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991.
Stefan Müllegger Kathrin H?nel Thomas Strunskus Christof W?ll Adolf Winkler 《Chemphyschem》2006,7(12):2552-2558
Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy has been applied to reveal the molecular arrangement of ultrathin oligophenyl films [p-quaterphenyl (4P) and p-hexaphenyl (6P)] on Au(111). In the half-monolayer films the molecules lie flat on the surface but still have a considerable inter-ring twist of 30 degrees -40 degrees , similar to the gas-phase conformation. In the saturated monolayer film the second half of the molecules is side-tilted by an angle of less than 66 degrees with respect to the surface. This arrangement is already similar to that in bulk net planes of thicker films parallel to the surface, that is, the 4P(211) and 6P(21-3) planes, respectively. 相似文献
992.
煤的孔结构特征对水煤浆性质的影响 总被引:7,自引:3,他引:7
本文选用17种不同变质程度的中国煤,详细研究了煤孔结构特征对煤浆性质的影响。发现煤孔体积通过影响煤在分散体系中的吸水性,从而影响煤之成浆性。但由于不同变质程度煤表面亲水性的显著差异,煤孔体积在影响煤成浆性的能力方面差别很大,这使得煤吸水性和浆体最高煤浓度与煤孔体积并不存在直接的相关性,而是取决于煤孔体积V和以煤-水接触角(θ)的余弦值表示的煤表面亲水性因子的乘积,即煤之有效孔体积:V×cos(θ/ 相似文献
993.
The coupled-column (LC-LC) system, consisting of a first column packed with internal surface reversed phase (ISRP) (50 x 4.6mm ID) and a Chrompack C18 (100 x 4.6 mm ID) as second column, allowed the simultaneous determination of five benzoylurea insecticides in dichloromethane (CH2Cl2) extracts of vegetable samples without any clean-up step. This system was combined with a photochemically induced fluorescence (PIF) post-column derivatization in order to provide strongly fluorescent photoproducts from the non-fluorescent benzoylureas. Limits of detection ranged from 0.21 to 0.98 microg L(-1) of pesticide (equivalent to 0.14-0.65 microg kg(-1) in vegetable samples) and limits of determination ranged from 4.0 to 10.0 microg L(-1) (equivalent to 2.7-6.7 microg kg(-1)). Linearity of the method was established between 2 and 1800 microg L(-1), depending upon the compound. Validation of the total method was performed by randomly analyzing recoveries of four vegetable samples (aubergine, cucumber, green bean, and tomato) spiked at two levels of concentration (10.0 and 33.3 microg kg(-1)). The combination of the LC-LC system with PIF detection provides a sensitive, selective, and rapid method for the determination of pesticides in vegetable samples at levels lower than the maximum residue levels (MRLs) established for these compounds by Spanish legislation. 相似文献
994.
The micro construction of poly(epsilon-caprolactone) (PCL) and poly(L-lactic acid) (PLLA) blend films fabricated by solution casting under microwave irradiation was investigated by selective enzymatic degradation and scanning electron microscopy (SEM). The results were totally different from the blends obtained by conventional methods. The blend was more homogeneous and the PCL continuous phase more compact as no spherulites and tiny zone separation were observed from the film surface and no PCL network was observed inside the film, and the degradation of a PCL plank by Pseudomonas lipase was significantly retarded. The distributed PLLA micro spheres were enlarged and amorphous. The thermal behavior of the blend by microwave heating revealed that PCL and PLLA underwent a melting process, which induced the variations of the PCL phase and PLLA spheres. The weight loss caused by degradation of the PCL/PLLA blend obtained by conventional methods (B50c) is greater than that of the blend obtained by microwave methods (B50m), which reflects the change in morphology from a loose PCL network (B50c) to a dense PCL plank (B50m). 相似文献
995.
An essential element of implicit solvent models, such as the generalized Born method, is a knowledge of the volume associated with the individual atoms of the solute. Two approaches for determining atomic volumes for the generalized Born model are described; one is based on Voronoi polyhedra and the other, on minimizing the fluctuations in the overall volume of the solute. Volumes to be used with various parameter sets for protein and nucleic acids in the CHARMM force field are determined from a large set of known structures. The volumes resulting from the two different approaches are compared with respect to various parameters, including the size and solvent accessibility of the structures from which they are determined. The question of whether to include hydrogens in the atomic representation of the solute volume is examined. Copyright 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1857-1879, 2001 相似文献
996.
Transmission electron microscopy of freeze fractured and replicated samples (TEM) and polarizing light microscopy (PLM) are
used to investigate the defect structures of the thermotropic and lyotropic mesophases of the non-steroidal antiinflammatory
drug fenoprofen sodium and of the thermotropic mesophase of the nonionic surfactant sucrose oleate (O1570). All mesophases
have a layered, smectic structure. The thermotropic liquid crystal of feno-profen sodium is an interdigitated smectic A phase
(smectic Ad) having the highest viscosity of the investigated samples. The thermotropic mesophase of the sugar ester is also
of the type smectic A, likely to be of subtype smectic A2 (bilayered smectic structure). The lyotropic mesophase is of lamellar
liquid crystalline nature and has a much lower viscosity than the thermotropic mesophases. In the PLM the lyotropic fenoprofen
mesophase has a strong tendency to form a pseudoisotropic texture, indicating a strong tendency to form undisturbed layered
structures. Other textures exhibited in the PLM are fan-shaped texture and maltese-cross texture. Confocal domains, cylinders,
pits and peaks as well as screw dislocations are found in great number in the TEM. However, no greater regions of undisturbed
lamellar arrangement in the lyotropic mesophase could be detected. The only texture of the thermotropic fenoprofen mesophase
visible in the PLM is the fan-shaped texture, indicating confocal domains as predominant structural elements. However, no
confocal domains (tori or Dupin cyclides) are found in the TEM. In the PLM the sugar–ester mesophase exhibited a fan-shaped
texture, maltese crosses and oily streaks as dominant textures. In the TEM only a few +π and −π disclinations and imperfect
confocal domains could be detected. The discrepancies in the appearance of defect structures and textures between the mesophases
as well as the discrepancies in the findings in the PLM and in the TEM investigations are caused by the different sample preparation
and the different viscosities of the mesophases.
