全文获取类型
收费全文 | 6398篇 |
免费 | 539篇 |
国内免费 | 357篇 |
专业分类
化学 | 3969篇 |
晶体学 | 58篇 |
力学 | 300篇 |
综合类 | 40篇 |
数学 | 827篇 |
物理学 | 2100篇 |
出版年
2023年 | 73篇 |
2022年 | 195篇 |
2021年 | 204篇 |
2020年 | 254篇 |
2019年 | 205篇 |
2018年 | 174篇 |
2017年 | 163篇 |
2016年 | 258篇 |
2015年 | 270篇 |
2014年 | 256篇 |
2013年 | 434篇 |
2012年 | 433篇 |
2011年 | 511篇 |
2010年 | 326篇 |
2009年 | 320篇 |
2008年 | 378篇 |
2007年 | 364篇 |
2006年 | 328篇 |
2005年 | 281篇 |
2004年 | 228篇 |
2003年 | 195篇 |
2002年 | 165篇 |
2001年 | 141篇 |
2000年 | 86篇 |
1999年 | 99篇 |
1998年 | 59篇 |
1997年 | 53篇 |
1996年 | 69篇 |
1995年 | 57篇 |
1994年 | 71篇 |
1993年 | 56篇 |
1992年 | 49篇 |
1991年 | 39篇 |
1990年 | 41篇 |
1989年 | 30篇 |
1988年 | 22篇 |
1987年 | 23篇 |
1986年 | 18篇 |
1985年 | 30篇 |
1984年 | 40篇 |
1983年 | 16篇 |
1982年 | 35篇 |
1981年 | 19篇 |
1980年 | 22篇 |
1979年 | 37篇 |
1978年 | 26篇 |
1977年 | 15篇 |
1976年 | 23篇 |
1975年 | 15篇 |
1974年 | 20篇 |
排序方式: 共有7294条查询结果,搜索用时 312 毫秒
801.
Mazuela J Norrby PO Andersson PG Pàmies O Diéguez M 《Journal of the American Chemical Society》2011,133(34):13634-13645
A modular set of phosphite-oxazoline (P,N) ligands has been applied to the title reaction. Excellent ligands have been identified for a range of substrates, including previously challenging terminally disubstituted olefins, where we now have reached enantioselectivities of 99% for a range of substrates. The selectivity is best for minimally functionalized substrates with at least a moderate size difference between geminal groups. A DFT study has allowed identification of the preferred pathway. Computational prediction of enantioselectivities gave very good accuracy. 相似文献
802.
New mesoporous organic?Cinorganic spheres were prepared by one step co-condensation of trialkoxysilylated camphorsulfonamide (CSA) and 1,2-bis(triethoxysilyl)ethane (BTSE) using octadecyltrimethylammonium chloride (C18TMACl) as template and ethanol as co-solvent in basic medium. The materials have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), nitrogen sorption measurement, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and elemental analysis (EA). Then the mesoporous organic?Cinorganic spheres were demonstrated to be novel packing materials for potential application in the normal-phase high performance liquid chromatography (HPLC). 相似文献
803.
Ordered mesoporous silicas (OMSs) with spherical morphology were synthesized by using mixed surfactants of anionic sodium dodecyl sulfate and nonionic block copolymer EO20PO70EO20 (P123) as template through an acid-catalyzed silica sol?Cgel process. A variety of characterizations demonstrated that the silica products exhibited well-formed spherical morphology, ordered mesostructure, narrow pore size distribution and large surface area (~700 m2 g?1). It was found that the synthesized OMSs had high adsorption capacity by using oxymatrine as model solute. The column packed with the silica spheres exhibited low back pressure and baseline separation of aromatic compounds such as benzene and nitrobenzene could be achieved. These results demonstrated the synthesized OMSs as a potential stationary phase for liquid chromatography. 相似文献
804.
