全文获取类型
收费全文 | 2518篇 |
免费 | 42篇 |
国内免费 | 3篇 |
专业分类
化学 | 1429篇 |
晶体学 | 15篇 |
力学 | 71篇 |
综合类 | 1篇 |
数学 | 368篇 |
物理学 | 679篇 |
出版年
2021年 | 19篇 |
2020年 | 15篇 |
2019年 | 24篇 |
2018年 | 21篇 |
2016年 | 46篇 |
2015年 | 29篇 |
2014年 | 39篇 |
2013年 | 107篇 |
2012年 | 87篇 |
2011年 | 88篇 |
2010年 | 41篇 |
2009年 | 26篇 |
2008年 | 94篇 |
2007年 | 91篇 |
2006年 | 87篇 |
2005年 | 108篇 |
2004年 | 79篇 |
2003年 | 94篇 |
2002年 | 75篇 |
2001年 | 69篇 |
2000年 | 61篇 |
1999年 | 53篇 |
1998年 | 28篇 |
1997年 | 44篇 |
1996年 | 55篇 |
1995年 | 40篇 |
1994年 | 34篇 |
1993年 | 36篇 |
1992年 | 46篇 |
1991年 | 33篇 |
1990年 | 56篇 |
1989年 | 44篇 |
1988年 | 41篇 |
1987年 | 25篇 |
1986年 | 32篇 |
1985年 | 46篇 |
1984年 | 44篇 |
1983年 | 37篇 |
1982年 | 46篇 |
1981年 | 38篇 |
1980年 | 36篇 |
1979年 | 30篇 |
1978年 | 38篇 |
1977年 | 34篇 |
1976年 | 26篇 |
1975年 | 32篇 |
1974年 | 31篇 |
1973年 | 38篇 |
1972年 | 14篇 |
1969年 | 15篇 |
排序方式: 共有2563条查询结果,搜索用时 15 毫秒
91.
Philip S. Hall Graham E. Jackson John R. Moss David A. Thornton Paul F. M. Verhoeven Gareth M. Watkins 《光谱学快报》2013,46(7):1247-1267
Abstract The infrared spectra (4000 - 50 cm?1) of the square planar rhodium(I) complexes cis-[Rh(CO)2 (pyridine) (X)] (X = Cl, Br) and their isotopomers with pyridine-d 5 and 13CO have been determined. Assignments are based on earlier studies on pyridine and its complexes and on the shifts in infrared bands which are caused by the isotopic substitutions employed. Normal coordinate analysis following the procedure of Becher and Mattes has been used to confirm the empirical assignments. The two v(RhC) bands are observed near 490 and 450 cm?1. v(RhN) is found near 210 cm?1 and v(RhX) occurs at 310 (X = Cl) and 235 (X = Br) cm?1. At frequencies below 200 cm?1, the bands are assigned to bending modes in the following sequence: δ (RhN) > δ (CRhC) > δ (RhCl) > γ (RhCl) > γ (RhN). 相似文献
92.
The observed change in the phosphorescence decay of the spin-aligned triplet state of pyrazine at 1·6K upon application of a magnetic field is examined both experimentally and theoretically. Experimentally, the decay curve is resolved into the three decay components of the three triplet sublevels in the field range of 0–6000 G. Both the decay constants and the fraction of total initial intensity of each decay component are determined for each field strength. Theoretically, the observed change in the decay characteristics is assumed to be solely due to the Zeeman mixing of the zero-field levels in the absence of spin-lattice relaxation processes. This has the effect of distributing the radiative strength of the strongly radiative zero-field level among the other two weakly radiative zero field levels. A simple approximate calculation gives excellent and encouraging agreement with experimental quantities in the range of validity of the approximations made (below 1000 G). A rigorous calculation was then performed using the exact solution of the secular equation resulting from the Hamiltonian including the spin-spin and Zeeman interactions. Due to the difficulty in finding a host of known crystal structure in which pyrazine can dissolve substitutionally and uniquely, the comparison between theory and experiment is made using a polycrystalline sample. A special averaging procedure is used in calculating a theoretical decay curve for each magnetic field strength used. The theoretical decay curve is then decomposed into three components employing the same computer programme used for decomposing the experimental decay curve. The agreement between the observed and the more rigorous calculated decay quantities is excellent up to 2000 G, but observed disagreement appears above 3000 G and increases with field strength. The calculated lifetimes above 3000 G are found to be longer than the observed ones. The difference is due to other relaxation mechanisms at these high fields, for example, in spin-lattice relaxation processes between the Zeeman sublevels of the lowest triplet state. 相似文献
93.
