全文获取类型
收费全文 | 26132篇 |
免费 | 601篇 |
国内免费 | 160篇 |
专业分类
化学 | 17534篇 |
晶体学 | 214篇 |
力学 | 664篇 |
综合类 | 1篇 |
数学 | 4423篇 |
物理学 | 4057篇 |
出版年
2021年 | 176篇 |
2020年 | 213篇 |
2019年 | 284篇 |
2018年 | 232篇 |
2017年 | 208篇 |
2016年 | 446篇 |
2015年 | 346篇 |
2014年 | 460篇 |
2013年 | 1328篇 |
2012年 | 1193篇 |
2011年 | 1510篇 |
2010年 | 781篇 |
2009年 | 626篇 |
2008年 | 1367篇 |
2007年 | 1418篇 |
2006年 | 1410篇 |
2005年 | 1416篇 |
2004年 | 1241篇 |
2003年 | 1044篇 |
2002年 | 1018篇 |
2001年 | 368篇 |
2000年 | 296篇 |
1999年 | 246篇 |
1998年 | 286篇 |
1997年 | 313篇 |
1996年 | 397篇 |
1995年 | 298篇 |
1994年 | 284篇 |
1993年 | 290篇 |
1992年 | 275篇 |
1991年 | 239篇 |
1990年 | 224篇 |
1989年 | 241篇 |
1988年 | 268篇 |
1987年 | 250篇 |
1986年 | 245篇 |
1985年 | 386篇 |
1984年 | 438篇 |
1983年 | 322篇 |
1982年 | 427篇 |
1981年 | 402篇 |
1980年 | 342篇 |
1979年 | 331篇 |
1978年 | 347篇 |
1977年 | 332篇 |
1976年 | 275篇 |
1975年 | 270篇 |
1974年 | 260篇 |
1973年 | 239篇 |
1972年 | 145篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
181.
The oxymercuration—demercuration (OM—DM) of representative trimethylsilylalkenes in aqueous tetrahydrofuran was investigated. Vinyltrimethylsilane gives only the anti-Markovnikov alcohol, 2-trimethylsilylethanol in 90% yield. Allyltrimethylsilane gives mainly allylmercuric acetate which reacts further to give a 1,3-dimercurated-2-propanol. This species reacts slowly with allyltrimethylsilane to give allylmercuric acetate. 3-Buten-1-yltrimethylsilane gives only the Markovnikov product, 1-trimethylsilyl-3-butanol in 99% yield. cis-1-Propenyl-trimethylsilane gives 1-trimethylsilyl-2-propanol in 44% yield along with cleavage products. The formation of one of these products, 2-propanol, was found by PMR to arise from the OM—DM of cis-1-propenylmercuric acetate which gives the 1,1-dimercurated-2-propanol. While the oxymercuration of cis-1-propenyl-mercuric acetate is regiospecific giving exclusive placement of the mercury α to the silicon, it is completely nonstereospecific giving equal amounts of diastereomeric adducts. The OM—DM of 2-propenyl trimethylsilane (XIX) leads only to desilylation and oxidation products. Possible reasons for the diverse behavior of these silylated alkenes are discussed. 相似文献
182.
HYDROXYSTILBAZOLES AND HYDROXYAZAPHENANTHRENES: PHOTOCYCLIZATION AND FLUORESCENCE STUDIES 总被引:1,自引:0,他引:1
Abstract— As models for novel fluorescent probes, we have synthesized three isomeric hydroxystilbazole systems (4′-hydroxy-substituted 2-, 3-, and 4-stiIbazoles), examined their photocyclization-oxi-dation to four hydroxyazaphenanthrene systems, and made a preliminary study of their absorption and fluorescence spectra. All three stilbazoles can be prepared easily by addition of the isomeric picoline anions to 4-methoxybenzaldehyde, followed by dehydration and deprotection. Photocyclization proceeds efficiently, furnishing a single product isomer from each of the 2- and 4-stilbazole systems, and two isomeric azaphenanthrenes from the 3-stilbazole. The stilbazoles all have intense UV absorbance bands whose maxima depend upon solvent and pH; all three isomers have relatively similar spectra under neutral conditions and all three show a large red shift in base; in acid, however, the 2-and 4-stilbazole isomers show a greater red shift than the 3-stilbazole. The fluorescence of the stilbazoles is also solvent dependent, shifting to the red in more polar medium; red shifts are also observed in acid and base, but in acid, the 3-stilbazole shows a larger shift. The azaphenanthrene photocyclization products show absorbance spectra typical for quinolines and isoquinolines; their absorptivities are less than the stilbazoles, but their fluorescence is more intense. In general, the benzoquinolines have longer wavelength but weaker fluorescence than the benzoisoquinolines. Also, those isomers in which the resonance effects of the hydroxy and nitrogen groups can reinforce one another show longer wavelength emissions of greater intensity. All seven systems show dual fluorescence in water under neutral conditions, suggesting the emission from both non-ionized and ionized species in the excited state. In one case, the benzoisoquinoline system derived from 4′-hydroxy-4-stilbazole, an emission at 640 nm, observed in water over a wide pH range, is ascribed to a zwitterionic phototautomer. These stilbazoles, benzoquinolines and benzoisoquinolines may prove to be useful spectroscopic probes. 相似文献
183.
