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71.
The 1H and 13C nmr spectra of 1,4,5,7-tetrahydro-3H-2,6-benzodiselenine (1) and three 4-spiro derivatives 2–4 as well as the 77Se nmr spectra of 2 have been recorded at different temperatures in order to investigate their conformational behavior. It was found that in analogy to corresponding dithionins the molecules adopt a chiral ground state conformation (Figure 2), and coalescence effects are due to racemization. 相似文献
72.
Monika Schuster Robert Inführ Claudia Turecek Jürgen Stampfl Franz Varga Robert Liska 《Monatshefte für Chemie / Chemical Monthly》2006,137(7):843-853
Summary. To substitute cross-linked photopolymers in rapid prototyping of mold materials and therefore extend the range of materials
which can be casted, organo-soluble photopolymers were developed. Branched bisalkylacrylamides were suitable as base component
for such formulations, due to their high reactivity, good mechanical properties, and excellent solubility of the formed polymers.
These molding materials were used to prepare cellular biocompatible materials which could be used as bone replacement materials.
Biocompatible crosslinkers based on methacrylates from hydrolyzed gelatine or lactic acid ethyleneglycol blockcopolymers and
commercially available reactive diluents are the base components of such a formulation. Biocompatibility was investigated
by osteoblast-like cells. Cellular biocompatible parts were obtained by thermal polymerization in soluble mould materials
prepared by 3D-photoshaping. 相似文献
73.
Biener MM Biener J Friend CM 《Langmuir : the ACS journal of surfaces and colloids》2005,21(5):1668-1671
The Au-S interaction is probably the most intensively studied interaction of Au surfaces with nonmetals, as, for example, it plays an important role in Au ore formation(1) and controls the structure and dynamics of thiol-based self-assembled monolayers (SAMs). Various S-induced surface structures on Au(111) were recently reported for different conditions and predominantly interpreted in terms of a static Au surface. Here, we demonstrate that the Au(111) surface exhibits a very dynamic character upon interaction with adsorbed sulfur: large-scale surface restructuring and incorporation of Au atoms into a growing 2D AuS phase were observed in situ. These results provide new insight into the Au-S surface chemistry. 相似文献
74.
The use of fenugreek mucilage, a natural polysaccharide and a direct food additive, as a flocculating agent for removal of suspended and dissolved solids from sewage effluent has been reported. A flocculation study has been done by the standard jar test method. The percent removal of suspended solid (SS) and dissolved solid (TDS) was determined by varying the polymer dose, pH and contact time. X-ray diffraction patterns of the solid waste material of mucilage and flocs (so obtained after treatment) were used to suggest the incorporation of the crystalline waste material in the mucilage. The optimal mucilage concentration was found to be 0.16 mg/l. The suitable pH range for maximum solid removal (SS and TDS) was alkaline and the time required for treatment was 1-3 h. 相似文献
75.
The beginning of the twentieth century saw the development of new theories of acidity and basicity, which are currently well accepted. The thermochemistry of proton transfer in the absence of solvent attracted much interest during this period, because of the fundamental importance of the process. Nevertheless, before the 1950s, few data were available, either from lattice energy evaluations or from calculations using the emerging molecular orbital theory. Advances in mass spectrometry during the last 40 years allowed studies of numerous systems with better accuracy. Thousands of accurate gas-phase acidities or basicities are now available, for simple atomic and molecular systems and for large biomolecules. The intrinsic effect of structure on the Br?nsted basic or acidic properties of molecules and the influence of solvents have been unravelled. In this tutorial, the basics of the thermodynamic principles involved are given, and the mass spectrometric techniques are briefly reviewed. Advances in the design and measurements of gas-phase superacids and superbases are described. Recent studies concerning biomolecules are also evoked. 相似文献
76.
Rappolt M Amenitsch H Strancar J Teixeira CV Kriechbaum M Pabst G Majerowicz M Laggner P 《Advances in colloid and interface science》2004,111(1-2):63-77
In this work, we report on recent investigations, both on the global and on the local molecular architecture of supported phospholipid model membranes. A brief theoretical introduction explains how global structural information on supramolecular lipid ensembles can be retrieved from surface X-ray diffraction measurements as well as how spin-label electron paramagnetic resonance spectroscopy (EPR) provides complementary information on the local environment of probe molecules. The combination of especially designed X-ray cells with the technique of small- and wide-angle X-ray surface scattering makes it possible to explore various fields of lipid research and its applications. Examples for different physico-chemical conditions are presented: (i) in situ chemistry under excess of water conditions demonstrating how solid-supported lipid films sense salinity, (ii) the 3D electron density reconstruction of a vesicle-fusion intermediate under controlled humidity, and (iii) complementary temperature and pressure effects on oriented phospholipid samples. Further, special attention has been given to the influence of different film preparation techniques with respect to quality and the defect structure manifestation. To resolve the proportions and local properties of defects in a hydrated lipid-deposited surface, spin-label EPR was applied. The results from 9.6 GHz EPR as well as from 1.2 GHz EPR suggest the alignment to be in the range between 30% and 80%. In addition, slow time-dependent EPR measurements point to nano-structural rearrangements due to water flow and reduction of alignment quality. 相似文献
77.
