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排序方式: 共有86条查询结果,搜索用时 31 毫秒
1.
A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NO3, and the reduced organic sulphur compounds CH3CH2SH, (CH3CH2)2S, (CH3CH2)2S2, and CH3CH2SCH3 in air. The products CH3CH2SO3H, SO2, H2SO4, CH3CHO, and CH3CH2ONO2 were identified and quantified in the reactions of the first three compounds, CH3CH2SH, (CH3CH2)2S, and (CH3CH2)2S2. The reaction products were CH3CH2SO3H, CH3SO3H, SO2, H2SO4, CH3CHO, and CH2O in the reaction of CH3CH2SCH3. On the basis of identified reaction products and intermediates observed in the infrared spectra, mechanisms are proposed for the reactions between the NO3 radical and the four reduced organic sulphur compounds. The results of this study, together with those from previous experiments performed in this laboratory on CH3SCH3, CH3SH, and CH3SSCH3 lead to the conclusion that all these species, in the reaction with the NO3 radical, follow a similar degradation mechanism producing SO2, H2SO4, R? SO3H, R? CHO, and R? CH2ONO2, as the main reaction products. The inital step of the reaction of NO3 with R? S? R and R? S? H type (R = CH3, CH2CH3) reduced organic sulphur compounds was found to be H-atom abstraction, probably after the formation of an initial adduct. For the reaction between NO3 and R? S? S? R type compounds, evidence for an addition-decomposition reaction, as the initial steps, was obtained. R? S·, R? S(O)·, and R? S(O)2· appear to be formed as intermediates in all the reactions. © John Wiley & Sons, Inc. 相似文献
2.
Lone Skov Henrik Hansen Henning C. Dittmar Jonathan N. W. N. Barker Jan C. Simon Ole Baadsgaard 《Photochemistry and photobiology》1998,67(6):714-719
Sensitization on skin exposed to acute low-dose UVB irradiation separates normal humans into two phenotypically distinct groups: One group, following sensitization on UVB-irradiated skin, develops contact sensitivity, designated UVB resistant (UVB-R) and the second group, following sensitization on UVB-irradiated skin, fails to develop contact sensitivity, designated UVB susceptible (UVB-S). To investigate whether UVB susceptibility in humans is related to antigen-presenting activity in the skin we studied the effect of UVB irradiation on the number and function of the epidermal antigen-presenting cells in volunteers identified as UVB-R and UVB-S. Single cell suspensions of epidermal cells from control skin and skin exposed to 3 minimal erythema doses (MED) of UVB 3 days previously were stained for Langerhans cells (CD1a+HLA-DR+) and epidermal macrophages (CD1a-HLA-DR+). The UVB exposure of the skin significantly decreased the percentage of Langerhans cells (UVB-R: n = 7, P < 0.02, UVB-S: n = 6, P < 0.03) and increased the percentage of epidermal macrophages (UVB-R: n = 7, P < 0.03, UVB-S: n = 6, P < 0.03) however to the same degree in both the UVBR and the UVB-S group. To study the effect on Langerhans cell alloreactivity, epidermal cells were harvested immediately after UVB irradiation. However, in both UVB-R and UVB-S subjects the Langerhans cell alloreactivity was blocked to the same degree immediately after UVB irradiation compared to nonirradiated epidermal cells. To determine the effect of UVB irradiation on epidermal macrophages, epidermal cells were harvested 3 days after UVB irradiation. Irradiated epidermal cells from both UVB-R and UVB-S subjects demonstrated a strong antigen-presenting capacity compared to epidermal cells from control skin leading to activation of T cells that mainly secrete interferon (1FN)-γ and not interleukin (IL)-4. In conclusion we found that UVB susceptibility was not correlated with the number of Langerhans cells or epidermal macrophages in the skin at the same time of sensitization. Neither was it correlated with the capacity of Langerhans cells nor UVB-induced epidermal macrophages to activate T cells in vitro. 相似文献
3.
4.
