Fast and continuous chemical isolation of short-lived isotopes of Hf,Ta and W as homologs of elements 104, 105 and 106

Some short-lived isotopes of Hf, Ta and W, synthesized at the U-400 cyclotron of JINR-Dubna, have been isolated using a previously elaborated fast continuous method of chemical isolation of element 104 from nuclear reaction products. The products were transported by a NaCl aerosol jet, from the irradiated targets to a separation device in which Hf, Ta and W were isolated by using three coupled ion-exchange columns.     

Reactions de photoaddition de benzo[b]selenophenes avec l'acetylene dicarboxylate de methyle et avec le dichloro-1,2 ethylene

Photoirradiated in presence of acetophenone, benzo[b]selenophene and its 3-methyl derivative add to dimethyl acetylenedicarboxylate. In each ease, the primary reaction product is unstable and has not been isolated. Photoexeited in its triplet state (the energy of which is in the neighbourhood of 69 $\text{kcal}\text{mole}$) benzo[b]selenophene and its 2- and 3-methyl, 2,3 dimethyl, 3 acetoxy and 2-methyl-3-acetoxy derivatives add to 1,2 dichloroethylene leading to cyclobutanes. Neither cyclo-addition occurs in absence of photosensitiser. Single-crystal X-ray analysis gave the structures of the two adducts of 3-acetoxybenzo[b]selenophene with trans-1,2-dichloroethylene. In both compounds the chlorine atoms are trans.     

Surface-enhanced Raman study of organic sulfides adsorbed on silver

The surface-enhanced Raman scatterings of dimethyl sulfide, diethyl sulfide and dimethyl disulfide have been investigated in silver sol. The dimethyl disulfide molecule decomposes on silver to the corresponding mercaptide implying facile cleavage of its S---S bond. The C---S bond in dialkyl monosulfide appears not to cleave on silver. For diethyl sulfide, the C₂ conformation seems to be favorable on silver than other conformations.     

New labdane-type diterpenoids from Leonurus heterophyllus SW

Five new natural labdane-type diterpenoids (5-9), designated leoheteronins A-E, together with four known diterpenoids (1-4), two phytosterols as a mixture of beta-sitosterol and stigmasterol, and the flavone genkwanin (10) were isolated from the aerial parts of Leonurus heterophyllus SW. (Lamiaceae) collected in northern Vietnam. Compound 1 was isolated for the first time from a Leonurus species, and 10 is considered to be a chemotaxonomic marker of the Leonurus genus. Their structures were determined using spectroscopic analyses.     

An improved method for quantitative sugar analysis of glycoproteins

Although there are numerous methods available to hydrolyze glycans utilizing strong acids, it all requires lengthy steps to obtain quantitative yield. We have developed a new simple one-step method for analysis of amino and neutral monosaccharides of glycoproteins quantitatively. Free monosaccharides were found to be stable during hydrolysis of glycans with 6 N HCI at 80 degrees C up to 2 h. Using this condition, analysis of free monosaccharides hydrolyzed from the bovine fetuin showed sugar composition of Gal: Man: GlcN: GaIN = 13.2: 11.0: 15.5: 2.6, which is closely matched with the reported value of 12.4: 9.6: 17.2: 2.7 (Townsend et al., ABRF News 8: 14, 1997). This method was shown to be applicable to varieties of well-characterized glycoproteins, erythropoietin, fibrinogen and soybean agglutinin. The amounts of sugars released under the condition were very close to the experimental values by other procedures or to the theoretical ones. This condition was found to be suitable for direct sugar analysis of fetuin, which have been immobilized onto polyvinylidene difluoride membrane. Based on these results, it support that the 6 N HCl/80 degrees C/2 h is the simplest method for quantitative analysis of monosaccharide composition of glycoproteins.     

