全文获取类型
收费全文 | 345篇 |
免费 | 18篇 |
国内免费 | 1篇 |
专业分类
化学 | 245篇 |
晶体学 | 1篇 |
力学 | 8篇 |
数学 | 64篇 |
物理学 | 46篇 |
出版年
2023年 | 1篇 |
2022年 | 6篇 |
2021年 | 2篇 |
2020年 | 9篇 |
2019年 | 8篇 |
2018年 | 9篇 |
2017年 | 3篇 |
2016年 | 5篇 |
2015年 | 6篇 |
2014年 | 16篇 |
2013年 | 19篇 |
2012年 | 26篇 |
2011年 | 37篇 |
2010年 | 14篇 |
2009年 | 13篇 |
2008年 | 29篇 |
2007年 | 33篇 |
2006年 | 30篇 |
2005年 | 18篇 |
2004年 | 19篇 |
2003年 | 9篇 |
2002年 | 11篇 |
2001年 | 7篇 |
2000年 | 5篇 |
1999年 | 4篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1985年 | 3篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有364条查询结果,搜索用时 62 毫秒
101.
Chen W Wang L Huang C Lin TT Gao XY Loh KP Chen ZK Wee AT 《Journal of the American Chemical Society》2006,128(3):935-939
Electron transfer at the molecule-metal interface of self-assembled monolayers of 1,1';4',1'-terphenyl-4'-thiol (BBB) and its partially fluorinated counterpart (BFF: p-thiophenyl-nonafluorobiphenyl) on Au(111) is investigated by core-hole clock spectroscopy. Ultrafast electron transfer at the BBB/Au(111) interface in the low-femtosecond regime (on the same time scale as the C 1s core-hole lifetime, approximately 6 fs) was observed. In contrast, for BFF/Au(111), the interface electron transfer was forbidden during the core-hole decay. This strongly suggests that fluorination of phenyl rings significantly enhances the localization of the excited electrons in the LUMO. 相似文献
102.
Xie XN Deng M Xu H Yang SW Qi DC Gao XY Chung HJ Sow CH Tan VB Wee AT 《Journal of the American Chemical Society》2006,128(8):2738-2744
We report the creation of polymeric micro/nanostructures which exhibit distinct chemical and physical characteristics from the matrix poly(N-vinyl carbazole) (PVK). The structure formation is based on atomic force microscopy (AFM) facilitated cross-linking and oxygenation. The reaction of PVK with AFM lithographically induced nanoscale discharge produces raised structures in which bridge oxygen links neighboring carbazole groups. The cross-linking by bridge oxygen converts the initially insulating PVK matrix to chemically modified conducting patterns through the formation of extended pi-conjugations. A comprehensive AFM, PES (photoelectron spectroscopy), FTIR (Fourier transform infrared spectroscopy), and DFT (density functional theory) analysis is presented to address the chemophysical identity of the patterned structures. Our results demonstrate new capabilities of AFM nanolithography in generating heterogeneous functional structures in a polymer matrix. 相似文献
103.
Let VI be the category whose objects are the finite dimensional vector spaces over a finite field of order q and whose morphisms are the injective linear maps. A VI-module over a ring is a functor from the category VI to the category of modules over the ring. A VI-module gives rise to a sequence of representations of the finite general linear groups. We prove that the sequence obtained from any finitely generated VI-module over an algebraically closed field of characteristic zero is representation stable - in particular, the multiplicities which appear in the irreducible decompositions eventually stabilize. We deduce as a consequence that the dimension of the representations in the sequence {V n } obtained from a finitely generated VI-module V over a field of characteristic zero is eventually a polynomial in q n . Our results are analogs of corresponding results on representation stability and polynomial growth of dimension for FI-modules (which give rise to sequences of representations of the symmetric groups) proved by Church, Ellenberg, and Farb. 相似文献
104.
Seung Geol Choi Dana Dachman-Soled Tal Malkin Hoeteck Wee 《Designs, Codes and Cryptography》2018,86(3):641-663
We give a new black-box transformation from any semantically secure encryption scheme into a non-malleable one which has a better rate than the best previous work of Coretti et al. (in: Kushilevitz and Malkin (eds) TCC 2016-A, Part I, Springer, Heidelberg, 2016). We achieve a better rate by departing from the “matrix encoding” methodology used by previous constructions, and working directly with a single codeword. We also use a Shamir secret-share packing technique to improve the rate of the underlying error-correcting code. 相似文献
105.
106.
We obtain the exact convergence rate of the stationary distribution (K) of the embedded Markov chain in GI/M/c/K queue to the stationary distribution of the embedded Markov chain in GI/M/c queue as K. Similar result for the time-stationary distributions of queue size is also included. These generalize Choi and Kim's results of the case c=1 by nontrivial ways. Our results also strengthen the Simonot's results [5]. 相似文献
107.