Received: 28 May 1997 Accepted: 2 September 1997 相似文献
997.
《Electroanalysis》2006,18(23):2305-2313
The multiple square‐wave voltammetry (MSWV) allied to gold microelectrode (Au‐ME) was used to establish an electroanalytical procedure for the determination of the paraquat and diquat pesticides in river sediment samples. For both pesticides, two reduction peaks, at around ?0.70 V (peak 1) and around ?1.00 V vs. Ag/AgCl 3.00 mol L?1 (peak 2), with profile of the totally reversible redox process, were observed. The experimental and voltammetric conditions showed that the best conditions to reduce paraquat and diquat were a pH of 6.0, a frequency of 250 s?1, a scan increment 2 mV, a square‐wave amplitude of 50 mV and pulse number of 8 pulses of potential in each step of staircase of potential. Under such conditions, the detection limit of 0.044 μg L?1 (0.044 ppb) and 0.360 μg L?1 (0.360 ppb ) for peak 1 and peak 2 of paraquat and 0.159 μg L?1 (0.159 ppb) and 0.533 μg L?1 (0.533 ppb) for peak 1 and peak 2 of diquat, respectively, were obtained. These results are an order of magnitude of about two less than those obtained and published in the literature. Also, the electroanalytical procedure proposed was applied for the determination of adsorption isotherms of pesticides on river sediments samples collected from Mogi‐Guaçu River in Sao Paulo State, Brazil. The experimental data were fitted using the Langmuir and Freundlich isotherms models; and the results indicated low intensities of adsorption process of the pesticides in the samples employed with distribution coefficients (Kd) lower 5.0, and paraquat showed slightly higher affinity than diquat in the sediments. The increase in organic matter and organic carbon leads to an increase in the Kd values, and consequently an increase in the organic matter constant (KOM) organic carbon constant (KOC) values. All results demonstrated that isotherms “L” type in the Giles classification were obtained, indicating that sediments have a medium affinity for the pesticides, and no strong competition from the solvent used (in this case Na2SO4) for adsorption sites occurs. 相似文献
998.
Odin C 《Magnetic resonance in chemistry : MRC》2004,42(4):381-388
A variable-temperature high-resolution 13C and 87Rb solid-state NMR study of powder rubidium hydrogencarbonate, RbHCO3, is presented for the first time. At ambient temperature, RbHCO3 is formed by centrosymmetric dimers linked by hydrogen bonds, but almost no information is available on this compound concerning proton disorder and the low-temperature phase. However, potassium hydrogencarbonate, KHCO3, which has an isomorphic structure for the high temperature phase, was well studied: it undergoes a non-ferroic, non-ferroelectric phase transition at Tc = 318 K between two monoclinic structures. The protons are disordered in an asymmetric double-well potential in the low-temperature phase, and the double-well potential becomes symmetric in the high-temperature phase. By comparison with recent solid-state NMR experimental results on KHCO3, we show that RbHCO3 undergoes a phase transition at Tc approximately 245 K, and give evidence that the proton dynamic disorder in both compounds is very similar. 相似文献
999.
A novel extraction method, namely dynamic ultrasound-assisted extraction, is investigated. This technique is efficient with respect to both time and solvent consumption because it utilizes ultrasonic energy in dynamic mode during extraction. Polyphenols (chlorogenic acid, esculetin, rutin, scopoletin, and quercitrin) are extracted from a tobacco (Nicotina tobaccum L.) sample for 10 min with 6 mL of solvent. Fresh solvent is continuously pumped through the sample, with which the analytes can be rapidly extracted, and the possibility of degradation efficiently avoided. Methanol involving 0.5% w/v ascorbic acid was used as extraction solvent; optimal flow rate and extraction time were investigated. The extract was cleaned up by C18 disposable cartridge. The spiked and nonspiked tobacco samples were used for the evaluation of the proposed method. Recoveries obtained were varied from 96 to 108% and RSDs from 2.0 to 4.6%. This extraction technique was revealed to recover larger amounts of polyphenols from tobacco, compared to the static ultrasound-assisted extraction method. 相似文献
1000.
19F and 1H NMR spectra of halocarbons 总被引:1,自引:0,他引:1
Foris A 《Magnetic resonance in chemistry : MRC》2004,42(6):534-555
19F NMR chemical shifts and coupling constants are reported for 215 compounds. For 77 of these compounds, 1H NMR spectral data are also given. Long-range couplings, including 8J(F,F) and 5J(F,H), are reported. The complexity of halocarbon spectra owing to the presence of rotational isomers, asymmetric centers, long-range couplings, and chlorine isotope effects are illustrated, and the methods used for analyzing such complex spectra are briefly discussed. 相似文献