全文获取类型
收费全文 | 2321篇 |
免费 | 60篇 |
国内免费 | 19篇 |
专业分类
化学 | 1434篇 |
晶体学 | 20篇 |
力学 | 84篇 |
数学 | 439篇 |
物理学 | 423篇 |
出版年
2021年 | 24篇 |
2020年 | 27篇 |
2019年 | 34篇 |
2018年 | 24篇 |
2017年 | 16篇 |
2016年 | 40篇 |
2015年 | 48篇 |
2014年 | 33篇 |
2013年 | 100篇 |
2012年 | 79篇 |
2011年 | 99篇 |
2010年 | 58篇 |
2009年 | 37篇 |
2008年 | 69篇 |
2007年 | 88篇 |
2006年 | 102篇 |
2005年 | 120篇 |
2004年 | 92篇 |
2003年 | 96篇 |
2002年 | 79篇 |
2001年 | 50篇 |
2000年 | 43篇 |
1999年 | 25篇 |
1998年 | 21篇 |
1997年 | 35篇 |
1996年 | 35篇 |
1995年 | 35篇 |
1994年 | 33篇 |
1993年 | 35篇 |
1992年 | 42篇 |
1991年 | 36篇 |
1990年 | 27篇 |
1989年 | 31篇 |
1988年 | 29篇 |
1987年 | 17篇 |
1986年 | 21篇 |
1985年 | 41篇 |
1984年 | 35篇 |
1983年 | 35篇 |
1982年 | 35篇 |
1981年 | 32篇 |
1980年 | 37篇 |
1979年 | 26篇 |
1978年 | 37篇 |
1977年 | 27篇 |
1976年 | 34篇 |
1975年 | 29篇 |
1974年 | 40篇 |
1973年 | 39篇 |
1972年 | 16篇 |
排序方式: 共有2400条查询结果,搜索用时 31 毫秒
81.
Ramanan Krishnamoorti William W. Graessley Achim Zirkel Dieter Richter Nikos Hadjichristidis Lewis J. Fetters David J. Lohse 《Journal of Polymer Science.Polymer Physics》2002,40(16):1768-1776
The unperturbed chain dimensions (〈R2〉o/M) of cis/trans‐1,4‐polyisoprene, a near‐atactic poly(methyl methacrylate), and atactic polyolefins were measured as a function of temperature in the melt state via small‐angle neutron scattering (SANS). The polyolefinic materials were derived from polydienes or polystyrene via hydrogenation or deuteration and represent structures not encountered commercially. The parent polymers were prepared via lithium‐based anionic polymerizations in cyclohexane with, in some cases, a polymer microstructure modifier present. The polyolefins retained the near‐monodisperse molecular weight distributions exhibited by the precursor materials. The melt SANS‐based chain dimension data allowed the evaluation of the temperature coefficients [dln 〈R2〉o/dT(κ)] for these polymers. The evaluated polymers obeyed the packing length (p)‐based expressions of the plateau modulus, G = kT/np3 (MPa), and the entanglement molecular weight, Me = ρNanp3 (g mol?1), where nt denotes the number (~21) of entanglement strands in a cube with the dimensions of the reptation tube diameter (dt) and ρ is the chain density. The product np3 is the displaced volume (Ve) of an entanglement that is also expressible as pd or kT/G. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1768–1776, 2002 相似文献
82.
83.
Andrew Mitchinson Wesley P. Blackaby Sylvie Bourrain Robert W. Carling Richard T. Lewis 《Tetrahedron letters》2006,47(13):2257-2260
Novel syntheses of 2,3,8-trisubstituted pyrido[2,3-d]pyridazines and 2,3,5-trisubstituted pyrazino[2,3-d]pyridazines are described. Two complementary routes to pyrido[2,3-d]pyridazines were developed, the first of which began by constructing the pyridine ring, and the second of which started by constructing the pyridazine ring. Pyrazino[2,3-d]pyridazines were prepared in a route employing an aza-Wadsworth-Emmons cyclization as the key step. The resulting compounds were found to be high affinity ligands for the GABAA receptor benzodiazepine binding site. 相似文献
84.
Yano J Pushkar Y Glatzel P Lewis A Sauer K Messinger J Bergmann U Yachandra V 《Journal of the American Chemical Society》2005,127(43):14974-14975
The biological generation of oxygen by the oxygen-evolving complex in photosystem II (PS II) is one of nature's most important reactions. The recent X-ray crystal structures, while limited by resolutions of 3.2-3.5 A, have located the electron density associated with the Mn4Ca cluster within the multiprotein PS II complex. Detailed structures critically depend on input from spectroscopic techniques, such as EXAFS and EPR/ENDOR, as the XRD resolution does not allow for accurate determination of the position of Mn/Ca or the bridging and terminal ligand atoms. The number and distances of Mn-Mn/Ca/ligand interactions determined from EXAFS provide important constraints for the structure of the Mn4Ca cluster. Here, we present data from a high-resolution EXAFS method using a novel multicrystal monochromator that show three short Mn-Mn distances between 2.7 and 2.8 A and, hence, the presence of three di-mu-oxo-bridged units in the Mn4Ca cluster. This result imposes clear limitations on the proposed structures based on spectroscopic and diffraction data and provides input for refining such structures. 相似文献
85.
