首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   796篇
  免费   25篇
  国内免费   18篇
化学   546篇
晶体学   9篇
力学   15篇
数学   111篇
物理学   158篇
  2023年   4篇
  2022年   14篇
  2021年   19篇
  2020年   20篇
  2019年   8篇
  2018年   12篇
  2017年   13篇
  2016年   18篇
  2015年   29篇
  2014年   24篇
  2013年   50篇
  2012年   39篇
  2011年   60篇
  2010年   38篇
  2009年   25篇
  2008年   51篇
  2007年   57篇
  2006年   42篇
  2005年   38篇
  2004年   33篇
  2003年   26篇
  2002年   21篇
  2001年   11篇
  2000年   12篇
  1999年   7篇
  1998年   10篇
  1997年   12篇
  1996年   8篇
  1995年   11篇
  1994年   8篇
  1993年   10篇
  1992年   7篇
  1991年   8篇
  1990年   7篇
  1989年   9篇
  1988年   12篇
  1987年   10篇
  1986年   10篇
  1985年   7篇
  1984年   7篇
  1983年   6篇
  1982年   4篇
  1980年   2篇
  1979年   3篇
  1975年   3篇
  1974年   2篇
  1973年   2篇
  1971年   2篇
  1887年   1篇
  1885年   3篇
排序方式: 共有839条查询结果,搜索用时 31 毫秒
41.
42.
Cyclodextrins (CDs) are cyclic oligosaccharides that have found widespread application in numerous fields. CDs have revealed a number of various health benefits, making them potentially useful food supplements and nutraceuticals. In this study, the impact of α-, β-, and γ-CD at different concentrations (up to 8% of the flour weight) on the wheat dough and bread properties were investigated. The impact on dough properties was assessed by alveograph analysis, and it was found that especially β-CD affected the viscoelastic properties. This behavior correlates well with a direct interaction of the CDs with the proteins of the gluten network. The impact on bread volume and bread staling was also assessed. The bread volume was in general not significantly affected by the addition of up to 4% CD, except for 4% α-CD, which slightly increased the bread volume. Larger concentrations of CDs lead to decreasing bread volumes. Bread staling was investigated by texture analysis and low field nuclear magnetic resonance spectroscopy (LF-NMR) measurements, and no effect of the addition of CDs on the staling was observed. Up to 4% CD can, therefore, be added to wheat bread with only minor effects on the dough and bread properties.  相似文献   
43.
Phosphoniumylidyl and phosphazenyl groups are effective substituents to increase the electron-donating ability of tertiary phosphines. However, the influence of structural variations among those substituents on the electronic properties of the phosphines is little explored. Herein, we show that protonation of the ylidic carbon atom of phosphoniumylidyl phosphines increases the Tolman electronic parameter (TEP) by ΔTEP = 16.0–18.8 cm–1. Furthermore, phosphazenyl phosphines were synthesized with isopropyl groups (NP{iPr}3) and tetramethylguanidino groups (NP{tmg}3) at the phosphonium center. Determination of their TEP values reveals a remarkable low substituent parameter of χ = –18.5 cm–1 for the NP(tmg)3 group. In addition, we prepared the corresponding gold(I) complexes and determined their solid-state structures using single-crystal X-ray diffraction studies to analyze the steric profile of the new phosphine ligands.  相似文献   
44.
The understanding of biomolecular function is coupled to knowledge about the structure and dynamics of these biomolecules, preferably acquired under native conditions. In this regard, pulsed dipolar EPR spectroscopy (PDS) in conjunction with site‐directed spin labeling (SDSL) is an important method in the toolbox of biophysical chemistry. However, the currently available spin labels have diverse deficiencies for in‐cell applications, for example, low radical stability or long bioconjugation linkers. In this work, a synthesis strategy is introduced for the derivatization of trityl radicals with a maleimide‐functionalized methylene group. The resulting trityl spin label, called SLIM, yields narrow distance distributions, enables highly sensitive distance measurements down to concentrations of 90 nm , and shows high stability against reduction. Using this label, the guanine‐nucleotide dissociation inhibitor (GDI) domain of Yersinia outer protein O (YopO) is shown to change its conformation within eukaryotic cells.  相似文献   
45.
It has previously been proposed (Ref. 1) that in the cationic vinyl polymerizations, proceeding with termination due to the collapse of ion pairs, addition of bases increases “livingness”, because of the fast convertion of the otherwise dead (within the time of polymerization) covalent species into the onium ions; these, in turn, fast convert into carbenium ions, the actually propagating species. Equilibria between carbenium ions (CH3OCH2+A has been used as a model) and their onium counterparts ((CH3)2O taken as a model base) as well as between covalent species (CH3OCH2OSO2CF3) and the corresponding oxonium ion (with a (CH3)2O ligand) have been studied by dynamic 1H and 19F NMR. Total ionization of methoxymethyl triflate (CH3OCH2OSO2CF3) has been shown to increase indeed from 104 (-10°C) to 106 (-70°C) times when 1,0 mol·L−1 of (CH3)2O is added. Although this model system better describes polymerization of cyclic acetals than that of vinyl ethers, it shows at least qualitatively the importance of bases in ionization of covalent species, which may be responsible for reinitiation in the cationic polymerization of vinyl ethers.  相似文献   
46.
