全文获取类型
收费全文 | 467篇 |
免费 | 15篇 |
国内免费 | 7篇 |
专业分类
化学 | 361篇 |
晶体学 | 2篇 |
力学 | 10篇 |
数学 | 53篇 |
物理学 | 63篇 |
出版年
2023年 | 2篇 |
2022年 | 1篇 |
2021年 | 6篇 |
2020年 | 4篇 |
2019年 | 6篇 |
2018年 | 6篇 |
2017年 | 3篇 |
2016年 | 5篇 |
2015年 | 13篇 |
2014年 | 16篇 |
2013年 | 23篇 |
2012年 | 35篇 |
2011年 | 35篇 |
2010年 | 12篇 |
2009年 | 13篇 |
2008年 | 33篇 |
2007年 | 38篇 |
2006年 | 32篇 |
2005年 | 47篇 |
2004年 | 36篇 |
2003年 | 26篇 |
2002年 | 27篇 |
2001年 | 3篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1996年 | 1篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 7篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1970年 | 1篇 |
1929年 | 1篇 |
排序方式: 共有489条查询结果,搜索用时 218 毫秒
71.
Brent S. Lindsay Allen G. Oliver Cliff E. F. Rickard Brent R. Copp 《Journal of chemical crystallography》1998,28(8):645-648
2-Bromoleptoclinidinone methanol solvate, C18H8BrN3O·CH4O, crystallizes in the orthorhombic space group Pbca with a = 15.7013(2), b = 7.3308(1), and c = 26.9326(1) Å. The molecule is essentially planar, with the largest deviations occurring at bromine (–0.21 Å), carbonyl oxygen O(l) (+0.19 Å) and in ring-A (C(9) –0.15 Å, C(10) –0.15 Å). Methanol occupies the 1,10-phenanthroline-like metal binding site of the title compound. 相似文献
72.
Atiyah and Bott used equivariant Morse theory applied to theYang–Mills functional to calculate the Betti numbers ofmoduli spaces of vector bundles over a Riemann surface, rederivinginductive formulae obtained from an arithmetic approach whichinvolved the Tamagawa number of SLn. This article attempts tosurvey and extend our understanding of this link between Yang–Millstheory and Tamagawa numbers, and to explain how methods usedover the last three decades to study the singular cohomologyof moduli spaces of bundles on a smooth projective curve over can be adapted to the setting of 1-homotopy theory to studythe motivic cohomology of these moduli spaces over an algebraicallyclosed field. 相似文献
73.
High throughput screening (HTS) for complex diseases is challenging. This stems from the fact that complex phenotypes are difficult to adapt to rapid, high throughput assays. We describe the recent development of high throughput and high-content screens (HCS) for neurodegenerative diseases, with a focus on inherited neurodegenerative disorders, such as Huntington's disease. We describe, among others, HTS assays based on protein aggregation, neuronal death, caspase activation and mutant protein clearance. Furthermore, we describe high-content screens that are being used to prioritize hits identified in such HTS assays. These assays and screening approaches should accelerate drug discovery for neurodegenerative disorders and guide the development of screening approaches for other complex disease phenotypes. 相似文献
74.
Munro-Leighton C Delp SA Alsop NM Blue ED Gunnoe TB 《Chemical communications (Cambridge, England)》2008,(1):111-113
Monomeric Cu(I) amido and thiolate complexes that are supported by the N-heterocyclic carbene ligand 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) catalyze the hydroamination and hydrothiolation of electron-deficient vinylarenes with reactivity patterns that are consistent with an intermolecular nucleophilic addition of the amido/thiolate ligand of (IPr)Cu(XR) (X = NH or S; R = Ph, CH2Ph) to free vinylarene. 相似文献
75.