Ballou S Goodpaster J MacCrehan W Reeder D 《Analytical and bioanalytical chemistry》2003,376(8):1149-1150
184.
Effects of sugar inhibition on cellulases and β-glucosidase during enzymatic hydrolysis of softwood substrates 总被引:1,自引:0,他引:1
Zhizhuang Xiao Xiao Zhang David J. Gregg John N. Saddler 《Applied biochemistry and biotechnology》2004,115(1-3):1115-1126
A quantitative approach was taken to determine the inhibition effects of glucose and other sugar monomers during cellulase
and β-Glucosidase hydrolysis of two types of cellulosic material: Avicel and acetic acid-pretreated softwood. The increased
glucose content in the hydrolysate resulted in a dramatic increase in the degrees of inhibition on both β-Glucosidase and
cellulase activities. Supplementation of mannose, xylose, and galactose during cellobiose hydrolysis did not show any inhibitory
effects on β-Glucosidase activity. However, these sugars were shown to have significant inhibitory effects on cellulase activity
during cellulose hydrolysis. Our study suggests that high-substrate consistency hydrolysis with supplementation of hemicellulose
is likely to be a practical solution to minimizing end-product inhibition effects while producing hydrolysate with high glucose
concentration. 相似文献
185.
One unit of S(IV) (SO2 or SHO3?) is oxidized per 2 units of [NiIII(cyclam)] species to obtain sulfate. Kinetic analyses have been done by varying the acidities (0.013 ? [H+] ? 1.0 M) and halide concentrations (0.000 ? [X?] ? 0.012 M; X=Cl and Br) at constant ionic strength (μ = 1.0 M). The rate law that incorporates the [X?] and [H+] dependence is ?d[NiIII]T/dt=2k[NiIII]T[S(IV)]T where 2k={ka[H+] + kbK + kK′X[H+] [X?] + kK′XK[X?]} {[H+] + K}?1 {1 + K′X[X?]}?1, here ka=87 ± 7 M?1 s?1, kb=(2.5 ± 0.5)×103 M?1 s?1 and pK = 1.8 ± 0.2. Rate constants ka and kb are attributed to the reactions of [NiIII(cyclam) (H2O)2]3+ with SO2 and SHO3?, respectively. Monohalo species apparent equilibrium constants K′Cl=(1600 ± 400) M?1 and K′Br=(190 ± 20) M?1 and rate constants k=80 ± 8 M?1 s?1 and k = 140 ± 15 M?1 s?1 are ascribed to the protonated pathway, involving the [NiIII(cyclam) (H2O)X]2+ and SO2(aq) reaction pairs. The other two rate constants of k=(5 ± 1)×103 M?1 s?1 and k=(3.1 ± 0.5)×104 M?1 s?1, refer to the deprotonated pathway and are assigned to the [NiIII(cyclam) (H2O)X]2+ /SHO3? redox couple. A deuterium H2O / D2O isotope effect of 2.1–2.8 can be attributed partially to an equilibrium isotope effect at low acidity though a small kinetic isotope (2.5 ± 0.5) effect is evident for the dihydrogen sulfito pathway, ka. The kinetic isotope effect and the absence of sulfite radical scavenging effects are explained by a mechanism entailing migration of a hydride from sulfur to the NiIII center to produce a NiIII—H species, which rapidly comproportionates, and S(VI). © 1993 John Wiley & Sons, Inc. 相似文献
186.