The π? p→e + e ? n and π+ n→e + e ? p reaction cross sections are calculated below and in the vicinity of the vector-meson (?0,ω) production threshold. These processes are largely responsible for the emission of e +e? pairs in pion-nucleus reactions and contribute to the dilepton spectra observed in relativistic heavy ion collisions. They are dominated by the decay of low-lying baryon resonances into vector-meson-nucleon channels. The vector mesons materialize subsequently into e + e? pairs. Using πN→?0 N and πN→ωN, amplitudes calculated in the center of mass energy interval 1.4 < √s<1.8 GeV, we compute the π? p→e + e ? n and π+ n→e + e ? p reaction cross sections in these kinematics. Below the vector-meson production threshold, the π0?ω interference in the e + e? channel appears largely destructive for the π? p→e + e ? n cross section and constructive for the π+ n→e + e ? p cross section. The pion beam and the HADES detector at GSI offer a unique possibility to measure these effects. Such data would provide strong constraints on the coupling of vector-meson-nucleon channels to low-lying baryon resonances. 相似文献
94.
Carolina de Gregorio Lemont B. Kier Lowell H. Hall 《Journal of computer-aided molecular design》1998,12(6):557-561
A structure-activity analysis of a series of steroids binding to corticosteroid-binding globulin was made using the electrotopological state index for each atom in the molecule. Two indices were found to correlate well with the binding affinity. The indices encode structural characteristics in the A and the D rings of the steroids in the study. One of the indices was formulated as the difference between two indices in the A ring. The two were not intercorrelated, suggesting that the composite index signals the influence of structure changes in or near the A ring that can be monitored by the composite index. This is a new observation using this structure-activity method. It is suggested that this model makes some contributions towards detection of the pharmacophore. 相似文献
95.
T. C. Gilmer P. K. Hall H. Ehrenfeld K. Wilson T. Bivens D. Clay C. Endreszl 《Journal of polymer science. Part A, Polymer chemistry》1996,34(6):1025-1037
Semi-interpenetrating polymer networks (IPNs) composed of poly(methyl methacrylate) (PMMA) and aromatic/aliphatic siloxanes have been made via sequential and simultaneous polymerizations. As the percentage of aliphatic siloxane increases, flexibility and, in general, toughness of the IPNs increases and clarity is reduced. This loss in clarity is due to the mismatch of refractive indices (1.49 form PMMA vs. 1.43 for aliphatic siloxane). PMMA is quite transparent. On the other hand, in making aromatic siloxane/PMMA IPNs clarity is retained as aromatic siloxane is increased due to better matching refractive index (1.49 for PMMA and −1.49 for poly(diphenyl siloxane)). Gel permeation chromatography (GPC) indicates slightly crosslinked IPNs with the THF soluble portions having number-average molecular weight, M¯n, of 105–106. NMRs of IPNs essentially show peaks for the components, PMMA and the siloxane, which make up the respective IPNs. 29Si-NMRs indicate cross-linking and grafting. Mechanical properties show increased toughness of IPNs versus PMMA as percentage of siloxane and crosslinker increases, but with a corresponding loss in tensile strength. © 1996 John Wiley & Sons, Inc. 相似文献
96.
We report a novel class of C2-symmetric chiral diols derived from the hydrobenzoin skeleton. The combination of these diols with SnCl4 under Yamamoto's concept of Lewis acid assisted Br?nsted acidity (LBA catalysis) leads to high levels of asymmetric induction in the allylboration of aldehydes by commercially available allylboronic acid pinacol ester 1a. The corresponding homoallylic alcohol products of synthetically useful aliphatic aldehydes are obtained in excellent yields with up to 98:2 er. This combined acid manifold is also efficient in catalyzing the diastereo- and enantioselective crotylboration of aldehydes, thus providing the propionate units in >95:5 dr and up to 98:2 er. The X-ray crystal structure of the optimal diol x SnCl4 complex, Vivol (4m) x SnCl4, unambiguously shows the Br?nsted acidic character of this LBA catalyst and its highly dissymmetrical environment. Further controls have ruled out a possible boron trans-esterification mechanism with the chiral diol and point to LBA catalyst-derived activation of the pinacol allylic boronates 1. Due to slow dissociation of the diol x SnCl4 complex, a small excess of diol is required in order to suppress a competing racemic cycle catalyzed by free SnCl4. 相似文献
97.
Transgenic plants offer a promising system for large-scale production of therapeutic proteins such as monoclonal antibodies (mAbs). This paper describes a membrane-based process suitable for purification of a humanized mAb expressed in tobacco. Most monoclonal antibody purification schemes rely on the use of Protein A as the affinity ligand for antibody capture. The main objective of our work was to develop non-Protein A-based purification methods to avoid some of the problems and limitations associated with this ligand, e.g. cost, immunotoxicity, and antibody aggregation during elution. Ion exchange membrane chromatography (IEMC) was used for primary capture and preliminary purification of the mAb from tobacco juice. Hydrophobic interaction membrane chromatography (HIMC) was then used for high-resolution purification, followed by ultrafiltration for polishing, desalting and buffer exchange. Using this scheme, both high mAb purity (single peak in size exclusion chromatogram, i.e., ca. 100% purity) and high recovery (77% of mAb spiked into the tobacco extract) were achieved. Membrane chromatography is generally considered unsuitable for resolving bound proteins by gradient elution and is therefore commonly used in the bind and elute mode with a single-step change of mobile phase. We show that the gradient elution process in the HIMC step can be optimized to increase the resolution and thereby obtain product of high purity. 相似文献
98.