Electrospray ionization (ESI) tandem mass spectrometry (MS/MS) of ternary transition metal complexes of [M(L(3))(N)](2+) (where M = copper(II) or platinum(II); L(3) = diethylenetriamine (dien) or 2,2':6',2'-terpyridine (tpy); N = the nucleobases: adenine, guanine, thymine and cytosine; the nucleosides: 2'deoxyadenosine, 2'deoxyguanosine, 2'deoxythymine, 2'deoxycytidine; the nucleotides: 2'deoxyadenosine 5'-monophosphate, 2'deoxyguanosine 5'-monophosphate, 2'deoxythymine 5'-monophosphate, 2'deoxycytidine 5'-monophosphate) was examined as a means of forming radical cations of the constituents of nucleic acids in the gas phase. In general, sufficient quantities of the ternary complexes [M(L(3))(N)](2+) could be formed for MS/MS studies by subjecting methanolic solutions of mixtures of a metal salt [M(L(3))X(2)] (where M = Cu(II) or Pt(II); L(3) = dien or tpy; X = Cl or NO(3)) and N to ESI. The only exceptions were thymine and its derivatives, which failed to form sufficient abundances of [M(L(3))(N)](2+) ions when: (a) M = Pt(II) and L(3) = dien or tpy; (b) M = Cu(II) and L(3) = dien. In some instances higher oligomeric complexes were formed; e.g., [Pt(tpy)(dG)(n)](2+) (n = 1-13). Each of the ternary complexes [M(L(3))(N)](2+) was mass-selected and then subjected to collision-induced dissociation (CID) in a quadrupole ion trap. The types of fragmentation reactions observed for these complexes depend on the nature of all three components (metal, auxiliary ligand and nucleic acid constituent) and can be classified into: (i) a redox reaction which results in the formation of the radical cation of the nucleic acid constituent, N(+.); (ii) loss of the nucleic acid constituent in its protonated form; and (iii) fragmentation of the nucleic acid constituent. Only the copper complexes yielded radical cations of the nucleic acid constituent, with [Cu(tpy)(N)](2+) being the preferred complex due to suppression, in this case, of the loss of the nucleobase in its protonated form. The yields of the radical cations of the nucleobases from the copper complexes follow the order of their ionization potentials (IPs): G (lowest IP) > A > C > T (highest IP). Sufficient yields of the radical cations of each of the nucleobases allowed their CID reactions (in MS(3) experiments) to be compared to their even-electron counterparts. 相似文献
108.
Solid-phase syntheses of 1,2,4-trisubstituted urazole and thiourazole derivatives have been accomplished. The synthesis began with the coupling of carbonylimidazole-Wang resin with a disubstituted hydrazine. The resultant carbazate was coupled with an isocyanate or isothiocyanate. Subsequent heating of the resin in the presence of triethylamine or potassium t-butoxide induced cyclization and released the desired (thio)urazole into solution. Most of the products were obtained in high yields and purities. Structural diversity can be further expanded at the R(2) substituent by performing the palladium-mediated Suzuki coupling reaction. 相似文献
109.
Five closed-vessel microwave digestion methods were compared for the accurate determination of arsenic and selenium in NIST SRM 1645 River Sediment by flow-injection hydride-generation atomic absorption spectrometric methods. The digestion methods using five different acid mixtures (HNO3/ H2SO4, HNO3/HCl04, HNO3/HCl, HNO3/HCl/HF, HNO3/H2SO4/HClO4) were all found to be reliable for the determination of the analytes. Taking into consideration the safety and suitability for the analysis of other metals, the methods based on the use ofaqua regia are recommended for closed vessel microwave digestion with pressure control. Using the quick digestion program, the presence of up to 10% organic content in soil samples did not adversely affect the closed vessel digestion and did not cause the loss of volatile analytes. After digestion, opening the vessel under an inner pressure of below 345 kPa (50 psi) had no effect on the accuracy of the results. The recommended digestion methods (HNO3/HCl and HNO3/ HCl/HF) for the reliable determination of arsenic and selenium in different sediment samples were demonstrated. The calculated detection limits (3
b
) were less than 0.030 g/g and 0.033 g/g for arsenic and selenium, respectively. All analytical results for arsenic and selenium in SRM 1645 River sediment, NRCC BCSS-1 Marine Sediment and NIES CRM Pond Sediment were within or near the certified and reported ranges, with the exception of selenium in NIES CRM No. 2 Pond Sediment. 相似文献
110.
The thermal depolarization of crystals of NH4Cl polarized above the phase transition temperature (242.5K) by an applied electric field was studied in 13 crystals prepared under a variety of conditions in order to examine the effects of doping with divalent anions or cations and of acid or alkaline conditions during crystal growth. All the features found in crystals grown from solution also occur in a crystal grown from the vapor. We may conclude, therefore, that the depolarization effects observed are properties of crystalline NH4Cl and are not due to water or urea occluded during crystal growth. Four main depolarizations were observed: one of these is ascribed to space charge and the other three are attributed to dipole relaxation processes. The activation energies for these are 0.58, 0.73, and 0.85 eV, respectively. The various doping experiments lead to the conclusion that one of these is favored by acid conditions and the presence of cation vacancies and the other two by alkaline conditions and the presence of anion vacancies. Specific models for the dipolar defects are formulated and discussed. 相似文献