Mariacristina Cocca Maria Laura Di Lorenzo Mario Malinconico Vincenzo Frezza 《European Polymer Journal》2011,(5):1073-1080
The effect of crystal polymorphism on barrier and mechanical properties of PLLA is detailed in this contribution. PLLA films containing different amounts of α and α′ crystal forms were prepared by annealing quenched PLLA at different temperatures. The polymorphic structure of the films was analyzed by X-ray diffraction. Mechanical properties and permeability to water vapor were investigated as a function of degree of crystallinity (wC) and related to crystal polymorphism developed during annealing. The polymorphic structure of PLLA significantly affects mechanical and barrier properties. The α crystal modification provides a better barrier to water vapor and a higher Young’s modulus, compared to films containing the α′ modification, but a lower elongation at break. The varied barrier and mechanical properties were correlated to the different packing of PLLA chains in the two analyzed polymorphs. The conformational disorder of the α′ form makes this structure a mesophase (condis crystal), with remarkable effects on material properties. 相似文献
805.
Jing Ning Ying‐Tong Di Shi‐Fei Li Zhao‐Liang Geng Hong‐Ping He Yue‐Hu Wang Yuan‐Yuan Wang Yan Li Shun‐Lin Li Xiao‐Jiang Hao 《Helvetica chimica acta》2011,94(3):376-381
A phytochemical investigation of Toona ciliata var. ciliata afforded three new polyynes, 1 – 3 . Their structures were elucidated on the basis of spectroscopic analysis and chemical methods. Only compound 3 exhibited potent cytotoxicity against the HL‐60 cell line with an IC50 value of 6.7±0.27 μM . 相似文献
806.
Di Michele A Brinchi L Di Profio P Germani R Savelli G Onori G 《Journal of colloid and interface science》2011,358(1):160-166
The critical micelle concentration (cmc) and ionisation degree (α), of micelles of cetyltrimethylammonium bromide (CTABr), cetyltrimethylammonium chloride (CTACl), cetyltripropylammonium bromide (CTPABr) and cetyltripropylammonium chloride (CTPACl) have been measured over a narrow temperature range at 2 degree intervals using electrical conductivity. CTPACl and CTPABr are very soluble in water and were measured in the temperature range 275.15-323.15K. The Krafft temperatures for CTABr and for CTACl are 293.15K and 284.15K, respectively and established a lower temperature limit for our studies on these two surfactants. The cmc vs temperature curves have a smooth minimum near room temperature and α linearly increases with temperature. The changes of cmc and α with temperature are smaller than those associated with the modification of head group size or counterion nature. Using these results, basic thermodynamic quantities associated with the phenomena of micellization have been evaluated. Thermodynamic properties of the surfactant solutions were discussed in terms of temperature dependence of the free energy, enthalpy and entropy of micellization. A close similarity between the effects of change in temperature on protein folding and micellization process appears from the data. 相似文献
807.
As part of our ongoing project involving the study of (1-C(n)H(2n+1)NH(3))(2)MCl(4)(s) (where M is a divalent metal ion and n = 8-18), we have synthesized the compounds (1-C(n)H(2n+1)NH(3))(2)ZnCl(4)(s) (n = 8, 10, 12, and 13), and the details of the structures are reported herein. All of the compounds were crystallized in the monoclinic form with the space group P2(1)/n for (1-C(8)H(17)NH(3))(2)ZnCl(4)(s), P21/c for (1-C(10)H(21)NH(3))(2)ZnCl(4)(s), P2(1)/c for (1-C(12)H(25)NH(3))(2)ZnCl(4)(s), and P2(1)/m for (1-C(13)H(27)NH(3))(2)ZnCl(4)(s). The lattice potential energies and ionic volumes of the cations and the common anion of the title compounds were obtained from crystallographic data. Molar enthalpies of dissolution of the four compounds at various molalities were measured at 298.15 K in the double-distilled water. According to Pitzer's theory, molar enthalpies of dissolution of the title compounds at infinite dilution were obtained. Finally, using the values of molar enthalpies of dissolution at infinite dilution (Δ(s)H(m)(∞)) and other auxiliary thermodynamic data, the enthalpy change of the dissociation of [ZnCl(4)](2-)(g) for the reaction [ZnCl(4)](2-)(g)→ Zn(2+)(g) + 4Cl(-)(g) was obtained, and then the hydration enthalpies of cations were calculated by designing a thermochemical cycle. 相似文献
808.
