全文获取类型
收费全文 | 6374篇 |
免费 | 257篇 |
国内免费 | 37篇 |
专业分类
化学 | 4072篇 |
晶体学 | 24篇 |
力学 | 202篇 |
数学 | 1262篇 |
物理学 | 1108篇 |
出版年
2023年 | 59篇 |
2022年 | 143篇 |
2021年 | 188篇 |
2020年 | 160篇 |
2019年 | 157篇 |
2018年 | 134篇 |
2017年 | 123篇 |
2016年 | 252篇 |
2015年 | 233篇 |
2014年 | 246篇 |
2013年 | 357篇 |
2012年 | 427篇 |
2011年 | 497篇 |
2010年 | 287篇 |
2009年 | 259篇 |
2008年 | 399篇 |
2007年 | 368篇 |
2006年 | 335篇 |
2005年 | 317篇 |
2004年 | 263篇 |
2003年 | 198篇 |
2002年 | 211篇 |
2001年 | 75篇 |
2000年 | 51篇 |
1999年 | 71篇 |
1998年 | 56篇 |
1997年 | 76篇 |
1996年 | 53篇 |
1995年 | 59篇 |
1994年 | 53篇 |
1993年 | 41篇 |
1992年 | 28篇 |
1991年 | 35篇 |
1990年 | 28篇 |
1989年 | 23篇 |
1988年 | 27篇 |
1987年 | 32篇 |
1986年 | 29篇 |
1985年 | 37篇 |
1984年 | 29篇 |
1983年 | 24篇 |
1982年 | 37篇 |
1981年 | 23篇 |
1980年 | 22篇 |
1979年 | 21篇 |
1978年 | 25篇 |
1977年 | 15篇 |
1976年 | 13篇 |
1973年 | 10篇 |
1972年 | 7篇 |
排序方式: 共有6668条查询结果,搜索用时 15 毫秒
101.
102.
Garzotti M 《Rapid communications in mass spectrometry : RCM》2003,17(4):272-278
Inflamed tissues are often characterised by the production of *NO and O(2)(-) radicals, which are known to react at an extremely fast rate to produce peroxynitrite (ONOO(-)). This highly oxidising entity reacts with protein-bound tyrosine to give 3-nitrotyrosine, which is considered a biochemical marker of peroxynitrite-induced damage. Lacidipine is a calcium antagonist indicated for the treatment of mild to moderate hypertension. In the present work, electrospray mass spectrometry with and without liquid chromatography was used to evaluate the capability of lacidipine and two other related molecules as ONOO(-) scavengers. This capability is compared with that associated with a number of commercial polyphenols described in the literature as efficient scavengers of this cytotoxic agent. The use of mass spectrometry provided rapid quantitative assessment of both the nitration and its reduction, and showed that lacidipine possesses a reasonable capability for reducing in vitro nitration of superoxide dismutase. 相似文献
103.
Rudolf Schmid Joseph Foricher Marco Cereghetti Peter Schnholzer 《Helvetica chimica acta》1991,74(2):370-389
The new axially dissymmetric diphosphines (R)- and (S)-(6,6′-dimethoxybiphenyl-2,2′-diyl)bis(diphenyl phosphine) ((R)- and (S)- 5a ; ‘MeO-BIPHEP’) and the analogues (R)- and (S)- 5b and 5c have been synthesized in enantiomerically pure form. These ligands have become readily available by a synthetic scheme which employs, as key steps, an ortho-lithiation/iodination reaction of the (m-methoxyphenyl)diprienylphosphine oxides 8 and a subsequent Ullmann reaction of the resulting iodides 9 to provide the racemic bis(phosphine oxides) 10 . The bis(phosphine oxides) 10 subsequently are resolved with (?)-(2R,3R)- and (+)-(2S,3S)-O-2,3-dibenzoyltartaric acid and reduced to diphosphines 5 . The Ullmann reaction constitutes a new and efficient route to 2,2′-bis(phosphinoyl)-substituted biphenyl systems. Absolute configurations were established for (R)- 5a by X-ray analysis of the derived Pd complex (R,R)- 17a , and for 5b and 5c by means of 1H-NMR comparisons of the derived Pd complexes 16 or 17 , respectively, and by means of CD comparisons. The MeO-BIPHEP diphosphine 5a proved to be as efficient as the previously described BIPHEMP diphosphine ((6,6′-dimethylbiphenyl-2,2′-diyl)bis(diphenylphosphine)) in enantioselective isomerizations and hydrogenations. 相似文献
104.