Thermally produced biodegradable scaffolds for cartilage tissue engineering

A novel process was developed to fabricate biodegradable polymer scaffolds for tissue engineering applications, without using organic solvents. Solvent residues in scaffolds fabricated by processes involving organic solvents may damage cells transplanted onto the scaffolds or tissue near the transplantation site. Poly(L-lactic acid) (PLLA) powder and NaCl particles in a mold were compressed and subsequently heated at 180 degrees C (near the PLLA melting temperature) for 3 min. The heat treatment caused the polymer particles to fuse and form a continuous matrix containing entrapped NaCl particles. After dissolving the NaCl salts, which served as a porogen, porous biodegradable PLLA scaffolds were formed. The scaffold porosity and pore size were controlled by adjusting the NaCl/PLLA weight ratio and the NaCl particle size. The characteristics of the scaffolds were compared to those of scaffolds fabricated using a conventional solvent casting/particulate leaching (SC/PL) process, in terms of pore structure, pore-size distribution, and mechanical properties. A scanning electron microscopic examination showed highly interconnected and open pore structures in the scaffolds fabricated using the thermal process, whereas the SC/PL process yielded scaffolds with less interconnected and closed pore structures. Mercury intrusion porosimetry revealed that the thermally produced scaffolds had a much more uniform distribution of pore sizes than the SC/PL process. The utility of the thermally produced scaffolds was demonstrated by engineering cartilaginous tissues in vivo. In summary, the thermal process developed in this study yields tissue-engineering scaffolds with more favorable characteristics, with respect to, freedom from organic solvents, pore structure, and size distribution than the SC/PL process. Moreover, the thermal process could also be used to fabricate scaffolds from polymers that are insoluble in organic solvents, such as poly(glycolic acid). Cartilage tissue regenerated from thermally produced PLLA scaffold.     

Theoretical and experimental reevaluation of the basicity of lambda3-phosphinine

We have investigated the basicity of phosphinine (C5H5P, phosphabenzene) in reevaluating its proton affinity (PA) and gas-phase basicity (GB) and the pK(a) value of its protonated form. As a necessary step, we have first determined its gas-phase proton affinity. Using both mass spectrometric and quantum chemical methods, we have obtained the values PA(C5H5P) = 195.8 +/- 1.0 kcal mol(-1) and GB(298)(C5H5P) = 188.1 +/- 1.0 kcal mol(-1), in good agreement with previous results. We then derived a value of pK(a)(C5H6P+) = -16.1 +/- 1.0 in aqueous solution using three different approaches: the latter markedly differs from the currently available value of -10. The reason for such a discrepancy in the pK(a) of protonated phosphinine in solution is discussed. In the theoretical determination of PAs, evaluation of the basis set superposition error (BSSE) showed that this effect is quite small, being 0.1-0.2 kcal mol(-1) for phosphinine, when a density functional theory (DFT) method in conjunction with a large basis set were used.     

β-蒎烯和马来酸酐的反应及产物表征

研究了β-蒎烯和马来酸酐的烯反应、溶剂中自由基共聚反应和本体热共聚反应,得到了β-蒎烯和马来酸酐烯反应产物和共聚产物,并用IR、1H NMR、13C NMR、GPC、DSC进行表征,研究了引发剂浓度、溶剂体系、单体配比、温度等因素对产物的影响.对聚合物进行皂化改性,测量了皂化物浓度对水表面张力的影响.     

Study on oxidation of polymers treated by high LET radiation

The oxidation of medical silicone rubber and segmented polyether urethane which were bombarded with 11.2 MeV Si⁺ or F⁺ at the dose of 5 × 10¹⁴ ions/cm² was studied. In XPS measurements, it was found that the oxygen concentration on the surface of the implanted polymeric membranes had been increasing in three months at least. ESR measurement showed that some free radicals existed in these membranes and their quantities decreased with time. Chemical analysis proved that peroxides were generated in the γ irradiated membranes. The reason for the increasing of oxygen concentration was that free radicals combined with oxygen in the air and produced peroxides on the membrane surface. Moreover, in order to demonstrate the radiation mechanism, low LET (γ rays) radiation of such polymeric membranes was carried out for comparison     

The cellulose system in viscin from mistletoe berries

The cellulose system of the viscous fibrous cellulosic polysaccharide (viscan) in the viscin tissue of the European mistletoe, Viscum album L., was analyzed by chemical and physicochemical techniques including sugar analysis, optical and transmission electron microscopy, X-ray and electron diffraction together with solid state CP/MAS ¹³C-NMR spectroscopy. The results confirmed that in the elongated thin viscin cells, the cellulose microfibrils (having a diameter of around 3 nm) were tightly coiled with their axes perpendicular to the long axis of the cell. Upon stretching these cells became deformed by more than a hundred fold. In such a deformation, the cellulose microfibrils became unwound to be perfectly aligned along the stretching direction. Based on solid-state CP/MAS ¹³C-NMR spectroscopic analysis of the viscin tissue, it was found that its cellulose consisted of I and I polymorphs in the ratio 1:1.