Millare B Thomas M Ferreira A Xu H Holesinger M Vullev VI 《Langmuir : the ACS journal of surfaces and colloids》2008,24(22):13218-13224
Treatment with oxygen-containing plasma is an essential step for the fabrication of devices containing components of polydimethylsiloxane (PDMS). Such oxidative treatment chemically modifies the surface of PDMS allowing it to permanently adhere to glass, quartz, PDMS and other silica-based substrates. Overexposure of PDMS to oxidative gas plasma, however, compromises its adhesiveness. Therefore, regulation of the duration and the conditions of the plasma treatment is crucial for achieving sufficient surface activation without overoxidation. Using a semiquantitative ternary approach, we evaluated the quality of adhesion ( QA) between flat PDMS and glass substrates pretreated with oxygen plasma under a range of different conditions. The quality of adhesion manifested good correlation trends with the surface properties of the pretreated PDMS. Examination of the QA dependence on the treatment duration and on the pressure and the RF power of the plasma revealed a range of oxidative conditions that allowed for permanent adhesion with quantitative yields. 相似文献
76.
Thompson DW Fleming CN Myron BD Meyer TJ 《The journal of physical chemistry. B》2007,111(24):6930-6941
The salts [Ru(bpy)3](PF6)2, cis-[Ru(bpy)2(py)2](PF6)2, trans-[Ru(bpy)2(4-Etpy)2](PF6)2, [Ru(tpy)2](PF6)2, and [Re(bpy)(CO)3(4-Etpy)](PF6) (bpy=2,2'-bipyridine, py=pyridine, 4-Etpy=4-ethylpyridine, and tpy=2,2':6',2-terpyridine) have been incorporated into poly(methyl methacrylate) (PMMA) films and their photophysical properties examined by both steady-state and time-resolved absorption and emission measurements. Excited-state lifetimes for the metal salts incorporated in PMMA are longer and emission energies enhanced due to a rigid medium effect when compared to fluid CH3CN solution. In PMMA part of the fluid medium reorganization energy, lambdaoo, contributes to the energy gap with lambdaoo approximately 700 cm-1 for [Ru(bpy)3](PF6)2 from emission measurements. Enhanced lifetimes can be explained by the energy gap law and the influence of the excited-to-ground state energy gap, Eo, on nonradiative decay. From the results of emission spectral fitting on [Ru(bpy)3](PF6)2* in PMMA, Eo is temperature dependent above 200 K with partial differentialEo/ partial differentialT=2.8 cm-1/deg. cis-[Ru(bpy)2(py)2](PF6)2 and trans-[Ru(bpy)2(4-Etpy)2](PF6)2 are nonemissive in CH3CN and undergo photochemical ligand loss. Both emit in PMMA and are stable toward ligand loss even for extended photolysis periods. The lifetime of cis-[Ru(bpy)2(py)2](PF6)2* in PMMA is temperature dependent, consistent with a contribution to excited-state decay from thermal population and decay through a low-lying dd state or states. At temperatures above 190 K, coinciding with the onset of the temperature dependence of Eo for [Ru(bpy)3](PF6)2*, lifetimes become significantly nonexponential. The nonexponential behavior is attributed to dynamic coupling between MLCT and dd states, with the lifetime of the latter greatly enhanced in PMMA with tau approximately 3 ns. On the basis of these data and data in 4:1 (v/v) EtOH/MeOH, the energy gap between the MLCT and dd states is decreased by approximately 700 cm-1 in PMMA with the dd state at higher energy by DeltaH0 approximately 1000 cm-1. The "rigid medium stabilization effect" for cis-[Ru(bpy)2(py)2](PF6)2* in PMMA is attributed to inhibition of metal-ligand bond breaking and a photochemical cage effect. 相似文献
77.
