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81.
The synthesis and characterization of novel optically-active macrocycles, obtained by esterification reaction from a binaphthyl-containing diol and phthalic or terephthalic acids, and possessing overall D2 or D3 symmetry, is described. 相似文献
82.
Dalvit C Ardini E Flocco M Fogliatto GP Mongelli N Veronesi M 《Journal of the American Chemical Society》2003,125(47):14620-14625
High-throughput screening is usually the method of drug-lead discovery. It is now well accepted that, for a functional assay, quality is more important than quantity. The ligand-based or protein-based NMR screening methodologies for detecting compounds binding to the macromolecular target of interest are now well established. A novel and sensitive NMR method for rapid, efficient, and reliable biochemical screening is presented. The method named 3-FABS (three fluorine atoms for biochemical screening) requires the labeling of the substrate with a CF(3) moiety and utilizes (19)F NMR spectroscopy for the detection of the starting and enzymatically modified substrates. The method allows for high-quality screening of large compound or natural product extract collections and for measuring their IC(50) values. Applications of this technique to the screening of inhibitors of the Ser/Thr kinase AKT1 and the protease trypsin are presented. In addition, an interesting application of 3-FABS to functional genomics is also presented. 相似文献
83.
Romanato Filippo Berti Marina Mazzer Massimo Drigo Antonio Vittorio Lazzarini Laura Franzosi Paolo Salviati Giancarlo Bertone Daniele 《Mikrochimica acta》1994,114(1):431-440
A combined method for structural characterization of strained epitaxial heterostructures involving different techniques such as Rutherford backscattering spectrometry (RBS), multiple crystal X-ray diffractometry (MCD) and transmission electron microscopy (TEM) is presented. In order to obtain a complete characterization of the analysed structure, three different quantities are measured independently: the epilayer thickness, the density of misfit dislocations which may appear at the interface, and the significant components of the strain tensor, mainly the tetragonal distortion, affecting the epilayer lattice. In this way the thermodynamic state and the mechanisms of plastic deformation of the structures can be fully investigated. In this contribution we present and discuss the experimental results concerning a set of InP/GaAs samples having different layer thicknesses ranging from 5 to 500 nm. The thickness of the samples has been determined by RBS. Measurements of in-plane strain and tetragonal distortion have been performed by MCD and RBS-channelling respectively, finally TEM has been used for determining the defects densities and distribution. 相似文献
84.
Giancarlo Cravotto Marina Beggiato Giovanni Palmisano Stefano Tollari Werner Bonrath 《Tetrahedron letters》2005,46(13):2267-2271
Pd-catalyzed homo- and cross-couplings of boronic acids and aryl halides were successfully carried out both in aqueous media under high-intensity ultrasound (US) and in DME under microwave (MW). Heterogeneous catalysis with Pd/C was employed, avoiding phosphine ligands and phase-transfer catalysts. In a trial series involving 15 different iodo- and bromoaryls and 7 boronic acids, both energy sources drastically reduced reaction times affording biaryls in acceptable to good yields. With palladium(II) acetate as catalyst, electron-deficient aryl chlorides also reacted, affording a few biaryls in acceptable yields. Ullmann-type zinc-mediated homocoupling of iodo- and bromoaryls in the presence of Pd/C under CO2 atmosphere was achieved in aqueous media under US, though not under MW. Suzuki homo- and cross-couplings were also carried out in a new reactor developed in our laboratory, featuring combined US and MW irradiation, further improving a green synthetic method. 相似文献
85.
Dalvit C Flocco M Veronesi M Stockman BJ 《Combinatorial chemistry & high throughput screening》2002,5(8):605-611
High-throughput ligand-based NMR screening with competition binding experiments is extended to (19)F detection. Fluorine is a favorable nucleus for these experiments because of the significant contribution of the Chemical Shift Anisotropy (CSA) to the (19)F transverse relaxation of the ligand signal when bound to a macromolecular target. A low to moderate affinity ligand containing a fluorine atom is used as a reference molecule for the detection and characterization of new ligands. Titration NMR experiments with the selected reference compound are performed for finding the optimal set-up conditions for HTS and for deriving the binding constants of the identified NMR hits. Rapid HTS of large chemical mixtures and plant or fungi extracts against the receptor of interest is possible due to the high sensitivity of the (19)F nucleus and the absence of overlap with the signals of the mixtures to be screened. Finally, a novel approach for HTS using a reference molecule in combination with a control molecule is presented. 相似文献
86.
87.
