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101.
Camilla Fonseca Silva Luciana Guimarães Keyller Bastos Borges Clebio Soares Nascimento Jr. 《Chirality》2020,32(1):53-63
Dinotefuran is a low-cost agrochemical considered a highly toxic product. In this sense, there is a need for its constant environmental, biological, and food control, aiming to ensure its use to humans as well as to preserve biodiversity and ecosystems. In the present work, we developed an experimental and theoretical method for dinotefuran chiral discrimination. According to the main results, the dinotefuran enantioselective separation was efficiently optimized by high-performance liquid chromatography evaluating the influence of different percentage compositions in the mobile phase to improve the resolution of the peaks in the chromatogram. The novelty of this work was the proposition of a reduced molecular model for the chiral selector amylose-Tris-(3,5-dimethylphenylcarbamate) polysaccharide that was able to adequately describe at the molecular level its interaction with the dinotefuran enantiomers. Besides, the thermodynamic and structural parameters obtained via density functional theory calculations pointed out the chiral discrimination as well as the enantiomeric elution order of the analyte studied, confirming the experimental data, thus validating our proposed method. Finally, hydrogen bonds and repulsive interactions played a key role in the discrimination between the diastereomeric complexes, and consequently, for the dinotefuran enantioselective separation. 相似文献
102.
A SXRF method for determining the relative concentration of trace elements in plasma protein affected by cisplatin 总被引:2,自引:0,他引:2
This article presents an analytical method for the determination of the relative concentrations of trace elements in plasma
protein by gel chromatography combined with SXRF (synchrotron radiation X-ray fluorescence). The fraction of plasma protein
of male Kunming mice (body weight 24.2±0.3 g), treated with a cisplatin ip injection at a dose of 10 mg/kg, was obtained by
the separation of a Sephadex G-50 column (buffered with ammonium acetate, pH 5.7). The SXRF experiments were performed at
the Beijing Electron Positron Collider synchrotron radiation facility. The elements (Pt, S, Ca, Fe, Ni, Cu, Zn, Se, Br, and
Sr) in the fraction of the plasma proteins (>22 kDa) were assayed using highly sensitive SXRF. The relative concentrations
of elements were calculated by a normalization of Compton scattering intensity around 22 keV, after the normalization for
the collection time of the X-ray spectrum and the counting of the ion chamber, and subtracting the contribution of the polycarbonate
film for the supporting sample. The determination could prove that the element Pt in plasma was bound with macromolecular
protein. Cu and S were present in the fraction of the protein in mice treated with cisplatin increase, and their ratios of
treated/control were 1.66±0.06 and 1.78±0.33, respectively; Zn decreased to a ratio of 0.78±0.09. Our results are in agreement
with others that cisplatin exposure leads to a marked loss of kidney copper and a moderate rise in kidney zinc. However, this
article primarily describes one of the analytical methods used; it does not emphasize the results of the effect of cisplatin
on trace elements in plasma protein. 相似文献
103.
Scytalidoglutamic peptidase (SGP) is the first-discovered member of the eqolisin family of peptidases with a unique structure and a presumed novel catalytic dyad (E136 and Q53) [Fujinaga et al., PNAS 101 (2004) 3364-3369]. Mutants of SGP, E136A, Q53A, and Q53E lost both the autoprocessing and enzymatic activities of the wild-type enzyme. Coupled with the results from the structural analysis of SGP, Glu136 and Gln53 were identified as the catalytic residues. The substrate specificity of SGP is unique, particularly, in the preference at the P3 (basic amino acid), P1' (small a.a.), and P3' (basic a.a.) positions. Superior substrates and inhibitors have been synthesized for kinetic studies based on the results reported here. kcat, Km, and kcat/Km of SGP for D-Dap(MeNHBz)-GFKFF*ALRK(Dnp)-D-R-D-R were 34.8 s-1, 0.065 microM, and 535 microM-1 s-1, respectively. Ki of Ac-FKF-(3S,4S)-phenylstatinyl-LR-NH2 for SGP was 1.2x10(-10) M. Taken together, we can conclude that SGP has not only structural and catalytic novelties but also a unique subsite structure. 相似文献
104.
《Expert review of proteomics》2013,10(6):815-829
Viruses constantly adapt to and modulate the host environment during replication and propagation. Both DNA and RNA viruses encode multifunctional proteins that interact with and modify host cell proteins. While viral genomes were the first complete sequences known, the corresponding proteomes are only now elucidated, with some surprising results. Even more daunting is the task to globally monitor the impact of viral infection on the proteome of the host cell and many technical hurdles must still be overcome in order to facilitate robust and reproducible measurements. Further complicating the picture is the dynamic nature of proteins, including post-translational modifications, enzymatic cleavage and activation or destruction by proteolytic events. Nevertheless, several promising studies have been published using high-throughput methods directly measuring protein abundance. Particularly, quantitative or semiquantitative mass spectrometry-based analysis of viral and cellular proteomes are now being used to characterize viruses and their host interaction. In addition, the full set of interactions between viral and host proteins, the interactome, is beginning to emerge, with often unexpected interactions that need to be carefully validated. In this review, we will discuss two major areas of viral proteomics: first, virion proteomics (such as the protein characterization of viral particles) and second, proteoviromics, including the viral protein interactomics and the quantitative analysis of host cell proteome during viral infection. 相似文献
105.
