全文获取类型
收费全文 | 65950篇 |
免费 | 2073篇 |
国内免费 | 217篇 |
专业分类
化学 | 41033篇 |
晶体学 | 390篇 |
力学 | 1121篇 |
综合类 | 5篇 |
数学 | 12148篇 |
物理学 | 13543篇 |
出版年
2023年 | 412篇 |
2022年 | 698篇 |
2021年 | 968篇 |
2020年 | 976篇 |
2019年 | 1008篇 |
2018年 | 1231篇 |
2017年 | 1158篇 |
2016年 | 2225篇 |
2015年 | 1882篇 |
2014年 | 1924篇 |
2013年 | 4084篇 |
2012年 | 3960篇 |
2011年 | 4051篇 |
2010年 | 2709篇 |
2009年 | 2391篇 |
2008年 | 3565篇 |
2007年 | 3349篇 |
2006年 | 3059篇 |
2005年 | 2935篇 |
2004年 | 2489篇 |
2003年 | 2091篇 |
2002年 | 1815篇 |
2001年 | 1337篇 |
2000年 | 1282篇 |
1999年 | 926篇 |
1998年 | 745篇 |
1997年 | 688篇 |
1996年 | 848篇 |
1995年 | 611篇 |
1994年 | 685篇 |
1993年 | 637篇 |
1992年 | 655篇 |
1991年 | 552篇 |
1990年 | 582篇 |
1989年 | 472篇 |
1988年 | 464篇 |
1987年 | 450篇 |
1986年 | 428篇 |
1985年 | 569篇 |
1984年 | 555篇 |
1983年 | 415篇 |
1982年 | 425篇 |
1981年 | 436篇 |
1980年 | 380篇 |
1979年 | 346篇 |
1978年 | 331篇 |
1977年 | 325篇 |
1976年 | 329篇 |
1974年 | 287篇 |
1973年 | 314篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Summary The photodegradation behaviour of 12 nitrogen-containing herbicides (atrazine, cyanazine, terbuthylazine, terbutryn, EPTC,
buthylate, molinate, cycloate, vernolate, fenuron, chloroxuron, and methabenzthiazuron) has been examined. The compounds were
degraded completely when exposed to a mercury-vapour lamp; the degradation process was followed by consecutive GC measurements.
All the compounds studied had measurable photochemical activity, although actual and average degradation rates varied significantly.
All the compounds except terbutryn furnished more than one major degradation product, in different ratios.
Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001 相似文献
942.
Sénèque O Rager MN Giorgi M Prangé T Tomas A Reinaud O 《Journal of the American Chemical Society》2005,127(42):14833-14840
The coordination chemistry of Zn in an N(3)ArOH environment has been explored. The ligands are based on calix[6]arenes that present two imidazole arms and an amino phenol moiety at the narrow rim. Three different types of complexes have been characterized. One is dicationic with Zn(2+) coordinated to the three nitrogen atoms and to the oxygen of the phenol group of the calix[6]ligand. This complex is very sensitive to exogenous coordinating molecules and exists as a 5-coordinate species due to the endo-complexation of a guest. The second species is a monocationic complex for which the phenol group has been deprotonated. The resulting N(3)ArOZn complex can also bind a guest ligand albeit with a lower affinity than the dicationic complex. The third species is neutral. It can be obtained upon reaction with a base to yield a hydroxo complex or with an anion such as a chloride that coordinates the metal center from the outside of the calixarene cavity. The simultaneous binding of two anionic donors decreases the Zn Lewis acidity, allowing an impressive conformational reorganization of the system. One imidazole arm is released by the metal center. The other one undergoes self-inclusion into the pi-basic calixarene cavity because the low affinity of the metal center for neutral ligand does not allow the endo-coordination of an exogenous guest. Hence, the calix[6]N(3)ArOH-based Zn complexes act as an acid-base switch for guest binding. Several aspects of this system appear reminiscent of Zn-peptidases of the astacin and serralisin families. 相似文献
943.
We present a quantum-mechanical investigation of the LiH depletion reaction LiH+H-->Li+H2 and of the H exchange reaction LiH+H'-->LiH'+H. We report product distributions, rate constant, and mechanism of the former, and rate constant and mechanism of the latter reaction. We use the potential-energy surface by Dunne et al. [Chem. Phys. Lett. 336, 1 (2001)], the real-wave-packet method by Gray and Balint-Kurti [J. Chem. Phys. 108, 950 (1998)], and the J-shifting approximation. The 1H2 nuclear-spin statistics and progressions of vib-rotational states (v',j') rule both initial-state-resolved and thermal product distributions, which have saw-toothed shapes with odd j' preferred with respect to even j'. At high collision energies and temperatures, we obtain a regular 3-to-1 intensity alternation of rotational states. At low collision energies and temperatures, the degeneracy and density of many H2 levels can, however, give more irregular distributions. During the collision, the energy flows from the reactant translational mode to the product vibration and recoil ones. The rate constants of both reactions are not Arrhenius type because the reactions are barrier-less. The low-temperature, LiH depletion rate constant is larger than the H exchange one, whereas the contrary holds at high temperature. The real-time mechanisms show the nuclear rearrangements of the nonreactive channel and of the reactive ones, and point out that the LiH depletion is preferred over the H exchange at short times. This confirms the rate-constant results. 相似文献
944.
