of the ozone generator, and the rotation speed for the cooling effect is most effective at about 500 rpm. The maximum generation efficiency is estimated to be 61 g/kWh at 800 rpm, and this value is twice as large as in the case of 0 rpm.     

Guinea pig bone marrow cells treated with platelet-activating factor generate factor(s) which affects their DNA synthesis and microbicidal activity

We have previously reported that platelet-activating factor (PAF) induces proliferation and microbicidal activity of guinea pig bone marrow cells. In the present study, we have found that the conditioned medium of PAF- or nonmetabolizable PAF agonist-treated guinea pig bone marrow cells augmented DNA synthesis and induced microbicial activity of bone marrow cells. A PAF specific antagonist, CV-6209, inhibited generation of the active conditioned medium by PAF. Addition of the PAF antagonist only partially suppressed the augmentative effect of the active conditioned medium on DNA synthesis; this is consistent with the fact that, because of the rapid breakdown, no appreciable amount of PAF remained in the conditioned medium of PAF-treated cells. Although mouse bone marrow cells did not respond to PAF unlike guinea pig cells, their DNA synthesis was significantly enhanced by the conditioned medium of PAF-treated guinea pig bone marrow cells. Thus, some newly generated factor(s) distinct from the originally inoculated PAF seemed to modulate the bioactions of PAF on bone marrow cells. An appreciable amount of PAF was produced by calcium ionophore-treated guinea pig bone marrow cells. These findings indicate that PAF synthesized in guinea pig bone marrow cells induces generation in the cells of some factor(s) which affects proliferation or microbicidal activity. Presented at The Third International Conference on Platelet-Activating Factor and Structurally Related Ether Lipids, Tokyo, Japan, May 1989.     

Unique molecular aggregation of novel naphthalocyanine (near IR absorbing dye)

A series of organic-soluble naphthalocyanine derivatives (Y_mMNcX₄) have been synthesized. Their spectroscopic properties in organic solutions and in thin films were studied. MNcX₄ such as MNc(t-Bu)₄ (5a-5c) and MNc(On-Bu)₄ (5j) formed H-aggregates even in dilute solutions. MNc(CO₂R')₄ (5d-5i) had much stronger H-aggregation properties compared with those ofMNc(t-Bu)₄ and MNc(On-Bu)₄. Especially, MNc(CO₂R')₇ complexes (M=Cu, Pd and Ni) existed exclusively without monomers in the aggregated state even in highly dilute solutions. MNcX₄, which has strong H-aggregation properties, showed merely H- aggregate absorption maxima in thin films. In contrast, Y₂MNcX₄ (4), which has sterically hindered Y groups, showed monomerically pure characteristics in solution. However, thin films of Y₂MNcX₄ have a J-type molecular arrangement, exhibiting a red shift of Q-band absorption. The monomeric properties of Y₂MNcX₄ in solutions and J-type molecular arrangement in thin films arise from steric hindrance of two Y groups, such as R₃SiO-in Y₂MNcX₄, which prevents strong H-aggregation of naphthalocyanine.     

Radical-induced ionic polymerization in the presence of maleic anhydride. I. Mechanism of polymerization of maleic anhydride by radical initiators

Three kinds of trapped radicals are observed in poly(maleic anhydride) (Poly-MAH) which were prepared by the use of radical initiators such as AIBN or BPO. It was found that these radicals were transformed to the active species so as to initiate the cationic polymerization. The structure of these radicals was studied by the ESR and the kinetic analysis of MAH polymerization in the presence of various additives.