全文获取类型
收费全文 | 10402篇 |
免费 | 611篇 |
国内免费 | 43篇 |
专业分类
化学 | 7310篇 |
晶体学 | 32篇 |
力学 | 159篇 |
数学 | 1504篇 |
物理学 | 1431篇 |
无线电 | 620篇 |
出版年
2023年 | 88篇 |
2022年 | 111篇 |
2021年 | 177篇 |
2020年 | 249篇 |
2019年 | 220篇 |
2018年 | 153篇 |
2017年 | 136篇 |
2016年 | 445篇 |
2015年 | 425篇 |
2014年 | 439篇 |
2013年 | 531篇 |
2012年 | 714篇 |
2011年 | 750篇 |
2010年 | 535篇 |
2009年 | 444篇 |
2008年 | 675篇 |
2007年 | 602篇 |
2006年 | 564篇 |
2005年 | 577篇 |
2004年 | 490篇 |
2003年 | 357篇 |
2002年 | 326篇 |
2001年 | 165篇 |
2000年 | 144篇 |
1999年 | 159篇 |
1998年 | 126篇 |
1997年 | 171篇 |
1996年 | 116篇 |
1995年 | 112篇 |
1994年 | 114篇 |
1993年 | 94篇 |
1992年 | 88篇 |
1991年 | 59篇 |
1990年 | 45篇 |
1989年 | 68篇 |
1988年 | 57篇 |
1987年 | 33篇 |
1986年 | 31篇 |
1985年 | 46篇 |
1984年 | 37篇 |
1983年 | 23篇 |
1982年 | 46篇 |
1981年 | 30篇 |
1980年 | 25篇 |
1979年 | 23篇 |
1978年 | 20篇 |
1977年 | 26篇 |
1975年 | 25篇 |
1974年 | 15篇 |
1973年 | 19篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
111.
Andreas Holzmeister 《European Polymer Journal》2007,43(12):4859-4867
Homogeneous nonwovens composed of polymer nanofibers of a given diameter are characterized by structural parameters such as the average pore sizes and internal surfaces as well as by transport properties, which are strongly correlated to the fiber diameter at a given porosity. Such nonwovens are used among others for filter applications, protective clothing or as scaffolds for tissue engineering. A frequent requirement is that, to be able to prepare nonwovens optimised for the specific application, one has to find ways to disrupt this strong correlation allowing independent modification of pore diameter, transport properties and internal surface or to induce local chemical and structural heterogeneities within the nonwoven. The route explored in this paper is based on the electrospinning of heterogeneous nonwovens composed of nanofibers with two different average diameters (by a ratio of up to 10 and more) on the one hand and/or different chemical nature on the other hand. Spinning parameters have been optimised to achieve this goal. In addition, nonwovens composed of fibers with circular cross-section and with ribbon-like cross-section have been prepared. 相似文献
112.
To screen for organic pigments, like fringelites or porphyrins, in sediments and fossil specimen, a simple diffuse reflectance UV-vis spectroscopic determination was developed. In contrast to common inorganic pigments, like Fe2O3, these pigments exhibit well-structured characteristic absorption peaks which allow their recognition. This method was then used to identify fringelite H in a non-crinoidSolenopora species from the Jurassic. Reflectance FTIR spectroscopy proved not to be useful for this purpose. 相似文献
113.
Glycine and proline residues are frequently found in turn and loop structures of proteins and are believed to play an important role during chain compaction early in folding. We investigated their effect on the dynamics of intrachain loop formation in various unstructured polypeptide chains. Loop formation is significantly slower around trans prolyl peptide bonds and faster around glycine residues compared to any other amino acid. However, short loops are formed fastest around cis prolyl bonds with a time constant of 6 ns for end-to-end contact formation in a four-residue loop. Formation of short loops encounters activation energies in the range of 15 to 30 kJ/mol. The altered dynamics around glycine and trans prolyl bonds can be mainly ascribed to their effects on the activation energy. The fast dynamics around cis prolyl bonds, in contrast, originate in a higher Arrhenius pre-exponential factor, which compensates for an increased activation energy for loop formation compared to trans isomers. All-atom simulations of proline-containing peptides indicate that the conformational space for cis prolyl isomers is largely restricted compared to trans isomers. This leads to decreased average end-to-end distances and to a smaller loss in conformational entropy upon loop formation in cis isomers. The results further show that glycine and proline residues only influence formation of short loops containing between 2 and 10 residues, which is the typical loop size in native proteins. Formation of larger loops is not affected by the presence of a single glycine or proline residue. 相似文献
114.
Ivar Ugi Johannes Bauer Klemens Bley Alf Dengler Andreas Dietz Eric Fontain Bernhard Gruber Rainer Herges Michael Knauer Klaus Reitsam Natalie Stein 《Angewandte Chemie (International ed. in English)》1993,32(2):201-227
The topic of this article is the development and the present state of the art of computer chemistry, the computer-assisted solution of chemical problems. Initially the problems in computer chemistry were confined to structure elucidation on the basis of spectroscopic data, then programs for synthesis design based on libraries of reaction data for relatively narrow classes of target compounds were developed, and now computer programs for the solution of a great variety of chemical problems are available or are under development. Previously it was an achievement when any solution of a chemical problem could be generated by computer assistance. Today, the main task is the efficient, transparent, and non-arbitrary selection of meaningful results from the immense set of potential solutions—that also may contain innovative proposals. Chemistry has two aspects, constitutional chemistry and stereochemistry, which are interrelated, but still require different approaches. As a result, about twenty years ago, an algebraic model of the logical structure of chemistry was presented that consisted of two parts: the constitution-oriented algebra of be- and r-matrices, and the theory of the stereochemistry of the chemical identity group. New chemical definitions, concepts, and perspectives are characteristic of this logic-oriented model, as well as the direct mathematical representation of chemical processes. This model enables the implementation of formal reaction generators that can produce conceivable solutions to chemical problems—including unprecedented solutions—without detailed empirical chemical information. New formal selection procedures for computer-generated chemical information are also possible through the above model. It is expedient to combine these with interactive methods of selection. In this review, the Munich project is presented and discussed in detail. It encompasses the further development and implementation of the mathematical model of the logical structure of chemistry as well as the experimental verification of the computer-generated results. The article concludes with a review of new reactions, reagents, and reaction mechanisms that have been found with the PC-programs IGOR and RAIN. 相似文献
115.
