全文获取类型
收费全文 | 175篇 |
免费 | 4篇 |
国内免费 | 1篇 |
专业分类
化学 | 138篇 |
晶体学 | 1篇 |
数学 | 7篇 |
物理学 | 34篇 |
出版年
2021年 | 1篇 |
2019年 | 1篇 |
2017年 | 2篇 |
2016年 | 1篇 |
2015年 | 2篇 |
2014年 | 3篇 |
2013年 | 8篇 |
2012年 | 4篇 |
2011年 | 7篇 |
2010年 | 3篇 |
2009年 | 3篇 |
2008年 | 12篇 |
2007年 | 14篇 |
2006年 | 9篇 |
2005年 | 16篇 |
2004年 | 13篇 |
2003年 | 7篇 |
2002年 | 11篇 |
2001年 | 10篇 |
2000年 | 5篇 |
1999年 | 2篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1970年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有180条查询结果,搜索用时 0 毫秒
51.
Schatte G Chivers T Tuononen HM Suontamo R Laitinen R Valkonen J 《Inorganic chemistry》2005,44(2):443-451
The hydrolysis of (t)BuNTe(mu-N(t)Bu)(2)TeN(t)Bu (1) with 1 or 2 equiv of (C(6)F(5))(3)B.H(2)O results in the successive replacement of terminal imido groups by oxo ligands to give the telluroxane-Lewis acid adducts (C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)TeN(t)Bu (2) and [(C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)Te(mu-O)](2) (3), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. The Te=O distance in 2 is 1.870(2) A. The di-adduct 3 involves the association of four (t)()BuNTeO monomers to give a tetramer in which both terminal Te=O groups [d(TeO) = 1.866(3) A] are coordinated to B(C(6)F(5))(3). The central Te(2)O(2) ring in 3 is distinctly unsymmetrical [d(TeO) = 1.912(3) and 2.088(2) A]. The X-ray structure of (C(6)F(5))(3)B.NH(2)(t)()Bu (4), the byproduct of these hydrolysis reactions, is also reported. The geometries and energies of tellurium(IV) diimides and imido telluroxanes were determined using quantum chemical calculations. The calculated energies for the reactions E(NR)(2) + Te(NR)(2) (E = S, Se, Te; R = H, Me, (t)Bu, SiMe(3)) confirm that cyclodimerization of tellurium(IV) diimides is strongly exothermic. In the mixed-chalcogen systems, the cycloaddition is energetically favorable for the Se/Te combination. The calculated energies for the further oligomerization of the dimers XE(mu-NMe)(2)EX (E = Se, Te; X = NMe, O) indicate that the formation of tetramers is strongly exothermic for the tellurium systems but endothermic (X = NMe) or thermoneutral (X = O) for the selenium systems, consistent with experimental observations. 相似文献
52.
A systematic approach to the design of ultrasonic test tanks is outlined in which criteria are given first for the choice of tank length and subsequently for the choice of tank width and height. Calculations are presented for typical transducer beam measurements in the low megahertz frequency range, indicating the individual and combined effects of side lobe inclusion and excitation pulse length. The methods used may be easily extended to determine, for a given situation, either the minimum tank size that needs to be used, or the limits imposed by an existing tank on the experiments that can be performed in it. 相似文献
53.
54.
We reveal the existence of asymmetric vortex solitons in ideally symmetric periodic lattices and show how such nonlinear localized structures describing elementary circular flows can be analyzed systematically using the energy-balance relations. We present the examples of rhomboid, rectangular, and triangular vortex solitons on a square lattice and also describe novel coherent states where the populations of clockwise and anticlockwise vortex modes change periodically due to a nonlinearity-induced momentum exchange through the lattice. Asymmetric vortex solitons are expected to exist in different nonlinear lattice systems, including optically induced photonic lattices, nonlinear photonic crystals, and Bose-Einstein condensates in optical lattices. 相似文献
55.
Yunyan Qiu Jacob Mohin Chia‐Hua Tsai Stephanie Tristram‐Nagle Roberto R. Gil Tomasz Kowalewski Kevin J. T. Noonan 《Macromolecular rapid communications》2015,36(9):840-844
A commercially available palladium N‐heterocyclic carbene (Pd‐NHC) precatalyst is used to initiate chain‐growth polymerization of 2‐bromo‐3‐hexyl‐5‐trimethylstannylthiophene. The molecular weight of the resultant poly(3‐hexylthiophene) can be modulated (7 to 73 kDa, Đ = 1.14 to 1.53) by varying the catalyst concentration. Mass spectrometry data confirm control over the polymer end groups and 1H NMR spectroscopy reveals that the palladium catalyst is capable of “ring‐walking”. A linear relationship between Mn and monomer conversion is observed. Atomic force microscopy and X‐ray scattering verify the regioregular nature of the resultant polythiophene.
