全文获取类型
收费全文 | 28242篇 |
免费 | 636篇 |
国内免费 | 172篇 |
专业分类
化学 | 18790篇 |
晶体学 | 229篇 |
力学 | 692篇 |
综合类 | 1篇 |
数学 | 4877篇 |
物理学 | 4461篇 |
出版年
2021年 | 195篇 |
2020年 | 240篇 |
2019年 | 303篇 |
2018年 | 251篇 |
2017年 | 226篇 |
2016年 | 482篇 |
2015年 | 374篇 |
2014年 | 494篇 |
2013年 | 1420篇 |
2012年 | 1270篇 |
2011年 | 1593篇 |
2010年 | 832篇 |
2009年 | 670篇 |
2008年 | 1444篇 |
2007年 | 1505篇 |
2006年 | 1500篇 |
2005年 | 1495篇 |
2004年 | 1327篇 |
2003年 | 1108篇 |
2002年 | 1067篇 |
2001年 | 400篇 |
2000年 | 322篇 |
1999年 | 258篇 |
1998年 | 303篇 |
1997年 | 333篇 |
1996年 | 435篇 |
1995年 | 329篇 |
1994年 | 303篇 |
1993年 | 311篇 |
1992年 | 301篇 |
1991年 | 260篇 |
1990年 | 241篇 |
1989年 | 258篇 |
1988年 | 284篇 |
1987年 | 266篇 |
1986年 | 267篇 |
1985年 | 414篇 |
1984年 | 468篇 |
1983年 | 337篇 |
1982年 | 463篇 |
1981年 | 430篇 |
1980年 | 382篇 |
1979年 | 368篇 |
1978年 | 378篇 |
1977年 | 372篇 |
1976年 | 319篇 |
1975年 | 312篇 |
1974年 | 294篇 |
1973年 | 264篇 |
1972年 | 159篇 |
排序方式: 共有10000条查询结果,搜索用时 734 毫秒
991.
2-Phenylthio-1,3-butadiene (1) and 2-phenylseleno-1,3-butadiene (2) have been generated in situ from their SO2 adducts and reacted with a series of unsymmetrical dienophiles. The regiochemical results have been analyzed in terms of qualitative perturbation theory. 相似文献
992.
He X Allan JF Noll BC Kennedy AR Henderson KW 《Journal of the American Chemical Society》2005,127(19):6920-6921
The reactions of magnesium and calcium bis(hexamethyldisilazide) with propiophenone have been studied with a view to determine the utility of these bases in the stereoselective enolization of ketones and to uncover the nature of the metal enolate intermediates produced. Both base systems are highly Z-selective when the reactions are conducted in the presence of polar solvents. However, in situ monitoring of the magnesium system in arene solution revealed a preference for E-enolate formation, which was confirmed by silyl enol ether trapping studies. Solution NMR studies of the magnesium system in toluene-d8 show the presence of a monomer-dimer equilibrium for the intermediate amidomagnesium enolates. This assignment is supported by the characterization of a disolvated amidomagnesium enolate dimer by crystallographic analysis. Comparative studies of the calcium system show distinctly different behavior. This is exemplified by the characterization of a novel solvent-separated ion pair complex and a monomeric amidocalcium enolate in the solid state. Solution NMR studies of the calcium system in pyridine-d5 reveal the co-existence of the heteroleptic amidocalcium enolate, the bisamide, the bisenolate and the ion pair complex. 相似文献
993.
Krishnakumar V Xavier RJ Chithambarathanu T 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):931-939
This work deals with the vibrational spectroscopy of succinimide and N-bromosuccinimide. The mid and far FTIR and FT-Raman spectra were measured in the condensed state. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT) using standard B3LYP/6-31G(*) and B3LYP/6-311+G(**) methods and basis set combinations. The vibrational spectra were interpreted, with the aid of normal coordinate analysis based on a scaled quantum mechanical force field. The infrared and Raman spectra were also predicted from the calculated intensities. Comparison of simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. Unambiguous vibrational assignment of all the fundamentals were made using the total energy distribution (TED). 相似文献
994.
Bakaoukas N Kapolos J Koliadima A Karaiskakis G 《Journal of chromatography. A》2005,1087(1-2):169-176
Reversed-flow gas chromatography, which is a sub-technique of inverse gas chromatography, is an experimental arrangement simulating a simple model for the action of air pollutants on buildings and monuments, in laboratory scale. By using a commercial gas chromatograph and an appropriate mathematical analysis, kinetic parameters such as rate constants for adsorption k1, adsorption/desorption kR and surface reaction k2, as well as surface diffusion coefficients Dgamma, deposition velocities Vd and reaction probabilities gamma of SO2 on marble surfaces at different temperatures (303.15-353.15 K) in the presence or in the absence of protective materials (an acrylic copolymer, Paraloid B-72 or a siloxane, CTS Silo 111) were calculated. From the above mentioned physicochemical quantities the ability of the examined materials to minimize the dry deposition of SO2 on marble is carrying out and a possible mechanism for the interaction between SO2 and Paraloid B-72 was suggested. Both materials (CTS SILO 111 and Paraloid B-72) are good enough for protecting marble against SO2 at low temperatures (303.15-323.15), while at high temperatures (333.15-353.15), siloxane seems to protect marble better than acrylic copolymer. 相似文献
995.
