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81.
Matteo Scampicchio Nathan S. Lawrence Alessandra Arecchi Stella Cosio Saverio Mannino 《Electroanalysis》2007,19(1):85-90
Cyclic voltammetry has been applied to the rapid measurement of free SH‐compounds in food flours samples. The protocol is based on the electrochemical adaptation of the Ellman's test, where the DTNB reacts with SH‐compounds present in food flour extracts, resulting in the equimolar production of the electroactive compound TNBA which, in turns, reacts with phenylendiamine. The reaction is found to provide an analytical signal from which to quantify indirectly free sulfhydryl compounds in flours extracts. 相似文献
82.
Asphaltenes from four different crude oils (Arab Heavy, B6, Canadon Seco, and Hondo) were fractionated in mixtures of heptane and toluene and analyzed chemically, by vapor pressure osmometry (VPO), and by small angle neutron scattering (SANS). Solubility profiles of the asphaltenes and their subfractions indicated strong cooperative asphaltene interactions of a particular subfraction that is polar and hydrogen bonding. This subfraction had lower H/C ratios and modestly higher N, V, Ni, and Fe contents than the less polar and more soluble subfraction of asphaltenes. VPO and SANS studies indicated that the less soluble subfractions formed aggregates that were considerably larger than the more soluble subfractions. In general, asphaltene aggregate size increased with decreasing solvent aromaticity up to the solubility limit, beyond which the aggregate size decreased with heptane addition. The presence of a low wavevector Q feature in the scattering curves at 25 degrees C indicated that the individual aggregates were flocculating; however, the intensity of the feature was diminished upon heating of the samples to 80 degrees C. The solubility mechanism for Canadon Seco asphaltenes, the largest aggregate formers, appears to be dominated by aromatic pi-bonding interactions due to their low H/C ratio and low nitrogen content. B6 and Hondo asphaltenes formed similar-sized aggregates in heptol and the solubility mechanism is most likely driven by polar interactions due to their relatively high H/C ratios and high nitrogen contents. Arab Heavy, the least polar asphaltene, had a H/C ratio similar to Canadon Seco but formed the smallest aggregates in heptol. The enhancement in polar and pi-bonding interactions for the less soluble subfraction indicated by elemental analysis is reflected by the aggregate size from SANS. The less soluble asphaltenes contribute the majority of species responsible for aggregation and likely cause many petroleum production problems such as pipeline deposition and water-in-oil emulsion stabilization. 相似文献
83.
Mueller JA Cowell A Chandler BD Sigman MS 《Journal of the American Chemical Society》2005,127(42):14817-14824
A kinetic investigation into the origin of enantioselectivity for the Pd[(-)-sparteine]Cl(2)-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(-)-sparteine]Cl(2) prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(-)-sparteine]Cl(2) to form cationic Pd(-)-sparteine]Cl, (2) alcohol binding, (3) deprotonation of Pd-bound alcohol to form a Pd-alkoxide, and (4) beta-hydride elimination of Pd-alkoxide to form ketone product and a Pd-hydride. Utilizing the addition of (-)-sparteine HCl to control the [Cl(-)] and [H(+)] and the resulting derived rate law, the key microscopic kinetic and thermodynamic constants were extracted for each enantiomer of sec-phenethyl alcohol. These constants allow for the successful simulation of the oxidation rate in the presence of exogenous (-)-sparteine HCl. A rate law for oxidation of the racemic alcohol was derived that allows for the successful prediction of the experimentally measured k(rel) values when using the extracted constants. Besides a factor of 10 difference between the relative rates of beta-hydride elimination for the enantiomers, the main enhancement in enantiodetermination results from a concentration effect of (-)-sparteine HCl and the relative rates of reprotonation of the diastereomeric Pd-alkoxides. 相似文献
84.