The temperature dependence of the counting rate, F(T), has been measured in tin. A sudden increase in the counting rate, connected with the creation of vast defects acting as positron traps, has been observed on passing through the melting point. Both the F(T) and angular correlation curves indicate that the defected areas decay with increasing temperature. The kinetics of this effect has been discussed and the vacancy formation energy, being equal to Eν = 0.50 ± 0.02 eV, has been determined.  相似文献   
47.
The mechanism of polymerization is discussed, in which cyclic esters of phosphoric acid, and related compounds are converted into linear macromolecules, modelling nucleic and teichoic acid backbones. Structures like deoxyribose polyphosphate and glycerol polyphosphate were prepared from the corresponding cyclic compounds. These polymerizations involve heterolytic breaking of the P-O bond in the cyclic monomer and proceed by ionic mechanism. Both 5- and 6-membered monomers have been polymerized. The thermodynamic parameters of the ring-chain interconversion were determined; the 5-membered rings polymerization is driven by the exothermicity of the ring-opening, whereas polymerization of several 6-membered rings is endothermic and allowed because of the positive change of entropy. Anionic polymerization, and particularly the pseudo(coordinate)anionic polymerization provides, in contrast to the cationic process, high-molecular-weight polymers with more uniform structure. Anionic polymerization proceeds mostly (at the applied conditions) on the macroion – -pairs. The elementary reactions consist of the nucleophilic attack of the paired macroanions on the phosphorus atom in the cyclic monomer molecule. Rate constants of the elementary reactions for the model monomers will be presented. Stereochemistry of the propagation steps is shown to be governed by the statistical ring-opening, leading to the three kinds of polymer units (head-to-tail and two symmetrical units). Apart from the ring-opening, the polyaddition of diepoxides to phosphorous and phosphoric acids is described. Finally, a few examples of preparation of models of biopolymers are given, namely poly(deoxyribose phosphate) and poly(glycerol phosphate).  相似文献   
48.
The aim of the present study was to investigate the changes in the content of phytochemical compounds and in vitro antioxidant, antibacterial, and anti-inflammatory activities of Teucrium polium L. aerial parts and root methanolic extracts at different phenological stages (vegetative, flowering, and seeding). The T. polium extracts were analyzed using gas chromatography–mass spectrometry (GC-MS), and their antioxidant properties were tested with the 2,2-diphenyl-1-picrylhydrazyl (DPPH), nitric oxide (NO), ferrous ions (Fe2+), and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid (ABTS) methods. Forty-nine compounds were identified with the majority of germacrene D, t-cadinol, β-pinene, carvacrol, bicyclogermacrene, α-pinene, and limonene. The results show that the extracts significantly differ between different phenological stages of the plant material used in terms of the phytochemical composition (total phenolic compounds, total flavonoids, total alkaloids, and total saponin contents) and bioactivities (antioxidant, antibacterial, and anti-inflammatory) (p < 0.05). The highest total contents of phenolics (72.4 ± 2.5 mg gallic acid equivalent (GAE)/g dry weight), flavonoids (36.2 ± 3.1 mg quercetin equivalent (QE)/g dry weight), alkaloids (105.7 ± 2.8 mg atropine equivalent (AE)/g dry weight), and saponins (653 ± 6.2 mg escin equivalent (EE)/g dry weight), as well as antioxidant, antibacterial, and anti-inflammatory activities, were measured for the extract of the aerial parts obtained at the flowering stage. The minimum inhibitory concentration (MIC) values for the extracts were varied within 9.4–300 µg/mL, while the minimum bactericidal concentration (MBC) values were varied within 18.75–600 µg/mL. In addition, they were more active on Gram-positive bacteria than Gram-negative bacteria. The data of this work confirm that the T. polium extracts have significant biological activity and hence can be used in the pharmaceutical industry, clinical applications, and medical research, as well as cosmetic and food industries.  相似文献   
49.
50.
Airborne microand nanoparticles-aerosols-play an important role in many natural phenomena and in a variety of industrial processes,as well as the public health issue. They may be of natural or anthropogenic origin;their presence in an environment might be intentional or due to undesirable release. In any case,merely the particle detection and characterization,ideally in real-time,provide an insight into the potential burden allowing also controlling and abatement measures. Due to the broad size range it is ...  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号