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91.
92.
Alessandro lovino Camillo La Mesa Donatella Capitani Anna Laura Segre 《Colloid and polymer science》2003,281(12):1136-1141
Longitudinal NMR relaxation times were used to investigate the thermal transitions occurring in an aqueous triblock copolymer of the poly(oxyethylene)–poly(oxypropylene)–poly(oxyethylene) family. In such a system molecule–micelle and micelle–liquid crystal transitions are observed, depending on temperature and composition. The longitudinal relaxation time, R 1, significantly changes when the aforementioned phase transitions take place. In the case of molecule–micelle equilibrium, changes in R 1 values of the methyl (and methynic) group signal, located in the lipophilic portion of block copolymers, are observed. The effect is ascribed to a significant dehydration of the poly(oxypropylene) chains, as a consequence of micelle formation. Conversely, the thermal transitions from micelles to liquid-crystalline phases are associated with significant changes in the relaxation time of poly(oxyethylene) units. The latter effect is tentatively ascribed to a partial dehydration and/or interdigitation of the poly(oxyethylene) moieties in the block copolymer. 相似文献
93.
Laura Linati Gigliola Lusvardi Gianluca Malavasi Ledi Menabue M. Cristina Menziani Piercarlo Mustarelli Alfonso Pedone Ulderico Segre 《Journal of Non》2008,354(2-9):84-89
The medium-range order of phospho-silicate bioactive glasses (with compositions (2 ? p)SiO2 · 1Na2O · 1.1CaO · pP2O5, in which p = 0.10, 0.20, 0.26) has been studied by means of a combined-experimental (MAS-NMR, chemical durability measurements) and computational (classical molecular dynamics (MD)) approach. The structural model obtained by MD is showed to be helpful in the interpretation of the NMR spectra. A small amount of Si–O–P link units has been detected in glasses with low P2O5-content, but at high P2O5 concentration the percentage of Si–O–P bridges becomes important. However, Qn distributions show that the HP5 (p = 0.20) glass structure is less polymerized with respect to the H (p = 0.10) and HP6.5 (p = 0.26) glasses. These results provide useful explanation of the behavior of these glasses in water and highlight the influence of the medium-range order on a very important property of potential bioactive glasses such as the chemical durability. 相似文献
94.
Proietti N Capitani D Rossi E Cozzolino S Segre AL 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,186(2):311-318
Wall paintings in the XVI century Serra Chapel in the "Chiesa di Nostra Signora del Sacro Cuore" Rome, have been studied using unilateral NMR. In order to map the distribution of moisture content in the wall painted, a large number of Hahn echo measurements, covering large areas of the wall painting were performed. Because the intensity of the Hahn echo is proportional to the amount of moisture in the area under study, the experimental data were transformed into 2D gradient colour maps which allowed an easy visualization of the moisture content of the wall. The state of conservation of the wall painting was monitored using T2 measurements specially with regards to outcropping salt. 相似文献
95.
Sinibaldi R Casieri C Melchionna S Onori G Segre AL Viel S Mannina L De Luca F 《The journal of physical chemistry. B》2006,110(17):8885-8892
Two binary aqueous mixtures which contain the small amphiphilic molecules TMAO (trimethylamine-N-oxide) and TBA (tert-butyl alcohol) have been investigated by molecular dynamics simulations and NMR chemical shift and self-diffusion measurements. TMAO is an osmolyte, while TBA is a monohydrate alcohol. Both possess bulky hydrophobic groups and polar heads, namely, NO in TMAO and OH in TBA. The hydrophilic/hydrophobic content of these isosteric molecules strongly modulates the structure and dynamics of the hydration shell, which is thought to be responsible for the effects observed on proteins and phospholipids. Simulation results, especially on hydrogen-bond networking, spatial correlations, and self-diffusivity, are consistent with NMR data and agree well with previous numerical studies on similar solutions. The methods employed allow the elucidation of the microscopic features of the solutions. For TBA solutions, the hydration shell is found to have a low density and a large spatial spread, and thus, above the molar fraction of 0.03, reduction of hydrophobic hydration drives self-aggregation of the solute. This effect does not take place in TMAO solutions, where the hydration shell is more compact and stable, maintaining its structure over a wider range of solute concentrations. 相似文献
96.
Pedone A Malavasi G Menziani MC Cormack AN Segre U 《The journal of physical chemistry. B》2006,110(24):11780-11795
A new empirical pairwise potential model for ionic and semi-ionic oxides has been developed. Its transferability and reliability have been demonstrated by testing the potentials toward the prediction of structural and mechanical properties of a wide range of silicates of technological and geological importance. The partial ionic charge model with a Morse function is used, and it allows the modeling of the quenching of melts, silicate glasses, and inorganic crystals at high-pressure and high-temperature conditions. The results obtained by molecular dynamics and free energy calculations are discussed in relation to the prediction of structural and mechanical properties of a series of soda lime silicate glasses. 相似文献
97.
Stoupin S Chung EH Chattopadhyay S Segre CU Smotkin ES 《The journal of physical chemistry. B》2006,110(20):9932-9938
In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides. 相似文献
98.
Hetterscheid DG Hendriksen C Dzik WI Smits JM van Eck ER Rowan AE Busico V Vacatello M Van Axel Castelli V Segre A Jellema E Bloemberg TG de Bruin B 《Journal of the American Chemical Society》2006,128(30):9746-9752
Unprecedented rhodium-catalyzed stereoselective polymerization of "carbenes" from ethyl diazoacetate (EDA) to give high molecular mass poly(ethyl 2-ylidene-acetate) is described. The mononuclear, neutral [(N,O-ligand)M(I)(cod)] (M = Rh, Ir) catalytic precursors for this reaction are characterized by (among others) single-crystal X-ray diffraction. These species mediate formation of a new type of polymers from EDA: carbon-chain polymers functionalized with a polar substituent at each carbon of the polymer backbone. The polymers are obtained as white powders with surprisingly sharp NMR resonances. Solution and solid state NMR data for these new polymers reveal a highly stereoregular polymer, with a high degree of crystallinity. The polymer is likely syndiotactic. Material properties are very different from those of atactic poly(diethyl fumarate) polymer obtained by radical polymerization of diethyl fumarate. Other diazoacetates are also polymerized. Further studies are underway to reveal possible applications of these new materials. 相似文献
99.
100.
Inpreviouspaperswehavereportedtheisolationandidentificationofescinsla,fo,IVa.IVbandIVel2.Nowwedescribethestructureelucidationofthreemorenewtriterpenoidsaponins.namedescinsIVc(l),IVd(2)andIVf(3).CompoundIwasisolatedaswhiteamorphouspowder.HR-SI-MSrevealedthecompositionofC,,H,,O,,bymolecularionpeakatm/z1129.5438.Comparedwiththe:3CandiHNMRspectraofescinla,compoundIisalsoaglycosideofprotoaescigeninacylatedbythetigloylandtheacetylgroup.Thesignificantdifferencesbetweenthemwerethechemicals… 相似文献