首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   547篇
  免费   15篇
化学   373篇
晶体学   2篇
力学   24篇
数学   85篇
物理学   78篇
  2023年   3篇
  2022年   9篇
  2021年   25篇
  2020年   17篇
  2019年   16篇
  2018年   12篇
  2017年   10篇
  2016年   12篇
  2015年   18篇
  2014年   15篇
  2013年   20篇
  2012年   32篇
  2011年   28篇
  2010年   20篇
  2009年   30篇
  2008年   32篇
  2007年   38篇
  2006年   31篇
  2005年   25篇
  2004年   21篇
  2003年   10篇
  2002年   15篇
  2001年   5篇
  2000年   3篇
  1999年   5篇
  1998年   5篇
  1996年   7篇
  1995年   3篇
  1994年   4篇
  1992年   4篇
  1991年   4篇
  1990年   3篇
  1987年   2篇
  1986年   2篇
  1985年   6篇
  1984年   6篇
  1983年   6篇
  1982年   5篇
  1981年   4篇
  1980年   3篇
  1979年   4篇
  1978年   3篇
  1977年   3篇
  1976年   4篇
  1975年   2篇
  1974年   7篇
  1973年   3篇
  1972年   3篇
  1971年   4篇
  1968年   2篇
排序方式: 共有562条查询结果,搜索用时 31 毫秒
111.
Let u μ, x, s (., 0) be the solution of the following well-posed inhomogeneous Cauchy Problem on a complex Banach space X $$\left \{\begin{array}{ll}\dot{u}(t) = A(t)u(t) + e^{i\mu t}x, \quad t > s \\ u(s) = 0. \end{array} \right.$$ Here, x is a vector in X,?μ is a real number, q is a positive real number and A(·) is a q-periodic linear operator valued function. Under some natural assumptions on the evolution family ${\mathcal{U} = \{U(t, s): t \geq s\}}$ generated by the family {A(t)}, we prove that if for each?μ, each s?≥ 0 and every x the solution u μ, x, s (·, 0) is bounded on R + by a positive constant, depending only on x, then the family ${\mathcal{U}}$ is uniformly exponentially stable. The approach is based on the theory of evolution semigroups.  相似文献   
112.
A Calix[6]arene scaffold was functionalized to provide a tridentate binding site at the small rim and three bidentate chelate sites at the large rim of the cone to generate a heteropolytopic ligand. Its complexation to one equivalent of Zn(II) at the small rim yields a funnel complex displaying both host-guest properties and preorganization of the three chelate groups at the large rim. These two aspects allowed the full control of the binding events to regioselectively form dinuclear Zn(II) and heteropolynuclear Zn(II)/Cu(I) complexes. The heteropolynuclear systems all rely on the host-guest relationship thanks to the induced-fit behavior of the calix cavity. With the short guest MeCN, the large rim is preorganized into a trigonal tris-triazole core and accommodates a single Cu(I) ion. A long guest breaks this spatial arrangement, and three Cu(I) ions can then be bound at the tris-bidentate triazole-dimethylamine site at the large rim. In a noncoordinating solvent however, the tetranuclear complex is submitted to scrambling and the addition of exogenous π-acceptor ligands is required to control the binding of Cu(I) in a well-defined environment. Hindrance selectivity was then induced by the accessibility at the small rim site. Indeed, while CO can stabilize Cu(I) at both coordination sites, PPh(3) cannot fit into the cavity and forces Cu(I) to relocate at the large rim. The resulting well-defined symmetrical tetranuclear complex thus arises from the quite remarkable selective supramolecular assembly of nine partners (1 Zn(II), 3 Cu(I), 1 calixarene, 1 guest alkylamine, 3 PPh(3)).  相似文献   
113.
Reduction of dimensionality is crucial for the deeper understanding of the mechanism for large-amplitude conformational transitions of complex molecules. By taking up a six-atomcluster as an illustrative example, we present a general methodology to understand conformational transitions of molecules in terms of the low-dimensional dynamics of molecular gyration radii. The dynamics of gyration radii is generally governed by the interplay between the ordinary potential force and a dynamical force called the internal centrifugal force. We show that the internal centrifugal force can be more important than the original potential barrier and gives rise to a new dynamical barrier that truly dominates the conformational transitions of the system. This kind of dynamical effect should be crucially important in a wide class of molecular reaction dynamics. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
114.
