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81.
Papadimitriou VC Lazarou YG Talukdar RK Burkholder JB 《The journal of physical chemistry. A》2011,115(2):167-181
Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF in the presence of O(2) were investigated using density functional theory (DFT). 相似文献
82.
We discuss a simple transformation that allows to generate SU(3) structure solutions of Type IIB supergravity with RR fluxes, starting from non-Kähler solutions of Type I supergravity. The method may be applied also in the presence of supersymmetric source branes. We apply this transformation to a solution describing fivebranes wrapped on the S2 of the resolved conifold with additional flavour fivebrane sources. The resulting solution is a generalisation of the resolved deformed conifold solution of Butti et al. (2005) [1] by the addition of D5 brane and D3 brane sources. We propose that this solution may be interpreted in terms of a combined effect of Higgsing and cascade of Seiberg dualities in the dual field theory. 相似文献
83.
Vassiliki G. Kontogianni Alexandra Primikyri Marianna Sakka Ioannis P. Gerothanassis 《Magnetic resonance in chemistry : MRC》2020,58(3):232-244
Artemisia annua is a promising and potent antimalarial herbal drug. This activity has been ascribed to its component artemisinin, a sesquiterpene lactone. The ability to determine artemisinin and its known analogs in plant extracts is an especially difficult task because the compounds are present in low concentrations, are thermolabile, and lack ultraviolet or fluorescent chromophores. We report herein a facile and rapid 1-D 1H, 1-D total correlation spectroscopy, 2-D 1H–13C heteronuclear single quantum coherence, and 1H–13C heteronuclear multiple bond correlation nuclear magnetic resonance techniques for the simultaneous identification and quantification of artemisinin and five of its analogs along with five flavonoids, an aromatic ketone, and camphor (in total, 13 compounds) in crude diethyl ether A. annua extract without the need of laborious isolation of the individual analytes. The above method was validated in terms of precision, linearity, and limit of detection. The analytical results were found to be in excellent agreement with those obtained with the use of the time consuming high-performance liquid chromatography with diode-array detection and liquid chromatography with tandem mass spectrometry for the compounds that standards were available. 相似文献
84.
Katherine Koh Udishnu Sanyal Mal‐Soon Lee Guanhua Cheng Miao Song Vassiliki‐Alexandra Glezakou Yue Liu Dongsheng Li Roger Rousseau Oliver Y. Gutirrez Abhijeet Karkamkar Miroslaw Derewinski Johannes A. Lercher 《Angewandte Chemie (International ed. in English)》2020,59(4):1501-1505
Acid functionalization of a carbon support allows to enhance the electrocatalytic activity of Pd to hydrogenate benzaldehyde to benzyl alcohol proportional to the concentration of Brønsted‐acid sites. In contrast, the hydrogenation rate is not affected when H2 is used as a reduction equivalent. The different responses to the catalyst properties are shown to be caused by differences in the hydrogenation mechanism between the electrochemical and the H2‐induced hydrogenation pathways. The enhancement of electrocatalytic reduction is realized by the participation of support‐generated hydronium ions in the proximity of the metal particles. 相似文献
85.
Zoumpanioti M Stamatis H Papadimitriou V Xenakis A 《Colloids and surfaces. B, Biointerfaces》2006,47(1):1-9
A series of water-in-oil microemulsion systems formulated without surfactant were used to solubilize lipases from Rhizomucor miehei and Candida antarctica B. The effect of the system's composition on the velocity of enzymic reactions was investigated following a model esterification reaction. The interaction between enzymes and the microemulsion environment was studied by steady state fluorescence spectroscopy. The site of localization of the enzyme within the different microdomains of the dispersed phase was investigated by applying the fluorescence energy transfer technique. To determine the properties of the interface between water and organic solvent of the surfactantless microemulsion systems the Electron Paramagnetic Resonance (EPR) spectroscopic technique was applied. The results indicated that even at low water content, water-rich structures are formed. This was confirmed by conductivity measurements. By the addition of enzyme it was observed that when the aqueous phase of the surfactantless microemulsion systems exceeds 2% (v/v) the enzyme retains its catalytic activity, as it is located within the water pools that protect it from the organic solvent. These confined water phases show a propanol rich interface with hexane and their structure depends on the system's composition. 相似文献
86.
