全文获取类型
收费全文 | 1805篇 |
免费 | 53篇 |
国内免费 | 10篇 |
专业分类
化学 | 1073篇 |
晶体学 | 14篇 |
力学 | 43篇 |
数学 | 430篇 |
物理学 | 308篇 |
出版年
2020年 | 16篇 |
2019年 | 18篇 |
2018年 | 12篇 |
2017年 | 16篇 |
2016年 | 32篇 |
2015年 | 32篇 |
2014年 | 33篇 |
2013年 | 92篇 |
2012年 | 80篇 |
2011年 | 94篇 |
2010年 | 53篇 |
2009年 | 44篇 |
2008年 | 84篇 |
2007年 | 81篇 |
2006年 | 97篇 |
2005年 | 93篇 |
2004年 | 65篇 |
2003年 | 67篇 |
2002年 | 84篇 |
2001年 | 21篇 |
2000年 | 32篇 |
1999年 | 26篇 |
1998年 | 28篇 |
1997年 | 30篇 |
1996年 | 27篇 |
1995年 | 15篇 |
1994年 | 31篇 |
1993年 | 27篇 |
1992年 | 21篇 |
1991年 | 22篇 |
1990年 | 19篇 |
1989年 | 17篇 |
1988年 | 13篇 |
1987年 | 18篇 |
1986年 | 18篇 |
1985年 | 20篇 |
1984年 | 30篇 |
1983年 | 21篇 |
1982年 | 30篇 |
1981年 | 33篇 |
1980年 | 28篇 |
1979年 | 23篇 |
1978年 | 30篇 |
1977年 | 23篇 |
1976年 | 20篇 |
1975年 | 17篇 |
1974年 | 20篇 |
1973年 | 19篇 |
1972年 | 14篇 |
1971年 | 13篇 |
排序方式: 共有1868条查询结果,搜索用时 15 毫秒
41.
Jerald S. Bradshaw Ralph B. Nielsen Pui-Kwan Tse Giuseppi Arena Bruce E. Wilson N. Kent Dalley John D. Lamb James J. Christensen Reed M. Izatt 《Journal of heterocyclic chemistry》1986,23(2):361-368
A series of macrocyclic polyether (crown) ligands containing the proton-ionizable s-triazole subcyclic unit were prepared by reacting the 1-THP blocked 3,5-bis(chloromethyl)-1H-1,2,4-triazole with various oligoethylene glycols. The starting bis(chloromethyl)triazole is a vessicant and must be used with caution. Triazolo-18-crown-6 ( 5 ) formed stable complexes with barium, strontium, copper and benzylammonium cations but not with potassium or lithium. The crystal structure of 5 showed the triazole proton to be on nitrogen 3 which is outside the macroring cavity. 相似文献
42.
Love JC Wolfe DB Haasch R Chabinyc ML Paul KE Whitesides GM Nuzzo RG 《Journal of the American Chemical Society》2003,125(9):2597-2609
The adsorption of n-alkanethiols onto polycrystalline thin films of palladium containing a strong (111) texture produces well-organized, self-assembled monolayers. The organization of the alkane chains in the monolayer and the nature of the bonding between the palladium and the thiol were studied by contact angle measurements, optical ellipsometry, reflection absorption infrared spectroscopy (RAIRS), and X-ray photoelectron spectroscopy (XPS). The XPS data reveals that a compound palladium-sulfide interphase is present at the surface of the palladium film. The RAIR spectra, ellipsometry data, and wetting properties show that the palladium-sulfide phase is terminated with an organized, methyl-terminated monolayer of alkanethiolates. The local molecular environment of the alkane chains transitions from a conformationally disordered, liquidlike state to a mostly all-trans, crystalline-like structure with increasing chain length (n = 8-26). The intensities and dichroism of the methylene and methyl stretching modes support a model for the average orientation of an ensemble of all-trans-conformer chains with a tilt angle of approximately 14-18 degrees with respect to the surface normal and a twist angle of the CCC plane relative to the tilt plane of approximately 45 degrees. The SAMs are stable in air, although the sulfur present at the surface oxidizes in air over a period of 2-5 days at room temperature. The differences in chain organization between SAMs formed by microcontact printing and by solution deposition are also examined by RAIRS and XPS. 相似文献
43.
