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101.
Baldacci A Theurillat R Caslavska J Pardubská H Brenneisen R Thormann W 《Journal of chromatography. A》2003,990(1-2):99-110
γ-Hydroxybutyric acid (GHB), a minor metabolite or precursor of γ-aminobutyric acid (GABA), acts as a neurotransmitter/neuromodulator via binding to GABA receptors and to specific presynaptic GHB receptors. Based upon the stimulatory effects, GHB is widely abused. Thus, there is great interest in monitoring GHB in body fluids and tissues. We have developed an assay for urinary GHB that is based upon liquid–liquid extraction and capillary zone electrophoresis (CZE) with indirect UV absorption detection. The background electrolyte is composed of 4 mM nicotinic acid (compound for indirect detection), 3 mM spermine (reversal of electroosmosis) and histidine (added to reach a pH of 6.2). Having a 50 μm I.D. capillary of 40 cm effective length, 1-octanesulfonic acid as internal standard, solute detection at 214 nm and a diluted urine with a conductivity of 2.4 mS/cm, GHB concentrations ≥2 μg/ml can be detected. Limit of detection (LOD) and limit of quantitation (LOQ) were determined to be dependent on urine concentration and varied between 2–24 and 5–60 μg/ml, respectively. Data obtained suggest that LOD and LOQ (both in μg/ml) can be estimated with the relationships 0.83 κ and 2.1 κ, respectively, where κ is the conductivity of the urine in mS/cm. The assay was successfully applied to urines collected after administration of 25 mg sodium GHB/kg body mass. Negative electrospray ionization ion-trap tandem mass spectrometry was used to confirm the presence of GHB in the urinary extract via selected reaction monitoring of the m/z 103.1→m/z 85.1 precursor–product ion transition. Independent of urine concentration, this approach meets the urinary cut-off level of 10 μg/ml that is required for recognition of the presence of exogenous GHB. Furthermore, data obtained with injection of plain or diluted urine indicate that CZE could be used to rapidly recognize GHB amounts (in μg/ml) that are ≥ 4 κ. 相似文献
102.
L. Viaene D. Meerschaut M. Van Der Auweraer F. C. De Schryver F. Wilkinson 《Research on Chemical Intermediates》1995,21(7):711-723
The absorption and fluorescence of 16-(1-pyrene)-hexadecanoicacid adsorbed on silica have been investigated. Time-resolved transient diffuse reflectance spectra were recorded following pulsed nanosecond laser excitation at 355 nm of pyrene, 1-methylpyrene and 16-(1-pyrene)-hexadecanoicacid adsorbed on silica. In addition to a rapidly decaying transient, absorbing at 420 nm assigned as the triplet state, and of the radical cation, absorbing at 460 nm, another long living transient species absorbing at 420 nm was observed for 16-(1-pyrene)-hexadecanoic acid. The decay is reversible but complete recovery takes several hours. Although no definitive assignment could be made for this transient several possibilities are discussed. The radical cations of the investigated molecules are formed by a biphotonic process. The non-exponential decay of the radical cations could be analyzed in the framework of a Gaussian distribution of free energy barriers. 相似文献
103.
Fumio Watari J. Van Landuyt P. Delavignette S. Amelinckx 《Journal of solid state chemistry》1979,29(1):137-150
A study by means of electron microscopy at high resolution has enabled the analysis of the microstructure of hematite as produced by dehydration from goethite. The apparently “polycrystalline” structure is found to consist of aggregates of well-oriented twin-related hematite crystals, separated by regularly spaced H(001) walls of voids resulting from the loss of water. The material is thus broken up into blocks with sizes smaller than 50 Å. The crystallography of the twinned structure can be analyzed by electron diffraction data and dark-field imaging. These aggregates of hematite crystals provide an ideal mosaic structure. In particular the effect of this mosaic structure on the individual reflections of the diffraction patterns has been analyzed and discussed. 相似文献
104.
