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991.
The enantioresolution of zolmitriptan was performed using cyclodextrin (CD)-modified capillary zone electrophoresis (CZE)
with hydroxypropyl-β-CD (HP-β-CD) as the chiral selector. The influence of experimental conditions on the enantioseparation
of zolmitriptan, such as pH, temperature, applied voltage, and concentrations of running electrolyte and CD, was systematically
investigated, obtaining a baseline separation of two enantiomers by the use of a 25 mM sodium dihydrogen phosphate (SDPH)
running electrolyte (pH 2.4) containing 30 mM HP-β-CD at 15 °C. Binding constants for each enantiomer–HP-β-CD pair at different
temperatures, as well as thermodynamic parameters for binding, were calculated. A nonlinear van’t Hoff plot was obtained,
indicating that the thermodynamic parameters of complexation were temperature-dependent for zolmitriptan enantiomers. The
significant contribution of the enthalpy difference to the Gibbs free energy change suggested a stereomeric barrier mechanism
for chiral recognition.
Figure Resolution of zolmitriptan enantiomers was achieved by using CD-modified CZE
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
992.
Amanda L. Santos Gilberto O. Chierice Kenneth S. Alexander Alan Riga Ellen Matthews 《Journal of Thermal Analysis and Calorimetry》2009,96(3):821-825
Eugenol is the main volatile compound extracted oil from clove bud, Syzygium aromaticum L., and used in traditional medicine, as a bactericide, fungicide, anesthetic, and others. Its extraction was performed using
hydrodistillation which is the most common extraction technique. Its components and thermal behavior were evaluated using
gas chromatography (GC) and differential scanning calorimetry (DSC), which provide a better characterization of these natural
compounds. This extracted product was compared to the standard eugenol results. The GC results suggested ~90% eugenol was
found in the total extracted oil, and some of its boiling characteristics were 270.1 °C for peak temperature and 244.1 J g−1 for the enthalpy variation.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
993.
Wang F Weidt S Xu J Mackay CL Langridge-Smith PR Sadler PJ 《Journal of the American Society for Mass Spectrometry》2008,19(4):544-549
Reactions of the anticancer complex [(eta(6)-bip)Ru(en)Cl](+) (where bip is biphenyl and en is ethylenediamine) with the tripeptide glutathione (gamma-L-Glu-L-Cys-Gly; GSH), the abundant intracellular thiol, in aqueous solution give rise to two ruthenium cluster complexes, which could not be identified by electrospray mass spectrometry (ESI-MS) using a quadrupole mass analyzer. Here we use Fourier transform ion cyclotron mass spectrometry (nanoLC-FT-ICR MS) to identify the clusters separated by nanoscale liquid chromatography as the tetranuclear complex [{(eta(6)-bip)Ru(GSO(2))}(4)](2-) (2) and dinuclear complex [{(eta(6)-bip)Ru(GSO(2))(2)}(2)](8-) (3) containing glutathione sulfinate (GSO(2)) ligands. Use of (18)OH(2) showed that oxygen from water can readily be incorporated into the oxidized glutathione ligands. These data illustrate the power of high-resolution MS for identifying highly charged multinuclear complexes and elucidating novel reaction pathways for metallodrugs, including ligand-based redox reactions. 相似文献
994.
The heterogeneously catalyzed liquid phase Fries rearrangement reaction of phenyl acetate was carried out on Beta zeolites reexchanged with different amounts of metal cations. The aim of this work was to determine the influence of the amount of Brønsted acid sites as the catalytic active centers on the conversion. Sodium and potassium ions as well as divalent calcium and zinc ions were used in the reexchange procedure. The conversion shows a linear dependency on the degree of ion reexchange following the theoretically expected values. So the results prove that the bridged hydroxyl groups are indeed the dominating active centers and that their strength seems to be independent of the degree of reexchange; consequently, their acidic strength should be identical. A special emphasis was placed on the reexchange with divalent metal ions. It was shown that one divalent ion is not able to replace two protons as is supposed to be necessary for the charge balance—so a 1:1 stoichiometry is needed to assume to explain the catalytic results. 相似文献
995.
The cytochrome P450 (P450) enzymes are mainly localized to the endoplasmic reticulum (ER), where they function within catalytic
complexes metabolizing xenobiotics and some endogenous substrates. However, certain members of families 1–3 were also found
in other subcellular compartments, such as mitochondria, plasma membrane, and lysosomes. The physiological function of these
enzymes in non-ER locations is not known, although plasma-membrane-associated P450s have been described to be catalytically
active and to participate in immune-mediated reactions with autoantibody formation that can trigger drug-induced hepatitis.
