全文获取类型
收费全文 | 4625篇 |
免费 | 138篇 |
国内免费 | 16篇 |
专业分类
化学 | 2926篇 |
晶体学 | 13篇 |
力学 | 236篇 |
数学 | 801篇 |
物理学 | 803篇 |
出版年
2023年 | 51篇 |
2022年 | 139篇 |
2021年 | 132篇 |
2020年 | 109篇 |
2019年 | 97篇 |
2018年 | 82篇 |
2017年 | 92篇 |
2016年 | 186篇 |
2015年 | 143篇 |
2014年 | 142篇 |
2013年 | 264篇 |
2012年 | 259篇 |
2011年 | 288篇 |
2010年 | 175篇 |
2009年 | 151篇 |
2008年 | 281篇 |
2007年 | 276篇 |
2006年 | 226篇 |
2005年 | 239篇 |
2004年 | 166篇 |
2003年 | 162篇 |
2002年 | 113篇 |
2001年 | 53篇 |
2000年 | 51篇 |
1999年 | 45篇 |
1998年 | 32篇 |
1997年 | 33篇 |
1996年 | 53篇 |
1995年 | 44篇 |
1994年 | 38篇 |
1993年 | 35篇 |
1992年 | 26篇 |
1991年 | 29篇 |
1990年 | 29篇 |
1989年 | 29篇 |
1988年 | 29篇 |
1987年 | 39篇 |
1986年 | 23篇 |
1985年 | 39篇 |
1984年 | 38篇 |
1983年 | 19篇 |
1982年 | 21篇 |
1981年 | 26篇 |
1980年 | 27篇 |
1979年 | 19篇 |
1978年 | 16篇 |
1977年 | 28篇 |
1975年 | 14篇 |
1974年 | 13篇 |
1858年 | 11篇 |
排序方式: 共有4779条查询结果,搜索用时 0 毫秒
41.
Riccardo d'Agostino Vincenzo Colaprico Francesco Cramarossa 《Plasma Chemistry and Plasma Processing》1981,1(4):365-375
The spectroscopic emission intensities from excited F atoms in SF6-O2 discharges at 1 torr have been correlated to the densities of atoms in their ground electronic state by measuring the excitation efficiencies of the electrons in the energy range 11 to 17 eV with a method which essentially consists in the analysis of the emission of Ar or N2, added as actinometer gases to the discharge mixtures. The general applicability of the method has been tested by a direct titration of F atoms with chlorine. The spectroscopic analysis has allowed the determination of useful information on the trends of both the electron densities and their energies as a function of the oxygen percent in the feed. 相似文献
42.
An experimental design procedure was applied to optimize the operating conditions of an axially-viewed inductively coupled plasma emission spectrometer instruments equipped with echelle optics with cross dispersion and charge transfer device. The multivariate effect of carrier gas flow rate and r.f. power on several analytical figures was investigated and discussed. Both ultrasonic and pneumatic nebulization were used. For the final choice of the optimum, different criteria were taken into account, mainly plasma robustness, instrumental precision, analyte and background net emission, detection limits and signal-to-background ratios. It was found that the use of moderate power (1100W) and mean carrier gas flow rate (0.75 L/min) allows to obtain sufficient plasma robustness, satisfactory precision, and excellent signal-to-background ratios and limits of detection, favorable for ultratrace element determinations in environmental matrices. 相似文献
43.
A kinetic assay for total calcium in serum was developed which is based on the activation of Ca(++)-ATPase by free Ca(++) [Ca(++)](f) maintained by EGTA in the reaction mixture. The concentration of Ca(++)(f) was dependent on total reference calcium added or serum calcium. Ca(++)-ATPase activity was coupled to the reduction of NADH by pyruvate kinase (PK) and lactate dehydrogenase (LDH) and monitored by change in absorbance at 340 nm. The calcium in normal serum was 10.08 +/- 0.24 mg/dl (n = 35) by our method while with o-cresolphthalein complexone (CPC) method, the total calcium in the same 35 serum samples was 10.14 +/- 0.54 mg/dl. The range of within-run coefficient of variations (CVs) by this method was 0.9-2.87% at 8-12 mg/dl and day-to-day CVs were 0.72-3.17%. The presence of other ions and standard clinical interfering agents did not affect this assay system. The correlation between values obtained with our method (y) and CPC method (x) for normal serum was: y = 1.064x-0.580 mg/dl (r = 0.912, n = 59). 相似文献
44.