Very potent inhibitors were synthesized for the enzymatic deacetylation of N-acetyl-d-glucosamine-6-phosphate (NagA) and N-acetyl-d-glutamate (DGD). The methyl phosphonamidate derivative of d-glucosamine-6-phosphate bound to N-acetyl-d-glucosamine-6-phosphate deacetylase with an equilibrium dissociation constant of 34 +/- 5 nM at pH 7.5 and an association rate constant of 6.1 x 103 M-1 s-1. The inhibition constant is 4000-fold lower than the Michaelis constant for the substrate N-acetyl-d-glucosamine-6-phosphate. N-Acetyl-d-glutamate deacetylase was inhibited by the methyl phosphonamidate derivative of d-glutamate with an inhibition constant of 460 +/- 70 pM at pH 7.6. The inhibitor bound to the enzyme 500 000-fold tighter than the Michaelis constant for N-formyl-d-glutamate. These compounds mimic the putative tetrahedral intermediate formed upon nucleophilic attack of an activated water molecule on the amide bond of the target substrate. These inhibitors should prove useful in the elucidation of the enzyme-substrate interactions for enzymes within the amidohydrolase superfamily. 相似文献
99.
Lu Y Jaeckel B Parkinson BA 《Langmuir : the ACS journal of surfaces and colloids》2006,22(10):4472-4475
Simple polishing and relatively low temperature annealing procedures for preparing atomically flat terraced surfaces of various single-crystal TiO2 polymorphs are described. Anatase (101), anatase (001), rutile (100), rutile (110), and brookite (111) surfaces could all be prepared with a terraced surface structure as revealed in AFM images. The rutile (100) and (110) and anatase (101) surfaces were also shown to produce acceptable LEED patterns immediately upon insertion into a UHV system without the usual sputter and anneal cycles. 相似文献
100.
Kail BW Pérez LM Zarić SD Millar AJ Young CG Hall MB Basu P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(28):7501-7509
The oxygen-atom-transfer (OAT) reactivity of [LiPrMoO2(OPh)] (1, LiPr=hydrotris(3-isopropylpyrazol-1-yl)borate) with the tertiary phosphines PEt3 and PPh2Me in acetonitrile was investigated. The first step, [LiPrMoO2(OPh)]+PR3-->[LiPrMoO(OPh)(OPR3)], follows a second-order rate law with an associative transition state (PEt3, DeltaH not equal=48.4 (+/-1.9) kJ mol-1, DeltaS not equal=-149.2 (+/-6.4) J mol-1 K-1, DeltaG not equal=92.9 kJ mol-1; PPh2Me, DeltaH not equal=73.4 (+/-3.7) kJ mol-1, DeltaS not equal=-71.9 (+/-2.3) J mol-1 K-1, DeltaG not equal=94.8 kJ mol-1). With PMe3 as a model substrate, the geometry and the free energy of the transition state (TS) for the formation of the phosphine oxide-coordinated intermediate were calculated. The latter, 95 kJ mol-1, is in good agreement with the experimental values. An unexpectedly large O-P-C angle calculated for the TS suggests that there is significant O-nucleophilic attack on the P--C sigma* in addition to the expected nucleophilic attack of the P on the Mo==O pi*. The second step of the reaction, that is, the exchange of the coordinated phosphine oxide with acetonitrile, [LiPrMoO(OPh)(OPR3)]+MeCN-->[LiPrMoO(OPh)(MeCN)]+OPR3, follows a first-order rate law in MeCN. A dissociative interchange (Id) mechanism, with activation parameters of DeltaH not equal=93.5 (+/-0.9) kJ mol-1, DeltaS not equal=18.2 (+/-3.3) J mol-1 K-1, DeltaG not equal=88.1 kJ mol-1 and DeltaH not equal=97.9 (+/-3.4) kJ mol-1, DeltaS not equal=47.3 (+/-11.8) J mol-1 K-1, DeltaG not equal=83.8 kJ mol-1, for [LiPrMoO(OPh)(OPEt3)] (2 a) and [LiPrMoO(OPh)(OPPh2Me)] (2 b), respectively, is consistent with the experimental data. Although gas-phase calculations indicate that the Mo--OPMe3 bond is stronger than the Mo--NCMe bond, solvation provides the driving force for the release of the phosphine oxide and formation of [LiPrMoO(OPh)(MeCN)] (3). 相似文献