Apparent specific densities of aqueous solutions of the diblock copolymers C18(EO)100, C18(EO)20, and (EO)92(BO)18 and the triblock copolymers (EO)25(PO)40(EO)25 and (EO)21(PO)47(EO)21 in the micellar state have been measured over a temperature range from 10 to 90 degrees C at concentrations between 1% and 5%, using an oscillating tube densitometer. From these measurements, apparent specific volumes of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), poly(butylene oxide) (PBO), and octadecane in the micellar state have been determined. The composition of the block copolymers was checked by NMR spectroscopy. Results were compared with published data for the polymers and bulk values for octadecane, respectively. The apparent specific density of PEO chains in the dissolved state was also measured for PEG4600 solutions at different concentrations and compared with results in the micellar state. The results presented in the paper are crucial in connection with analysis and modeling of small-angle X-ray scattering (SAXS) data from polymer and block copolymer micellar systems. PEO and PPO have a relatively low apparent partial specific volume in water at low temperatures. It is associated with water molecules making strong hydrogen bonds with the oxygen atoms on the polymer backbone. These water molecules gradually become disordered when the temperature is increased and the polymer apparent specific volume increases. For PBO in the micellar cores of PBO-PEO block copolymer micelles and in PNiPAM microgels, pronounced temperature dependence with the same origin is also found. The application of the derived results for the apparent specific volume of PEO for deriving contrast factors is demonstrated and the results are used in the analysis of SAXS data for semidilute solutions of PEG4600 in a broad temperature range. 相似文献
5.
Jørgensen JM Erlacher K Pedersen JS Gothelf KV 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10320-10323
The influence of preparation temperature on the size and size distribution of dodecylthiol monolayer protected gold clusters was studied. The monolayer protected clusters (MPCs) were synthesized by two different variations of the Brust-Schiffrin procedure. In all of the experiments, the stoichiometry of the reactants dodecylthiol, HAuCl(4), and sodium borohydride was kept constant, while the temperature was varied in the range of -18 to +90 degrees C. Two series were performed in which an aqueous solution of NaBH(4) was either added over 30 s or all in one portion. The size and size distribution of the MPCs were determined by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). It has been demonstrated that in general the MPC size increases with elevated preparation temperatures. 相似文献
6.
Small-angle neutron scattering study of structural changes in temperature sensitive microgel colloids 总被引:3,自引:0,他引:3
Stieger M Richtering W Pedersen JS Lindner P 《The Journal of chemical physics》2004,120(13):6197-6206
The structure of temperature-sensitive poly(N-isopropylacrylamide) microgels in dilute suspension was investigated by means of small-angle neutron scattering. A direct modeling expression for the scattering intensity distribution was derived which describes very well the experimental data at all temperatures over an extensive q range. The overall particle form as well as the internal structure of the microgel network is described by the model. The influence of temperature, cross-linking density, and particle size on the structure was revealed by radial density profiles and clearly showed that the segment density in the swollen state is not homogeneous, but gradually decays at the surface. The density profile reveals a box profile only when the particles are collapsed at elevated temperatures. An increase of the cross-linking density resulted in both an increase of the polymer volume fraction in the inner region of the particle and a reduction of the smearing of the surface. The polymer volume fraction inside the colloid decreased with increasing particle size. The structural changes are in good agreement with the kinetics of the emulsion copolymerization used to prepare the microgel colloids. 相似文献
7.
Monitoring the Transition from Spherical to Polymer‐like Surfactant Micelles Using Small‐Angle X‐Ray Scattering
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Dr. Grethe Vestergaard Jensen Dr. Reidar Lund Dr. Jérémie Gummel Dr. Theyencheri Narayanan Prof. Jan Skov Pedersen 《Angewandte Chemie (International ed. in English)》2014,53(43):11524-11528
Despite over a century of modern surfactant science, the kinetic pathways of morphological transitions in micellar systems are still not well understood. This is mainly as a result of the lack of sufficiently fast methods that can capture the structural changes of such transitions. Herein, a simple surfactant system consisting of sodium dodecyl sulfate (SDS) in aqueous NaCl solutions is investigated. Combining synchrotron radiation small‐angle X‐ray scattering (SAXS) with fast stopped‐flow mixing schemes allows monitoring the process where polymer‐like micelles are formed from globular micelles when the salt concentration is suddenly increased. The results show that “worm‐like” micelles are formed by fusion of globular micelles and short cylinders in a fashion that bears similarities to a step‐like polymerization process. 相似文献
8.