Lukyanenko NG Kirichenko TI Lyapunov AY Mazepa AV Simonov YA Fonari MS Botoshansky MM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):262-270
The first three representatives of the new family of oxacyclophanes incorporating two 2,7-dioxyfluorenone fragments, connected by [-CH(2)CH(2)O-](m) spacers (m=2-4), have been synthesized. The yield of the smallest oxacyclophane (m=2) is considerably higher with respect to the larger ones (m=3 and m=4), which are formed in comparable yields. Molecular modeling and NMR spectra analysis of the model compounds suggest that an essential difference in oxacyclophanes yields is caused by formation of quasi-cyclic intermediates, which are preorganized for macrocyclization owing to intramolecular pi-pi stacking interactions between the fluorenone units. The solid-state structures of these oxacyclophanes exhibit intra- and intermolecular pi-pi stacking interactions that dictate their rectangular shape in the fluorenone backbone and crystal packing of the molecules with the parallel or T-shape arrangement. The crystal packing in all cases is also sustained by weak C--HO hydrogen bonds. FAB mass spectral analysis of mixtures of the larger oxacyclophanes (m=3 and m=4) and a paraquat moiety revealed peaks corresponding to the loss of one and two PF(6) (-) counterions from the 1:1 complexes formed. However, no signals were observed for complexes of the paraquat moiety with the smaller oxacyclophane (m=2). Computer molecular modeling of complexes revealed a pseudorotaxane-like incorporation of the paraquat unit, sandwiched within a macrocyclic cavity between the almost parallel-aligned fluorenone rings of the larger oxacyclophanes (m=3 and m=4). In contrast to this, only external complexes of the smallest oxacyclophane (m=2) with a paraquat unit have been found in the energy window of 10 kcal mol(-1). 相似文献
88.
Dalvit C Mongelli N Papeo G Giordano P Veronesi M Moskau D Kümmerle R 《Journal of the American Chemical Society》2005,127(38):13380-13385
NMR-based binding and functional screening performed with FAXS (fluorine chemical shift anisotropy and exchange for screening) and 3-FABS (three fluorine atoms for biochemical screening) represents a potential alternative approach to high-throughput screening for the identification of novel potential drug candidates. The major limitation of this method in its current status is its intrinsic low sensitivity that limits the number of tested compounds. One approach for overcoming this problem is the use of a cryogenically cooled (19)F probe that reduces the thermal noise in the receiver circuitry. Sensitivity improvement in the two screening techniques achieved with the novel cryogenic (19)F probe technology permits an increased throughput, detection of weaker binders and inhibitors (relevant in a fragment-based lead discovery program), detection of slow binders, and reduction in protein and substrate consumption. These aspects are analyzed with theoretical simulations and experimental quantitative performance evaluation. Application of 3-FABS combined with the cryogenic (19)F probe technology to rapid screening at very low enzyme concentrations and the current detection limits reached with this approach are also presented. 相似文献
89.
The impending implementation of billions of Internet of Things and wireless sensor network devices has the potential to be the next digital revolution, if energy consumption and sustainability constraints can be overcome. Ambient photovoltaics provide vast universal energy that can be used to realise near-perpetual intelligent IoT devices which can directly transform diffused light energy into computational inferences based on artificial neural networks and machine learning. At the same time, a new architecture and energy model needs to be developed for IoT devices to optimize their ability to sense, interact, and anticipate. We address the state-of-the-art materials for indoor photovoltaics, with a particular focus on dye-sensitized solar cells, and their effect on the architecture of next generation IoT devices and sensor networks.The impending implementation of billions of Internet of Things and wireless sensor network devices has the potential to be the next digital revolution, if energy consumption and sustainability constraints can be overcome. 相似文献
90.
Nonaqueous capillary electrophoresis (NACE) which makes use of organic solvents in place of conventional aqueous electrophoresis buffers is gaining increasing importance among modern separation techniques. Recently, it has been shown that amperometric detection in conjunction with acetonitrile-based NACE offers an extended accessible potential range and an enhanced long-term stability of the amperometric responses generated at solid electrodes. The present contribution takes advantage of the latter aspect to develop reliable systems for NACE with indirect electrochemical detection (IED). In this context, several compounds such as (ferrocenylmethyl)trimethylammonium perchlorate, tris(1,10-phenanthroline)cobalt(III) perchlorate and bis(1,4,7-triazacyclononane)nickel(II) perchlorate were studied regarding their suitability to act as electroactive buffer additives for IED in NACE. The performance characteristics for the respective buffer systems were evaluated. Tetraalkylammonium perchlorates served as model compounds for the optimization of the NACE-IED system. Target analytes choline and acetylcholine could easily be separated and determined by means of NACE-IED. In the case of a buffer system containing 10(-4) M tris(1,10-phenanthroline)cobalt(III) perchlorate the limits of detection were 2.5 x 10(-7) M and 4.6 x 10(-7) M for choline and acetylcholine, respectively. With the elaborated analytical procedure choline could be determined in pharmaceutical preparations. 相似文献