全文获取类型
收费全文 | 1621篇 |
免费 | 86篇 |
国内免费 | 6篇 |
专业分类
化学 | 1319篇 |
晶体学 | 5篇 |
力学 | 10篇 |
数学 | 156篇 |
物理学 | 223篇 |
出版年
2023年 | 20篇 |
2022年 | 13篇 |
2021年 | 39篇 |
2020年 | 46篇 |
2019年 | 29篇 |
2018年 | 31篇 |
2017年 | 19篇 |
2016年 | 82篇 |
2015年 | 39篇 |
2014年 | 50篇 |
2013年 | 83篇 |
2012年 | 124篇 |
2011年 | 163篇 |
2010年 | 56篇 |
2009年 | 54篇 |
2008年 | 121篇 |
2007年 | 101篇 |
2006年 | 89篇 |
2005年 | 91篇 |
2004年 | 75篇 |
2003年 | 59篇 |
2002年 | 52篇 |
2001年 | 12篇 |
2000年 | 10篇 |
1999年 | 8篇 |
1998年 | 13篇 |
1997年 | 10篇 |
1996年 | 17篇 |
1995年 | 7篇 |
1994年 | 7篇 |
1993年 | 10篇 |
1992年 | 8篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1985年 | 11篇 |
1984年 | 7篇 |
1983年 | 7篇 |
1982年 | 15篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1977年 | 6篇 |
1976年 | 5篇 |
1974年 | 9篇 |
1972年 | 7篇 |
1971年 | 5篇 |
1968年 | 7篇 |
1966年 | 6篇 |
排序方式: 共有1713条查询结果,搜索用时 15 毫秒
11.
A new transient in the photocyclization reaction of diphenylamines to carbazoles has been detected. It absorbs at 430 nm and is assigned to the excited triplet state of the intermediate photoproduct 11,12-dihydrocarbazole. 相似文献
12.
Makoto?OhtsukaEmail author Christina?Wedel Kimio?Itagaki 《Monatshefte für Chemie / Chemical Monthly》2005,136(11):1909-1914
Summary. Isothermal sections of the Ni–Mn–Ga ternary phase diagram at 1073 and 1273 K were investigated over a wide range of alloy
compositions. The range of the β-Ni2MnGa phase, its equilibria with the γ-(Mn, Ni), α′-Ni3Ga, and γ-Ni3Ga2 phases, and the liquidus and solidus lines were determined experimentally. The aging effect on the shape memory effect (SME)
of Ni2MnGa sputtered films was also investigated. The two-way SME of the constraint-aged films was confirmed by the temperature
change. 相似文献
13.
Mechanically attached, solid-state films of [Os(4,4'-diphenyl-2,2'-dipyridyl)2Cl2] have been formed on gold macro- and microelectrodes and their voltammetric properties investigated. The voltammetric response of these films associated with the Os(2+/3+) redox reaction is reminiscent of that observed for an ideal reversible, solution phase redox couple only when the contacting electrolyte contains of the order of 40% v/v of acetonitrile (ACN). The origin of this effect appears to involve preferential solvation of the redox centres by acetonitrile which facilitates the incorporation of charge compensating counterions. Scanning electron microscopy reveals that voltammetric cycling in 40:60 ACN-H2O containing 1.0 M LiClO4 as the electrolyte induces the formation of microcrystals. Voltammetry conducted under semi-infinite linear diffusion conditions has been used to determine the apparent diffusion coefficient, Dapp, for homogeneous charge transport through the deposit. The dynamics of charge transport decrease with increasing film thickness but appear to increase with increasing electrolyte concentration. These observations suggest that ion transport rather than the rate of electron self-exchange limit the overall rate of charge transport through these solids. When in contact with 40:60 ACN-H2O containing 1.0 M LiClO4 as electrolyte, Dapp values for oxidation and reduction are identical at 1.7 +/- 0.4 x 10(-12) cm2 s(-1). In the same electrolyte, the standard heterogeneous electron transfer rate constant, k(o), determined by fitting the full voltammogram using the Butler-Volmer formalism, is 8.3 +/- 0.5 x 10(-7) cm s(-1). The importance of these results for the rational design of solid state redox active materials for battery, display and sensor applications is considered. 相似文献
14.
Siwy Z Trofin L Kohli P Baker LA Trautmann C Martin CR 《Journal of the American Chemical Society》2005,127(14):5000-5001
There is increasing interest in the concept of using nanopores as the sensing elements in biosensors. The nanopore most often used is the alpha-hemolysin protein channel, and the sensor consists of a single channel embedded within a lipid bilayer membrane. An ionic current is passed through the channel, and analyte species are detected as transient blocks in this current associated with translocation of the analyte through the channel-stochastic sensing. While this is an extremely promising sensing paradigm, it would be advantageous to eliminate the very fragile lipid bilayer membrane and perhaps to replace the biological nanopore with an abiotic equivalent. We describe here a new family of protein biosensors that are based on conically shaped gold nanotubes embedded within a mechanical and chemically robust polymeric membrane. While these sensors also function by passing an ion current through the nanotube, the sensing paradigm is different from the previous devices in that a transient change in the current is not observed. Instead, the protein analyte binds to a biochemical molecular-recognition agent at the mouth of the conical nanotube, resulting in complete blockage of the ion current. Three different molecular-recognition agents, and correspondingly three different protein analytes, were investigated: (i) biotin/streptavidin, (ii) protein-G/immunoglobulin, and (iii) an antibody to the protein ricin with ricin as the analyte. 相似文献
15.
