Polyamine polymers from active hydrogen compounds,formaldehyde, and amines

Active hydrogen compounds such as hydroquinone (HQ), cyclohexanone (CH), acetophenone (AP), and 4,4′-methylene bis-N-methylaniline (MNA) polymerized with formaldehyde (F) and secondary diamines to produce Mannich base polyamine polymers. The HQ-containing polymers were oxidized to benzoquinone (BQ)-containing polymers and their redox properties were investigated in the desulfurization of hydrogen sulfide.     

Estimation of frequency- and time-dependence of polymer composite system by viscoelasticity in three dimensions

This paper is concerned with the comparison between mechanical properties of polymer composite system and those of each individual constituent. The comparison is mainly performed with respect to the viscoelastic Young's modulus and the relaxation Young's modulus. These mechanical constants may be obtained from the correspondence principle by applying the Laplace transform to the constitutive equation. The calculated results exhibit that the mechanical property of polymer composite system strongly depends on that of matrix with respect to frequency- and time-dependences. That is, as for the vibration and dynamic response in the steady state, the frequency-dependence of peak position about imaginary part of dynamic modulus of composite system is similar to that of matrix, while the magnitude of dynamic modulus depends on volume fraction of dispersed particles to total volume. As for the stress relaxation, the time-dependence of the relaxation Young's modulus of composite system resemble that of matrix each other, while the magnitude depends on the volume fraction of dispersed particles to total volume. This is due to the calculating condition that particle is assumed to be very rigid in comparison with matrix in this paper.     

Prodrugs of 2',3'-dideoxyinosine (DDI): improved oral bioavailability via hydrophobic esters.

Five ester prodrugs of 2'3'-dideoxyinosine (DDI) were synthesized for the purpose of improving oral bioavailability. The prodrugs, acetate (C2-DDI), octanoate (C8-DDI), stearate (C18-DDI), benzoate (Bz-DDI), and hemisuccinate (Suc-DDI) were proved to quantitatively regenerate their parent drug by enzymatic hydrolysis. Though the chemical stability of the prodrugs under acidic conditions was not improved, their solubility in water was significantly decreased by esterification, except for Suc-DDI. Bioavailability was evaluated by oral administration to rats. Two hydrophobic prodrugs (C8-DDI and Bz-DDI) showed higher absolute bioavailability (23.5% and 31.0%, respectively) than did DDI (15.2%), though that of C2-DDI (11.5%) and Suc-DDI (4.5%) was poor.     

PULSE RADIOLYSIS STUDIES IN MODEL LIPID SYSTEMS: FORMATION AND BEHAVIOR OF PEROXY RADICALS IN FATTY ACIDS

Abstract— Radiolytic formation and peroxidation of fatty acid radicals have been investigated by pulse radiolysis techniques in oleate, linoleate, linolenate and arachidonate systems. A strong absorption band at 280 nm associated with conjugated radicals, R_conj, formed in polyunsaturated fatty acid moieties has been used as a probe for kinetic processes occurring at doubly allylic sites in the hydrocarbon chain. Formation of R_conj by O^- has been found to be more efficient than the less selective OH radical. Peroxidation of R_conj is shown to be somewhat slower, ( k _R+ O₂˜ 3 × 10⁸ M ^-1 s^-1), than O₂ reactions with radicals in oleate ( k _R+ O₂= 1 × 10⁹ M ^-1 s^-1). Peroxy radicals generated in these reactions disappear slowly by essentially second order processes (2 k RO₁˜ 10⁷ M ^-1 s^-1). The superoxide radical, O^-₂, shows little if any reactivity towards 0.01 M linolenate or arachidonate over periods of 20 s.     