Fabbrizzi L Foti F Licchelli M Maccarini PM Sacchi D Zema M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(21):4965-4972
A cyclam-like macrocycle has been synthesized with a pendant arm containing a dansylamide group. In the corresponding nickel(II) complex, binding of the pendant arm to the metal is pH controlled. In particular, at pH 4.3, the sulfonamide group deprotonates and coordinates the NiII center, giving rise to a complex of trigonal bipyramidal stereochemistry, as shown by X-ray diffraction studies performed on the crystalline complex salt. At pH 7.5, an OH- ion binds the metal and a six-coordinate species forms. The binding-detachment of the pendant arm to/from the NiII center is signaled by changes in the emission properties of the dansyl subunit in the side chain; the fluorescence of this side chain is high when the pendant arm is not coordinated and low when the sulfonamide group is bound to the metal. The system investigated represents the prototype of a light-emitting molecular machine, driven by a pH change. 相似文献
45.
Guldi DM Hirsch A Scheloske M Dietel E Troisi A Zerbetto F Prato M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(20):4968-4979
Control over the interchromophore separation, their angular relationship, and the spatial overlap of their electronic clouds in several ZnP-C(60) dyads (ZnP=zinc porphyrin) is used to modulate the rates of intramolecular electron transfer. For the first time, a detailed analysis of the charge transfer absorption and emission spectra, time-dependent spectroscopic measurements, and molecular dynamics simulations prove quantitatively that the same two moieties can produce widely different electron-transfer regimes. This investigation also shows that the combination of ZnP and C(60) consistently produces charge recombination in the inverted Marcus region, with reorganization energies that are remarkably low, regardless of the solvent polarity. The time constants of electron transfer range from the mus to the ps regime, the electronic couplings from a few tens to several hundreds of cm(-1), and the reorganization energies remain below 0.54 eV and can be as low as 0.16 eV. 相似文献
46.
NMR data have been used to assign the stereochemistry to some new (E)- and (Z)-α-phenyl-β-[2-(N-methyl)nitropyrrolyl]acrylic acids. The (E)-molecules are biased in the s-cis conformation showing NMR spectroscopic features strictly depending on the conformation.The analysis of the NMR spectra reveals that the (Z)-isomers exist also in the s-cis conformation. 相似文献
47.
PI3Kα controls several cellular processes and its aberrant signalling is implicated in tumorigenesis. One of its hotspot mutations, E545K, increases PI3Kα lipid kinase activity, but its mode of action is only partially understood. Here, we perform biased and unbiased molecular dynamics simulations of PI3Kα and uncover, for the first time, the free energy landscape of the E545K PI3Kα mutant. We reveal the mechanism by which E545K leads to PI3Kα activation in atomic-level detail, which is considerably more complex than previously thought.The mechanism by which the cancer-causing E545K mutation may lead to PI3Kα activation is described in atomic-level detail. 相似文献
48.
The apparent molar volumes V of KCl, BaCl2, K2SO4, LaCl3, Co(en)3Cl3 [Tris(ethylenediamine)cobalt(III) chloride], K3Co(CN)6, K3Fe(CN)6, K4Fe(CN)6, and Ba3[Co(CN)6]2 have been determined at 25°C in both light and heavy water. The V values in D2O are systematically lower and increase more rapidly with salt concentration than the V in H2O. The volume of transfer from H2O to D2O as well as the partial molar volume at infinite dilution in both solvents have also been calculated. These results together with literature values for other electrolytes were used to estimate both of these quantities for D2O solutions of individual ions. The predictions of ion hydration models and ion-ion interactions are compared with experimental observations. 相似文献
49.
The reaction of some primary amines with the methyl 2-[(α-oxobenzyl)-(α-bromo)methyl]phenylacetate ( 5 ) afforded the isoquinolinones 7a-d , which in turn were hydrogenated to 10a-d . The synthesis of these compounds was designed on the basis of a potential depressant and antiinflammatory activity found in other structurally related compounds. 相似文献
50.
A convenient route to new 3-quinolinonyl-pyrazoles and isoxazoles is described through cyclization of 3-[(E)-3-(dimethylamino)-2-propenoyl]-4-hydroxy-1-methyl-2(1H)-quinolinone. The phototoxicity as well as the cytotoxic activities of the title compounds are evaluated against leukemia- and adenocarcinoma-derived cell lines in comparison to the normal human keratinocytes. 相似文献