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   378篇
  免费   16篇
  国内免费   3篇
化学   234篇
晶体学   5篇
力学   3篇
数学   61篇
物理学   94篇
  2021年   8篇
  2020年   16篇
  2019年   9篇
  2018年   6篇
  2017年   5篇
  2016年   12篇
  2015年   9篇
  2014年   12篇
  2013年   13篇
  2012年   14篇
  2011年   15篇
  2010年   7篇
  2009年   14篇
  2008年   12篇
  2007年   17篇
  2006年   14篇
  2005年   21篇
  2004年   14篇
  2003年   13篇
  2002年   8篇
  2001年   13篇
  2000年   7篇
  1999年   11篇
  1998年   4篇
  1996年   6篇
  1995年   11篇
  1994年   7篇
  1993年   11篇
  1992年   2篇
  1991年   5篇
  1990年   7篇
  1989年   5篇
  1988年   4篇
  1985年   3篇
  1984年   2篇
  1983年   2篇
  1981年   4篇
  1979年   2篇
  1978年   3篇
  1977年   4篇
  1976年   2篇
  1974年   5篇
  1973年   6篇
  1972年   7篇
  1971年   2篇
  1970年   3篇
  1969年   3篇
  1968年   3篇
  1967年   2篇
  1955年   2篇
排序方式: 共有397条查询结果,搜索用时 15 毫秒
41.
A procedure for obtaining explicit expressions for Feynman integrals ofp-adic argument in momentum space is described, and the connection with Feynman amplitudes over a finite field and chromatic polynomials is indicated. Simple explicit expressions are given for the results of integration over the region of large and small momenta.Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 104, No. 3, pp. 371–392, September, 1995.  相似文献   
42.
Silicon analogues of the most prominent carbon nanostructures, namely, hollow spheroidals such as C60 and the fullerene family, have been unknown to date. Herein we show that discrete Si20 dodecahedra, stabilized by an endohedral guest and valence saturation, are accessible in preparative yields through a chloride‐induced disproportionation reaction of hexachlorodisilane in the presence of tri(n‐butyl)amine. X‐ray crystallography revealed that each silicon dodecahedron contains an endohedral chloride ion that imparts a net negative charge. Eight chloro substituents and twelve trichlorosilyl groups are attached to the surface of each cluster in a strictly regioregular arrangement, a thermodynamically preferred substitution pattern according to quantum‐chemical assessment. Our results demonstrate that the wet‐chemical self‐assembly of a complex, monodisperse Si nanostructure is possible under mild conditions starting from simple Si2 building blocks.  相似文献   
43.
Herein we show that replacing the two meso carbon atoms of the polycyclic aromatic hydrocarbon (PAH) bisanthene by boron atoms transforms a near‐infrared dye into an efficient blue luminophore. This observation impressively illustrates the impact of boron doping on the frontier orbitals of PAHs. To take full advantage of this tool for the targeted design of organic electronic materials, the underlying structure–property relationships need to be further elucidated. We therefore developed a modular synthesis sequence based on a Peterson olefination, a stilbene‐type photocyclization, and an Si–B exchange reaction to substantially broaden the palette of accessible polycyclic aromatic organoboranes and to permit a direct comparison with their PAH congeners.  相似文献   
44.
The targeted hydrolysis of the 9,10-dihydro-9,10-diboraanthracene adduct (Me(2)S)HB(C(6)H(4))(2)BH(SMe(2)) (1) with 0.5 equiv of H(2)O leads to formation of the borinic acid anhydride [(Me(2)S)HB(C(6)H(4))(2)B](2)O (2) and thereby provides access to the field of unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracenes. Compound 2 reacts with tBuC≡CH to give the corresponding vinyl derivative in an essentially quantitative conversion. Subsequent cleavage of the B-O-B bridge by LiAlH(4) with formation of hydridoborate functionalities is possible but is accompanied by partial B-C(vinyl) bond degradation. This situation changes when the related mesityl derivative [MesB(C(6)H(4))(2)B](2)O (7) is employed, which can be synthesized from BrB(C(6)H(4))(2)BBr (6) by treatment with 1 equiv of MesMgBr and subsequent hydrolysis. The reaction of 7 with LiAlH(4) in tetrahydrofuran (THF) furnishes Li[MesB(C(6)H(4))(2)BH(2)] (8); hydride elimination with Me(3)SiCl leads to formation of the THF adduct MesB(C(6)H(4))(2)BH(THF) (9·THF). Alternatively, 7 can be transformed into the bromoborane MesB(C(6)H(4))(2)BBr (10) by treatment with BBr(3). A Br/H-exchange reaction between 10 and Et(3)SiH yields the donor-free borane MesB(C(6)H(4))(2)BH (9), which forms B-H-B bridged dimers (9)(2) in the solid state. The vinyl borane MesB(C(6)H(4))(2)BC(H)=C(H)Mes (14) is accessible from MesC≡CH and either 9·THF or 9. Compared with the related compound Mes(2)BC(H)=C(H)Mes, the electronic absorption and emission spectra of 14 reveal bathochromic shifts of Δλ(abs)=17 nm and Δλ(em)=74 nm, which can be attributed to the rigid, fully delocalized π framework of the [MesB(C(6)H(4))(2)B] chromophore.  相似文献   
45.
