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881.
Kim BY Swearingen CB Ho JA Romanova EV Bohn PW Sweedler JV 《Journal of the American Chemical Society》2007,129(24):7620-7626
Interfacing nanoscale elements into a microfluidic device enables a new range of fluidic manipulations. Nanocapillary array membranes (NCAMs), consisting of thin (5 microm < d < 20 microm) membranes containing arrays of nanometer diameter (10 nm < a < 500 nm) pores, are a convenient method of interfacing vertically separated microchannels in microfluidic devices that allow the external control of analyte transport between microfluidic channels. To add functionality to these nanopores beyond simple fluid transport, here we incorporate an antibody-based molecular recognition element onto the pore surface that allows selective capture, purification, and release of specific analytes from a mixture. The pores are fabricated by electroless plating of gold into the nanopores of an NCAM (Au-NCAM). An antibody is then immobilized on the Au-NCAM via gold-thiol chemistry as a thiolated fragment of antigen-binding (Fab') prepared by direct digestion of the antibody followed by reduction of the disulfide linkage on the hinge region. The successful immobilization and biological activity of the resultant Fab' through this protocol is verified on planar gold by fluorescence microscopy, scanning electron microscopy, and atomic force microscopy. Selective capture and release of human insulin is verified using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The relative mass spectral peak intensities for insulin versus nonantigenic peptides increase more than 20-fold after passing through the Fab'-Au-NCAM relative to the control Au-NCAM. The affinity-tagged Au-NCAM can be incorporated into microfluidic devices to allow the concentration, capture, and characterization of analytes in complex mixtures with high specificity. 相似文献
882.
Yu F Wolff JJ Amster IJ Prestegard JH 《Journal of the American Chemical Society》2007,129(43):13288-13297
A new method is presented for the retrieval of information on the conformation of glycosaminoglycan oligomers in solution. The method relies on the replacement of acetyl groups in isolated native oligomers with 13C labeled acetyl groups and the extraction of orientational constraints from residual dipolar couplings (RDCs) and chemical shift anisotropy (CSA) offsets observed in NMR spectra of partially oriented samples. A novel method for assignment of resonances based on the correlation of resonance intensities with isotope ratios determined from mass spectrometric analysis is also presented. The combined methods are used in conjunction with more traditional NMR structural data to determine the solution structure of a pentasaccharide, GalNAc6S(beta1-4)GlcA(beta1-3)GalNAc4S(beta1-4)GlcA(beta1-3)GalNAc4S-ol, derived by enzymatic hydrolysis of chondroitin sulfate. The geometry derived is compared to that for similar molecules that have been reported in the literature, and prospects for use of the new types of data in the study of protein-bound oligosaccharides are discussed. 相似文献
883.
Thalassinos K Jackson AT Williams JP Hilton GR Slade SE Scrivens JH 《Journal of the American Society for Mass Spectrometry》2007,18(7):1324-1331
Novel software has been developed to aid the interpretation of tandem mass spectrometry (MS/MS) data from synthetic polymers. The software is particularly focused toward aiding the end-group determination of these materials by significantly speeding up the interpretation process. This allows information on the initiator and/or chain transfer agents, used to generate the polymer, and the mechanism of termination to be inferred from the data much more rapidly. The software allows the validity of hypothesized structures to be rapidly tested by automatically annotating the data file using previously proposed fragmentation rules for synthetic polymers. Low-energy collision-induced dissociation (CID) data from methacrylate, styrene, and polyether oligomers are used as example data for the software. Exact-mass CID information was used to aid the understanding of the dissociation mechanism of the polymers. The software can use exact-mass data to provide more confidence in the results. The MS/MS results indicate that the fragmentation pathways are those previously proposed for these polymers. 相似文献
884.