A high‐performance liquid chromatography (HPLC) method was established to detect Xeljanz enantiomers in active pharmaceutical ingredients (APIs) and tablets. The separation was achieved on a Chiralpak IC column using a mobile phase of hexane‐ethanol‐diethylamine (65:35:0.1, v/v). The detection wavelength was 289 nm. The peak areas and the enantiomer concentrations in the range of 0.15–2.25 μg?mL?1 were in high linearity, with correlation coefficients higher than 0.999. The recoveries were 86.44% at the concentrations of 7.5, 18.75, and 37.5 μg?mL?1. The limit of detection (LOD) and limit of quantification (LOQ) were 0.042 and 0.14 μg?mL?1, respectively. This HPLC method is suitable for detecting the enantiomers of Xeljanz in its APIs and tablets. Chirality 27:235–238, 2015. © 2014 Wiley Periodicals, Inc. 相似文献
106.
An Edge Selection Mechanism for Chirally Selective Solubilization of Binaphthyl Atropisomeric Guests by Cholate and Deoxycholate Micelles 下载免费PDF全文
Kyle W. Eckenroad Gregory A. Manley Jenna B. Yehl Ross T. Pirnie Timothy G. Strein David Rovnyak 《Chirality》2016,28(7):525-533
Combining micellar electrokinetic capillary chromatography (MEKC) and nuclear magnetic resonance (NMR) experimentation, we shed light on the structural basis for the chirally selective solubilization of atropisomeric binaphthyl compounds by bile salt micelles comprised of cholate (NaC) or deoxycholate (NaDC). The model binaphthyl analyte R,S‐BNDHP exhibits chirally selective interactions with primary micellar aggregates of cholate and deoxycholate, as does the closely related analyte binaphthol (R,S‐BN). Chiral selectivity was localized, by NMR chemical shift analysis, to the proton at the C12 position of these bile acids. Correspondingly, MEKC results show that the 12α‐OH group of either NaC or NaDC is necessary for chirally selective resolution of these model binaphthyl analytes by bile micelles, and the S isomer is more highly retained by the micelles. With NMR, the chemical shift of 12β‐H was perturbed more strongly in the presence of S‐BNDHP than R‐BNDHP. Intermolecular NOEs demonstrate that R,S‐BNDHP and R,S‐BN interact with a similar hydrophobic planar pocket lined with the methyl groups of the bile salts, and are best explained by the existence of an antiparallel dimeric unit of bile salts. Finally, chemical shift data and intermolecular NOEs support different interactions of the enantiomers with the edges of dimeric bile units, indicating that R,S‐BNDHP enantiomers sample the same binding site preferentially from opposite edges of the dimeric bile unit. Chirality 28:525–533, 2016. © 2016 Wiley Periodicals, Inc. 相似文献
107.
Molecular dynamic simulations of systems of single-walled carbon nanotubes (CNTs) in liquid crystalline solvents were performed, in order to investigate the effect of the molecular structure and phase of the liquid crystal (LC) on the interactions between the CNTs. Three different LC molecules (5CB, 8CB and 5CF) were considered in our study. Our results with 5CB and 8CB suggest that increasing the chain length of the hydrophobic part of the LC molecule by three carbon atoms is insufficient to decrease the tendency for the CNTs to aggregate in the LCs. Additionally, varying the phase of the LC is also insufficient to decrease the aggregation tendency of the CNTs. However, simulations with 5CF (which has fluorine atoms in the head group of the LC molecule) suggest that this LC solvent can decrease the tendency of the CNTs to aggregate. This study is relevant to assist experimentalists with the development of high-quality dispersions of large concentrations of CNTs in the LCs. 相似文献
108.
S. M. Stanis˘ić Stojić L. M. Ignjatović S. Popov S. Škrivanj A. R. Đorđević A. Stojić 《Plant biosystems》2016,150(1):104-110
An experiment was undertaken to evaluate the effect of liquid manure amendment on heavy metal accumulation in wheat and barley. For this purpose, both kinds of seedlings were grown simultaneously in a Petri dish, while wheat seedlings were also grown in pots containing unpolluted agricultural soil. All of the seedlings were irrigated with one of the three prepared solutions: artificial rainwater solution, heavy metal solution and liquid manure solution containing NH4NO3, H3PO4 and KOH along with equal amounts of heavy metals as in the second solution. Twenty days later, 1 g of plant tissue was digested with the mixture of HNO3 and H2O2 for ICP-OES/HG-ICP-OES analysis. The results showed that the uptake of arsenic and mercury was highest for both plants grown in a Petri dish. Furthermore, the wheat grown in a Petri dish also had a high content of nickel, cadmium and copper, while the pot-grown wheat contained high amounts of iron and manganese, probably due to the adsorption of nickel, cadmium, copper and mercury on soil phases. The lower uptake of all heavy metals was observed after the amendment of liquid manure, with the exception of manganese in wheat and mercury in all plants. 相似文献
109.
Vera Muders Silke Kerruth Víctor A. Lórenz-Fonfría Christian Bamann Joachim Heberle Ramona Schlesinger 《FEBS letters》2014
Channelrhodopsin-1 from Chlamydomonas augustae (CaChR1) is a light-activated cation channel, which is a promising optogenetic tool. We show by resonance Raman spectroscopy and retinal extraction followed by high pressure liquid chromatography (HPLC) that the isomeric ratio of all-trans to 13-cis of solubilized channelrhodopsin-1 is with 70:30 identical to channelrhodopsin-2 from Chlamydomonas reinhardtii (CrChR2). Critical frequency shifts in the retinal vibrations are identified in the Raman spectrum upon transition to the open (conductive P2380) state. Fourier transform infrared spectroscopy (FTIR) spectra indicate different structures of the open states in the two channelrhodopsins as reflected by the amide I bands and the protonation pattern of acidic amino acids. 相似文献
110.
Péter Nagy Zoltán Pálinkás Attila Nagy Barna Budai Imre Tóth Anita Vasas 《Biochimica et Biophysica Acta (BBA)/General Subjects》2014