Development and features of hydro-membrane gas chromatography.

Hydro-membrane gas chromatography (HMGC) is achieved by the annular condensation of water in a capillary column at less than 70 degrees C. The annular membrane of water is formed as a result of the wettability of the stationary phase, which is induced at a water contact angle ranging from 75 degrees to 79 degrees, as derived from a solubility parameter (delta) range of 15.7 +/- 0.3 MPa(1/2) of the coated resin. The range of the liquid to gas volume ratio (beta) required to support the annular membrane should be kept between 0.00005 and 0.0003. In the case of a 0.25-mm i.d. column, the ratio can be set by the combination of a 0.1 to 0.2 microl min(-1) water supply rate and helium gas flow rate. Separation by HMGC develops not only a gas-solid partition but also a focusing effect on the water membrane. One feature of HMGC is that it gives a non-adsorption chromatogram based on the blocking effect of pre-adsorbed water; furthermore, despite the presence of a relatively large quantity of water, the electron impact ionization efficiency is kept the same as in the usual GC/MS condition. The detection limit with the injection of 1 microl of aquatic solution was estimated to be less than 0.1 ppb of low-molecular-weight fatty acids with s/n = 5 on a mass chromatogram at m/z 45. The HMGC/EI-MS system can be applied to the trace analysis of C1 to C3 volatile acids, volatile inorganic acids, and halogenated organic acids in water.     

Studies of nucleosides and nucleotides—LXXIV: Purine cyclonucleosides—34 a new method for the synthesis of 2'-substituted 2'-deoxyadenosines

8,2'-O-Cycloadenosine was protected at 3' and 5'-OHs with acetyl groups and cleaved using liq. H₂S. Subsequent dethiolation and mesylation gave 2'-O-mesyl-3',5'-di-O-acetyl-arabinosyladenine (6). When 6 or its deacetylated parent compound (7) was heated with sodium azide in DMF, 3'-azido-3'-deoxyxylofuranosyladenine (9) was the only product. The cyclonucleoside was then protected with tetrahydropyranyl groups and subjected to a similar series of reactions as above to give 2'-O-mesyl-3',5'-di-O-tetrahydropyranylarabinosyladenine (14). The compound 14 was heated with sodium azide after which acidic deprotection afforded 2'-azido-2'-deoxyadenosine (16). Hydrogenation of 16 gave 2'-amino-2'-deoxyadenosine (18). 2'-Chloro-2'-deoxyadenosine (19) was also obtained by treatment of 14 with lithium chloride and subsequent deprotection. UV, IR and NMR spectral data of these compounds are described.     

ESR study of free radicals produced in polyethylene irradiated by ultraviolet light

ESR studies of ultraviolet-irradiated polyethylene (PE) were carried out. Irradiation effects different from those of high-energy radiation are observed. Ultraviolet radiation is absorbed selectively, and especially in carbonyl groups in PE produced by oxidation. Radicals produced were identified as \documentclass{article}\pagestyle{empty}\begin{document}$ \hbox{---} {\rm CH}_2 \hbox{---} {\dot {\rm C}} {\rm H} \hbox{---}{\rm CHO}$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \hbox{---} {\rm CH}_2 \hbox{---} {\dot {\rm C}} {\rm H} \hbox{---}{\rm CH}_2 \hbox{---}$\end{document}. Some radicals giving a quintet signal stable at room temperature were also observed but remained unidentified. The radical \documentclass{article}\pagestyle{empty}\begin{document}$ \hbox{---} {\rm CH}_2 \hbox{---} {\dot {\rm C}} {\rm H} \hbox{---}{\rm CHO}$\end{document} undergoes a mutual conversion with the acyl radical:      

The interface of the Ising model and the Brownian sheet

We study the limit theorem related to the interface of the three-dimensional Ising model. Dobrushin proved that the interface does not fluctuate and becomes rigid for sufficiently large. We define the random fieldX ^L (t, s), 0t, s1, on the interface, and prove that X^L(t, s) converges to the Brownian sheet as L for sufficiently large, whereL denotes the size of the system. This result does not mean that the interface itself converges to the Brownian sheet.     

Imprinting modulates processing of visual information in the visual wulst of chicks

Background

Results of the Women's Health Initiative Memory Study (WHIMS) raised concerns regarding the timing and formulation of hormone interventions. Conjugated equine estrogens (CEE), used as the estrogen therapy in the WHIMS trial, is a complex formulation containing multiple estrogens, including several not secreted by human ovaries, as well as other biologically active steroids. Although the full spectrum of estrogenic components present in CEE has not yet been resolved, 10 estrogens have been identified. In the present study, we sought to determine which estrogenic components, at concentrations commensurate with their plasma levels achieved following a single oral dose of 0.625 mg CEE (the dose used in the WHIMS trial) in women, are neuroprotective and whether combinations of those neuroprotective estrogens provide added benefit. Further, we sought, through computer-aided modeling analyses, to investigate the potential correlation of the molecular mechanisms that conferred estrogen neuroprotection with estrogen interactions with the estrogen receptor (ER).