Synthetic Studies on Sialoglycoconjugates 22: Total Synthesis of Tumor-Associated Ganglioside,Sialyl Lewis X1

ABSTRACT

The first total synthesis of tumor-associated glycolipid antigen, sialyl Lewis X is described. Glycosylation of 2-(trimethylsilyl)ethyl O-(2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranosyl)-(1→3)-O-(2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside (1) with methyl 2,3,4-tri-O-benzyl-1-thio-β-L-fuco-pyranoside (4) gave the α-glycoside (5), which was converted by reductive ring-opening of the benzylidene acetal into the glycosyl acceptor (6). Dimethyl(methylthio)sulfonium triflate-promoted coupling of 6 with methyl O-(methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosylonate)-(2→3)-2,4,6-tri-O-benzoyl-1-thio-β-D-galactopyranoside (7) afforded the desired hexasaccharide 8 in good yield. Compound 8 was converted into the α-trichloroacetimidate 11, via reductive removal of the benzyl groups, O-acetylation, removal of the 2-(trimethylsilyl)ethyl group, and treatment with trichloroacetonitrile, which, on coupling with (2S, 3R, 4E)-2-azido-3-O-benzoyl-4-octa-decene-1,3-diol (12), gave the β-glycoside 13. Finally, 13 was transformed, via selective reduction of the azide group, condensation with octadecanoic acid, O-deacylation, and hydrolysis of the methyl ester group, into the title compound 16.     

Identification of Tim4 as a phosphatidylserine receptor

In programmed cell death, a large number of cells undergo apoptosis, and are engulfed by macrophages to avoid the release of noxious materials from the dying cells. In definitive erythropoiesis, nuclei are expelled from erythroid precursor cells and are engulfed by macrophages. Phosphatidylserine is exposed on the surface of apoptotic cells and on the nuclei expelled from erythroid precursor cells; it works as an 'eat me' signal for phagocytes. Phosphatidylserine is also expressed on the surface of exosomes involved in intercellular signalling. Here we established a library of hamster monoclonal antibodies against mouse peritoneal macrophages, and found an antibody that strongly inhibited the phosphatidylserine-dependent engulfment of apoptotic cells. The antigen recognized by the antibody was identified by expression cloning as a type I transmembrane protein called Tim4 (T-cell immunoglobulin- and mucin-domain-containing molecule; also known as Timd4). Tim4 was expressed in Mac1+ cells in various mouse tissues, including spleen, lymph nodes and fetal liver. Tim4 bound apoptotic cells by recognizing phosphatidylserine via its immunoglobulin domain. The expression of Tim4 in fibroblasts enhanced their ability to engulf apoptotic cells. When the anti-Tim4 monoclonal antibody was administered into mice, the engulfment of apoptotic cells by thymic macrophages was significantly blocked, and the mice developed autoantibodies. Among the other Tim family members, Tim1, but neither Tim2 nor Tim3, specifically bound phosphatidylserine. Tim1- or Tim4-expressing Ba/F3 B cells were bound by exosomes via phosphatidylserine, and exosomes stimulated the interaction between Tim1 and Tim4. These results indicate that Tim4 and Tim1 are phosphatidylserine receptors for the engulfment of apoptotic cells, and may also be involved in intercellular signalling in which exosomes are involved.     

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.     

Comparative extreme ultraviolet emission measurements for lithium and tin laser plasmas

Detailed spectroscopic studies on extreme UV emission from laser plasmas using tin and lithium planar solid targets were completed. At 13.5 nm, the best conversion efficiency (CE) for lithium was found to be 2.2% at intensities near 7 x 10(10) W/cm(2). The highest CE measured for tin was near 5.0% at an intensity close to 1 x 10(11) W/cm(2).     

Surface state density distribution at vacuum-annealed InP(1 0 0) surface as derived from the rigorous analysis of photoluminescence efficiency

The surface state density distribution N_SS(E) and surface Fermi level E_Fs position on a sequentially ultra-high vacuum-annealed n-InP(1 0 0) sample are investigated using rigorous computer analysis of dependences of the room temperature band-edge photoluminescence efficiency (Y_PL) on the photon flux density (Φ). We have found that the minimum density of a U-shaped N_SS(E) distribution as well as the donor-like surface state density are reduced by one order of magnitude after the annealing at 250 and 300 °C. This can be assigned to the decrease in the disorder in the unintentionally formed InP native oxides. On the other hand, we demonstrate that the annealing simultaneously generates discrete surface states probably due to missing group V element (P) in the interface region which may account for electrical interface instabilities observed in InP-based devices. The results are discussed quantitatively and compared to other reports.