Butirosin, an aminoglycoside antibiotic produced by Bacillus circulans, bears the unique (S)-4-amino-2-hydroxybutyrate (AHBA) side chain, which protects the antibiotic from several common resistance mechanisms. The AHBA side chain is advantageously incorporated into clinically valuable antibiotics such as amikacin and arbekacin by synthetic methods. Therefore, it is of significant interest to explore the biosynthetic origins of this useful moiety. We report here that the AHBA side chain of butirosin is transferred from the acyl carrier protein (ACP) BtrI to the parent aminoglycoside ribostamycin as a gamma-glutamylated dipeptide by the ACP:aminoglycoside acyltransferase BtrH. The protective gamma-glutamyl group is then cleaved by BtrG via an uncommon gamma-glutamyl cyclotransferase mechanism. The application of this pathway to the in vitro enzymatic production of novel AHBA-bearing aminoglycosides is explored with encouraging implications for the preparation of unnatural antibiotics via directed biosynthesis. 相似文献
885.
Aerosol optical tweezers coupled with Raman spectroscopy can allow the detailed investigation of aerosol dynamics. We describe here measurements of the evolving size, composition, and phase of single aqueous aerosol droplets containing the surfactant sodium dodecyl sulfate and the inorganic salt sodium chloride. Not only can the evolving wet particle size be probed with nanometer accuracy, but we show that the transition to a metastable microgel particle can be followed, demonstrating that optical tweezers can be used to manipulate both spherical and non-spherical aerosol particles. Further, through the simultaneous manipulation and characterization of two aerosol droplets of different composition in two parallel optical traps, the phase behavior of a surfactant-doped particle and a surfactant-free droplet can be compared directly in situ. We also illustrate that the manipulation of two microgel particles can allow studies of the coagulation and interaction of two solid particles. Finally, we demonstrate that such parallel measurements can permit highly accurate comparative measurements of the evolving wet particle size of a surfactant-doped droplet with a surfactant-free droplet. 相似文献
886.
The partitioning of an immiscible and volatile organic component between the gas and aqueous condensed phases of an aerosol is investigated using optical tweezers. Specifically, the phase segregation of immiscible decane and aqueous components within a single liquid aerosol droplet is characterized by brightfield microscopy and by spontaneous and stimulated Raman scattering. The internally mixed phases are observed to adopt equilibrium geometries that are consistent with predictions based on surface energies and interfacial tensions and the volume fractions of the two immiscible phases. In the limit of low organic volume fraction, the stimulated Raman scattering signature is consistent with the formation of a thin film or lens of the organic component on the surface of an aqueous droplet. By comparing the nonlinear spectroscopic signature with Mie scattering predictions for a core-shell structure, the thickness of the organic layer can be estimated with nanometer accuracy. Time-dependent measurements allow the evolving partitioning of the volatile organic component between the condensed and vapor phases to be investigated. 相似文献
887.
Szanyi J Kwak JH Kim do H Wang X Hanson J Chimentao RJ Peden CH 《Chemical communications (Cambridge, England)》2007,(9):984-986
Exposure of NO(2)-saturated BaO/gamma-Al(2)O(3) NO(x) storage materials to H(2)O vapour results in the conversion of surface nitrates to Ba(NO(3))(2) crystallites, causing dramatic morphological changes in the Ba-containing phase, demonstrating a role for water in affecting the NO(x) storage/reduction properties of these materials. 相似文献
888.
The conversion of primary amines into secondary amines has been achieved using alcohols as the alkylating agent, catalysed by [Ru(p-cymene)Cl2]2 and a bidentate phosphine ligand. 相似文献
889.
Yoon ZS Noh SB Cho DG Sessler JL Kim D 《Chemical communications (Cambridge, England)》2007,(23):2378-2380
Using the bidirectional NICS scan method in conjunction with two-photon absorption (TPA) measurements, it has proved possible to determine the relationship between pi-conjugation and aromaticity in two structurally related expanded porphyrin systems, sapphyrin and inverted sapphyrin, and establish that differences in these defining factors depend on the presence or absence of a key sp3 hybrid molecular orbital within the macrocyclic periphery. 相似文献
890.
Steed JW Goeta AE Lipkowski J Swierczynski D Panteleon V Handa S 《Chemical communications (Cambridge, England)》2007,(8):813-815
Templation of a daughter phase by a parent crystal results from an equilibrating mixture of two very different copper(ii) N,N',N'-trimethyltriazacyclononane complexes. 相似文献