Tapan Kumar Lal John F. Richardson Mark S. Mashuta Robert M. Buchanan Rabindranath Mukherjee 《Polyhedron》1997,16(24):1248-4336
Synthesis and characterization of a nitrite-bound copper(II) compound [CuL4)2(ONO)]ClO4 have been achieved (L4 = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L4 provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the dx2−y2 orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible CuII---CuI response [cathodic peak potential, Epc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible CuII---CuI redox response [
]. 相似文献
996.
Torquato Mussini Maurizio Cicognini Paolo Longhi Sandra Rondinini Arthur K. Covington 《Analytica chimica acta》1984
Standard pH(S) values for 0.05 mol kg?1 potassium hydrogenphthalate (KHpH) reference buffer solutions in 10, 30 and 50% (w/w) 1,4-dioxane/water solvent mixtures within the temperature range 288.15–318.15 K are determined from e.m.f. measurements of the cell without transference Pt|H2|KHPh + KCl|AgCl|Ag|Pt. The consistency of the results is analysed by a recently described method of multilinear regression of the quantity p(aHγCl) as a function of both solution composition and temperature. The standard pH(S) determined can be reproduced to within ±0.01 by the equation pH(S) - 4.004 + 3.309w + 0.408z + 1.037w3 - 14.95zw2 + 27.1zw3, where w is the weight fraction of dioxane in the solvent mixture,z = (T –θ)/θ, and θ - 298.15 K. Values of the first ionization constant of phthalic acid (H2Ph; benzene-1,2-dicarboxylic acid) in the above solvent mixtures are also determined from e.m.f. measurements of the cell without transference Pt|H2|H2Ph + KHPh + KCl|AgCl|Ag|Pt. 相似文献
997.
The Ru(II) organometallic antitumor complex [(eta(6)-biphenyl)RuCl(en)][PF(6)] (1) reacts slowly with the amino acid L-cysteine (L-CysH(2)) in aqueous solution at 310 K. Reactions were followed over periods of up to 48 h using HPLC, electronic absorption spectroscopy, LC-ESI-MS, and 1D or 2D (1)H and (15)N NMR spectroscopy. Reactions at a 1 mM/2 mM (Ru/L-CysH(2)) ratio were multiphasic in acidic solutions (pH 5.1) and appeared to involve aquation as the first step. Initially, 1:1 adducts involving substitution of Cl by S-bound or O-bound L-CysH(2), [(eta(6)-biphenyl)Ru(S-L-CysH)(en)](+) (4a) and [(eta(6)-biphenyl)Ru(O-L-CysH(2))(en)](2+) (4b) formed, followed by the cystine adduct [(eta(6)-biphenyl)Ru(O-Cys(2)H(2))(en)](2+) (3), and two dinuclear complexes from which half or all of the chelated ethylenediamine had been displaced, [(eta(6)-biphenyl)Ru(H(2)O)(microS,N-L-Cys)Ru(eta(6)-biphenyl)(en)](2+) (5) containing one bridging cysteine, and [(eta(6)-biphenyl)Ru(O,N-L-Cys-S)(S-L-Cys-N)Ru(eta(6)-biphenyl)(H(2)O)] (6) containing two bridging cysteines. The unusual cluster species [(biphenyl)Ru](8) (7a) was also detected by MS and was more prevalent in reactions at higher L-CysH(2) concentrations. Complex 5 was the dominant product at pH 2-5, but overall, only ca. 50% of 1 reacted with L-CysH(2) in these conditions. The reaction between 1 and L-CysH(2) was suppressed in 50 mM triethylammonium acetate solution at pH > 5 or in 100 mM NaCl. Only 27% of complex 1 reacted with L-methionine (L-MetH) at an initial pH of 5.7 after 48 h at 310 K and gave rise to only one adduct [(eta(6)-biphenyl)Ru(S-L-MetH)(en)](2+) (8). 相似文献
998.