Conformational properties of polymers, such as average dihedral angles or molecular alpha-helicity, display a rather weak dependence on the detailed arrangement of the elementary constituents (atoms). We propose a computer simulation method to explore the polymer phase space using a variant of the standard multicanonical method, in which the density of states associated to suitably chosen configurational variables is considered in place of the standard energy density of states. This configurational density of states is used in the Metropolis acceptance/rejection test when configurations are generated with the help of a hybrid Monte Carlo algorithm. The resulting configurational probability distribution is then modulated by exponential factors derived from the general principle of the maximal constrained entropy by requiring that certain average configurational quantities take preassigned (possibly temperature dependent) values. Thermal averages of other configurational quantities can be computed by using the probability distributions obtained in this way. Moments of the energy distribution require an extra canonical sampling of the system phase space at the desired temperature, in order to locally thermalize the configurational degrees of freedom. As an application of these ideas we present the study of the structural properties of two simple models: a bead-and-spring model of polyethylene with independent hindered torsions and an all-atom model of alanine and glycine oligomers with 12 amino acids in vacuum. 相似文献
105.
Mihaylov M Chakarova K Hadjiivanov K Marie O Daturi M 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11821-11828
Different carbonyls are formed after CO adsorption at ambient temperature on a Pt-Na-mordenite (Pt-Na-MOR) sample. Pt(3+)(CO)(2) dicarbonyls (nu(s) at 2205 cm(-1) and nu(as) at 2167 cm(-1)) are decomposed without formation of monocarbonyls. The respective mixed-ligand species, Pt(3+)((12)CO)((13)CO), formed after (12)CO-(13)CO coadsorption, display bands at 2192 and 2131 cm(-1), in excellent agreement with the theoretically calculated values. Pt(2+)-CO species absorb at 2145 cm(-1) and are not able to accept a second CO molecule. Pt(+)-CO carbonyls are characterized by a band at 2111 cm(-1). Under CO equilibrium pressure, these species are converted into dicarbonyls (nu(s) at 2135 cm(-1) and nu(as) at 2101 cm(-1)). The respective mixed-ligand species, Pt(+)((12)CO)((13)CO), manifest bands at 2123 and 2069 cm(-1), in good agreement again with the theory. Different carbonyls of metallic platinum are observed below 2100 cm(-)(1). In addition, weakly adsorbed CO was registered as Na(+)-CO complexes (2177 and 2165 cm(-1)) and Na(+)-OC-Na(+) species (2138 cm(-1)). It was found that during desorption of CO platinum was reduced, ultimately to metal. However, heating in a NO + O(2) mixture leads to reoxidation of the metal particles and restoration of the initial state of the sample. 相似文献
106.
Marta Catellani Gian Paolo Chiusoli Mirco Costa 《Journal of organometallic chemistry》1995,500(1-2):69-80
Chelating or metallacycle-forming substrates are very useful for directing organometallic reactions. This review covers the more recent research that has been carried out in the authors' laboratory. Rhodium(I)- and (III)-catalysed reactions of C---C coupling of butadiene with N-allylamides or N-alkylbutenamides are described. These reactions are controlled by the size and strength of the chelate ring formed by double-bond insertion into the crotyl-rhodium bond (formed from butadiene) and their regioselectivity can change with the oxidation state of the metal. Rhodium(I)-catalysed reactions of butadiene with enamides are also chelation controlled and lead to different products, depending on the substituents at nitrogen. Cobalt(II) metallacycles have been utilized for promoting some organic reactions. It has been shown that alkenes can be catalytically incorporated into cobaltacyclopentadiene rings, that spirocycles can be obtained from diynes, carbon monoxide and acrylic esters and that a Pauson-Khand-type reaction can be combined with a Michael-type reaction to prepare catalytically new cyclopentenones. The use of palladacycles, derived from norbornene insertion into aryl-palladium bonds, followed by cyclization, has allowed the selective functionalization of either end of the metallacycle and the formation of condensed rings. Conversion of a palladium(II) into a palladium(IV) metallacycle, and catalytic processes involving these intermediates, have been achieved. The formation of alkylaromatic palladacycles has also been exploited for the selective meta functionalization of the aromatic moiety by means of alkyl groups, accompanied by expulsion of the norbornene molecule. 相似文献
107.