Several retention/retrieval mechanisms are active in the ER retention of the P450s and inverse integration of the translated
P450 into the ER membrane appears to be responsible for transport to the plasma membrane. Furthermore, hydrophilic motifs
in the NH2-terminal part have been suggested to be important for mitochondrial import. Phosphorylation of P450s has been described to
be important for increased rate of degradation as well as for targeting into mitochondria. It was also suggested that the
mitochondria-targeted P450s from families 1–3 could be active in drug metabolism using an alternative electron transport chain.
In this review we present an update of the field emphasizing studies concerning localization, posttranslational modification,
such as phosphorylation, and intracellular transport of microsomal P450s. 相似文献
996.
Inis Jenemann Susanne Kiefer E. Robens 《Journal of Thermal Analysis and Calorimetry》2008,94(3):607-612
The short survey covers the development of the balance since its invention in the Neolithic era. Scales have been used most
probably first as tools in trading, but already in Old Egyptian papyrus its use in techniques is documented. Its theory was
cleared by Aristotle and Archimedes and at least at that time it was used as a scientific instrument. Today the balance is
still the most widely used instrument in science and there are still improvements. 相似文献
997.
Using Stuttgart/Dresden effective core potentials MWB28, MWB60, and GTO valence basis sets (8s7p6d)/[6s5p3d], (8s7p6d)/[6s5p3d]
for Zr and Hf atoms and 6-311++G(3df,3pd) basis set for C, H, O, and Ti atoms, tight convergence criteria geometry optimizations
and harmonic frequency calculations are performed at B3LYP and B3LYP/IEF-PCM levels of theory so as to model the gas phase
and argon matrix infrared spectra of the tetrahedral molecules R2MH2 (R = D(H), CH3, OH; M = Ti, Zr, Hf). Influence of the transition metal and/or substituent group on the symmetric and asymmetric stretching
frequencies of the MH2 fragment of the R2MH2 molecules is investigated at both the levels of theory. The modelling of the argon matrix effect improves the agreement between
the calculated frequencies and the experimental ones. The calculated argon matrix to gas phase frequency shifts is compared
reasonably to the experimental argon to neon matrix shifts. 相似文献
998.
A. Varesano C. Tonin F. Ferrero Marinella Stringhetta 《Journal of Thermal Analysis and Calorimetry》2008,94(2):559-565
Electro-conducting doped polypyrrole was deposited by in situ oxidative polymerisation on PET non-wovens. Thermal properties were evaluated by means of DSC and TG in nitrogen and air.
Flame resistance tests reveal that coated PET fibres resist to direct contact with fire. By thermal analysis, it was found
that PPy reduces the temperature at which thermo-oxidative degradation of PET occurs. Polypyrrole-coated PET non-wovens were
heated above the melting point of PET for 30 min. After the heating the fibres become brittle and frail, but SEM observations
revealed that they maintained their fibrous shape. A loss of chlorine was found because of intense heating. 相似文献
999.
The molecular geometries and vibrational frequencies of aluminum oxyhalides, AlOX, and their dimers, (AlOX)2, have been calculated by MP2 and density functional methods. The monomeric molecules are linear while the dimers have a D
2h
-symmetry geometry with a four-membered ring, in which the oxygen atoms serve as bridging ligands. Different thermodynamic
properties have been calculated; for AlOBr and AlOI for the first time. 相似文献
1000.
3,5-Bis(2-hydroxyphenyl)-1H-1,2,4-triazole (H2La) and 4-[3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazol-1-yl]benzoic acid (H3Lb) have been prepared, and crystal structure of the intermediate 2-(2-hydroxyphenyl)-4H-1,3-benzoxazin-4-one has been determined. Temperature dependent 1H NMR spectroscopic measurements of H2La indicated dynamic behavior with the equilibrium between the two asymmetric tautomers. For H3Lb, pD-dependent 1H NMR spectroscopic measurements showed small but characteristic shifts in the range of 0 ≤ pD ≤ 1, indicative of a triazole
nitrogen atom protonation; the corresponding pK
a of 0.98 ± 0.04 was determined by spectrophotometric titrations. (H2O, 26°C, 1 M KCl/HCl). Formation of [FeIII(La)]+ (pH 2.5) and [FeIII(La)2]− (pH > 6) was verified by UV-Vis spectroscopy. Complex formation of H3Lb with Al3+ and VO2+ was investigated by 1H NMR spectroscopic titration and cyclic voltammetry, respectively. Single crystals of the phenoxo bridged [VVO(HLb)(EtO)]2·2EtOH were characterized by X-ray structural analysis.
Dedicated to Professor Milan Melník on the occasion of his 70th birthday 相似文献