Alexandru Vlasceanu Dr. Søren L. Broman Anne S. Hansen Anders B. Skov Prof. Dr. Martina Cacciarini Prof. Dr. Anders Kadziola Prof. Dr. Henrik G. Kjaergaard Prof. Dr. Kurt V. Mikkelsen Prof. Dr. Mogens Brøndsted Nielsen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(31):10796-10800
The conversion and efficient storage of solar energy is recognized to hold significant potential with regard to future energy solutions. Molecular solar thermal batteries based on photochromic systems exemplify one possible technology able to harness and apply this potential. Herein is described the synthesis of a macrocycle based on a dimer of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermal couple. By taking advantage of conformational strain, this DHA–DHA macrocycle presents an improved ability to absorb and store incident light energy in chemical bonds (VHF–VHF). A stepwise energy release over two sequential ring‐closing reactions (VHF→DHA) combines the advantages of an initially fast discharge, hypothetically addressing immediate energy consumption needs, followed by a slow process for consistent, long‐term use. This exemplifies another step forward in the molecular engineering and design of functional organic materials towards solar thermal energy storage and release. 相似文献
9.
T.P. Leervad Pedersen J. Skov Jensen J. Chevallier O. Hansen J.M. Jensen B. Bech Nielsen A. Nylandsted Larsen 《Applied Physics A: Materials Science & Processing》2005,81(8):1591-1593
The synthesis of evenly distributed Ge nanoclusters in plasma-enhanced chemical-vapour-deposited (PE-CVD) SiO2 thin films containing 8 at. % Ge is reported. This is of importance for the application of nanoclusters in semiconductor
technology. The average diameter of the Ge nanoclusters can be controlled in the range of 3–6 nm by variation of the annealing
parameters. Using a combination of transmission electron microscopy and Raman-scattering spectroscopy, the nanoclusters were
shown to be crystalline. However, photoluminescence measurements showed no light emission that could be definitively correlated
to the presence of the nanoclusters.
PACS 61.82.Rx; 78.67.Bf; 81.07.Bc 相似文献
10.
New non-ionic microemulsions consisting of pentaethyleneglycol dodecyl ether, water, and 1-chloroalkanes were prepared, and their phase behavior was studied. A homologous series of five different 1-chloroalkanes from 1-chlorooctane to 1-chlorohexadecane was studied. The phase behavior of the microemulsions was determined by vertical sections through the Gibbs' phase prism ("fish" plots), from which valuable information such as the microemulsion balance temperature (T(0)), efficiency of the surfactant (phi*), temperature extension of the three-body phase (DeltaT), mean temperature (T(m)), and the monomeric solubility in oil (phi(mon,oil)) was obtained. The chlorinated alkanes in the microemulsions shift the balance temperature to about 14 degrees C lower compared with their n-alkane counterparts. This indicates the polar nature of the chlorinated oils and their ability to penetrate the surfactant film. The chlorinated alkanes thus behave as short n-alkane molecules and lower the spontaneous curvature of the microemulsion droplets. The efficiency of the surfactant and the monomeric solubility in oil systematically depend on the alkyl chain length of the oil, with the efficiency and solubility decreasing with increasing alkyl chain length of 1-chloroalkane. The size and shape of the microemulsion droplets in the microemulsion phase were studied by small-angle X-ray scattering (SAXS). For a surfactant-to-oil volume fraction ratio of 0.80, the droplets can be described by ellipsoidal shapes, and the size of the droplets increased with increasing alkyl chain length. 相似文献