The dimethyl sulfide adduct 2(DMS) is a crystalline storage form of the unstable hydroboration reagent 9-H-9-borafluorene (2); 2(DMS) is available by the addition of DMS to either in situ generated [2](2) or 1,2-(2,2'-biphenylylene)diborane(6) (7).  相似文献   
46.
The isoelectronic replacement of C Created by potrace 1.16, written by Peter Selinger 2001-2019 C bonds with B Created by potrace 1.16, written by Peter Selinger 2001-2019 N+ bonds in polycyclic aromatic hydrocarbons (PAHs) is a widely used tool to prepare novel optoelectronic materials. Far less well explored are corresponding B,O-doped PAHs, although they have a similarly high application potential. We herein report on the modular synthesis of B,N- and B,O-doped PAHs through the [Au(PPh3)NTf2]-catalyzed 6-endo-dig cyclization of BN–H and BO–H bonds across suitably positioned C Created by potrace 1.16, written by Peter Selinger 2001-2019 C bonds in the key step. Readily available, easy-to-handle o-alkynylaryl boronic and borinic acids serve as starting materials, which are either cyclized directly or first converted into the corresponding aminoboranes and then cyclized. The reaction even tolerates bulky mesityl substituents on boron, which later kinetically protect the formed B,N/O-PAHs from hydrolysis or oxidation. Our approach is also applicable for the synthesis of rare doubly B,N/O-doped PAHs. Specifically, we prepared 1,2-B,E-naphthalenes and -anthracenes, 1,5-B2-2,6-E2-anthracenes (E = N, O) as well as B,O2-containing and unprecedented B,N,O-containing phenalenyls. Selected examples of these compounds have been structurally characterized by X-ray crystallography; their optoelectronic properties have been studied by cyclic voltammetry, electron spectroscopy, and quantum-chemical calculations. Using a new unsubstituted (B,O)2-perylene as the substrate for late-stage functionalization, we finally show that the introduction of two pinacolatoboryl (Bpin) substituents is possible in high yield and with perfect regioselectivity via an Ir-catalyzed C–H borylation approach.

Singly and doubly B,E-doped PAHs were synthesized using a protocol that starts from easy-to-handle boronic and borinic acids and offers the possibility to choose between the preparation of B,O- and B,N-PAHs in the final reaction step.  相似文献   
47.
Despite the great promise of carbon nanotube field-effect transistors (CNT FETs) for applications in chemical and biochemical detection, a quantitative understanding of sensor responses is lacking. To explore the role of electrostatics in sensor transduction, experiments were conducted with a set of highly similar compounds designed to adsorb onto the CNT FET via a pyrene linker group and take on a set of known charge states under ambient conditions. Acidic and basic species were observed to induce threshold voltage shifts of opposite sign, consistent with gating of the CNT FET by local charges due to protonation or deprotonation of the pyrene compounds by interfacial water. The magnitude of the gate voltage shift was controlled by the distance between the charged group and the CNT. Additionally, functionalization with an uncharged pyrene compound showed a threshold shift ascribed to its molecular dipole moment. This work illustrates a method for producing CNT FETs with controlled values of the turnoff gate voltage, and more generally, these results will inform the development of quantitative models for the response of CNT FET chemical and biochemical sensors.  相似文献   
48.
A quantum diffusion of 2-D electrons at a metal substrate has been shown to arise because of surface-bulk interaction via hybridization provided that the surface Fermi momentum has been smaller than the bulk one. The diffusion coefficient D has been found to depend nonmonotonously on sample dimensions L. An initial decrease in D has turned into an increase for sufficiently large L. The minimum in D has nonanalytically depended on the hybridization constant: Dmin~g43. The effects predicted have resulted from the instability of the zero-component nonlinear σ-model with respect to inclusion of certain symmetry — breaking terms which have proved to increase under RG transformations.  相似文献   
49.
50.
Solvent-free [LiCH2SMe]infinity forms a layer structure consisting of four- (Li2C2), five- (Li2CS2), and six-membered (Li2C2S2) rings in the solid state; the compound violently explodes upon heating to T=160+/-5 degrees C under an argon atmosphere.  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