Multi-residue method for the determination of chlorinated phenol metabolites in urine 总被引:1,自引:0,他引:1
Thomas R. Edgerton Robert F. Moseman Ralph E. Linder Lynn H. Wright 《Journal of chromatography. A》1979,170(2):331-342
Electron-capture-gas chromatographic (EC-GC) methods for the determination of chlorinated phenol metabolites of hexachlorobenzene (HCB) and pentachlorophenol (PCP) in urine are presented. After extraction the sample was reacted with diazomethane to produce the methyl ether of each metabolite prior to determination by EC-GC. An acid alumina column was used for cleanup and separation of methylated phenols into groups. Average recoveries of greater than 80% were obtained from urine fortified with known amounts of the phenol metabolites under investigation. A level of 1 ppb1 was established as minimum detection limit for each phenol metabolite. Previously unreported urinary metabolites of HCB and PCP were found as a result of a rat feeding study. Levels of chlorinated phenol residues from (a) human general population and (b) a worker occupationally exposed to PCP are also included. 相似文献
44.
[reaction: see text] The synthesis of four bioactive analogues of the somatostatin (SRIF-14) mimetic, beta-d-glucoside (+)-2, in which the C1 indole side chain is replaced with indole surrogates, has been achieved. These congeners, possessing the naphthyl, benzothiophene, benzyl, and benzofuran substituents, were predicted to satisfy the electrostatic requirements of the tryptophan binding pocket of SRIF. Unlike the previously described C4 picolyl and pyrazinyl congeners, these ligands bind the hSST4 receptor. 相似文献
45.
Wang G Huang T Murray RW Menard L Nuzzo RG 《Journal of the American Chemical Society》2005,127(3):812-813
Visible-near-IR luminescence spectra of gold MPCs that are similar, irrespective of the number of core atoms (all <2 nm diameter) and different monolayers, are reported. The luminescence can be quantitatively invoked by introducing polar ligands into nonpolar MPC monolayers and by galvanic exchange of metal atoms on the MPC core surface with different metals. The observed emissions are believed to result from surface-localized states that depend on both the core metal of the nanoparticle and the ligands attached to the metal surface. 相似文献
46.
Ralph Jaquet 《Theoretical chemistry accounts》1987,71(6):425-448
We are trying to investigate systematically the application of the finite element method (FEM) for solving the Schrödinger equation. The present paper is devoted to the calculation of vibrational transition probabilities for the collinear reactive system A + BC (i.e. H+H2 and their isotopes). The calculations are fully two-dimensional and the results are compared with earlier FEM calculations and conventional basis set expansion methods using the the R-matrix or S-matrix propagation.We made extensive analysis of FEM on the vector-computer Cyber 205 and developed a vector code for the efficient use in two dimensions, so that in the near future applications even in three dimensions will be possible.For the hydrogen exchange reactions we investigated the following isotope combinations: (a) H + H2, b) H + DH, D + HD and H + MuH (symmetric reaction), (c) D + HH, H + DD and Mu + DD (asymmetric reaction). We calculated the transition probabilities for up to five open vibrational channels and found excellent agreement with known exact values. 相似文献
47.
Protease sensors for bioimaging 总被引:2,自引:0,他引:2
Optical imaging of specific molecular targets and pathways in vivo has recently become possible through continued developments in imaging equipment, reconstruction algorithms, and more importantly the availability of imaging reporter molecules. These reporter molecules encompass photoproteins expressed in vivo and exogenously administered probes detectable by fluorescence and/or bioluminescence imaging. One particularly enticing aspect of optical imaging is the ability to design activatible probes with inherent amplification. This review summarizes our experience in developing novel near-infrared fluorescent (NIRF) imaging agents that report on protease activities. These agents are designed to be biocompatible, highly activatible, and able to produce bright NIRF following protease cleavage. 相似文献
48.
