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241.
[3-3H]-valine was efficiently synthesised from sodium α-ketoisovalerate. With a β-lactam negative mutant of C. acremonium, l-[1-14C-3-3H]-valine and dl-[1-14C-3-3H]-valine were independently incorporated into the Arnstein tripeptide dimer, i.e. Bis-δ-(l-α-aminodipyl)-l-cystinyl-bis-d-valine, with full retention of trieium at C-3 of the d-valine residue. This result strongly suggested retention of configuration at C-3 of valine when the tripeptide was biosynthesised, and further limited the number of possible mechanisms for the biosynthesis of penicillins. 相似文献
242.
15-甲基-双环[10,3,0]十五碳-1(12)-烯-13-酮的单晶属空间群P2_1/n,晶胞参数:a=0.4838(1)nm,b=1.3949(2)nm,c=2.1645(4)nm,β=92.07(1)°,Z=4.其中平面五员环呈刚性。另一个含烯十二员环的实际构象与分子力学计算的最稳定构象一致。 相似文献
243.
Adams RD Miao S Smith MD Farach H Webster CE Manson J Hall MB 《Inorganic chemistry》2004,43(8):2515-2525
The reaction of Mn(2)(CO)(7)(mu-S(2)) with [CpNi(CO)](2) yielded the paramagnetic new compound Cp(2)Ni(2)Mn(CO)(3)(mu(3)-S)(2) (1) and a new hexanuclear metal product Cp(2)Ni(2)Mn(4)(CO)(14)(mu(6)-S(2))(mu(3)-S)(2) (2). Structurally, compound 1 contains two triply bridging sulfido ligands on opposite sides of an open Ni(2)Mn triangular cluster. EPR and temperature-dependent magnetic susceptibility measurements of 1 show that it contains one unpaired electron. The electronic structure of 1 was determined by Fenske-Hall molecular orbital calculations which show that the unpaired electron occupies a low lying antibonding orbital delocalized unequally across the three metal atoms. The selenium homologue Cp(2)Ni(2)Mn(CO)(3)(mu(3)-Se)(2) (3) was obtained from the reaction of a mixture of Mn(2)(CO)(10) and [CpNi(CO)](2) with elemental selenium and Me(3)NO.2H(2)O. It also has one unpaired electron. Compound 1 reacted with elemental sulfur to yield the dinickeldimanganese compound, Cp(2)Ni(2)Mn(2)(CO)(6)(mu(4)-S(2))(mu(4)-S(5)), 4, which can also be made from the reaction of Mn(2)(CO)(7)(mu-S(2)) with [CpNi(CO)](2) and sulfur. Compound 4 was converted back to 1 by sulfur abstraction using PPh(3). The reaction of Mn(2)(CO)(10) with [CpNi(CO)](2) in the presence of thiirane yielded the ethanedithiolato compound CpNiMn(CO)(3)(mu-SCH(2)CH(2)S) (5), which was also obtained from the reaction of Mn(4)(CO)(15)(mu(3)-S(2))(mu(4)-S(2)) with [CpNi(CO)](2) in the presence of thiirane. Compound 5 reacted with additional quantities of thiirane to yield the new compound CpNiMn(CO)(3)[mu-S(CH(2)CH(2)S)(2)], 6, which contains a 3-thiapentanedithiolato ligand that bridges the two metal atoms. Compound 6 was also obtained from the reaction of Mn(2)(CO)(10) with [CpNi(CO)](2) and thiirane. The molecular structures of the new compounds 1-6 were established by single-crystal X-ray diffraction analyses. 相似文献
244.
A new dihydrobenzodioxane derivative, origalignanol ( 10 ), together with nine polyphenolic compounds, salvianolic acid A ( 1 ), salvianolic acid C ( 2 ), lithospermic acid ( 3 ), apigenin 7‐O‐β‐D‐glucuronide ( 4 ), apigenin 7‐O‐β‐D‐(6″‐methyl)glucuronide ( 5 ), luteolin, ( 6 ), luteolin 7‐O‐β‐D‐glucopyranoside ( 7 ), luteolin 7‐O‐β‐D‐glucuronide ( 8 ), and luteolin 7‐O‐β‐D‐xylopyranoside ( 9 ), were isolated from the aqueous ethanolic extract of the aerial parts of Origanum vulgare for the first time. The structure of new compound 10 was determined on the basis of spectroscopic methods. Compound 5 is probably an artifact formed during the isolation. Compounds 1, 2 and 3 showed strong DPPH radical scavenging activity with an EC50 of 7.2 ± 0.4, 9.6 ± 0.9, and 9.5 ± 0.7 μM, respectively, and protected rat hepatocytes from CCl4‐damage at 100 μM. 相似文献
245.
