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991.
Hauchard C Pépin C Rowntree P 《Langmuir : the ACS journal of surfaces and colloids》2005,21(20):9154-9165
The adsorption of Fe(CO)(5) onto Au(111)/mica and C(4), C(8), C(12), and C(16) SAMs/Au(111)/mica surfaces has been studied using infrared spectroscopy to elucidate the coverage-dependent structures of these films and the intermolecular couplings that determine the form of the spectra. For all substrates, the first layer is composed of molecules physisorbed with one axial and two equatorial carbonyl groups directed toward the substrate; subsequent layers are preferentially oriented with the C(3) molecular axis aligned perpendicular to the substrate (i.e., one axial carbonyl group directed toward the substrate). The axial vibrational band systematically shifts to higher frequencies with increasing surface coverage because of the effects of intermolecular coupling of the quasiparallel transition dipole moments. The strong effects of dipolar coupling are also witnessed by the trends of the band positions when the distance to the image plane is systematically varied using highly organized self-assembled organic substrates; no band shifts are observed when dilute Fe(CO)(5) is embedded in Xe matrixes under identical experimental conditions. The as-deposited films are structurally stable below 125 K on Au(111)/mica surfaces and below 100 K on the organic self-assembled monolayers. The instability of the films above these temperatures demonstrates that the as-adsorbed films do not form thermodynamically well-defined phases but are structurally metastable. The results presented herein and in the companion paper provide a consistent framework to interpret the spectroscopy of these systems that resolves outstanding issues concerning these films and provides a structural model that explains the dynamic properties of these films during exposure to low-energy electron beams. 相似文献
992.
993.
Appleby I Boulton LT Cobley CJ Hill C Hughes ML de Koning PD Lennon IC Praquin C Ramsden JA Samuel HJ Willis N 《Organic letters》2005,7(10):1931-1934
Two methods to produce (2S)-5-amino-2-(1-n-propyl-1H-imidazol-4-ylmethyl)-pentanoic acid were investigated. Diastereoisomeric salt resolution, using the quinidine salt, gave the desired intermediate in 98% ee and 33% yield. Asymmetric hydrogenation of various substrates gave high conversions, with up to 83% ee. Integration of these two approaches via asymmetric hydrogenation of a quinidine salt substrate followed by crystallization provided the desired intermediate in 94% ee and 76% yield. 相似文献
994.
J. Goworek W. Stefaniak Agnieszka Kierys Mariola Iwan 《Journal of Thermal Analysis and Calorimetry》2007,87(1):217-222
Mesoporous silica material of MCM-41 type was synthesized by co-condensation
of highly concentrated octyltriethoxysilane (OTEOS), octadecyltriethoxysilane
(ODTEOS) and tetraethoxysilane (TEOS). The obtained hybrid materials were
characterized using XRD, TG-DSC and low temperature adsorption/desorption
of nitrogen. It was shown that the applied method of synthesis allows to obtain
silica of MCM-41 type with a high degree of hydrocarbon saturation. 相似文献
995.
Nanosized copolymer latex of hydroxypropylmethylcellulose (HPMC) grafted with ethyl acrylate (EA) and dimethylaminoethyl methacrylate
(DMAEMA) has been prepared by acidifying submicron-sized latex particles synthesized by soap-free emulsion graft copolymerization
using potassium persulfate (KPS) as initiator. The effects on the diameter of the latex particles of different conditions,
for example concentration of DMAEMA, amount of HPMC, and ratio of HCl to DMAEMA for acidification, were investigated. It was
found that increasing the mole ratio of HCl to DMAEMA to 1.0 and increasing the DMAEMA content both resulted in a decrease
in particle diameter, whereas increasing the amount of HPMC resulted in larger particle sizes. Measurement by dynamic light
scattering (DLS) revealed the diameter of the latex particles was >200 nm before acidification and <100 nm after acidification.
Evidence of grafting was obtained by use of Fourier transform infrared (FTIR) spectroscopy. Transmission electron microscopy
(TEM) was used to characterize the morphology of the copolymer particles before and after acidification. 相似文献
996.
Two lipids with similar melting ranges but of different composition were analyzed using differential scanning calorimetry and X-ray diffraction. The lipids were processed via extrusion or were tempered at different temperatures; they were analyzed directly after extrusion and after storage at 40°C. Precirol ATO 5® showed high sensitivity to storage time and varied temperature exposure. Extrusion showed only marginal influences on the solid state. Melting peaks were narrower and shifted to higher temperatures in comparison to the untreated powder. Dynasan 114® was more robust, changes in the solid state could only be shown for samples treated above the melting range. Thus, Dynasan 114® is more appropriate for solid lipid extrusion of pharmaceutical products. 相似文献
997.