In vivo and ex vivo studies of fluorescence from endogenous and exogenous molecules in tissues and cells are common for applications such as detection or characterization of early disease. A systematic determination of the excitation-emission matrices (EEM) of known and putative endogenous fluorophores and a number of exogenous fluorescent photodynamic therapy drugs has been performed in solution. The excitation wavelength range was 250-520 nm, with fluorescence emission spectra collected in the range 260-750 nm. In addition, EEM of intact normal and adenomatous human colon tissues are presented as an example of the relationship to the EEM of constituent fluorophores and illustrating the effects of tissue chromophore absorption. As a means to make this large quantity of spectral data generally available, an interactive database has been developed. This currently includes EEM and also absorption spectra of 35 different endogenous and exogenous fluorophores and chromophores and six photosensitizing agents. It is intended to maintain and extend this database in the public domain, accessible through the Photochemistry and Photobiology website (http://www.aspjournal. com/). 相似文献
49.
Categorical quasivarieties revisited 总被引:1,自引:0,他引:1
Ralph Mckenzie 《Algebra Universalis》1984,19(3):273-303
Quasivarieties (and varieties) which are categorical in some power not less than the power of their language have been completely characterized by S. Givant [6], [7] and independently by E. A. Palyutin [11], [12]. These classes fall into two radically different families. A class in the first family is derived from the class of permutational representations of a group. Its members are [n]-th powers of algebras whose operations are unary, for some fixed positive integern. A class in the second family consists of affine algebras. Its members are polynomially equivalent (but not usually definitionally equivalent) to modules over a ring which is isomorphic to the ring ofn-by-n matrices with entries in a division ring.The general results are faithfully represented in the family of-categorical quasivarieties of countable type. Each of them is generated by a finite algebra, and the results can be viewed as very interesting facts about finite algebras and the classes they generate. In this paper, we offer simple new characterizations of-categorical quasivarieties and varieties of countable type. Our arguments are distinguished by the absence of any sophisticated model theory. In the beginning we use some very basic model theory, but after that we find that combinatorial reasoning about finite sets and elementary algebraic arguments, combined with two classical theorems describing the structure of finite simple rings and their modules, suffice to derive the results. Theorems 3.1 and 4.12 combine to give the characterization of-categorical quasivarieties. Theorems 3.2 and 4.13 combine to give the characterization of-categorical varieties.The heart of this paper is §2. There we prove that a nontrivial algebra of least cardinality in an-categorical quasivariety (which must generate the class) is a finite tame algebra. Tameness is the principal tool used in a relatively quick and painless proof that the generating algebra must be affine or an [n]-th power of a unary algebra. The concept of a tame algebra was introduced in [9] where we proved, among other things, that finite simple algebras are tame. When we had gained some experience with this concept, it became clear to us that the arguments in this present paper should exist (and it didn't take long to find them).The author thanks the referee for a thoughtful critique of the first submitted version of this paper.Research supported by United States National Science Foundation grant MCS 8103455.Presented by W. Taylor. 相似文献
50.
Ralph C. Dougherty Derek Horton Kerstin D. Philips Joseph D. Wander 《Journal of mass spectrometry : JMS》1973,7(7):805-816
2-Acetamido-1,3,4,6-tetra-O-acetyl-2-deoxy-α-D-glucopyranose (I), and its analogs specifically mono (trideuterioacetylated) at O-1 (III), at N-2 (II), at O-4 (IV) and at O-6 (V), have been examined by high-resolution mass spectrometry. From the elemental compositions of the fragment ions, the mass-number shifts resulting from deuterium incorporation and analysis of metastable transitions, it has been possible to specify in detail the fragmentation pathways undergone by this molecule. The principal degradations of I proceed by initial rapid decomposition of the molecular ion (whose intensity is insignificant) by three routes: (i) by loss of the C-1 acetoxyl group as a radical to give the glycosyl cation (a), (ii) by loss of the 1-acetyl group as a radical to give an acyclic ion m/e 346 (b) and (iii) by loss of a C-6 fragment and acetic acid derived from the 3-acetate group to give m/e 241 (c). 相似文献