Results

Cultured basal forebrain neurons were exposed to either β-amyloid_25–35 or excitotoxic glutamate with or without pretreatment with estrogens followed by neuroprotection analyses. Three indicators of neuroprotection that rely on different aspects of neuronal damage and viability, LDH release, intracellular ATP level and MTT formazan formation, were used to assess neuroprotective efficacy. Results of these analyses indicate that the estrogens, 17α-estradiol, 17β-estradiol, equilin, 17α-dihydroequilin, equilinen, 17α-dihydroequilenin, 17β-dihydroequilenin, and Δ^8,9-dehydroestrone were each significantly neuroprotective in reducing neuronal plasma membrane damage induced by glutamate excitotoxicity. Of these estrogens, 17β-estradiol and Δ^8,9-dehydroestrone were effective in protecting neurons against β-amyloid_25–35-induced intracellular ATP decline. Coadministration of two out of three neuroprotective estrogens, 17β-estradiol, equilin and Δ^8,9-dehydroestrone, exerted greater neuroprotective efficacy than individual estrogens. Computer-aided analyses to determine structure/function relationships between the estrogenic structures and their neuroprotective activity revealed that the predicted intermolecular interactions of estrogen analogues with ER correlate to their overall neuroprotective efficacy.

Conclusion

The present study provides the first documentation of the neuroprotective profile of individual estrogens contained within the complex formulation of CEE at concentrations commensurate with their plasma levels achieved after an oral administration of 0.625 mg CEE in women. Our analyses demonstrate that select estrogens within the complex formulation of CEE contribute to its neuroprotective efficacy. Moreover, our data predict that the magnitude of neuroprotection induced by individual estrogens at relatively low concentrations may be clinically undetectable and ineffective, whereas, a combination of select neuroprotective estrogens could provide an increased and clinically meaningful efficacy. More importantly, these data suggest a strategy for determining neurological efficacy and rational design and development of a composition of estrogen therapy to alleviate climacteric symptoms, promote neurological health, and prevent age-related neurodegeneration, such as AD, in postmenopausal women.     

Complexability of o-bisguanidinobenzenes with arsenic and phosphoric acids in solution and solid states, and the potential use of their immobilized derivatives as solid base ligands for metal salts and arsenic acid

The role of o-bisguanidinobenzenes (BGBs) as new Brønsted base ligands for arsenic and phosphoric acids was examined. In solution state, complexation was evaluated by Job’s plot in ¹H NMR experiment, indicating a 1:1 complex formation, whereas in solid state crystalline structures of complexes obtained were addressed by X-ray crystallographic analysis and/or solid state ¹³C NMR experiment, in which 1:2 complexes between the BGB and the acid components were normally formed. Based on these results, Merrifield and Hypogel^® resin-anchored BGBs were designed and prepared as the corresponding polymer-supported host ligands. Evaluation of their coordination ability with metal salts (ZnCl₂ and CoCl₂) and arsenic acid in aqueous media by ICP-MS showed that the latter Hypogel^® resin-anchored BGBs acted as effective immobilized base ligands.     

Oxygen ion conduction in 12CaO·7Al2O3: O2− conduction mechanism and possibility of O− fast conduction

12CaO·7Al₂O₃ (C12A7) with a unique nano-porous structure and free O^2? ions entrapped in sub-nanometer-sized cages is a fast oxygen-ion-conducting material. These free O^2– may be replaced by various oxygen-related species, OH^?, O^2? and O^?, by tuning the atmosphere during the heat treatment. We examined the conduction mechanism for stoichiometric C12A7 (C12A7:O^2?), in which O^2? ions exist as counter anions in sub-nanometer-sized cages, by Raman measurement of C12A7:O^2? annealed in a dry ¹⁸O₂ atmosphere. It was revealed that the primary ion conducting species is an O^2? ion which diffuses via exchange with O^2? in the cage wall. An experimental result on the sample containing O^? ions implied that O^? is more mobile than O^2? in C12A7. Ab initio calculations on the diffusion paths of O^2? and O^? ions in C12A7 supported the above experimental results.     

Observation of phase transition of cesium manganese hexacyanoferrates by X-ray absorption spectroscopy

Cesium manganese hexacyanoferrates exhibit an interesting phenomenon of temperature-induced phase transition accompanied by a variation in the magnetic susceptibility. We observed the variation in the electronic state of Mn during the phase transition by using X-ray absorption spectroscopy. The results of the analyses showed that the content ratio of Fe^II-CN-Mn^III and Fe^III-CN-Mn^II systematically varied during the phase transition. However, the ratio of Fe^II-CN-Mn^II remained constant at almost all temperatures. These results suggest that the charge transfer between Fe and Mn ions in the Fe^III-CN-Mn^II or the Fe^II-CN-Mn^III bond produces the phase transition.