Marta Fernandez-Tarrio Carmen Alvarez-Lorenzo A. Concheiro 《Journal of Thermal Analysis and Calorimetry》2007,87(1):171-178
Tetronic®comprises X-shaped copolymers formed by four poly(propylene oxide) (PPO) andpoly(ethylene oxide) (PEO) block chains bonded to an ethylene diamine centralgroup. Micellization behaviour of three representative Tetronics (T304, T904and T1307) was characterized to gain an insight into the interactions betweenthe copolymer unimers and the state of water in their solutions. The enthalpyof demicellization, recorded at 37°C in an isoperibol microcalorimeter,indicated that the process was in all cases exothermic and the enthalpy rankedin the order T1307≥T904>>T304. Micellization is entropy-driven owing tohydrophobic interactions between the PPO chains.DSC analysisshowed that the crystallization and melting peaks of the free water remainingin T304 and T904 solutions were progressively shifted toward lower temperaturesas the surfactant proportion increased, owing to a colligative effect. Boundwater corresponded to 3 water molecules per EO repeating unit. In the caseof T1307, which has longer PEO chains, a splitting of the melting peak wasobserved, one peak appearing around 0°C due to free water and anotherat –15°C due to interfacial water. As T1307 proportion raised, theenthalpy of the former decreased, whilst the enthalpy of the latter increased.In 40% T1307 solutions, interfacial water overcame the proportion of freewater; there being 1 interfacial and 3 bound water molecules per EO repeatingunit. Gaussian deconvolution of FTIR spectra also enabled to characterizethe evolution of free water as a function of Tetronic proportion. The dependenceof micellization and water interaction behaviour on Tetronics structure shouldbe taken into account to use these copolymers as drug solubilizers and micellarcarriers. 相似文献
998.
Kótai László Gács István Kazinczy Béla Sajó István E. Sreedhar B. 《Transition Metal Chemistry》2003,28(3):292-295
The theoretical investigation on the distribution of chemical species obtainable as a function of the temperature of the aqueous solutions of metal complexes containing a basic ligand, altogether with the solubility relationship of the compounds to be formed, offers a simple means of planning the preparation of various types of complexes, double and single salts of the central metal cation and onium type compounds of protonated ligand of the central ion and the anion. 相似文献
999.
Zhen-Qian Zhang Hong Li Juan Xu Su Yao Zheng-He Xu Jin-Gang Liu Liang-Nian Ji 《Transition Metal Chemistry》2007,32(6):776-780
The effects of copper ion on the interaction of [Ru(bpy)2HPIP]2+(bpy = 2,2′-bipyridine, HPIP = 2-(2-hydroxyphenyl) imidazo [4,5-f] [1, 10] phenanthroline) with DNA have been investigated
by electronic absorption spectroscopy and fluorescence spectroscopy. HPIP ligand of the complex with an intramolecular hydrogen
bond can bind Cu2+ in the absence of DNA, as revealed by the absorbance and fluorescence decrease for [Ru(bpy)2HPIP]2+. The resultant heterometallic complex binds to DNA via intercalation of HPIP into the DNA base pairs and its DNA-binding ability is stronger than [Ru(bpy)2HPIP]2+ itself. The DNA bound [Ru(bpy)2HPIP]2+ cannot bind Cu2+ at low Cu2+ concentration and the intramolecular hydrogen bond in HPIP is located inside the DNA helix. While the Cu2+ concentration is relative high, Cu2+ can quench the fluorescence of DNA bound [Ru(bpy)2HPIP]2+. The quenching reason is proposed. 相似文献
1000.
G. Ortega Zarzosa S. A. Palomares Sánchez J. R. Martánez Facundo Ruiz M. G. Sánchez-Loredo 《Journal of Sol-Gel Science and Technology》2005,35(1):5-11
Composites containing Pd aggregates dispersed in amorphous silica are of interest from both a fundamental and applied point of view because of their attractive catalytic properties. The silica powders added with palladium, prepared by the sol-gel method, were studied using X-ray diffraction, and IR- and UV-Vis-spectrophotometry. Silica xerogel samples were prepared using a ethanol/H2O/TEOS molar ratio of 4:11.6:1 and loaded with sodium tetrachloropalladate. The silica xerogel microstructure of the powders was studied as a function of annealing temperature. Attention was paid to the evolution of the glass matrix as well as the palladium aggregates in the SiO2 matrix. We found in our samples partial crystallization of the glass matrix in form of quartz and cristobalite phases with palladium oxide and metallic palladium phase at 1000∘C. The Rietveld refinement method was used in order to determine the percentage of the phase contents. 相似文献