Rare gas containing cations with general formula [Rg, B, 2F](+) have been investigated theoretically by second-order Mo?ller-Plesset perturbation, coupled cluster, and complete active space self-consistent field levels of theory with correlation-consistent basis sets. Totally two types of minima, i.e., boron centered C(2) (v) symmetried RgBF(2) (+) (Rg = Ar, Kr, and Xe) which can be viewed as loss of F(-) from FRgBF(2) and linear FRgBF(+) (Rg = Kr and Xe) are obtained at the CCSD(T)∕aug-cc-pVTZ∕SDD and CASSCF(10,8)∕aug-cc-pVTZ∕SDD levels, respectively. It is shown that the RgBF(2) (+) are global minima followed by FRgBF(+) at 170.9 and 142.2 kcal∕mol on the singlet potential-energy surfaces of [Rg, B, 2F](+) (Rg = Kr and Xe) at the CASPT2(10,8) ∕aug-cc-pVTZ∕SDD∕∕CASSCF(10,8)∕aug-cc-pVTZ∕SDD, respectively. The interconversion barrier heights between RgBF(2) (+) and FRgBF(+) (Rg = Kr and Xe) are at least 39 kcal∕mol. In addition, no dissociation transition state associated with RgBF(2) (+) and FRgBF(+) can be found. This suggests that RgBF(2) (+) (Rg = Ar, Kr, and Xe) can exist as both thermodynamically and kinetically stable species, while linear FRgBF(+) (Rg = Kr and Xe) can exist as metastable species compared with the lowest dissociation limit energies just like isoelectronic linear FRgBO and FRgBN(-). From natural bond orbital and atoms-in-molecules calculations, it is found that the positive charge is mainly located on Rg and boron atoms for both types of minima, the Rg-B bonds of ArBF(2) (+), KrBF(2) (+), and XeBF(2) (+) are mostly electrostatic, thus can be viewed as ion-induced dipole interaction; while that of linear FKrBF(+) and FXeBF(+) are covalent in nature. The previous experimental observation of ArBF(2) (+) by Pepi et al. [J. Phys. Chem. B. 110, 4492 (2006)] should correspond to C(2) (v) minimum. The presently predicted spectroscopies of KrBF(2) (+), XeBF(2) (+), FKrBF(+), and FXeBF(+) should be helpful for their experimental identification in the future. 相似文献
809.
Bikiel DE González Solveyra E Di Salvo F Milagre HM Eberlin MN Corrêa RS Ellena J Estrin DA Doctorovich F 《Inorganic chemistry》2011,50(6):2334-2345
A new family of compounds is presented as potential carbon monoxide releasing molecules (CORMs). These compounds, based on tetrachlorocarbonyliridate(III) derivatives, were synthesized and fully characterized by X-ray diffraction, electrospray mass spectrometry, IR, NMR, and density functional theory calculations. The rate of CO release was studied via the myoglobin assay. The results showed that the rate depends on the nature of the sixth ligand, trans to CO, and that a significant modulation on the release rate can be produced by changing the ligand. The reported compounds are soluble in aqueous media, and the rates of CO release are comparable with those for known CORMs, releasing CO at a rate of 0.03-0.58 μM min(-1) in a 10 μM solution of myoglobin and 10 μM of the complexes. 相似文献
810.
Rodríguez L Lima JC Pina F Cacciapaglia R Di Stefano S Ruggi A 《The journal of physical chemistry. A》2011,115(2):123-127
The photophysical properties of two atropisomeric naphthalenophanes (1 and 2) have been studied. Their structure only differs in the relative arrangement, syn (1) or anti (2), of the two aromatic units. The compounds emission is mainly excimeric and is strongly quenched in the presence of oxygen. Comparison of emission intensities obtained from steady state and from decay times provides clear evidence of the formation of ground state charge transfer complexes between oxygen and the naphthalenophanes 1 and 2. The calculated values for the association constants are on the order of 10(3) M(-1) (ethanol, room temperature) for both naphthalenophanes. 相似文献