Sánchez ME Turina AV García DA Nolan MV Perillo MA 《Colloids and surfaces. B, Biointerfaces》2004,34(2):77-86
In the present work, we studied the ability of thymol to affect the organization of model membranes and the activity of an intrinsic membrane protein, the GABA(A) receptor (GABA(A)-R). In this last aspect, we tried to elucidate if the action mechanism of this terpene at the molecular level, involves its binding to the receptor protein, changes in the organization of the receptor molecular environment, or both. The self-aggregation of thymol in water with a critical micellar concentration approximately = 4 microM and its ability to penetrate in monomolecular layers of soybean phosphatidylcholine (sPC) at the air-water interface, even at surface pressures above the equilibrium, lateral pressure of natural bilayers were demonstrated. Thymol affected the self-aggregation of Triton X-100 and the topology of sPC vesicles. It also increased the polarity of the membrane environment sensed by the electrochromic dye merocyanine. A dipolar moment of 1.341 Debye was calculated from its energy-minimized structure. Its effect on the binding of [3H]-flunitrazepam ([3H]-FNZ) to chick brain synaptosomal membranes changed qualitatively from a tendency to the inhibition to a clear activatory regime, up on changing the phase state of the terpene (from a monomeric to a self-aggregated state). Above its CMC, thymol increased the affinity of the binding of [3H]-FNZ (K(d-control)= 2.9, K(d-thymol)= 1.7 nM) without changing the receptor density (B(max-control)= 910, B(max-thymol)= 895 fmol/mg protein). The activatory effect of thymol on the binding of [ [3H]-FNZ was observed even in the presence of the allosteric activator gamma-aminobutyric acid (GABA) at a concentration of maximal activity, and was blocked by the GABA antagonist bicuculline. Changes in the dipolar arrangement and in the molecular packing of GABA(A)-R environment are discussed as possible mediators of the action mechanism of thymol. 相似文献
945.
946.
Starting from the natural neo-clerodane diterpenoid teubotrin (1) several neo-clerodane derivatives (3-7,9-11) have been obtained. The naturally occurring diterpenoid teuscordinon (12) has also been synthesized from teubotrin (1), showing thereby how some of these transformations can be useful for the synthesis of other natural neo-clerodane diterpenes. The latter are of interest due to their activity as insect antifeedants and other important biological properties. 相似文献
947.
Ballesteros I. Ballesteros M. CabaÑas A. Carrasco J. MartÍn C. Negro M. J. Saez F. Saez R. 《Applied biochemistry and biotechnology》1991,(1):307-315
A total of 27 yeast strains belonging to the groupsCandida, Saccharomyces, andKluyveromyces were screened for their ability to grow and ferment glucose at temperatures ranging 32-45°C.
K. marxianus andK. fragilis were found to be the best ethanol producing organisms at the higher temperature tested and, so, were selected for subsequent
simultaneous saccharification and fermentation (SSF) studies. 相似文献
948.
Titanium - catalyzed dimerization of cycloheptatriene affords pentacyclo[7.5.0.02,8.05,14.07,11]tetradeca-3,12-diene, , and pentacyclo[8.4.0.03,7.04,14.06,11]tetradeca-8,12-diene, . By heating, is converted quantitatively into . 相似文献
949.
Bitter Istvn Hermecz Istvn Tth Gbor Dvortsk Pter Bende Zoltn Mszros Zoltn 《Tetrahedron letters》1979,20(52):5039-5040
The 9-carbamoyl derivatives /–/ can be prepared from title compound // with isocyanates //. – are mixtures of the cis /Z/ and trans /E/ imines and the enamine /e/. The equilibrium depends on the substituents R,X and on the solvent. 相似文献
950.
T. Lohner E. Kótai F. Pászti A. Manuaba M. Fried J. Gyulai 《Journal of Radioanalytical and Nuclear Chemistry》1984,83(1):75-81
It is demonstrated that the information obtained by Rutherford backscattering spectrometry and channeling technique can substantially help in the construction of a realistic optical model for the ellipsometry of ion-implanted silicon. In the case of fully amorphous ion-bombarded layers, the ellipsometry is a fast, non-destructive and contactless method to estimate the thickness of these films. For buried and partially disordered layers a qualitative interpretation of different trajectories in the - plance can be given on the basis of channeling measurements. 相似文献