Simone Gallarati Raimon Fabregat Rubn Laplaza Sinjini Bhattacharjee Matthew D. Wodrich Clemence Corminboeuf 《Chemical science》2021,12(20):6879
Hundreds of catalytic methods are developed each year to meet the demand for high-purity chiral compounds. The computational design of enantioselective organocatalysts remains a significant challenge, as catalysts are typically discovered through experimental screening. Recent advances in combining quantum chemical computations and machine learning (ML) hold great potential to propel the next leap forward in asymmetric catalysis. Within the context of quantum chemical machine learning (QML, or atomistic ML), the ML representations used to encode the three-dimensional structure of molecules and evaluate their similarity cannot easily capture the subtle energy differences that govern enantioselectivity. Here, we present a general strategy for improving molecular representations within an atomistic machine learning model to predict the DFT-computed enantiomeric excess of asymmetric propargylation organocatalysts solely from the structure of catalytic cycle intermediates. Mean absolute errors as low as 0.25 kcal mol−1 were achieved in predictions of the activation energy with respect to DFT computations. By virtue of its design, this strategy is generalisable to other ML models, to experimental data and to any catalytic asymmetric reaction, enabling the rapid screening of structurally diverse organocatalysts from available structural information.A machine learning model for enantioselectivity prediction using reaction-based molecular representations. 相似文献
85.
Matthew Ball 《Tetrahedron letters》2004,45(47):8737-8740
A synthesis of the C(1)-C(16) fragment of the brysostatins has been developed. Key steps are the stereoselective copper(I) catalysed addition of allylmagnesium bromide to an alkynyl ester, a condensation of a βγ-unsaturated aldehyde with a ketophosphonate, and the formation of the B-ring under mild conditions by stereoselective intramolecular conjugate addition. 相似文献
86.
Chen W Wu H Bernard D Metcalf MD Deschamps JR Flippen-Anderson JL MacKerell AD Coop A 《The Journal of organic chemistry》2003,68(5):1929-1932
Treatment of 5-trimethylsilylthebaine with L-Selectride gave rise to a rearrangement to 10-trimethylsilylbractazonine through migration of the phenyl group, whereas treatment of thebaine with strong Lewis acids is known to lead to a similar rearrangement through migration of the alkyl bridge to give, after reduction, (+)-neodihydrothebaine. It is suggested that the rearrangement of the alkyl group of thebaine is favored due to the formation of a tertiary benzylic cation. However, for 5-trimethylsilylthebaine, the lithium ion of L-Selectride acts as the Lewis acid and the beta-silyl effect dominates in the stabilization of any positive charge. This rearrangement provides a clear example of the greater relative migratory aptitude of phenyl groups over alkyl groups, and provides an efficient synthesis of (+)-bractazonine from thebaine. 相似文献
87.
Sternfeld T Thilgen C Hoffman RE Del Rosario Colorado Heras M Diederich F Wudl F Scott LT Mack J Rabinovitz M 《Journal of the American Chemical Society》2002,124(20):5734-5738
Reduction of the two "closed" [6,6] methanofullerenes, [6,6]C(61)H(2) (1) and [6,6]C(71)H(2) (5), to the corresponding hexaanions with lithium metal causes the bridgehead-bridgehead bonds to open, at least partially, and this change gives rise to diamagnetic ring currents in the resulting homoconjugated six-membered rings (6-MRs). These new ring currents shield the overlying hydrogen atoms on the methylene bridge and induce upfield shifts of 1.60 and 0.11 ppm in their (1)H NMR resonances, respectively. Analogous reduction of the already "open" [5,6]methanofullerenes, [5,6]C(61)H(2) (2) and [5,6]C(71)H(2) (3 and 4), only slightly enhances the shielding of the hydrogen atoms over the homoconjugated 6-MRs (upfield shifts of 0.13, 0.68, and 0.14 ppm, respectively) but leads to exceptionally strong diamagnetic ring currents in the homoconjugated five- membered rings (5-MRs), as evidenced by dramatic shielding of the hydrogen atoms situated over them (upfield shift of 5.01, 6.78, and 1.63 ppm, respectively). The strongest shielding is seen for the hydrogen atom sitting over the 5-MR at the pole of C(71)H(2)(6)(-) (delta = -0.255 ppm) indicating that the excess charge density is concentrated at the poles. 相似文献
88.