Zhu Y Nikolic D Van Breemen RB Silverman RB 《Journal of the American Chemical Society》2005,127(3):858-868
Nitric oxide synthases (NOS) are hemoproteins that catalyze the reaction of L-arginine to L-citrulline and nitric oxide. N-(3-(Aminomethyl)benzyl)acetamidine (1400W) was reported to be a slow, tight-binding, and highly selective inhibitor of iNOS in vitro and in vivo. Previous mechanistic studies reported that 1400W was recovered quantitatively after iNOS fully lost its activity and modification to iNOS was not detected. Here, it is shown that 1400W is a time-, concentration-, and NADPH-dependent irreversible inactivator of iNOS. HPLC-electrospray mass spectrometric analysis of the incubation mixture of iNOS with 1400W shows both loss of heme cofactor and formation of biliverdin, as was previously observed for iNOS inactivation by another amidine-containing compound, N5-(1-iminoethyl)-L-ornithine (L-NIO). The amount of biliverdin produced corresponds to the amount of heme lost by 1400W inactivation of iNOS. A convenient MS/MS-HPLC methodology was developed to identify the trace amount of biliverdin produced by inactivation of iNOS with either 1400W or L-NIO to be biliverdin IXalpha out of the four possible regioisomers. Two mechanisms were previously proposed for iNOS inactivation by L-NIO: (1) uncoupling of the heme peroxide intermediate, leading to destruction of the heme to biliverdin; (2) abstraction of a hydrogen atom from the amidine methyl group followed by attachment to the heme cofactor, which causes the enzyme to catalyze the heme oxygenase reaction. The second mechanistic proposal was ruled out by inactivation of iNOS with d3-1400W, which produced no d2-1400W. Detection of carbon monoxide as one of the heme-degradation products further excludes the covalent heme adduct mechanism. On the basis of these results, a third mechanism is proposed in which the amidine inactivators of iNOS bind as does substrate L-arginine, but because of the amidine methyl group, the heme peroxy intermediate cannot be protonated, thereby preventing its conversion to the heme oxo intermediate. This leads to a change in the enzyme mechanism to one that resembles that of heme oxygenase, an enzyme known to convert heme to biliverdin IXalpha. This appears to be the first example of a compound that causes irreversible inactivation of an enzyme without itself becoming modified in any way. 相似文献
105.
Liquid-liquid cloud point diagrams of solutions of nearly monodisperse samples of polystyrene (PS), and binary mixtures of nearly monodisperse PS’s, both in methylcyclohexane (MCH), were determined for several polymer molecular weights (Mw) at 0.1 MPa. The bimodal mixtures (PS[Mw(1),ρ(1)] + PS[Mw(2),ρ(2)], Mw(1)=90×103 g/mol, Mw(2)=13×103 g/mol, 5.78 × 103 g/mol, and 2.2 × 103 g/mol, ρ=1.06) were prepared constraining 〈Mw〉=38.6×103 g/mol, ρ=Mw/Mn is the polydispersity index. In each case the cloud point curves (CPC’s) for the bimodal mixtures are strongly skewed, lying well above CPC for 〈Mw〉 when φ<φCRITICAL, and below CPC for 〈Mw〉 when φ>φCRITICAL; φ is volume fraction polymer in the polymer/solvent mixture. The experimental results are discussed in the context of empirical and mean-field representations. 相似文献
106.
The uptake of several actinides [U(VI), Th(IV), Am(III), Cm(III)] and fission products was investigated from nitric acid solutions by two novel extraction chromatographic sorbents containing 2-(2-hexyloxy-ethyl)-N,N'-dimethyl-N,N'-dioctyl-malonamide (DMDOHEMA) and N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA), respectively. The kinetics of the uptake of actinides was studied. The sorption of metal ions fromz simulated Low Level Liquid Waste (LLLW) solutions was evaluated. The results of these experiments revealed that the actinides and lanthanides could be separated from the bulk of other fission products in simulated LLLW solutions on both sorbents.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
107.