Rapid and reversible G-quadruplex hairpin dimer formation is observed for bis(oligonucleotide) conjugates possessing stilbenediether (Sd) linkers connecting two short poly(G) sequences. 相似文献
86.
P. F. Crain James A. McCloskey Arthur F. Lewis Karl H. Schram Leroy B. Townsend 《Journal of heterocyclic chemistry》1973,10(5):843-847
The mass spectrum of pyrazomycin has been obtained and reveals a fragmentation pattern with several important peaks which are not normally found in the mass spectra of C-nucleosides. It has now been established, using model compounds, that these unusual fragment ions are a direct result of the juxtaposition of the exocyclic hydroxy and carboxamido groups of the aglycon. It appears that a facile elimination of ammonia and ethanol from o-hydroxycarboxamides and o-hydroxyethylesters, respectively, may be a general fragmentation reaction for aromatic heterocycles. A mass spectrum of the TMS derivative of pyrazomycin has also been obtained and factors which may result in exceptions to the empirical B+30 (M-103) rule for C-nucleosides are discussed. 相似文献
87.
Lewis WK Lindsay CM Bemish RJ Miller RE 《Journal of the American Chemical Society》2005,127(19):7235-7242
Electron impact ionization of a helium atom in a helium nanodroplet is followed by rapid charge migration, which can ultimately result in the localization of the charge on an atomic or molecular solute. This process is studied here for the cases of hydrogen cyanide, acetylene, and cyanoacetylene in helium, using a new experimental method we call optically selected mass spectrometry (OSMS). The method combines infrared laser spectroscopy with mass spectrometry to separate the contributions to the overall droplet beam mass spectrum from the various species present under a given set of conditions. This is done by vibrationally exciting a specific species that exists in a subset of the droplets (for example, the droplets containing a single HCN molecule). The resulting helium evaporation leads to a concomitant reduction in the ionization cross sections for these droplets. This method is used to study the charge migration in helium and reveals that the probability of charge transfer to a solvated molecule does not approach unity for small droplets and depends on the identity of the solvated molecule. The experimental results are explained quantitatively by considering the effect of the electrostatic potential (between the charge and the embedded molecule) on the trajectory of the migrating charge. 相似文献
88.
The oxidation of selected clinically important neurotransmitter metabolites with acidic potassium permanganate in the presence of polyphosphates evokes chemiluminescence of sufficient intensity to enable the sensitive determination of these species. Limits of detection for 5-hydroxyindole-3-acetic acid (5-HIAA), vanilmandelic acid (VMA; α,4-dihydroxy-3-methoxybenzeneacetic acid), 4-hydroxy-3-methoxyphenylglycol (MHPG), homovanillic acid (HVA, 4-hydroxy-3-methoxyphenylacetic acid) and 3,4-dihydroxyphenylacetic acid (DOPAC) were between 5 × 10−9 and 4 × 10−8 M, using flow-injection analysis methodology. In addition, we demonstrate the rapid determination of homovanillic acid and 5-hydroxyindole-3-acetic acid in human urine - without the need for extraction procedures - using monolithic column chromatography with chemiluminescence detection. 相似文献
89.
Abstract— Absorbance changes were monitored from 250 to 650 nm during the first microsecond after photolysis of detergent suspensions of bovine rhodopsin at 20°C. Global analysis of the resulting data produced difference spectra for bathorhodopsin, BSI and lumirhodopsin which give the change in absorbance of the aromatic amino acid side chains in these photointermediates relative to rhodopsin. These spectra show that the significant bleaching of absorbance near 280 nm, which has been seen previously for the lumirhodopsin, metarhodopsin I and metarhodopsin II intermediates, extends to times as early as bathorhodopsin. Because no corresponding absorbance increase is observed in the 250-275 nm region, the earliest bleaching of the 280 nm absorbance in rhodopsin is attributed to disruption of a hyperchromic interaction affecting Trp265 . Partial decay of this 280 nm bleaching as bathorhodopsin converts to BSI takes place maximally near 290 nm, where Trp265 has been shown to absorb, and could be due to the ring of the retinylidene chromophore resuming a position at the BSI stage that reestablishes the hyperchromic interaction with Trp265 . A subsequent change in the 250-300 nm region, which has no counterpart in the visible chromophore bands, indicates the possible presence of a protein-localized process as lumirhodopsin is formed. 相似文献
90.
It was in the 1980 s that the first papers in which the use of either combinatorial methods or microwave heating in organic chemistry were published. Unlike combinatorial chemistry, which quite readily became an accepted method, particularly in the pharmaceutical industry, it is only now that microwave heating is truly gaining acceptance. Our aim in this review is to attempt to rationalize this slow acceptance and to show the benefits to be gained by employing microwave heating in tandem with combinatorial chemistry. We will also give a number of examples of successful applications. 相似文献