Wipf P Coleman CM Janjic JM Iyer PS Fodor MD Shafer YA Stephenson CR Kendall C Day BW 《Journal of combinatorial chemistry》2005,7(2):322-330
Cascade reactions of internal and terminal alkynes, zirconocene hydrochloride, dimethylzinc, and phosphinoyl imines (prepared in one step from aldehydes and diphenylphosphinoyl amide) lead to allylic phosphinoyl amides after aqueous workup. Microwave acceleration allows the completion of this one-pot reaction sequence in 10 min. These allylic amides can be converted into a variety of derivatives, including carbamates and sulfonamides, or reacted prior to workup with diiodomethane to give novel C-cyclopropylalkylamides. A solution-phase "libraries from libraries" approach was used to generate an intermediate 20-member library which was subsequently expanded to a 100-member library by a series of N-functionalizations. The biological activity was evaluated in an assay for competitive binding to the estrogen receptor (ERalpha), revealing three potent lead compounds of a new structural type. 相似文献
89.
E.Gordon Muller Jeffrey L. Petersen Lawrence F. Dahl 《Journal of organometallic chemistry》1976,111(1):91-112
Our preparation of Ti(h5?C5H5)2 S5 by the reaction of elemental sulfur with Ti(h5?C5H5)2(CO)2 in hexane and of V(h5?C5H5)2S5? H2O by the reacti of V(h5?C5H5)2 Cl2 with Na2S5 in THF and structural analyses by single crystal X-ray diffraction (together with infrared, solution EPR, and temperaturedependent magnetic susceptibility measurements) represent an extension of our previous work on M(h5?C5H5)2 (SC6H5)2 (M = Ti, V). The crystallographic results provide further support of our previous conclusions that the Ballhausen—Dahl model is not valid for M(h5?C5H5)2L2 systems. The structuralfeatures of the chair-like titanium and vanadium pentasulfide molecules are compared to the corresponding phenylmercapto analogs and to the chair-like cyclohexasulfur molecule in rhombohedral sulfur. Ti(h5?C5H5)2S5 was isolated as a mixture of monoclinic and orthorhombic Crystalline phases-which were both characterized by preliminary X-ray data. A complete Structural determination and refinement of the monoclinic phase, which contains two independent molecules in a cell of dimensions a 22.843(2), b 7.958(1), c 14.465(1) Å, β 90.074(4)° and symmetry P21/c, yielded R1 5.3 % and R2 5.9 % for 2168 independent diffractometry-collected data with I≥ 2.5o(I). V(h5?C5H5)2S5- H2O contains four V(h5?C5H5)2S5 molecules and two water molecules of hydration (of crystallographic site symmetry C2-2) in onorthorhombic unit cell of symmetry P21212 and of dimensions a 13.491(1), b 12.748(1), c 7.715(1) Å. Least-squares refinement of 750 diffractometry data with I≥2.0σ(I) gave R1 2.4% and R2 3.0% Both of these compounds were independently synthesized and Spectroscopically characterized by Köpf and co-workers, and-a Complete X-ray diffraction study was performed by Epstein and Bernal on a different monoclinic phase of Ti(h5?C5H5)2S5 (isolated by-Köpf). An extraction of V(h5?C5H5)2S5 with re fluxing benzene under nitrogen atmosphere in a Soxhlet apparatus led to the formation of the previously reported [V2 (h5?C5H5)2S5]n compound which was characterized by physical measurements including a preliminary X-ray diffraction study. 相似文献
90.
Walter K. Dean Gary L. Simon Paul M. Treichel Lawrence F. Dahl 《Journal of organometallic chemistry》1973,50(1):193-207
The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2, has been accomplished by the reaction of NaMn(CO)5 with (CH3)3SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C6H5)3 bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C6H5)3 bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor. 相似文献