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   850篇
  免费   69篇
  国内免费   1篇
化学   578篇
晶体学   4篇
力学   21篇
数学   80篇
物理学   169篇
无线电   68篇
  2023年   9篇
  2022年   21篇
  2021年   24篇
  2020年   30篇
  2019年   28篇
  2018年   18篇
  2017年   13篇
  2016年   45篇
  2015年   26篇
  2014年   25篇
  2013年   40篇
  2012年   55篇
  2011年   74篇
  2010年   33篇
  2009年   28篇
  2008年   46篇
  2007年   46篇
  2006年   36篇
  2005年   37篇
  2004年   34篇
  2003年   28篇
  2002年   17篇
  2001年   6篇
  2000年   7篇
  1999年   6篇
  1998年   5篇
  1997年   16篇
  1996年   9篇
  1995年   7篇
  1994年   17篇
  1993年   8篇
  1992年   7篇
  1991年   12篇
  1990年   7篇
  1989年   4篇
  1988年   3篇
  1987年   6篇
  1986年   8篇
  1985年   4篇
  1983年   8篇
  1982年   3篇
  1978年   5篇
  1977年   4篇
  1976年   5篇
  1973年   4篇
  1968年   4篇
  1967年   5篇
  1966年   3篇
  1960年   4篇
  1958年   4篇
排序方式: 共有920条查询结果,搜索用时 15 毫秒
731.
In 1985, Erdős and Nešetřil conjectured that the square of the line graph of a graph , that is, , can be colored with colors. This conjecture implies the weaker conjecture that the clique number of such a graph, that is, , is at most . In 2015, Śleszyńska-Nowak proved that . In this paper, we prove that . This theorem follows from our stronger result that where .  相似文献   
732.
733.
734.
The photochemistry of several phthalimido acetamides and phthaloyl dipeptide esters has been investigated. Their photocyclization ability strongly depended on the substitution pattern of the amide linker group. While secondary amide-derived starting materials were largely unreactive, the corresponding tertiary amide-linked derivatives furnished the desired cyclic peptide model compounds in acceptable to good yields (41–80%). The structurally related ester-linked model derivatives also remained unreactive upon irradiation. Preferential hydrogen-abstraction from the E-cis-substituent is suggested to explain the observed differences in cyclization ability.  相似文献   
735.
The hydrogen-release reaction of a complex transition metal hydride, LaMg2NiH7, composed of La3+, 2×Mg2+, [NiH4]4− and 3×H, was studied by thermal analyses, powder X-ray, and neutron diffraction and inelastic neutron scattering. Upon heating, LaMg2NiH7 released hydrogen at approximately 567 K and decomposed into LaH2−3 and Mg2Ni. Before the reaction, covalently bound hydrogen (Hc°v.) in [NiH4]4− exhibited a larger atomic displacement than H, although a weakening of the chemical bonds around [NiH4]4− and H was observed. These results indicate the precursor phenomenon of a hydrogen-release reaction, wherein there is a large atomic displacement of Hc°v. that induces the hydrogen-release reaction rather than H. As an isothermal reaction, LaMg2NiH7 formed LaMg2NiH2.4 at 503 K in vacuum for 48 h, and LaMg2NiH2.4 reacted with hydrogen to reform LaMg2NiH7 at 473 K under 1 MPa of H2 gas pressure for 10 h. These results revealed that LaMg2NiH7 exhibited partially reversible hydrogen-release and uptake reactions.  相似文献   
736.
A novel bimodal fluorescence/MRI probe based on a cyclodextrin scaffold has been synthesized and characterized. The final agent employs the fluorescein (F) functionality as a fluorescence marker and the GdIII complex of a macrocyclic DOTA‐based ligand (GdL) having one aminobenzyl‐phosphinic acid pendant arm as an MRI probe, and has a statistical composition of (GdL)6.9‐F0.1‐β‐CD. Slow rotational dynamics (governed by a very rigid cyclodextrin scaffold) combined with fast water exchange (ensured by the chosen macrocyclic ligand) resulted in a high relaxivity of ~22 s?1 mM ?1 per GdIII or ~150 s?1 mM ?1 per molecule of the final conjugate (20 MHz, 25 °C). In vitro labelling of pancreatic islets (PIs) and rat mesenchymal stem cells has been successfully performed. The agent is not cytotoxic and is easily internalized into cells. The labelled cells can be visualized by MRI, as proved by the detection of individual labelled PIs. A fluorescence study performed on mesenchymal stem cells showed that the agent stays in the intracellular space for a long time.  相似文献   
737.
The preparation of tricyclic amines from acyclic precursors is described using a cascade of tandem reactions involving condensation of an aldehyde with a primary amine, cyclization (with displacement of a halide), and then in situ deprotonation or decarboxylation to give an azomethine ylide or nitrone followed by intramolecular dipolar cycloaddition. The methodology is straightforward, and the aldehyde precursors are prepared easily and quickly in high yield using nitrile alkylations followed by DIBAL-H reduction. The relative ease of reaction of various substrates with different tether lengths between the aldehyde and the halide or dipolarophile has been studied. Several primary amines including simple amino acids such as glycine, alanine, and phenylalanine and derivatives such as glycine ethyl ester and also hydroxylamine have been investigated. High yields are obtained in the formation of different tricyclic ring sizes; the dipolar cycloaddition necessarily creates a five-membered ring, and we have investigated the formation of five- and six-membered rings for the other two new ring sizes. In all cases, yields are high (except when using glycine when the tether to the terminal alkene dipolarophile leads to a six-membered ring), and most efficient is the formation of the tricyclic product in which all five-membered rings are formed. Examples with an alkyne as the dipolarophile were also successful. In all the reactions studied, the products are formed with complete regioselectivity and remarkably with complete stereoselectivity. The key step involves the formation of three new rings and potentially up to four new stereocenters in a single transformation. The power of the chemistry was demonstrated by the synthesis of the core ring systems of the alkaloids (+/-)-scandine and (+/-)-myrioneurinol and the total syntheses of the alkaloids (+/-)-aspidospermine, (+/-)-quebrachamine, and (+/-)-aspidospermidine.  相似文献   
738.
Vibrational properties of the gallium monohydrides SrGaGeH, BaGaSiH, BaGaGeH, and BaGaSnH (AeGaTtH) have been investigated by means of inelastic neutron scattering (INS) and first principles calculations. The compounds contain separated Ga–H units being part of a two dimensional polyanionic layer, [TtGaH]2− (Tt=Si, Ge, Sn). The INS spectra show internal Ga–H bending and stretching modes at frequencies around 900 and 1200 cm−1, respectively. While the stretching mode is virtually invariant with respect to the variable chemical environment of the Ga–H unit, the bending mode frequency varies and is highest for BaGaSiH and lowest for BaGaSnH. The stretching mode is a direct measure of the Ga–H bond strength, whereas the bending mode reflects indirectly the strength of alkaline earth metal–hydrogen interaction. Accordingly, the terminal Ga–H bond in solid state AeGaTtH is distinct, but—compared to molecular gallium hydrides—very weak.  相似文献   
739.
We construct a theory of distributions in the setting of analysis on post-critically finite self-similar fractals, and on fractafolds and products based on such fractals. The results include basic properties of test functions and distributions, a structure theorem showing that distributions are locally-finite sums of powers of the Laplacian applied to continuous functions, and an analysis of the distributions with point support. Possible future applications to the study of hypoelliptic partial differential operators are suggested.  相似文献   
740.
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