Experimental investigations on binary liquid mixtures near the critical mixing point are presently leading to a controversy about the anomaly in the thermal conductivity. A photopyroelectric technique is used to determine the thermal conductivity and the effusivity of the binary liquid mixture n-butoxyethanol-water at its critical concentration near the critical mixing point. It is proven that, contrary to previous reports, there is no critical enhancement in the thermal conductivity. The specific heat capacity is calculated from these results and compared with the results from measurements performed by adiabatic scanning calorimetry. 相似文献
108.
De Vriendt K Sandra K Desmet T Nerinckx W Van Beeumen J Devreese B 《Rapid communications in mass spectrometry : RCM》2004,18(24):3061-3067
The use of electrospray ionization mass spectrometry (ESI-MS) for studying non-covalent interactions between macromolecules and ligands is well established. ESI-MS can be a useful tool for the determination of dissociation constants between molecules in the gas phase. We validate this method by studying the binding of the catalytic domain of cellobiohydrolase I (CBH I) from Trichoderma reesei to the disaccharide inhibitor cellobiose. The method was further applied to study two newly synthesized cellobiose derivatives (m-iodobenzyl 2-deoxy-2-azido-beta-cellobioside and p-benzyloxybenzyl beta-cellobioside). In a titration experiment, peak areas of different charge states of the free enzyme and the complex were summed in order to determine the dissociation constant. For cellobiose and m-iodobenzyl 2-deoxy-2-azido-beta-cellobioside, the calculated values are in good agreement with those reported from either displacement titration or equilibrium binding experiments in solution. Due to non-specific binding, the dissociation constant of p-benzyloxybenzyl beta-cellobioside does not correspond with the solution-based value. Our results indicate the need for careful interpretation of data sets when using nanoESI to study non-covalent interactions. 相似文献
109.
Anna Worobiec Lucyna Samek Zoya Spolnik Velichka Kontozova Elzbieta Stefaniak René Van Grieken 《Mikrochimica acta》2006,156(3-4):253-261
The St. Michael Archangel’s Church in Szalowa, Poland, was selected for closer investigation with respect to the indoor/outdoor
air exchange and its influence on the air quality and work arts preservation. Chemical composition, size and abundance of
particulate matter and concentration of gases NO2, SO2, O3 inside and outside the church were determined. To study seasonal variation of the weather condition (temperature, inversion
level, wind direction) and the influence of seasonal sources of the air pollution (like heating of the nearby houses), samples
were collected in winter and summer time. It was stated that suspended particulate matter inside the wooden church has in
general an outdoor source. Several groups of particles were distinguished such as the organic ones, soil dust, nitrates and
sulphates. In case of organic and soil dust particles, the concentration inside was higher than outside. From the results,
in comparison to literature data, one can conclude that accumulation of particulate suspended matter in the church is more
intense than in other types of buildings. Gaseous pollutants were detected but their concentration was negligible. 相似文献
110.
J.C.M. De Wit W.H. Van Riemsdijk M.M. Nederlof D.G. Kinniburgh L.K. Koopal 《Analytica chimica acta》1990
Humic substances are characterized by a variable electric potential and by a variety of binding sites leading to chemical heterogeneity. Binding of ions to these substances is influenced by both factors. A methodology based on acid—base titrations at several salt levels is presented that allows for the assessment of an appropriate electrostatic double-layer model and the intrinsic proton affinity distribution. The double-layer model is used for the conversion of pH to pHS for each data point, where HS is the proton concentration in the diffuse layer near the binding site. It is shown that with an appropriate double-layer model the proton binding curves at different salt levels converge into one “master curve” when plotted as a function of pHS. The intrinsic proton affinity distribution can then be derived from the “master curve” using the LOGA method. A rigorous analysis of metal binding to humic substances is complex and in practice is not feasible. Under two different (simplifying) assumptions, namely fully coupled and uncoupled binding, it is shown how intrinsic metal ion affinity distributions can be obtained. Model calculations show that apparent metal ion affinity distributions do not resemble the intrinsic metal ion affinity distribution. 相似文献