Soft tissue sarcomas (STS) are a rare and highly heterogeneous group of solid tumors, originating from various types of connective tissue. Complete removal of STS by surgery is challenging due to the anatomical location of the tumor, which results in tumor recurrence. Additionally, current polychemotherapeutic regimens are highly toxic with no rational survival benefit. Cold atmospheric plasma (CAP) is a novel technology that has demonstrated immense cancer therapeutic potential. Canady Cold Helios Plasma (CHCP) is a device that sprays CAP along the surgical margins to eradicate residual cancer cells after tumor resection. This preliminary study was conducted in vitro prior to in vivo testing in a humanitarian compassionate use case study and an FDA-approved phase 1 clinical trial (IDE G190165). In this study, the authors evaluate the efficacy of CHCP across multiple STS cell lines. CHCP treatment reduced the viability of four different STS cell lines (i.e., fibrosarcoma, synovial sarcoma, rhabdomyosarcoma, and liposarcoma) in a dose-dependent manner by inhibiting proliferation, disrupting cell cycle, and inducing apoptosis-like cell death.  相似文献   
115.
The reaction of the chromium anionic carbene complex 1 towards diphenylacetylene and phenylacetylene is reported. In the former case the synthesis of γ-functionalized butenolides results after demetallation of the chromium complex 2 and the latter leads to the formation of a novel oligomer chromium complex 5. These complexes were characterized by mass spectrometry, IR and 1H and 13C NMR spectroscopies and their structures were confirmed by single-crystal X-ray analysis.  相似文献   
116.
Rotational spectra of three isotopic species of carbonyl chlorofluoride, OCCIF, have been extensively measured, and have been analyzed for rotational constants, quartic centrifugal distortion constants, and chlorine nuclear quadrupole coupling constants. Ab initio calculations of the harmonic force field have been made using several different sets of basis functions, and their relative cost efficiency has been assessed. The measured distortion constants have been combined with vibrational wavenumbers (both from the literature and from the present work) and with the ab initio force constants to refine the force field. Ground state effective (r0) and average (rz) structures have been evaluated for the molecule.  相似文献   
117.
Abstract— The damaging effects of near ultraviolet and visible light on WI-38 human diploid lung fibroblasts were investigated. WI-38 cells in culture were killed by light doses ranging from 2 to 10 × 103 W/m2 h. There was an inverse correlation between culture age, i.e. population doubling level and photosensitivity. However, this effect could not be related to capacity for DNA synthesis and cell division.
Flavins were clearly implicated as endogenous photosensitizers, and antioxidants such as d, l -α-tocopherol (vitamin E), BHT and ascorbic acid were found to afford the cells protection from light damage. Furthermore, products of lipid peroxidation could be detected in cell homogenates irradiated in the presence of ribofiavin.  相似文献   
118.
TFDA is readily prepared from the reaction of fluorosulfonyldifluoroacetic acid with trimethylsilyl chloride, and it is a very effective and efficient source of difluorocarbene for use in addition reactions to alkenes of a broad scope of reactivities. Acid-sensitive substrates may require an additional purification step involving treatment of the distilled TFDA with sufficient Et3N to remove the acid impurity. Other trialkylsilyl fluorosulfonyldifluoroacetates can also be prepared, and they have been found to have reactivities similar to TFDA. The triethyl derivative, TEFDA is more convenient to prepare in a pure state and has similar reactivity to TFDA. Thus, it may prove to be a superior reagent.  相似文献   
119.
Glass wool was placed within an NMR tube as a solid support for the covalent attachment of a molecule to allow for a simple one-dimensional 1H FT NMR solution analysis. This novel procedure avoids the use of expensive sample tubes or platforms, as required for magic angle or fast spinning, exotic pulse sequences, isotopic labeling or the use of a large number of scans to provide the ability to analyze the structure, mobility, ligand binding, and solvent interactions of the surface bound molecule.  相似文献   
120.
Laser-ablated U atoms react with discharged sulfur vapor in excess argon to form the US, US(2), and US(3) molecules, which are identified from matrix infrared spectra using sulfur isotopic substitution. Vibrational frequencies from quasirelativistic DFT calculations support these assignments and provide an insight into the bonding and structure. Unlike linear UO(2), US(2) is bent because of more favorable U(6d)-S(3p) overlap, and US(2) has a 118 +/- 5 degrees (experimental based on isotopic shift) or 121 degrees (calculated (3)B(2) ground state, B3LYP) S-U-S bond angle.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号