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991.
Hammond C Lopez-Sanchez JA Ab Rahim MH Dimitratos N Jenkins RL Carley AF He Q Kiely CJ Knight DW Hutchings GJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(15):3927-3937
The reaction of glycerol with urea to form glycerol carbonate is mostly reported in the patent literature and to date there have been very few fundamental studies of the reaction mechanism. Furthermore, most previous studies have involved homogeneous catalysts whereas the identification of heterogeneous catalysts for this reaction would be highly beneficial. This is a very attractive reaction that utilises two inexpensive and readily available raw materials in a chemical cycle that overall, results in the chemical fixation of CO(2). This reaction also provides a route to up-grade waste glycerol produced in large quantities during the production of biodiesel. Previous reports are largely based on the utilisation of high concentrations of metal sulfates or oxides, which suffer from low intrinsic activity and selectivity. We have identified heterogeneous catalysts based on gallium, zinc, and gold supported on a range of oxides and the zeolite ZSM-5, which facilitate this reaction. The addition of each component to ZSM-5 leads to an increase in the reaction yield towards glycerol carbonate, but supported gold catalysts display the highest activity. For gold-based catalysts, MgO is the support of choice. Catalysts have been characterised by XRD, TEM, STEM and XPS, and the reaction has been studied with time-on-line analysis of products via a combination of FT-IR spectroscopy, HPLC, (13)C NMR and GC-MS analysis to evaluate the reaction pathway. Our proposed mechanism suggests that glycerol carbonate forms via the cyclization of a 2,3-dihydroxypropyl carbamate and that a subsequent reaction of glycerol carbonate with urea yields the carbamate of glycerol carbonate. Stability and reactivity studies indicate that consecutive reactions of glycerol carbonate can limit the selectivity achieved and reaction conditions can be selected to avoid this. The effect of the catalyst in the proposed mechanism is discussed. 相似文献
992.
Qayyum H Herrick RS Ziegler CJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(28):7442-7445
The aqueous one-step reaction of Re(CO)(3)(H(2)O)(3)(+) with pyridine-2-carboxyaldehyde and glycine or alanine produces a new class of cyclic dimeric products. The ligands of the chiral C(2)-symmetric products are bound via the diimine at one rhenium centre and via the pendant carboxylate to a second rhenium center. 相似文献
993.
Baniodeh A Hewitt IJ Mereacre V Lan Y Novitchi G Anson CE Powell AK 《Dalton transactions (Cambridge, England : 2003)》2011,40(16):4080-4086
The reaction of triethanolamine (teaH(3)) with [Fe(III)(3)O(O(2)CCH(3))(6)(H(2)O)(3)]Cl·6H(2)O and Ln(NO(3))(3)·6H(2)O in acetonitrile yields [Fe(16)Ln(4)(tea)(8)(teaH)(12)(μ-O(2)CCH(3))(8)](NO(3))(4)·16H(2)O·xMeCN (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6); x = 10 or 11). These 20-membered metallo-ring complexes are the largest such single-stranded oxygen-bridged rings so far reported. The structure is stabilised by two of the acetate ligands, which form anti,anti-bridges across the centre of the ring, pinching the ring and giving it rigidity. The magnetic properties are dominated by the antiferromagnetic couplings between the Fe(III) centres. Although the Fe(2) and Fe(6) sub-chains within the ring are fully spin-compensated at low temperatures with S(subchain) = 0, coupling between the Gd(III) cations and the Fe(III) centres at the ends of the sub-chains (in 3) results in a pinning of the lanthanide spins. The (57)Fe M?ssbauer spectra of 3 and 5 obtained at low temperatures are consistent with the presence of Fe(III) intracluster strong antiferromagnetic coupling. The applied field spectrum for 3 reveals no magnetic hyperfine interaction apart from that of the nucleus with the applied field, while the one for 5 is a superposition of three subspectra which show contributions from each of the peripheral as well as from the central iron sites. 相似文献
994.
Azabicyclic [3.1.0] and [4.1.0] Kulinkovich products underwent a facile reduction/fragmentation to afford a variety of 3-piperidinones and 3-azepinones, respectively, in the presence of catalytic palladium on carbon and formic acid in an atmosphere of hydrogen. 相似文献
995.
The enzymatic activation of 3,4-dehydrolysine and subsequent formation of the 12-membered syringolin macrolactam were investigated. The timing of the desaturation was elucidated through the analysis of the initial adenylation domain of SylD. The SylD-TTE didomain was characterized and demonstrated to be the catalyst for formation of 12-membered macrocycles. When the SylD thioesterase domain was reacted with a family of acyclic CoA both natural and unnatural macrocycles were generated. 相似文献
996.
