In vitro and in vivo stability of polymerized mixed liposomes composed of 2,4‐octadecadienoyl groups of phospholipids

The in vitro stability, under freeze–thawing procedures, and in vivo degradation, in rat spleen, of two types of polymerized liposomes were examined: 1,2‐bis‐[2E, ­4E) ‐ octadecadienoyl] ‐ sn ‐ glycero ‐ 3 ‐ phosphocholine (DODPC) and 1‐acyl‐2‐[(2E, 4E)‐octadecadienoyl]‐sn‐glycero‐3‐phosphocholine (AODPC) were used as polymerizable phospholipids. The lipid composition of the liposomes was prepared as DODPC/Chol/SA (Chol = cholesterol, SA = stearicacid), AODPC/Chol/SA (7/7/2 by molar ratio), AODPC/DPPC/Chol/SA (3.5/3.5/7/2 by molar ratio). The liposomes were extruded through a 0.2 µm polycarbonate‐ filter to obtain the approximate particle size of 0.2 µm, and then irradiated with γ‐rays. Hemoglobin‐encapsulated liposomes were also prepared in the same manner with concentrated hemoglobin (Hb) solution. The DODPC/Chol/SA liposome exhibited no trace of particle size change nor Hb leakage. Although not as excellent as the former, the AODPC‐base liposome showed slightly diameter change (below 7.5%) with a substantial abatement of Hb leakage (<3.5%). Transmission electron microscopy observation of spleens also revealed more efficient degradability with AODPC/DPPC/Chol/SA liposome than with DODPC/Chol/SA liposome. Hb‐encapsulated AODPC/DPPC/Chol/SA liposome, after five freeze–thawing cycles, attained an Hb leakage below 3.5% with a particle size change of 0.7–7.5%, and reduced the spleen retention compared with the DODPC‐base liposome. These results suggest that AODPC/DPPC/Chol/SA liposome can be used as a long‐term preservable blood substitute. Copyright © 2000 John Wiley & Sons, Ltd.     

On the interfacial energy of extended-chain crystals from polyethylene melt by revised Flory equations of fusion

To analyze extended-chain crystalline systems composed of linear polyethylene, Flory's conventional theory of fusion is reconsidered by introducing a new concept of crystallinity. When this new treatment is applied to a melting case of a low molecular weight polyethylene fraction (M_n = 5600) isothermally bulk crystallized, a certain result that very large lamellar thickness was caused by a very small increase in crystallization temperature can satisfactorily be explained by a significant change in interfacial free energy of the crystallite end. Further, it shows 14–17 kJ/mol as a nonequilibrium value range of interfacial free energy for highly crystalline polyethylene fractions of low molecular weight M_n ≦ 5600 by using the previous data presented by other workers. A similar result is also obtained on the M_n = 5600 fraction by analyzing from a standpoint of equilibrium crystallinity. In either case, the estimated range of interfacial free energy is consistent with the conventional range. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1293–1303, 1998     

Facile synthesis of N,N‐dialkylselenoamides from amides

N,N‐Dialkylamides were chlorinated with oxalyl chloride and then allowed to react with LiAlHSeH to afford the corresponding N,N‐dialkyselenoamides in moderate to good yields. The N,N‐dialkylamides bearing bulky substituent groups were not converted into the corresponding selenoamides because of their steric hindrance. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:195–198, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10016     

Improvement in the Physical Function and Quality of Life through Exercise and Physical Activity Intervention Using a Smartphone after Allogeneic Hematopoietic Cell Transplantation: A Case Report

Purpose: Physical activity (PA) interventions positively affect the physical function (PF) in patients with advanced cancer. However, patients must remain motivated during the intervention. We report a case wherein a smartphone application for PA intervention was useful in motivating the patient to improve adherence. Methods: A 40-year-old woman underwent an allogeneic hematopoietic cell transplantation (allo-HCT) for an advanced extranodal natural killer/T-cell lymphoma. On day 6, she developed the posterior reversible encephalopathy syndrome. She was managed in the intensive care unit for 3 days, and her PF declined markedly. We initiated a smartphone-based PA intervention from day 35. She was instructed to maintain a PA diary for self-monitoring of the daily steps and to set a new step-count goal every week. Results: The PA and PF improved within a short period thereafter. However, she developed severe acute graft-versus-host disease and was administered with high-dose systemic corticosteroids from day 49. The PA, PF, and quality of life (QOL) decreased again. The intervention was continued for 5 months with a high adherence. The PA, PF, and QOL improved gradually. She resumed independent activities of daily living and was discharged on day 202. Conclusion: Smartphone-based PA intervention may be effective against post-allo-HCT physical dysfunction.     

Optical Properties and Photopolymerization of Liquid Crystalline (Acetyl) (Ethyl) Cellulose/Acrylic Acid System

The structure and properties of a chiral nematic phase, which reflects one hand of circularly polarized light in a narrow region of wavelength, of fully acetylated (ethyl) cellulose [(acetyl) (ethyl) cellulose, AEC] in acrylic acid (AA) were studied in comparison with (ethyl) cellulose (EC). AEC mesophase formed right-handed chiral nematic structure while EC formed left-handed one. AEC mesophase showed higher birefringence and reflection intensity. The relationship between the reflection wavelength and the polymer concentration was negatively correlated for both AEC and EC mesophases. The relationship between the reflection wavelength and the molecular weight was also negative for AEC mesophase whereas positive for EC mesophase. AEC mesophase was solidified by photopolymerization of AA moiety. It was revealed that the optical properties of AEC mesophase could be preserved by photopolymerization, since the resulting solid material reflects selectively one hand of circularly polarized light.     