56.
The reaction of BCl(3) with two equivalents of LiN(H)Dipp (Dipp = 2,6-diisopropylphenyl) in THF produces DippN(H)BO(CH(2))(4)NDipp, which contains a puckered seven-membered C(4)OBN ring. 相似文献
57.
We introduce a novel class of stable lattice solitons with a complex phase structure composed of many single-charge discrete vortices in a triangular photonic lattice. We demonstrate that such nonlinear self-trapped states are linked to the resonant Bloch modes, which bear a honeycomb pattern of phase dislocations. 相似文献
58.
We study the polytopes of affine maps between two polytopes—the hom-polytopes. The hom-polytope functor has a left adjoint—tensor product polytopes. The analogy with the category of vector spaces is limited, as we illustrate by a series of explicit examples exhibiting various extremal properties. The main challenge for hom-polytopes is to determine their vertices. A polytopal analogue of the rank-nullity theorem amounts to understanding how the vertex maps behave relative to their surjective and injective factors. This leads to interesting classes of surjective maps. In the last two sections we focus on two opposite extremal cases—when the source and target polytopes are both polygons and are either generic or regular. 相似文献
59.
Two-electron oxidation of the [C(PPh(2)S)(2)](2-) dianion with iodine afforded an unexpected mixture of a dimeric Li-I carbenoid [(Et(2)O)(mu-Li)][(mu(4)-Li){IC(PPh(2)S)(2)}(2)] and a novel, unsaturated six-membered C(2)P(2)S(2) ring in [(SPh(2)P)(2)C(2)(PPh(2))(2)S(2)]. 相似文献
60.
The reaction of R'NHLi (R = (t)Bu, (t)Oct) with Ph(2)P(NSiMe(3))(2)Te(Cl)NPPh(2)NSiMe(3) in toluene at -78 degrees C, followed by warming to 23 degrees C, produces the tellurium diimide dimers RNTe(&mgr;-NR')(2)TeNR (2a, R' = (t)Bu, R = NPPh(2)NSiMe(3); 2b, R' = (t)Oct, R = NPPh(2)NSiMe(3)) and Ph(2)P(NHSiMe(3))(NSiMe(3)). X-ray analyses revealed that 2a and 2b have centrosymmetric structures containing a planar four-membered Te(2)N(2) ring and short exocyclic tellurium-nitrogen bond lengths (d(Te-N) = 1.900(5) and 1.897(4) or 1.905(4) ? for 2a and 2b, respectively). The exocyclic imido substituents adopt a trans arrangement with respect to the Te(2)N(2) ring. By contrast, the reaction of 2,4,6-(t)Bu(3)C(6)H(2)NHLi with Ph(2)P(NSiMe(3))(2)Te(Cl)NPPh(2)NSiMe(3) in toluene under similar conditions produces the telluradiazole ((t)Bu(2)C(6)H(2)N(2)Te)(2) (3), which exists as a weakly associated dimer in the solid state with intramolecular Te-N distances of 2.628(4) ?. The tellurium diimide dimer (t)BuNTe(&mgr;-N(t)Bu)(2)TeN(t)Bu (2c'), prepared by the reaction of TeCl(4) with (t)BuNHLi in a 1:4 molar ratio, consists of a folded Te(2)N(2) ring with exocyclic N(t)Bu groups in a cis orientation. The (1)H, (31)P, and (125)Te NMR spectra of 2a and 2b indicate that the trans isomers slowly transform into the corresponding cis isomers in solution. Crystals of 2b are triclinic, space group P&onemacr; (No. 2), with a = 13.304(3) ?, b = 16.927(3) ?, c = 13.292(5) ?, alpha = 98.94(2), beta = 109.27(2), gamma = 69.04(2) degrees, V = 2636(1) ?(3), and Z = 4. The final R and R(w) values were 0.034 and 0.033, respectively. Crystals of 2c' are orthorhombic, space group Pnma (No. 62), with a = 9.535(3) ?, b = 14.264(3) ?, c = 16.963(4) ?, V = 2307.1(9) ?(3), and Z = 4. The final R and R(w) values were 0.040 and 0.040, respectively. Crystals of 3 are monoclinic, space group P2(1)/n (No. 14), with a = 9.117(3) ?, b = 11.481(4) ?, c = 16.550(4) ?, beta = 97.76(2) degrees, V = 1716.5(8) ?(3), and Z = 4. The final R and R(w) values were 0.031 and 0.034, respectively. 相似文献