108.
Ford S Hofmann M Morley CP Roberts JL Di Vaira M 《Organic & biomolecular chemistry》2005,3(21):3990-3995
Bis(1,2,3,4-tetramethylcyclopentadienyl)selane (1) has been prepared by the reaction of tetramethylcyclopentadienyllithium (Cp(t)Li) with selenium bis(diethyldithiocarbamate). Treatment of Cp(t)Li with elemental selenium, followed by air oxidation, led to loss of the allylic hydrogen atom, and formation of the novel tricyclic compound 1,4,5,6,7,10,11,12-octamethyltricyclo[7.3.0.0]-2,8-diselenadodeca-3,5,9,11-tetraene (2). The sulfur analogue of 2 has been obtained by a similar procedure. The X-ray crystal structures of compounds 1 and 2 have been determined, and the molecular geometry observed for has been probed using DFT calculations. 相似文献
109.
Garavelli M Ruggeri F Ogliaro F Bearpark MJ Bernardi F Olivucci M Robb MA 《Journal of computational chemistry》2003,24(11):1357-1363
MMVB is a QM/MM hybrid method, consisting of a molecular mechanics force field coupled to a valence bond Heisenberg Hamiltonian parametrized from ab initio CASSCF calculations on several prototype molecules. The Heisenberg Hamiltonian matrix elements Q(ij) and K(ij), whose expressions are partitioned here into a primary contribution and second-order correction terms, are calculated analytically in MMVB. When the original MMVB force field fails to produce potential energy surfaces accurate enough for dynamics calculations, we show that significant improvements can be made by refitting the second-order correction terms for the particular molecule(s) being studied. This "local" reparametrization is based on values of K(ij) extracted (using effective Hamiltonian techniques) from CASSCF calculations on the same molecule(s). The method is demonstrated for the photoisomerization of s-cis butadiene, and we explain how the correction terms that enabled a successful MMVB dynamics study [Garavelli, M.; Bernardi, F.; Olivucci, M.; Bearpark, M. J.; Klein, S.; Robb, M. A. J Phys Chem A 2001, 105, 11496] were refitted. 相似文献
110.
Alessandra Sussulini Jerusa S. Garcia Márcia F. Mesko Diogo P. Moraes Érico M. M. Flores Carlos A. Pérez Marco A. Z. Arruda 《Mikrochimica acta》2007,158(1-2):173-180
Two methods of protein extraction for soybean seeds were evaluated in terms of preservation of the metal ions bound to proteins
after the extraction and separation procedures. The proteins were firstly separated according to their molar masses by polyacrylamide
gel electrophoresis. Then, the protein bands were mapped by synchrotron radiation X-ray fluorescence in order to establish
which metal ions were present in each one. Finally, some mapped protein bands were decomposed by microwave-assisted combustion
and Ca, Cu, K, Mg, Mn, and Zn were quantified by inductively coupled plasma mass spectrometry or inductively coupled plasma
optical emission spectrometry. The extraction methods studied were Method A (based on the treatment of ground soybean seeds with hexane and their extraction with Tris–HCl and β-mercaptoethanol) and
Method B (based on the treatment of ground soybean seeds with petroleum ether and their extraction with Tris–HCl, dithiothreitol,
phenylmethanesulfonyl fluoride, sodium dodecyl sulfate and potassium chloride). The best method was Method B, in which a 78% higher extraction efficiency was obtained when compared to Method A. Additionally, the metal-protein interactions were more appropriately preserved when Method B was applied, where the most affected ions were those that are bound weakly to proteins, such as Ca, K, and Mg. 相似文献