Statistical considerations on electronic behavior of the gap states in amorphous semiconductors

The equilibrium distribution functions of the gap states taking into account the effective intrasite electronic correlation energy have been employed to discuss the electronic behaviors of amorphous semiconductors, especially to interpret the temperature dependence of dc and ac conductivity and also the effect of foreign impurity atoms on the conductivity in chalcogenide glasses. The dc conductivity of thermal activation type has been explained without assuming a negligible density of states near the Fermi level, and the gradual decrease in activation energy of conductivity with increasing impurity concentration, even in melt-quenched chalcogenide glasses, has been deduced.     

Michael reaction of indoles with 3-(2′-nitrovinyl)indole under solvent-free conditions and in solution. An efficient synthesis of 2,2-bis(indolyl)nitroethanes and studies on their reduction

Michael reaction of 3-(2′-nitrovinyl)indole with eight 3-unsubstituted indoles on TLC-grade silica gel furnished unsymmetrical bis(indolyl)nitroethanes in 7-12 min under microwave irradiation and in 8-14 h at rt. In contrast, the p-TsOH-catalysed reaction of the nitrovinylindole with the 3-unsubstituted and two 3-substituted indoles in solution under reflux furnished both unsymmetrical and symmetrical bis(indolyl)nitroethanes, the latter resulting from novel tandem Michael addition-elimination-Michael addition reactions. The synthesis of a 2′,3″-bis(indolyl)nitroethane, the precursor core structure of two bioactive marine metabolites, and the reduction of 2,2-bis(3′-indolyl)nitroethane to the corresponding ethylamine, isolated as its N-acetyl derivative, have been achieved. Significantly, attempted hydrolysis of three nitronates, derived from the corresponding bis(indolyl)nitroethanes, with buffered aqueous TiCl₃ has led to the first isolation of oximes (syn/anti-mixture) as the only products.     

Structure and properties of segmented poly(urethaneurea)s with relatively short hard‐segment chains

We report the structure and properties of segmented poly(urethaneurea) (SPUU) with relatively short hard‐segment chains. The SPUU samples comprised poly(tetramethylene glycol) prepolymer as a soft segment and 4,4′‐diphenylmethane diisocyanate (MDI) units as a hard segment that were extended with ethylenediamine. To discuss quantitatively the conformation of the soft‐segment chain in the microphase‐separated domain space, we used SPUU samples for which the molecular weights of the hard‐ and soft‐segment chains are well characterized. The effects of the cohesive force in the hard‐segment chains on the structure and properties of SPUU were also studied with samples of different chain lengths of the hard segment, although the window of x_H, the average number of MDI units in a hard‐segment chain, was narrow (2.38 ≤ x_H ≤ 2.77). There were urethane groups in the soft segments and urea groups in the hard segments. Because of a strong cohesive force between the urea groups, we could control the overall cohesive force in the hard‐segment chains by controlling the chain lengths of the hard segment. First of all, microphase separation was found to be better developed in the samples with longer hard‐segment chains because of an increase of the cohesive force. It was also found that the interfacial thickness became thinner. The long spacing for the one‐dimensionally repeating hard‐ and soft‐segment domains could be well correlated with the molecular characteristics when the assumption of Gaussian conformation was employed for the soft‐segment chains. This is unusual for strongly segregated block copolymers and might be characteristic of multiblock copolymers containing rod–coil chains. The tensile moduli and thermal stability temperature, T_H, increased with an increase of the cohesive force, whereas the glass‐transition temperature, the melting temperature, and the degree of crystallinity of the soft‐segment chains decreased. The increase in T_H especially was appreciable, although the variation in the chain length of the hard segment was not profound. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1716–1728, 2000     

Triterpenes and triterpene saponins from the stems of Akebia trifoliata

To characterize the stems of Akebia trifoliata chemically, a detailed phytochemical examination was carried out on A. trifoliata stems, with particular attention to the triterpene and triterpene saponin constituents, and resulted in the isolation of three new triterpenes (1-3) and three new triterpene saponins (11-13), together with seven known triterpenes (4-10) and 12 known triterpene saponins (14-25). The structures of the new compounds were determined on the basis of spectroscopic analysis, including two-dimensional NMR spectroscopic data, and the results of hydrolysis. Four saponins (22-25), which were obtained in good yields and were not isolated from Akebia quinata stems, are concluded to be applicable as marker compounds in chemically distinguishing between A. trifoliata and A. quinata by conventional TLC examination. To the best our knowledge, the current work is the first chemical investigation of A. trifoliata.     

Freeze-fracture electron microscopic and calorimetric studies on microscopic states of surface-modified liposomes with poly(ethylene glycol) chains

The differential scanning calorimetry (DSC) and the freeze-fracture electron microscopy of dipalmitoyl phosphatidylcholine (DPPC) liposomes containing distearoyl-N-monomethoxy poly(ethylene glycol)-succinyl-phosphatidylethanolamines (PEG-DSPE) were carried out. The DSC peak of DPPC liposomes containing PEG-DSPE had a shoulder. The main phase transition temperature of DPPC bilayer membranes containing PEG-DSPE whose molecular weight of PEG is less than 3000 was slightly shifted to a higher temperature, while that containing PEG-DSPE whose molecular weight of PEG is more than 5000 was slightly shifted to a lower temperature. The electron micrographs of freeze-fracture replicas of DPPC liposomes containing PEG-DSPE quenched from 37±2°C exhibited banded and planar textures, suggesting the lateral phase separation in the bilayer membranes.