We have explored the impact of a number of basic simulation parameters on the results of a recently developed hybrid molecular dynamics-quantum mechanics (MD-QM) method (Mercer et al., J Phys Chem B 1999, 103, 7720). The method utilizes MD simulations to explore the ground-state configuration space of the system and QM evaluation of those structures to yield the time-dependent electronic transition energy, which is transformed into the optical line-broadening function using the second-order cumulant expansion. Both linear and nonlinear optical spectra can then be generated for comparison to experiment. The dependence of the resulting spectra on the length of the MD trajectory, the QM sampling rate, and the QM model chemistry have all been examined. In particular, for the system of oxazine-4 in methanol studied here, at least 20 ps of MD trajectory are needed for qualitative convergence of linear spectral properties, and >100 ps is needed for quantitative convergence. Surprisingly, little difference is found between the 3-21G and 6-31G(d) basis sets, and the CIS and TD-B3LYP methods yield remarkably similar spectra. The semiempirical INDO/s method yields the most accurate results, reproducing the experimental Stokes shift to within 5% and the FWHM to within 20%. Nonlinear 3-pulse photon echo peak shift (3PEPS) decays have also been simulated. Decays are generally poorly reproduced, though the initial peak shift which depends on the overall coupling of motions to the solute transition energy is within 15% of experiment for all model chemistries other than those using the STO-3G basis. 相似文献
78.
79.
Foley NA Lail M Lee JP Gunnoe TB Cundari TR Petersen JL 《Journal of the American Chemical Society》2007,129(21):6765-6781
Complexes of the type TpRu(L)(NCMe)R [L = CO or PMe3; R = Ph or Me; Tp = hydridotris(pyrazolyl)borate] initiate C-H activation of benzene. Kinetic studies, isotopic labeling, and other experimental evidence suggest that the mechanism of benzene C-H activation involves reversible dissociation of acetonitrile, reversible benzene coordination, and rate-determining C-H activation of coordinated benzene. TpRu(PMe3)(NCMe)Ph initiates C-D activation of C6D6 at rates that are approximately 2-3 times more rapid than that for TpRu(CO)(NCMe)Ph (depending on substrate concentration); however, the catalytic hydrophenylation of ethylene using TpRu(PMe3)(NCMe)Ph is substantially less efficient than catalysis with TpRu(CO)(NCMe)Ph. For TpRu(PMe3)(NCMe)Ph, C-H activation of ethylene, to ultimately produce TpRu(PMe3)(eta3-C4H7), is found to kinetically compete with catalytic ethylene hydrophenylation. In THF solutions containing ethylene, TpRu(PMe3)(NCMe)Ph and TpRu(CO)(NCMe)Ph separately convert to TpRu(L)(eta3-C4H7) (L = PMe3 or CO, respectively) via initial Ru-mediated ethylene C-H activation. Heating mesitylene solutions of TpRu(L)(eta3-C4H7) under ethylene pressure results in the catalytic production of butenes (i.e., ethylene hydrovinylation) and hexenes. 相似文献
80.
Flickinger BD 《Journal of AOAC International》2007,90(5):1465-1469
The role of dietary fat in health and wellness continues to evolve. In today's environment, trans fatty acids and obesity are issues that are impacted by dietary fat. In response to new information in these areas, changes in the amount and composition of edible fats and oils have occurred and are occurring. These compositional changes include variation in fatty acid composition and innovation in fat structure. Soybean, canola, and sunflower are examples of oilseeds with varied fatty acid composition, including mid-oleic, high-oleic, and low-linolenic traits. These trait-enhanced oils are aimed to displace partially hydrogenated vegetable oils primarily in frying applications. Examples of oils with innovation in fat structure include enzyme interesterified (EIE) fats and oils and diacylglycerol oil. EIE fats are a commercial edible fat innovation, where a lipase is used to modify the fat structure of a blend of hard fat and liquid oil. EIE fats are aimed to displace partially hydrogenated vegetable oils in baking and spread applications. Diacylglycerol and medium-chain triglyceride (MCT)-based oils are commercial edible oil innovations. Diacylglycerol and MCT-based oils are aimed for individuals looking to store less of these fats as body fat when they are used in place of traditional cooking and salad oils. 相似文献