Enantioenriched 1-chloro-2-(1,3-dioxolan-2-yl)ethyllithium was generated by PhLi initiated sulfoxide-ligand exchange and deployed in situ for sequential double stereospecific reagent-controlled homologation (StReCH) of B-(2-chloro-pyrid-5-yl) pinacol boronate. This process afforded highly functionalized contiguous stereodiad motifs (typically, % ee ≥ 98%, dr ≥ 85:15) amenable to subsequent annulative transformations as demonstrated by the concise synthesis (5-7 steps) of cyclic adducts related to the analgesic alkaloid epibatidine. 相似文献
997.
Cammidge AN Goddard VH Schubert CP Gopee H Hughes DL Gonzalez-Lucas D 《Organic letters》2011,13(22):6034-6037
An intriguing class of quinones that efficiently catalyze the air oxidation (overall hydroxylation) of arylboronic acids to the corresponding phenol is reported. Autocatalysis in the parent system is particularly efficient and leads to rapid, quantitative synthesis of quinones such as 4 from boronic acid 1 at room temperature using air as stoichiometric oxidant. The efficiency results from a balance between two-stage conjugate addition and migration with each step driven by aromatization of a naphthalene fragment. 相似文献
998.
The radical-mediated addition of triphenylphosphonium tetrafluoroborate to olefins (hydrophosphonation) is reported. Both standard radical initiators and photochemical conditions are effective, up to the gram scale. The phosphonium salts are shown to serve as Z-selective Wittig olefination reagents, even without purification. 相似文献
999.
We coin a term of milli-free flow electrophoresis (mFFE) to describe mid-scale FFE with flow rates intermediate to macro-FFE and micro-FFE (μFFE). Introduced decades ago, mFFE did not find practical applications. We revive mFFE, as we view it as a viable purification complement to continuous synthesis in capillary reactors with product flow rates of ~5 to 2000 μL/min, too small for macro-FFE but too large for μFFE. The development of the tandem of continuous synthesis/purification will require the production and evaluation of a large number of prototypes of mFFE devices. As the first step, we developed a fast (<24 h) and economical (~$10) method for prototyping mFFE devices using a robotic milling machine. mFFE prototypes are constructed from two machined matching poly(methyl methacrylate) (PMMA) substrates, which are bonded in 10 min using dichloromethane to provide a strong and irreversible seal. Using the developed prototyping technology, we designed and evaluated 25 prototypes of mFFE devices. By optimizing the feed rates and rotational speeds of the drills, the depth of the electrode channels, the dimensions of the entrance and exit reservoirs, the sample flow rate, and the diameter and position of the sample input, we were able to achieve indefinitely long operation of the device with cycles of alternating 15-min electrophoresis and 0.5-min regeneration (bubble removal). The test analytes, rhodamine B and fluorescein, were baseline resolved by mFFE for flow rates ranging from 10 to 600 μL/min. These results prove that our prototyping approach is suitable for the challenging task of multi-parameter optimization of mFFE devices. 相似文献
1000.
Dreyfuss JM Jacobs C Gindin Y Benson G Staples GO Zaia J 《Analytical and bioanalytical chemistry》2011,399(2):727-735
Hydrophilic interaction chromatography (HILIC) liquid chromatography/mass spectrometry (LC/MS) is appropriate for all native
and reductively aminated glycan classes. HILIC carries the advantage that retention times vary predictably according to oligosaccharide
composition. Chromatographic conditions are compatible with sensitive and reproducible glycomics analysis of large numbers
of samples. The data are extremely useful for quantitative profiling of glycans expressed in biological tissues. With these
analytical developments, the rate-limiting factor for widespread use of HILIC LC/MS in glycomics is the analysis of the data.
In order to eliminate this problem, a Java-based open source software tool, Manatee, was developed for targeted analysis of
HILIC LC/MS glycan datasets. This tool uses user-defined lists of compositions that specify the glycan chemical space in a
given biological context. The program accepts high-resolution LC/MS data using the public mzXML format and is capable of processing
a large data file in a few minutes on a standard desktop computer. The program allows mining of HILIC LC/MS data with an output
compatible with multivariate statistical analysis. It is envisaged that the Manatee tool will complement more computationally
intensive LC/MS processing tools based on deconvolution and deisotoping of LC/MS data. The capabilities of the tool were demonstrated
using a set of HILIC LC/MS data on organ-specific heparan sulfates. 相似文献