Penna Thereza Christina Vessoni Marques Marcelo Machoshvili Irena A. Ishii Marina 《Applied biochemistry and biotechnology》2002,98(1-9):539-551
Large-volume parenteral solutions were submitted to heat treatments after being inoculated with Bacillus stearothermophilus ATCC 7953 (T
r
=121°C) and Bacillus subtilis ATCC 9372 (T
r
=104.5°C) spores. The average decimal reduction time for B. stearothermophilus ranged from a D
121°C value of 1.31 to 3.14 min, in glucophysiologic and Ringer’s solutions respectively. For B. subtilis, D
104.5°C value increased from 0.69 to 1.37 min, in Ringer’s (pH=5.91) and 50% glucose (pH 3.05) solutions respectively. The z value ranged from 7.95°C (20% mannitol solution) to 13.14°C (50% glucose solution), corresponding to an activation energy
(Ea) of 81.48 and 49.30 kcal/mol, respectively. 相似文献
16.
17.
Thiele CM 《The Journal of organic chemistry》2004,69(22):7403-7413
The concept of using residual dipolar couplings (RDCs) for the structure determination of organic molecules is applied to the simultaneous assignment of all diastereotopic protons in strychnine. To use this important NMR parameter the molecule has to be aligned in the magnetic field. Here we present a new alignment medium for organic substrates. The optimization of the alignment properties of mixtures of poly-gamma-ethyl-L-glutamate (PELG) and CDCl(3) are described and the alignment properties of PELG at different concentrations are evaluated. A comparison of PELG with poly-gamma-benzyl-L-glutamate (PBLG) shows considerable differences in the magnitude of alignment for strychnine in the two alignment media. PELG induces a lower degree of order and makes the measurement of residual dipolar couplings (RDCs) in strychnine possible. All one-bond C-H RDCs of strychnine in PELG were determined by using 2D heteronuclear single quantum coherence (HSQC) spectroscopy. The strategy for the extraction of RDCs for methylene groups is described in detail. The RDCs and order parameters are used to assign pairs of diastereotopic protons. This methodology can distinguish not only one pair of diastereotopic protons but it can be used to assign all pairs of diastereotopic protons simultaneously. Two different calculation approaches to achieve this task are described in detail. 相似文献
18.
Vasse JL Stranne R Zalubovskis R Gayet C Moberg C 《The Journal of organic chemistry》2003,68(8):3258-3270
Chiral P,N-ligands with pseudo-C2 and pseudo-Cs symmetry based on chiral pyrrolidine and phospholane rings or on dinaphthatodihydroazepino and dinaphthatodihydrophosphepino moieties were prepared and assessed in the palladium-catalyzed allylic substitutions of allylic acetates. Higher selectivity was achieved with pseudo-C2-symmetric ligands based on the binaphthyl skeleton than with the analogous C2-symmetric P,P- and N,N-analogues. Pseudo-C2-type ligands had properties superior to those of pseudo-meso-type ligands when 1,3-diphenyl-2-propenyl acetate was used as a substrate, whereas the reverse situation was found for 3-cyclohexenyl acetate. Chirally flexible ligands, prepared by substitution of one of the rigid binaphthyl skeletons for a flexible biphenyl system, were found to induce chirality to the same extent as a 1:1 mixture of the rigid ligands. 相似文献
19.
Thereza Christina Vessoni Penna Marina Ishii Adalberto Pessoa Junior Laura de Oliveira Nascimento Luciana Cambricoli de Souza Olivia Cholewa 《Applied biochemistry and biotechnology》2004,114(1-3):453-468
To determine the influence of various culture conditions, transformed cells of Escherichia coli expressing recombinant green fluorescent protein (GFPuv) were grown in nine cultures with four variable conditions (storage
of inoculated broth at 4°C prior to incubation, agitation speed, isopropyl-β-d-thiogalactopyranoside [IPTG] concentration, and induction time). The pelleted cells were resuspended in extraction buffer
and subjected to the three-phase partitioning (TPP) extraction method. To determine the most appropriate purification resin,
protein extracts were eluted through one of four types of HiTrap hydrophobic interaction chromatography (HIC) columns prepacked
with methyl, butyl, octyl, or phenyl resins and analyzed further on a 12% sodium dodecylsulfatepolyacrylamidegel. With Coomassie
staining, a single band between 27 (standard GFPuv) and 29 kDa (molecular weight standard) was visualized for every HIC column
sample. TPP extraction with HIC elution provided about 90% of the GFPuv recovered and eight-fold GFPuv enrichment related
to the specific mass. Rotary speed and IPTG concentration showed, respectively, greater negative and positive influences on
GFPuv expression at the beginning of the logarithmic phase for the set culture conditions (37°C, 24-h incubation). 相似文献
20.
Hjelm J Handel RW Hagfeldt A Constable EC Housecroft CE Forster RJ 《Inorganic chemistry》2005,44(4):1073-1081
The electropolymerization of a series of Ru and Os bis-terpyridine complexes that form rodlike polymers with bithienyl, quaterthienyl, or hexathienyl bridges has been studied. Absorption spectroscopy, scanning electron microscopy, and cyclic voltammetry have been used to characterize the monomers and resulting polymer films. The absolute dc conductivity of the quaterthienyl-bridged {Ru(tpy)2} and {Os(tpy)2} polymers is unusually large and independent of the identity of the metal center at 1.6 x 10(-3) S cm(-1). The maximum conductivity occurs at the formal potential of each redox process, which typically is observed for systems where redox conduction is the dominant charge transport mechanism. Significantly, the dc conductivity of the metal-based redox couple observed in these polymers is 2 orders of magnitude higher thanthat of a comparable nonconjugated system. 相似文献