Fotis A. Baltoumas Stavros J. Hamodrakas Vassiliki A. Iconomidou 《Journal of computational chemistry》2019,40(18):1727-1734
Outer membranes are a crucial component of Gram-negative bacteria, containing standard lipids in their inner leaflet, lipopolysaccharides (LPSs) in their outer leaflet, and transmembrane β-barrels known as outer membrane proteins (OMPs). OMPs regulate functions such as substrate transport and cell movement, while LPSs act as a protective barrier for bacteria and can cause toxic reactions in humans. However, the experimental study of outer membranes is challenging. Molecular dynamics simulations are often used for the computational study of membrane systems, but the preparation of complex, LPS-rich outer membranes is not straightforward. The Gram-Negative Outer Membrane Modeler (GNOMM) is an automated pipeline for preparing simulation systems of OMPs embedded in LPS-containing membranes in four different force fields. Given the physiological and clinical importance of outer membranes and their components, GNOMM can be a useful tool in the study of their structure, function, and implications in diseases. GNOMM is available at http://bioinformatics.biol.uoa.gr/GNOMM . © 2019 Wiley Periodicals, Inc. 相似文献
87.
Vassiliki Katsika-Tsigourakou 《Physica B: Condensed Matter》2009,404(20):3550-3553
The ac electrical measurements have been just reported for alkali halide mixed crystals that were melt grown from NaCl, KCl and KBr starting materials. They showed a nonlinear variation of all the electrical parameters with the bulk composition. In this short paper, we show that these mixed systems, depending on their major constituent, are classified into three categories in each of which, the activation energy for the ac conductivity increases linearly with BΩ, where B is the isothermal bulk modulus and Ω the mean volume per atom. In addition, the resulting three straight lines are formed to have almost the same slope. 相似文献
88.
89.
Metal matrix composites containing titanium nitrides or titanium borides raise great interest to researchers due to their high wear resistance and enhanced corrosion properties. In the present investigation composite coatings containing both titanium nitrides/carbonitrides and titanium diborides were produced on plain steel substrates using the plasma transferred arc (PTA) technique with argon-nitrogen mixtures in the plasma and shielding gas. The microstructure of the metal matrix composites (MMC) obtained was thoroughly studied and found to consist of primary titanium diboride particles surrounded by a eutectic matrix containing, apart from ferrite, both titanium diboride and titanium carbonitride particles. The wear behavior of the composite coatings was assessed by pin on disk experiments. The wear rate against both a tool steel counterbody and an alumina counterbody is of the order of 10−4 mm3/m. The friction coefficient for both the alloyed layer-tool steel system and the alloyed layer-alumina system increases up to sliding speed of 0.30 m/s and then decreases, when the sliding speed increases further. Specifically, the friction coefficients are varied between the values 0.5 and 0.65. The wear mechanism for the tribosystem alloyed layer-tool steel is characterized by plastic deformation and adherence of material coming from the alloyed layer to the surface of the ball, while for the tribosystem alloyed layer-alumina ball, severe plastic deformation and formation of oxide layer are observed. 相似文献
90.
Vassiliki A. Tegoulia Stuart L. Cooper 《Colloids and surfaces. B, Biointerfaces》2002,24(3-4):217-228
Staphylococcus aureus adhesion on self-assembled monolayers (SAMs) formed by the adsorption of alkanethiols on transparent gold films has been studied in real time under well-defined flow conditions using a radial flow chamber and an automated videomicroscopy system. SAMs terminated with methyl, hydroxyl, carboxylic acid and tri(ethylene oxide) groups were investigated. SAMs were characterized using contact angle measurements, ellipsometry and X-ray photoelectron spectroscopy. Adhesion experiments using the Newman strain of S. aureus were performed on bare monolayers and monolayers pre-incubated with fibrinogen. Adhesion was found to be lowest on the ethylene oxide-bearing surfaces, followed by the hydroxyl surfaces. Adhesion on the carboxylic- and methyl-terminated SAMs was much higher. Bacterial adhesion was higher on the hydrophobic surfaces. Pre-incubation of surfaces with fibrinogen minimized the effect of the surface properties of the substrate. Adhesion was increased on all surfaces when fibrinogen was present and no significant differences were observed between adhesion to the different SAMs. This study showed that surfaces rich in ethylene oxide groups can be effectively used to prevent bacterial adhesion. However, under physiological conditions, most of the substrate properties are masked by the presence of the adsorbed protein layer and the effect of substrate properties on bacteria adhesion under flow is minimal. 相似文献