Laurence E. Strong Christopher L. Brummel Robert Ryther John R. Radford Alan D. Pethybridge 《Journal of solution chemistry》1988,17(12):1145-1167
Precision molar conductances of benzoic, o-toluic, 2,6-dimethylbenzoic, 2,3,6-trimethylbenzoic, and, o-fluorobenzoic acids have been determined in aqueous solution as a function of temperature and of concentration up to near saturation (<0.035 M). At the higher concentrations molar conductances are found to be less than anticipated for the simple dissociation of a 1-1 electrolyte. Although the deviations are only 1% or less they have been interpreted to show that these acids are dimerized in solution. The interpretation includes an assumption that the dimer ionizes to produce a triple ion. Increasing numbers of methyl groups lead to increasing dimerization. For those acids with two ortho groups the dimerization increases with increasing temperature while the other three show decreasing dimerization with increasing temperature. Temperature functions have been determined for the dimerization constants and from these functions standard changes in enthalpy, entropy, and heat capacity have been determined. Comparisons are made with dimerization studies in non-aqueous solvents. From these as well as the behavior of benzene in water it is concluded that a major factor driving the dimerization is hydrophobic interaction. To provide a limiting conductance of the triple ion needed in the dimerization calculations a conductance study was also made for o-Phenylbenzoic acid on the assumption that its anion provides an approximate model of the triple ion. 相似文献
187.
Characterization of recombinant human serum albumin using matrix-assisted laser desorption ionization time-of-flight mass spectrometry 总被引:1,自引:0,他引:1
Chromatographically purified recombinant human serum albumin (rHSA), produced in genetically transformed yeast cells, was characterized using matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) MS techniques. The molecular mass of the intact protein was determined to be 66671, in good agreement with that of purified HSA which was used as a standard. The identity of rHSA to its natural counterpart was established with high precision using peptide mass fingerprinting of tryptic peptides. Partial amino acid sequence data for rHSA were obtained using Ettan CAF MALDI Sequencing Kit and post-source decay on the tryptic peptides. The results achieved provide strong evidence that MALDI-TOF-MS is an important analytical technique for characterising gene products and for establishing the identity and bio-compatibility of recombinant proteins relative to their natural counterparts. 相似文献
188.
John A Philip D Morgan KR Devanarayanan S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2000,56(14):2715-2723
The FT IR and FT Raman spectra of Co(en)3Al3P4O16.3H2O (compound I) and [NH4]3[Co(NH3)6]3[Al2 (PO4)4]2.2H2O (compound II) are recorded and analysed based on the vibrations of Co(en)(3)3+, Co(NH3)(6)3+, NH4, Al-O-P, PO3, PO2 and H2O. The observed splitting of bands indicate that the site symmetry and correlation field effects are appreciable in both the compounds. In compound I, the overtone of CH2 deformation Fermi resonates with its symmetric stretching vibration. The NH4 ion in compound II is not free to rotate in the crystalline lattice. Hydrogen bonding of different groups is also discussed. 相似文献
189.
M. Jonathan Fray Paul Allen Paul R. Bradley Clare E. Challenger Michael Closier Tim J. Evans Mark L. Lewis John P. Mathias Carly L. Nichols Yvonne M. Po-Ba Hayley Snow Mark H. Stefaniak Hannah V. Vuong 《Tetrahedron》2006,62(29):6869-6875
The synthesis of ten substituted aminomethylene tetrahydro-isoquinolines is described, proceeding in eight steps from 5-hydroxyisoquinoline via reductive amination of N-Boc tetrahydro-isoquinoline 5-carboxaldehyde. Likewise, reductive amination was used to prepare four substituted dihydro-isoindoles from the corresponding aldehyde. The dihydro-isoindole ring system was conveniently accessed via a 2+2+2 cycloaddition reaction. 相似文献
190.
Malkinson JP Anim MK Zloh M Searcey M Hampshire AJ Fox KR 《The Journal of organic chemistry》2005,70(19):7654-7661
[reaction: see text] In this article, the first solid-phase-based total synthesis of TANDEM, a synthetic analogue of triostin A, is described. In initial studies, the synthesis incorporated depsipeptide formation, introduction of chromophores, and disulfide bond formation on the solid phase, prior to a final solution-phase macrolactamization, to give the target molecule. Although pure TANDEM was obtained in an overall yield comparable to those for all syntheses to date, the yield of the final cyclization was low (11%). A more efficient approach involved removal from the solid phase prior to disulfide bond formation. The resulting linear peptide underwent macrolactamization under mild conditions and high dilution. Final disulfide bond formation was essentially quantitative and gave the target molecule, TANDEM, in an overall yield of 18%. The final compound was assessed for its ability to bind to 5'-TpA sequences on DNA by DNase I footprinting. This efficient synthesis sets the stage for a study of the structure-activity relationship of TANDEM and the natural product triostin A, with analogues containing "point mutations" at every site within the cyclic compounds. 相似文献