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131.
Andrew J. Barton Anthony R. J. Genge Nicholas J. Hill William Levason Simon D. Orchard Bhavesh Patel Gillian Reid Antony J. Ward 《Heteroatom Chemistry》2002,13(6):550-560
New routes developed recently to overcome the difficulties usually associated with the sequential introduction of Te centers into polytelluro‐ethers and the introduction of tellurium into macrocyclic compounds are described, including the synthesis of the first facultative telluro‐ethers, RTe(CH2)3Te(CH2)3TeR, R = Me or Ph, and the first tridentate S2Te‐donor macrocycles and a tetradentate S3Te‐donor macrocycle. The first systematic investigations into the preparation and characterization of coordination complexes of MX3 (M = As, Sb, Bi; X = Cl, Br, I) involving polydentate and macrocyclic thio‐ and seleno‐ether ligands are then discussed. The structures of examples of each class of compound are described, including the first examples of seleno‐ether adducts of the group 15 acceptors. A more limited range of telluro‐ether derivatives has been identified and the structure of the first example of this type is included. These species serve to demonstrate the wide structural diversity exhibited by these systems and the factors directing the assembly of these structures are highlighted. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:550–560, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10100 相似文献
132.
133.
Karla M. Robotti Hongfeng Yin Reid Brennen Lukas Trojer Kevin Killeen 《Journal of separation science》2009,32(20):3379-3387
Polyimide HPLC‐Chip devices containing poly(methylstyrene‐bis‐p‐vinylphenyl)ethane (MS/BVPE) stationary phase within the device channels and with wall attachment were prepared by thermally initiated free radical polymerization. The microfluidic devices were coupled to both UV and MS detectors. The potential of the MS/BVPE monolith as an alternative separation media within chip devices was investigated by side‐by‐side comparisons to particulate media within commercial devices. The chromatographic behavior of this stationary phase was comparable to particulate media for separations of proteins as the average peak width at half‐height was equal (6.2 s) for a separation within 8 min under gradient elution conditions. The ability to control the porosity characteristics of the MS/BVPE monolith with changes in polymerization time also extended its utility into small analyte (< 500 Da) applications, although more optimization is needed to match conventional RP media for these applications. The good mechanical stability of the MS/BVPE monolith within the microdevices enabled excellent run‐to‐run repeatability (%RSD retention time (? 0.16) and chip‐to‐chip reproducibility (%RSD retention time (1.4). The use of this material within enrichment channels also shows its potential value in more complex work flows. 相似文献
134.
Amunugama M Roberts KD Reid GE 《Journal of the American Society for Mass Spectrometry》2006,17(12):1631-1642
To enable the development of improved tandem mass spectrometry based methods for selective proteome analysis, the mechanisms, product ion structures, and other factors influencing the gas-phase fragmentation reactions of methionine side-chain derivatized "fixed-charge" phenacylsulfonium ion containing peptide ions have been examined. Dissociation of these peptide ions results in the exclusive characteristic loss of the derivatized side chain, thereby enabling their selective identification. The resultant product ion(s) are then subjected to further dissociation to obtain sequence information for subsequent protein identification. Molecular orbital calculations (at the B3LYP/6-31 + G (d,p) level of theory) performed on a simple peptide model, together with experimental evidence obtained by multistage dissociation of a regioselectively deuterated methionine derivatized sulfonium ion containing tryptic peptide, indicate that fragmentation of the fixed charge containing peptide ions occurs via SN2 reactions involving the N- and C-terminal amide bonds adjacent to the methionine side chain, resulting in the formation of stable cyclic five- and six-membered iminohydrofuran and oxazine product ions, respectively. These studies further indicate that the rings formed via these neighboring group reactions are stable to further dissociation by MS3. As a consequence, the formation of b- or y-type sequence ions are "skipped" at the site of cyclization. Despite this, complete sequence information is still obtained because of the presence of both cyclic products. 相似文献
135.
We report the first gas-phase observation of the electronic spectrum of a simple halocarbocation, CH2I+. The ion was generated rotationally cold (Trot approximately 20 K) using pulsed discharge methods and was detected via laser spectroscopy. The identity of the spectral carrier was confirmed by modeling the rotational contour observed in the excitation spectra and by comparison of ground state vibrational frequencies determined by single vibronic level emission spectroscopy with Density Functional Theory (DFT) predictions. The transition was assigned as 3A1 <-- X1A1. This initial detection of the electronic spectrum of a halocarbocation in the gas phase should open new avenues for study of the structure and reactivity of these important ions. 相似文献
136.
A femtosecond optical parametric oscillator is demonstrated that can operate in a regime where two signal pulses with well-separated center wavelengths are simultaneously resonant. Measurements show that the oscillator output contains a stable modulation at a frequency corresponding to the difference in the carrier-envelope phase-slip frequencies of the co-resonant pulses. The physical origin of this internal beat signal is attributed to second-order mixing effects, and its frequency is shown to be consistent with theory. 相似文献
137.