Herforth C Wiesner J Franke S Golisade A Jomaa H Link A 《Journal of combinatorial chemistry》2002,4(4):302-314
We have investigated the in vitro antimalarial activity of a new series of adenosine derivatives. The results show that N(6)-(1-naphthylmethyl)-5'-deoxy-5'-(amido)adenosines as well as N(6)-(4-phenylbenzyl)-5'-deoxy-5'-(amido)adenosines display significant activity against the malaria-causing parasites, with the sterically demanding bisubstituted species reported being active in most cases in the low-micromolar range. The novel compounds with unusual substitution pattern were obtained applying an efficient convergent polymer-assisted solution-phase (cPASP) synthesis protocol. Thus, we were able to prepare a series of substituted derivatives in parallel that would have been difficult to synthesize by standard techniques. The scope and limitations of the synthetic methodology are discussed. 相似文献
116.
Dissolved salts are known to affect properties of proteins in solution including solubility and melting temperature, and the effects of dissolved salts can be ranked qualitatively by the Hofmeister series. We seek a quantitative model to predict the effects of salts in the Hofmeister series on the deactivation kinetics of enzymes. Such a model would allow for a better prediction of useful biocatalyst lifetimes or an improved estimation of protein-based pharmaceutical shelf life. Here we consider a number of salt properties that are proposed indicators of Hofmeister effects in the literature as a means for predicting salt effects on the deactivation of horse liver alcohol dehydrogenase (HL-ADH), alpha-chymotrypsin, and monomeric red fluorescent protein (mRFP). We find that surface tension increments are not accurate predictors of salt effects but find a common trend between observed deactivation constants and B-viscosity coefficients of the Jones-Dole equation, which are indicative of ion hydration. This trend suggests that deactivation constants (log k(d,obs)) vary linearly with chaotropic B-viscosity coefficients but are relatively unchanged in kosmotropic solutions. The invariance with kosmotropic B-viscosity coefficients suggests the existence of a minimum deactivation constant for proteins. Differential scanning calorimetry is used to measure protein melting temperatures and thermodynamic parameters, which are used to calculate the intrinsic irreversible deactivation constant. We find that either the protein unfolding rate or the rate of intrinsic irreversible deactivation can control the observed deactivation rates. 相似文献
117.
Two types of commercial glass fibers were subjected to attack in strongly basic KOH solutions. The resulting leach solutions were analysed for Na, Ca, and Si. This showed that the corrosion process attacks the fibers incongruently. Although there are some distinct differences in the performance of these fibers, to a first approximation both types behave similarly. Further, the fibers were depth profiled using a recently developed SNMS technique for fiber in-depth analysis. This showed that both types of fibers behave in a quite dissimilar manner. The fibers were weathered already without any treatment. Although both fibers show alkali ion exchange and network splitting processes, on one of the fiber layers enriched in SiO2, Fe2O3, and CaO are formed by a redeposition process from the leach solution.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
118.
A new approach for design of improved interfacial bonding between carbon fibers and polymeric matrices is described. In this method the affinity of surface-treated carbon fibers to various polymer matrices is simulated by analyzing the adsorption characteristics of model compounds, typical of the polymer units, onto very high surface area carbon fibers. The affinity can be evaluated by the use of Thermogravimetric Analysis (TGA) to measure adsorption–desorption characteristics. Since high surface area, activated carbon fibers (ACF) can be chemically treated to obtain acidic, basic, nonpolar or highly polar surfaces, it should be possible to assess the interactions of chemically modified surfaces with model compounds such as methanol (MeOH), acetone, dimethylformamide (DMF), dimethylether, tetrahydrofuran (THF) and water. Some preliminary results are presented, indicating that surface treatments for carbon fibers other than oxidation may lead to enhanced bonding with polymeric matrices. 相似文献
119.
The synthesis of ( - ) 2S,3S,11S,12R-2, 3,11,12-tetraphenyl [18]-crown-6 from (-)-1S,2S-hydrobenzoin and meso-hydrobenzoin is described. Chemical shifts and vicinal coupling constants of the benzylic protons in the 2 S, 3 S and 11 S,12 R substructures in the free ligands and in complexes with KSCN and 1-phenylethylammonium bromides and a brief discussion of the related conformational changes are also presented. A detailed procedure for the resolution of racemic hydrobenzoin is given. 相似文献
120.
Reactive constituents have been investigated in a molecular beam generated in the cathode surface glow area and surface boundary layer. Mixtures of nitrogen and hydrogen form NHx(x=0–4) compounds, which are of relevance in heterogeneous, plasma vs. metal nitriding reactions. Ammonia decomposition leads to NHx(x=2–4). Strong cataphoretic enrichment of hydrogen has been observed in the cathode glow area. Heterogeneous reactions of NHx with iron lead to the formation of iron nitrides via intermediates such as FeNH2–3. In a pulsed d.c. glow discharge, increased sputtering and decreased hydrogen enrichment have been observed. 相似文献