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111.
112.
The first total synthesis of (-)-calicoferol B (III) is described. The cyclozirconation product I, prepared in enantiomerically pure form, was converted into the CD ring chiron II. This was coupled with the aromatic A-ring, and then the side chain was constructed with control of relative and absolute configuration to complete the total synthesis of III. The first total synthesis of (-)-calicoferol B (1) is described. The cyclozirconation product 8, prepared in enantiomerically pure form, was converted into the CD ring chiron 6. This was coupled with the aromatic A-ring, and then the side chain was constructed with control of relative and absolute configuration to complete the total synthesis of 1. 相似文献
113.
Two polyether bridged dihydroxamic acids and their mono-and binuclear manganese(Ⅱ), zinc(Ⅱ) complexes have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of p-nitrophenyl picolinate (PNPP). The reaction kinetics and the mechanism of hydrolysis of PNPP have been investigated. The kinetic mathematical model for PNPP cleaved by the complexes has been proposed. The effects of the different central metal ion, mono-and binuclear metal, the pseudo-macrocyclic polyether constructed by polyethoxy group of the complexes, and reactive temperature on the rate for catalytic hydrolysis of PNPP have been examined. The results showed that the transition metal dthydroxamates exhibited high catalytic activity to the hydrolysis of PNPP, the catalytic activity of binuclear complexes was higher than that of mononuclear ones, and the pseudo-macrocyclic polyether might synergetically activate H20 coordinated to metal ion with central metal ion together and promote the catalytic hydrolysis of PNPP. 相似文献
114.
The adsorption of H(2)O and its dissociation products, O, H, and OH, on Ag(100) has been studied using an ab initio embedding method. Results at different sites (atop, bridge, and hollow) are presented. The four-fold hollow site is found to be the most stable adsorption site for O, H, and OH, and the calculated adsorption energies are 87.1, 42.7, and 76.2 kcal mol(-1), respectively. The adsorption energy of water at the atop and bridge sites is almost identical with values of 11.1 and 12.0 kcal mol(-1), respectively. The formation of adsorbed OH species by adsorption of water on oxygen-precovered Ag(100) is predicted to be exothermic by 36 kcal mol(-1). 相似文献
115.
The cleavage of a disulfide bond and the redox equilibrium of thiol/disulfide are strongly related to the levels of glutathione (GSH)/oxidized glutathione (GSSG) or mixed disulfides in vivo. In this work, the cleavage of a disulfide bond in GSSG induced by a platinum(II) complex [Pt(Met)Cl2] (where Met = methionine) was studied and the cleavage fragments or their platinated adducts were identified by means of electrospray mass spectrometry, high-performance liquid chromatography, and ultraviolet techniques. The second-order rate constant for the reaction between [Pt(Met)Cl2] and GSSG was determined to be 0.4 M(-1) s(-1) at 310 K and pH 7.4, which is 100- and 12-fold faster than those of cisplatin and its monoaqua species, respectively. Different complexes were formed in the reaction of [Pt(Met)Cl2] with GSSG, mainly mono- and dinuclear platinum complexes with the cleavage fragments of GSSG. This study demonstrated that [Pt(Met)Cl2] can promote the cleavage of disulfide bonds. The mechanistic insight obtained from this study may provide a deeper understanding on the potential involvement of platinum complexes in the intracellular GSH/GSSG systems. 相似文献
116.
Xingang Kong Jiarui Zhang Jianfeng Huang Jiayin Li Yi Qin Ting Zhao Qi Feng 《中国化学快报》2019,30(3):771-774
SnNb2O6 and Sn2Nb2O7 nanosheets were synthetized via microwave assisted hydrothermal method, and innovatively employed as anode materials for lithium-ion battery. Compared with Sn2Nb2O7 and the previously reported pure Sn-based anode materials, the SnNb2O6 electrode exhibited outstanding cycling performance. 相似文献
117.
CuAl2O4 powder synthesis by sol-gel method and its photodegradation property under visible light irradiation 总被引:1,自引:0,他引:1
Jiang Yanyan Li Jinggang Sui Xiaotao Ning Guiling Wang Chengyu Gu Xiumei 《Journal of Sol-Gel Science and Technology》2007,42(1):41-45
Nanocrystalline spinel CuAl2O4 powders were prepared by sol-gel method from nitrate Cu(NO3)2·3H2O, Al(NO3)3·9H2O and complex C6H8O7·H2O. Sintering was carried out at 400, 500, 600, 700, 800°C respectively for 2 h in air. The XRD patterns started to appear
CuAl2O4 peaks after sintering of 500°C and consist of only CuAl2O4 peaks as spinel crystal after sintering of 700°C. The powders were analyzed by TEM and UV-vis diffuse reflectance spectrum
to be round, about 10–30 nm in size and Eg=1.77 eV. Photodegradation property of nanocrystalline CuAl2O4 powders was investigated by using methyl orange as model pollutant and mercury lamp (λ>400 nm) as energy source. The results
indicated that CuAl2O4 powders sintered at 700°C had the excellent visible photocatalytic property. Under the irradiation of visible light, methyl
orange could be degraded 97% in 120 min. 相似文献
118.
Reaction of an arylacetylene with an azide in hot water gave 1,4-disubstituted 1,2,3-triazoles in high yields, while similar reaction between a terminal aliphatic alkyne and an azide (except m-nitroazidobenzene) afforded a mixture of regioisomers with the ratio of 1,4- to 1,5-isomers ranging from 3:1 to 28.6:1. Reactions of m-nitroazidobenzene with either arylalkynes or aliphatic alkynes formed only 1,4-disubstituted derivatives in excellent yields. 相似文献
119.
Wen Lu Qin‐Yu Zhu Yong Zhang Xiao‐Min Lin Jie Dai 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):m496-m498
The title salt, bis[2,3‐bis(aminocarbonyl)‐8,9‐bis(methylsulfanyl)tetrathiafulvalenium] di‐μ‐bromido‐bis[bromidocopper(II)], (C10H10N2O2S6)2[Cu2Br4], contains 2,3‐bis(aminocarbonyl)‐8,9‐bis(methylsulfanyl)tetrathiafulvalenium radical cations, [DMT‐TTF(CONH2)2]·+, and [Cu2Br4]2− anions. The cations are associated across centres of inversion in a head‐to‐tail fashion via short face‐to‐face S...S stacking (TTF moiety). These dimers are further assembled into a one‐dimensional chain structure via interdimer double S...S contacts involving the methylsulfanyl groups. The one‐dimensional chains give rise to a two‐dimensional structure through intermolecular double N—H...O hydrogen bonds involving the amide group. The [Cu2Br4]2− anions, which straddle centres of inversion, are located between the cation layers. Electron paramagnetic resonance measurements show a radical signal, indicating that the two TTF·+ radicals are not completely coupled in the dimer. 相似文献
120.
A novel near infrared (NIR) modeling method—Laplacian regularized least squares regression (LapRLSR) was presented, which can take the advantage of many unlabeled spectra to promote the prediction performance of the model even if there are only few calibration samples. Using LapRLSR modeling, NIR spectral analysis was applied to the online monitoring of the concentration of salvia acid B in the column separation of Salvianolate. The results demonstrated that LapRLSR outperformed partial least squares (PLS) significantly, and NIR online analysis was applicable. 相似文献