State Miao Ming-Ming Liao Dai-Zheng Jiang Zong-Hui Cheng Peng Wang Geng-Lin 《中国化学》1996,14(4):326-330
Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-l,10-phenanthroline(NO2-phen) (2), 2,2′-bipyridyl(bpy) (S) and 4,4′-dimethyl-2,2′-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)23H2O has been studied in the 4–300 K range, giving the exchange integral J—109 cm?1. The HMT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure. 相似文献
246.
Yizhao Ouyang Miao Zhan Jing Zhou Jiao Jiao Hao Hu Yoichi M. A. Yamada Pengfei Li 《中国化学》2019,37(8):807-810
A rigid C2‐symmetric chiral bipyridine ligand Z‐bpy with a triptycene‐like backbone was designed and synthesized from simple chemicals in a scalable route. Using this new ligand, copper(I) catalyzed cyclopropanation of styrenes with commercial ethyl diazoacetate produced various corresponding cyclopropanes in high yields, diastereoselectivity and enantioselectivity up to 97% ee. 相似文献
247.
Free radical reactions induced by the photolysis of the lignin model compound α-guaiacoxylacetoveratrone have been studied by conventional and time-resolved ESR spectroscopy. In the presence of efficient hydrogen donors such as aqueous and hydroxylic solvents the primary reaction involves photoreduction of the triplet phenacyl ether to form the ketyl radical followed by rapid cleavage to the phenacyl radical and guaiacol. Subsequent formation of polarized guaiacoxyl radicals is due to secondary photo-oxidation. The cleavage of the ketyl radical is retarded in basic media and accelerated in acetic acid. Minor reaction pathways involving excited singlets cannot be ruled out by the current CIDEP observations. 相似文献
248.
We present a comprehensive survey of different C-H activation pathways over various kinds of active sites of terminal oxygens [=O] and bridge oxygens [-O-] by using Mo3O9 model systems. This allows us to provide some insights into fundamental issues concerning C-H activation by metal oxo species involved in many heterogeneous, homogeneous, and enzymatic processes. We show that H abstraction is the most feasible reaction pathway for the activation of a C-H bond on molybdenum oxides; and that [=O] is more active than [-O-]. Our calculations also suggest that (2+2) can be an alternative if M=O bond possesses a high polarity, while (5+2) can provide another effective pathway if two M=O bonds are in close proximity. Implications for the related heterogeneous, homogeneous, and enzymatic processes are discussed. 相似文献
249.
Xu QM Wang D Han MJ Wan LJ Bai CL 《Langmuir : the ACS journal of surfaces and colloids》2004,20(8):3006-3010
Scanning tunneling microscopy (STM) combined with cyclic voltammetry has been employed to investigate the adsorption of cinchonine on Cu(111). Similar to cinchonidine, cinchonine forms a long-range ordered adlayer with (4 x 4) symmetry on the substrate. The structural details on molecular adsorption were obtained by high-resolution STM images. On the basis of the previous results and obtained STM images, the quinoline ring is proposed to lie parallel to Cu(111) and serve as an anchoring group. The chiral quinuclidine moiety extends out of the surface to facilitate the interaction with the prochiral reactants. 相似文献
250.
Ning Fang Vincent Chan Kai-Tak Wan Hai-Quan Mao Kam W. Leong 《Colloids and surfaces. B, Biointerfaces》2002,25(4):347-362
High-resolution reflection interference contrast microscopy (HR-RICM) was developed for probing the deformation and adhesion of phospholipid vesicles induced by colloidal forces on solid surfaces. The new technique raised the upper limit of the measured membrane–substrate separation from 1 to 4.5 μm and improved the spatial resolution of the heterogeneous contact zones. It was applied to elucidate the effects of wall thickness, pH and osmotic stress on the non-specific adhesion of giant unilamellar vesicles (ULV) and multilamellar vesicles (MLV) on fused silica substrates. By simultaneous cross-polarization light microscopy and HR-RICM measurements, it was observed that ULV with the wall thickness of a single bilayer would be significantly deformed in its equilibrium state on the substrate as the dimension of its adhesive–cohesive zone was 29% higher than the theoretical value of a rigid sphere with the same diameter. Besides, electrostatic interaction was shown as a significant driving force for vesicle adhesions since the reduction in pH significantly increased the degree of deformation of adhering ULV and heterogeneity of the adhesion discs. The degree of MLV deformation on the solid surfaces was significantly less than that of ULV. When the wall thickness of vesicle increased, the dimension of contact zone was reduced dramatically due to the increase of membrane bending modulus. Most important, the adhesion strength of colloidal adhesion approached that of specific adhesion. Finally, the increase of osmotic stress led to the collapse of adhering vesicles on the non-deformable substrate and raised the area of adhesive contact zone. To interpret these results better, the equilibrium deformation of adhering vesicle was modeled as a truncated sphere and the adhesion energy was calculated with a new theory. 相似文献