Structure of colloid silica determined by viscosity measurements 总被引:3,自引:0,他引:3
The viscosity of nanosized colloid silica suspensions, used as binders in the investment casting, was determined as a function of their weight fraction reaching 52%. A new capillary viscometer was used whose construction eliminated sedimentation effects. The experiments have been carried out at fixed pH 10.0 and controlled ionic strength. It was found that for a low silica concentration range (weight fraction below 5%) the suspension viscosity increased more rapidly than the Einstein theory predicts. This anomalous behavior could not be explained in terms of the primary electroviscous effect predicted to be a few orders of magnitude smaller as observed. This discrepancy was accounted for by postulating a fuzzy, gel-like structure of colloid silicas used in our experiments. Hence, the apparent hydrodynamic radius of silica particles in aqueous suspensions was found to be larger than the primary particle size in accordance with previous observations. Based on this postulate, an apparent density of the silica sols was found to be 1.32-1.37 g/cm(3) instead of 2.2-2.32 g/cm(3) as determined from the suspension dilution method. This behavior was interpreted in terms of the core/shell model with high shell porosity, reaching 85%. Similarly, for higher concentration ranges, silica viscosity increased more rapidly with increased sol concentration than predicted by the Batchelor model derived for hard particles. The deviation was attributed to the secondary electroviscous effect stemming from the electrostatic interactions among silica particles in sheared suspensions. This effect has quantitatively been interpreted in terms of Russel's theory. On the other hand, for the high concentration range the experimental results were well accounted for by the Dougherty-Krieger model. By exploiting our experimental findings a sensitive method of determining the structure and apparent density of silica sols in aqueous media was proposed. 相似文献
78.
Voegtli WC Sommerhalter M Saleh L Baldwin J Bollinger JM Rosenzweig AC 《Journal of the American Chemical Society》2003,125(51):15822-15830
The R2 subunit of Escherichia coli ribonucleotide reductase contains a dinuclear iron center that generates a catalytically essential stable tyrosyl radical by one electron oxidation of a nearby tyrosine residue. After acquisition of Fe(II) ions by the apo protein, the resulting diiron(II) center reacts with O(2) to initiate formation of the radical. Knowledge of the structure of the reactant diiron(II) form of R2 is a prerequisite for a detailed understanding of the O(2) activation mechanism. Whereas kinetic and spectroscopic studies of the reaction have generally been conducted at pH 7.6 with reactant produced by the addition of Fe(II) ions to the apo protein, the available crystal structures of diferrous R2 have been obtained by chemical or photoreduction of the oxidized diiron(III) protein at pH 5-6. To address this discrepancy, we have generated the diiron(II) states of wildtype R2 (R2-wt), R2-D84E, and R2-D84E/W48F by infusion of Fe(II) ions into crystals of the apo proteins at neutral pH. The structures of diferrous R2-wt and R2-D48E determined from these crystals reveal diiron(II) centers with active site geometries that differ significantly from those observed in either chemically or photoreduced crystals. Structures of R2-wt and R2-D48E/W48F determined at both neutral and low pH are very similar, suggesting that the differences are not due solely to pH effects. The structures of these "ferrous soaked" forms are more consistent with circular dichroism (CD) and magnetic circular dichroism (MCD) spectroscopic data and provide alternate starting points for consideration of possible O(2) activation mechanisms. 相似文献
79.
At room temperature, three of the six polymorphic compounds described are not present in their highest melting-point form, owing to enantiotropy. These three are triphenyltin chloride (3 modifications), 1-(4,4-dimethyl-2-oxo-3-tetrahydrofuryl)thiourea (4 modifications), and 2-aminoethyl diphenylborinate (3 modifications). In the case of 4-amino-1-(2-phenylethyl)-1,2,4-triazoline-5-thione, in addition to the absolutely stable modificationI, a further six unstable crystal forms have been observed. The three modifications of,-dimethyl-[1,1-biphenyl]-4-methanol are also monotropic in character. 2,9-Dimethyl-1,10-phenanthroline, the three polymorphic forms of which are unstable, is a special case, since it absorbs water from the air and changes into a semi-hydrate. 相似文献
80.
Summary Rare earth elements 1,3,5-benzenetricarboxylates were prepared as solids of the general formula Ln(C9H3O6)·nH2O, where n=6 for La-Dy and n=4 for Ho-Lu,Y. Their solubilities in water at 293 K are of the order 10-4-10-6 mol dm-3. The IR spectra of the complexes indicate that the carboxylate groups are bridging and bidentate chelates. Hydrated 1,3,5-benzenetricarboxylates
lose water molecules during heating in one step (La-Tb), two steps (Y, Ho-Tm) or three steps (Dy, Yb, Lu). The anhydrous complexes
are stable up to 573-742 K and decompose to oxides (Ce-Lu) at higher temperatures. 相似文献