G. Reid Asbury Khalid Al-Saad William F. Siems Richard M. Hannan Herbert H. Hill 《Journal of the American Society for Mass Spectrometry》1999,10(10):983-991
Since the introduction of matrix-assisted laser desorption/ionization (MALDI) mass spectrometry the majority of research has focused on developing analytical methods for the qualitative determination of water soluble biomolecules such as proteins, peptides, carbohydrates, and oligonucleotides. This paper, however, reports the use of MALDI for the analysis of triacylglycerols and develops a new sample preparation method for nonpolar analytes. MALDI enables the rapid analyses of triacylglycerol (TAG) standards and mixtures of whole oils. The new method provides excellent shot to shot reproducibility, making quantification possible. Detection limits were in the mid femtomole range and the resolution was around 2000 which easily separated TAGs differing by one double bond. Sensitivity decreased with increasing molecular weight, causing biased results when analyzing complex mixtures with a significant range of molecular weight. In all cases only sodiated molecules and prompt losses of a fatty acid sodium salt were observed in the spectra. From this information it was possible to identify the three fatty acids on the glycerol backbone. Collision-induced dissociation was carried out on a triacylglycerol which proved to be useful for additional structural information, including the corroboration of the fatty acid components. With MALDI the percent compositions of TAGs in a standard olive oil was accurately determined. Finally, MALDI was used to examine the differences in lipid components between aged and fresh onion seeds, showing the potential of the technique for observing changes in lipid components in seeds. 相似文献
138.
The objective of this study is to measure the axial, circumferential, shear and radial residual stress distributions in three thick-walled glass fibre reinforced plastic (GFRP) filament-wound pipes, two of which are layered. The measurement of residual stresses was carried out using a recently published layer removal method which overcomes the limitations of previous techniques and can be applied to layered anisotropic pipes of any wall thickness. Layers of approximately 0.3 mm thickness were incrementally ground from the outer surface of the pipes. The resulting strains were measured on the inner surfaces. A least-squares polynomial was fitted to each measured data set, and used to calculate the corresponding stress distributions. All of the resulting axial, hoop and shear stress distributions adhere to the requirement of self-equilibrium and the radial stress distributions all vanish to zero at the inner and outer surfaces. The radial stresses of the layered pipes showed a tendency to have two peaks, one for each layer, a consequence of the two-stage manufacturing process of these pipes. The measured axial and hoop stresses of all three pipes were similar at the inner surfaces despite significant differences in the stiffnesses in the principal directions arising from different wind angles. 相似文献
139.
Ke J Bartlett PN Cook D Easun TL George MW Levason W Reid G Smith D Su W Zhang W 《Physical chemistry chemical physics : PCCP》2012,14(4):1517-1528
Several Ge(II) and Ge(IV) compounds were investigated as possible reagents for the electrodeposition of Ge from liquid CH(3)CN and CH(2)F(2) and supercritical CO(2) containing as a co-solvent CH(3)CN (scCO(2)) and supercritical CH(2)F(2) (scCH(2)F(2)). For Ge(II) reagents the most promising results were obtained using [NBu(n)(4)][GeCl(3)]. However the reproducibility was poor and the reduction currents were significantly less than the estimated mass transport limited values. Deposition of Ge containing films was possible at high cathodic potential from [NBu(n)(4)][GeCl(3)] in liquid CH(3)CN and supercritical CO(2) containing CH(3)CN but in all cases they were heavily contaminated by C, O, F and Cl. Much more promising results were obtained using GeCl(4) in liquid CH(2)F(2) and supercritical CH(2)F(2). In this case the reduction currents were consistent with mass transport limited reduction and bulk electrodeposition produced amorphous films of Ge. Characterisation by XPS showed the presence of low levels of O, F and C, XPS confirmed the presence of Ge together with germanium oxides, and Raman spectroscopy showed that the as deposited amorphous Ge could be crystallised by the laser used in obtaining the Raman measurements. 相似文献
140.
The binding of the fluorescent polyanionic probe 5(6)-carboxyfluorescein (CF) to various generations of dendrimers (G3-G7) was studied in buffered aqueous media by absorbance and fluorescence spectroscopy and by isothermal titration calorimetry (ITC). Absorbance, fluorescence, and fluorescence anisotropy data were collected concurrently by using a multiwell plate format. Because ITC does not depend on the presence of a chromophore/fluorophore for measurement, it allowed the exploration of concentration ratios otherwise unattainable in the spectroscopy experiments. Qualitative dendrimer generational trends were observed and found to be consistent with dendrimer size and charge. However, a number of significant anomalies were found in the spectroscopic titration profiles, which led us to propose a binding model comprising multiple, concurrent binding regimes. The predictive value of the model was ascertained by construction of a binding simulation, which was consistent with the experimental results. Finally, ITC results afforded insights into the fundamental thermodynamic properties of the binding process along with trends found across dendrimer generations. Thermodynamic data were found to be in accordance with the proposed model. 相似文献