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101.
Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface. 相似文献
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Cephalotanins A–D,Four Norditerpenoids Represent Three Highly Rigid Carbon Skeletons from Cephalotaxus sinensis 下载免费PDF全文
Dr. Jin‐Biao Xu Dr. Yao‐Yue Fan Prof. Dr. Li‐She Gan Dr. Yu‐Bo Zhou Prof. Dr. Jia Li Prof. Dr. Jian‐Min Yue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14648-14654
Four polycyclic norditerpenoids, cephalotanins A–D ( 1 – 4 ) representing three unprecedented carbon skeletons with highly rigid ring systems, were isolated from Cephalotaxus sinensis and structurally characterized by a combination of various methods. Compounds 1 and 2 are new skeletal norditerpenoid trilactones, while 3 and 4 are two norditerpenoids featuring different new carbon skeletons. Biosynthetic pathways for 1 – 4 were proposed by involving diverse and very fascinating chemical events with the coexisting cephalotane troponoids as the precursors. Compound 1 exhibited good NF‐κB inhibition with an IC50 value of 4.12±0.61 μΜ. 相似文献
105.
Dr. Shaodong Zhou Dr. Jilai Li Dr. Maria Schlangen Prof. Dr. Helmut Schwarz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(9):3073-3076
Carbon‐atom extrusion from the ipso‐position of a halobenzene ring (C6H5X; X=F, Cl, Br, I) and its coupling with a methylene ligand to produce acetylene is not confined to [LaCH2]+; also, the third‐row transition‐metal complexes [MCH2]+, M=Hf, Ta, W, Re, and Os, bring about this unusual transformation. However, substrates with substituents X=CN, NO2, OCH3, and CF3 are either not reactive at all or give rise to different products when reacted with [LaCH2]+. In the thermal gas‐phase processes of atomic Ln+ with C7H7Cl substrates, only those lanthanides with a promotion energy small enough to attain a 4fn5d16s1 configuration are reactive and form both [LnCl]+ and [LnC5H5Cl]+. Branching ratios and the reaction efficiencies of the various processes seem to correlate with molecular properties, like the bond‐dissociation energies of the C?X or M+?X bonds or the promotion energies of lanthanides. 相似文献
106.
He Haidong Yang Haifeng Zhou Longpeng Chen Tianchi 《Journal of Russian Laser Research》2015,36(3):292-299
Ni–Co alloys have a wide range of applications in various fields owning to their excellent physical, chemical, and mechanical properties. In this paper, we prepare Ni–Co alloy coatings on 316L stain steel surfaces by electroplating. We present a novel approach utilizing a nanosecond laser to induce microtextures on Ni–Co alloy coatings. We study experimentally the effects of laser power and scanning rate on the surface morphologies of Ni–Co alloy coatings. The results indicate that the shape and size of induced microtextures can be controlled by the laser power and scanning rate. The size of grains increases with increase in the work current of the laser (WCL) at a certain scanning rate. With the WCL constant, the size of grains decreases with increase in scanning rate while their average height increases. It is a simple and easily-controlled method for the fabrication of microstructures on Ni–Co alloy coatings, which has promising applications in investigations of the properties of microtextured surfaces, such as friction, adhesion, and wetting. 相似文献
107.
Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane catalyzed by thiazolium A has been developed. The reaction rate and efficiency are profoundly impacted by the presence of thiourea B. The reaction affords moderate to good yields of the Stetter product. Some factors influencing yield were discussed. 相似文献
108.
Octahedral Chiral‐at‐Metal Iridium Catalysts: Versatile Chiral Lewis Acids for Asymmetric Conjugate Additions 下载免费PDF全文
Xiaodong Shen Haohua Huo Chuanyong Wang Bo Zhang Dr. Klaus Harms Prof. Dr. Eric Meggers 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9720-9726
Octahedral iridium(III) complexes containing two bidentate cyclometalating 5‐tert‐butyl‐2‐phenylbenzoxazole ( IrO ) or 5‐tert‐butyl‐2‐phenylbenzothiazole ( IrS ) ligands in addition to two labile acetonitrile ligands are demonstrated to constitute a highly versatile class of asymmetric Lewis acid catalysts. These complexes feature the metal center as the exclusive source of chirality and serve as effective asymmetric catalysts (0.5–5.0 mol % catalyst loading) for a variety of reactions with α,β‐unsaturated carbonyl compounds, namely Friedel–Crafts alkylations (94–99 % ee), Michael additions with CH‐acidic compounds (81–97 % ee), and a variety of cycloadditions (92–99 % ee with high d.r.). Mechanistic investigations and crystal structures of an iridium‐coordinated substrates and iridium‐coordinated products are consistent with a mechanistic picture in which the α,β‐unsaturated carbonyl compounds are activated by two‐point binding (bidentate coordination) to the chiral Lewis acid. 相似文献
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