Silver(I) ion selective ionophores containing dithiocarbamoyl moieties on steroid backbone

Tweezer-type and non-tweezer-type ionophores containing dithiocarbamoyl groups on a 7-deoxycholic amide or cholane derivatives were designed and synthesized. Potentiometric evaluation of the poly(vinyl chloride) (PVC) membranes containing those deoxycholic amides/cholanes linked with tweezer-type dithiocarbamoyl moieties showed excellent affinity and selectivity to silver(I) ion over alkali, alkaline earth and other transition metal cations. On the other hand, deoxycholic amides/cholanes substituted with one dithiocarbamoyl group, i.e., non-tweezer-type ionophores, resulted in relatively poor potentiometric sensitivity and detection limits. The enhanced potentiometric properties of newly synthesized tweezer-type dithiocarbamoyl containing ionophores have been further improved by employing silver ion complexing reagent in the internal reference solution, which resulted in greatly reduced detection limit (∼100 ppt) for the electrodes based on them.     

Computer simulaion of gamma spectra in 14 MeV neutron activation analysis

The method of simulation of gamma-spectra based on the experimental library spectra of particular radioisotopes is described. The library spectra were obtained by activation of pure element sample with the use of a 14 MeV neutron generator, counting them with a NaI(T1) scintillation spectrometer and decomposing of mixed spectra to spectra of separate radioisotopes. The simulated and measured spectra of an artificial sample are compared.     

Efficient gene delivery in differentiated human embryonic stem cells

Human embryonic stem (hES) cells are capable of differentiating into pluralistic cell types, however, spontaneous differentiation generally gives rise to a limited number of specific differentiated cell types and a large degree of cell heterogeneity. In an effort to increase the efficiency of specified hES cell differentiation, we performed a series of transient transfection of hES cells with EGFP expression vectors driven by different promoter systems, including human cellular polypeptide chain elongation factor 1 alpha (hEF1alpha), human cytomegalo-virus, and chicken beta-actin. All these promoters were found to lead reporter gene expression in undifferentiated hES cells, but very few drug-selectable transfectants were obtained and failed to maintain stable expression of the transgene with either chemical or electroporation methods. In an attempt to increase transfection efficiency and obtain stable transgene expression, differentiated hES cells expressing both mesodermal and ectodermal markers were derived using a defined medium. Differentiated hES cells were electroporated with a hEF1alpha promoter-driven EGFP or human noggin expression vector. Using RT-PCR, immunocytochemistry and fluorescence microscopy, the differentiated hES cells transfected with foreign genes were confirmed to retain stable gene and protein expression during prolonged culture. These results may provide a new tool for introducing exogenous genes readily into hES cells, thereby facilitating more directed differentiation into specific and homogenous cell populations.     

熔石英的弹性模量和超声状态方程

利用“脉冲回波重合法”精密地测定了熔石英的2,3阶弹性模量C₁₁,C₄₄;C₁₂₃,C₁₄₄,C₄₅₆,由应变能对应变的级数展开,获得了由2,3,4阶弹性模量表示系数的熔石英超声状态方程。计算到3阶弹性模量的状态方程,与Bridgman的实验值比较,在压力增加时偏离增加。但当计入4阶弹性模量效应后,在熔石英发生状态改变前的区域,则两者之间符合得很好。 关键词：     

Photocrosslinking of polymers bearing epoxy or epithio groups by quinones in the solid state

Photocrosslinking of poly(glycidyl methacrylate) (PGMA) and a copolymer of 2,3-epithiopropyl methacrylate and methyl methacrylate [P(ETMA-co-MMA)] was studied in the solid state in the presence of various quinones. The efficiency of photocrosslinking was strongly dependent upon the structures of quinones and the kinds of polymers. For example, the alkyl-substituted quinones such as 2-ethyl-p-benzoquinone (EQ), 2-tert-butyl-p-benzoquinone (tBQ) and 2,5-di-tert-butyl-p-benzoquinone (2,5-dtBQ) did not induce photocrosslinking of poly(methyl methacrylate) (PMMA), whereas they acted as efficient photocrosslinking agents in PGMA and P(ETMA-co-MMA). The formation of charge transfer complexes did not play a principal role in this effective photocrosslinking, because the order of the photocrosslinking efficiency [EQ > tBQ > 2,5-dtBQ > p-benzoquinone (Q)] was not in agreement with that of the magnitude of the electron affinities of quinones, i.e., Q > EQ > tBQ > 2,5-dtBQ. Photopolymerization of propylene sulfide (PS) in the presence of tBQ or Q was also investigated. The presence of tBQ induced polymerization of PS upon UV irradiation. From these results, it was deduced that the photocrosslinking of P(ETMA-co-MMA) film containing tBQ proceeds via a cationic polymerization of epithio groups. A similar mechanism should be applicable to the photocrosslinking of PGMA film containing tBQ.     

Photochemical reactions of polymers containing thiocyanatoacetyl groups and dyeing the resulting polymer films

Poly(styrene-co-4-thiocyanatoacetylstyrene) and poly(4-acetylstyrene-co-4-thiocyanatoacetyl-styrene) were prepared and their photochemical reactions were studied in the solid state. It was found that the thiocyanatoacetyl groups were easily rearranged with the corresponding isothiocyanatoacetyl groups by ultraviolet (UV) irradiation and that the resulting isothiocyanatoacetyl groups underwent intramolecular cyclization when treated with triethylamine or ammonia to yield oxazole-2-thione moieties. The irradiated polymer films could be dyed selectively with cationic dyes in an appropriate dye bath because of the formation of anionic species by keto-enol tautomerization of oxazole-2-thione moieties in an alkaline state.     

Indium-mediated consecutive 1,2-shift reaction and regioselective allylation of vinyl epoxides

Allyl indium, prepared from allyl bromide and indium metal in aprotic solvent, reacts with terminal vinyl epoxides at room temperature to afford various bishomoallyl alcohols in moderate to high yields via consecutive 1,2-shift reaction and regioselective allylation.     

Effect of dissolved CO2 on the potential stability of all-solid-state ion-selective electrodes.

The influence of dissolved CO2 on the potentiometric responses of all-solid-state ion-selective electrodes (ISEs) was systematically examined with four different types of electrodes fabricated by pairing pH-sensitive and pH-insensitive metal electrodes (Pt and Ag/AgCl, respectively) with pH-sensitive and pH-insensitive ion-selective membranes (H+-selective membrane based on tridodecylamine and Na+-selective membrane based on tetraethyl calix[4]arenetetraacetate, respectively). The experimental results clearly showed that the carbonic acid formed by the diffused CO2 and water vapor at the membrane/metal electrode interface varies the phase boundary potentials both at the inner side of the H+-selective membrane (deltaE(in)mem) and at the metal electrode surface (deltaEelec). The potential changes, deltaE(in)mem and deltaEelec, occurring at the facing boundaries, are opposite in their sign and result in a canceling effect if both the membrane and metal surface are pH-sensitive. Consequently, the H+-selective membrane coated on a pH-sensitive electrode (Pt) tends to exhibit a smaller CO2 interference than that on a pH-insensitive electrode (Ag/AgCl). When the all-solid-state Na+ and K+ ISEs were fabricated with both pH-insensitive metal electrode and ion-selective membrane, they did not suffer from CO2 interference. It was also confirmed that plasticization of the PVC leads to increased CO2 permeation. Various types of intermediate layers were examined to reduce the CO2 interference problem in the fabrication of H+-selective all-solid-state ISEs. The results indicated that the H+-selective electrode needs an intermediate layer that maintains a constant pH unless the carbonic acid formation at the interfacial area is effectively quenched.