Warrener Ronald N. Malpass John R. Butler Douglas N. Sun Guangxing 《Structural chemistry》2001,12(3-4):291-304
The thermal addition of N-carbobenzyloxyisoindole (N-Z isoindole) 11a, generated by the reaction of 3,6-di(2-pyridyl)-s-tetrazine 9 with N-Z 7-azabenzonorbornadiene 8a, onto dimethyl tricyclo[4.2.1.02.5]nona-3,7-diene-3,4-dicarboxylate 17 occurred site selectively at the cyclobutene -bond to form a stereoisomeric mixture of 1 : 1-adducts 18 and 19, in which the bent-frame isomer 19 was dominant (ratio 5 : 1). In contrast, N-benzyl tetrafluoroisoindole 11c reacted with 17 only under high-pressure conditions (14 kbar, RT, 4 days) to afford 1 : 1-adducts at the cyclobutene site, in which the extended-frame isomer 18c was dominant and the accompanying bent-frame product 19c reverted to starting materials soon after isolation. These same stereoselectivities were used to prepare "windscreen wiper" compound 28c having two mobile N-benzyl substituents attached to a rigid scaffold by the reaction of N-benzyl tetrafluoroisoindole 11c with tetramethyl tetracyclo[4.4.1.0.2,5.07.10]undeca-3,8-diene-3,4,7,8-tetracarboxylate 23. Cavity bis-(cyclobutene-1,2-diester) 6 reacted with N-benzyl tetrafluoroisoindole 11c twice over to produce cavity structure 36 with two O- and two N-benzyl bridges on the inner face, whereas the narrower cavity bis-alkene 32 stopped at the 1 : 1-addition stage. The dynamics of the Z-group in the dual adducts 26a–28a are discussed briefly and key adducts and cavity systems have been structurally evaluated by X-ray crystallography, VT NMR, and molecular modeling. 相似文献
999.
Elena E. Ferapontova John Castillo Dmitri Hushpulian Vladimir Tishkov Tatiana Chubar Irina Gazaryan Lo Gorton 《Electrochemistry communications》2005,7(12):1291-1297
Direct electron transfer (DET) reactions of recombinant tobacco peroxidase (rTOP), namely direct electroreduction of Compound I/Compound II and heme Fe3+/2+ conversion, were studied on gold electrodes. rTOP of wild type, non-glycosylated, was produced using an Escherichia coli expression system. At pH 5.0, the redox potential for direct electrochemical transformation of the Fe3+/2+ of the peroxidase heme was −143 mV vs. AgAgCl, and 0.26 ± 0.07 pmol of the adsorbed rTOP were in DET contact with the gold electrode. The total amount of the adsorbed rTOP estimated from QCM data was 53 ± 5 pmol/cm2 or 1.67 pmol when referred to the surface area of the electrodes used for electrochemical measurements. Of 1.67 pmol of adsorbed rTOP, only 0.76 pmol were catalytically active. DET between Au and the enzyme was also studied in the reaction of the bioelectrocatalytic reduction of H2O2 by cyclic voltammetry and amperometric detection of H2O2 at +50 mV with rTOP-modified Au electrodes placed in a wall-jet flow-through electrochemical cell. Maximal bioelectrocatalytic current response of the rTOP-modified gold electrodes to H2O2 was observed at pH 5.0 and stemmed from its bioelectrocatalytic reduction based on DET between Au and the active site of rTOP. Kinetic analysis of the DET reactions gave 52% of the adsorbed rTOP molecules active in DET reactions (0.4 pmol of adsorbed catalytically active rTOP, correspondingly), which correlated well with the non-catalytic-voltammetry data. DET was characterised by a heterogeneous ET rate constant of 13.2 s−1, if one takes into account the QCM data, and 19.6 s−1, if the amount of rTOP estimated from the data on DET transformation of Fe3+/2+ couple of rTOP is considered. The sensitivity for H2O2 obtained for the rTOP-modified Au electrodes was 0.7 ± 0.1 A M−1 cm−2. These are the first ever-reported data on DET reactions of anionic plant peroxidases on bare gold electrodes. 相似文献
1000.
John E. Nicholas Andrew I. Spiers Nicholas A. Martin 《Plasma Chemistry and Plasma Processing》1986,6(1):39-51
Studies of time-resolved absorption spectra of transient species in the decomposition of NH3 by an r.f. pulse discharge together with product analysis showed that the major radical formed was NH at concentrations of the order of 10–6 mol dm–3 (105 molec. cm–3). Possible mechanisms for the formation of the radical during the discharge and its decay following pulse cut-off were tested by computer simulation of the kinetic data. Following zero-order formation with rate coefficient 0.19±0.03 mol dm–3 s–1, the decay was second order in NH with rate coefficient 2.1±0.5×109 mol–1 dm3 s–1 both for pure NH3 and where NH3/rare gas mixtures were investigated. The kinetic data are consistent with NH removal in a nonassociative radical-radical reaction proceeding via a short-lived collision complex, probably 2NH N2H2 N2 + H2. 相似文献