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   12574篇
  免费   1568篇
  国内免费   1612篇
化学   5259篇
晶体学   97篇
力学   2002篇
综合类   200篇
数学   5865篇
物理学   2331篇
  2024年   19篇
  2023年   149篇
  2022年   197篇
  2021年   346篇
  2020年   469篇
  2019年   412篇
  2018年   407篇
  2017年   485篇
  2016年   576篇
  2015年   384篇
  2014年   597篇
  2013年   1164篇
  2012年   718篇
  2011年   713篇
  2010年   623篇
  2009年   779篇
  2008年   811篇
  2007年   861篇
  2006年   702篇
  2005年   613篇
  2004年   578篇
  2003年   502篇
  2002年   496篇
  2001年   400篇
  2000年   370篇
  1999年   355篇
  1998年   282篇
  1997年   240篇
  1996年   211篇
  1995年   222篇
  1994年   178篇
  1993年   157篇
  1992年   109篇
  1991年   116篇
  1990年   78篇
  1989年   62篇
  1988年   49篇
  1987年   46篇
  1986年   37篇
  1985年   42篇
  1984年   39篇
  1983年   23篇
  1982年   27篇
  1981年   23篇
  1980年   23篇
  1979年   21篇
  1978年   8篇
  1977年   15篇
  1976年   7篇
  1957年   5篇
排序方式: 共有10000条查询结果,搜索用时 57 毫秒
51.
通过纳米二氧化硅的硅烷化改性, 使其在高矿化度盐水中可以稳定存在的前提下, 研究了改性纳米颗粒与阳离子表面活性剂十二烷基三甲基氯化铵混合体系的溶液稳定性及协同稳定CO2泡沫的效果. 研究结果表明, 无机盐离子对改性纳米颗粒与阳离子表面活性剂间的静电吸引力具有屏蔽作用, 且矿化度越高, 屏蔽效果越明显, 从而混合溶液更易于在高盐水中稳定; 纳米颗粒表面的活性剂吸附层受二者浓度的影响, 进而影响了颗粒的亲/疏水性; 当混合体系中的表面活性剂浓度低于临界胶束浓度(CMC)时, 混合溶液与CO2的界面张力高于单独活性剂溶液, 而当活性剂浓度高于CMC时, 对CO2-溶液界面张力几乎无影响, 最低界面张力可降至6 mN/m左右; 改性纳米颗粒的加入可以进一步提高CO2体相泡沫半衰期一倍以上, 但受二者浓度比例的影响; 纳米颗粒的加入有效提高了多孔介质中泡沫的表观黏度, 最大增幅由20 mPa·s增至55 mPa·s左右, 泡沫黏度增加接近3倍, 增强了CO2泡沫驱的封堵作用.  相似文献   
52.
In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC4H3X ( 1 X ), SiC4H2X2 ( 2 X ), SiC4HX3 ( 3 X ), and SiC4X4 ( 4 X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔEs-t, a possible indication of stability), and band gap (ΔEH-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 X > 1 X > 3 X > 4 X . Precedence of 2 X over 1 X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 I and 4 F . The trend of divalent angle () for each X is 4 X > 1 X > 3 X > 2 X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔEs-t and ΔEH-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.  相似文献   
53.
Sulfonated polytriazoles have drawn a great attention as high performance polymers and their good film forming ability. In the present study, a phosphorus containing new diazide monomer namely, bis-[4-(4′-aminophenoxy)phenyl]phenylphosphine was synthesized and accordingly, a series of phosphorus containing sulfonated polytriazoles (PTPBSH-XX) was synthesized by reacting equimolar amount of this diazide monomer (PAZ) in combination with another sulfonated diazide monomer (DSAZ) and a terminal bis-alkyne (BPALK) by the Cu (I) catalyzed azide–alkyne click polymerization. The polymers were characterized by nuclear magnetic resonance (1H, 13C, 31P NMR) and Fourier transform infrared spectroscopic techniques. The sulfonic acid content of the copolymers also determined from the different integral values obtained from the 1H NMR signals. The small-angle X-ray scattering results unfolded the well-separated dispersion of the hydrophilic and hydrophobic domains of the polymers. As a whole, the copolymer membranes displayed sufficient thermal, mechanical, and oxidative stabilities high with high proton conductivity and low water uptake that are essential for proton exchange membrane applications. The copolymers exhibited oxidative stability in the range of 15–24 h and had proton conductivity values were found as high as 38–110 mS cm−1 at 80 °C in completely hydrated condition. Among the all copolytriazoles, PTPBSH-90 (BPALK:DSAZ:PAZ = 100:90:10) having IECW = 2.44 mequiv g−1, showed proton conductivity as high as 119 mS cm−1 at 90 °C with an activation energy of 10.40 kJ mol−1 for the proton conduction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 263–279  相似文献   
54.
The two enantiomers of a compound often have profoundly different biological properties and thus their liability to racemisation in aqueous solutions is an important piece of information. The authors reviewed the available data concerning the process of racemisation in vivo, in the presence of biological molecules (e.g., racemase enzymes, serum albumin, cofactors and derivatives) and under purely chemical but aqueous conditions (acid, base and other aqueous systems). Mechanistic studies are described critically in light of reported kinetic data. The types of experimental measurement that can be used to effectively determine rate constants of racemisation in various conditions are discussed and the data they provide is summarised. The proposed origins of enzymatic racemisation are presented and suggest ways to promote the process that are different from processes taking place in bulk water. Experimental and computational studies that provide understanding and quantitative predictions of racemisation risk are also presented.  相似文献   
55.
As a hot topic of global concern, the distinguishing and detecting of antibiotic pollution is crucial owing to its adverse effect on ecosystems and human health stemming from excessive use and poor management. Herein, a water-stable lanthanide coordination polymer sensor (Dy-TCPB) with multiple emitting centers is prepared. The versatile Dy-TCPB can conveniently differentiate various antibiotics, and displays a self-calibration luminescent response to nitrofurazone (NFZ) and furazolidone (FZD). Each antibiotic exhibits notable correlation to a unique combination of the two ligand-to-Dy ion emission intensity ratios, enabling two-dimensional fingerprint recognition. Furthermore, the novel self-calibration sensor demonstrates effective recognition of NFZ and FZD with excellent sensitivity and selectivity, and detection limits as low as 0.0476 and 0.0482 μm for NFZ and FZD, respectively. The synthetic approach for the fabrication of a singular coordination polymer exhibiting multiple emissions provides a promising strategy for the development of facile and effective ratiometric sensors.  相似文献   
56.
  1. Download : Download high-res image (144KB)
  2. Download : Download full-size image
  相似文献   
57.
《Mendeleev Communications》2020,30(1):114-116
  1. Download : Download high-res image (64KB)
  2. Download : Download full-size image
  相似文献   
58.
We studied the effect of ultrasonic activation of brine (3%) during salting on the degree of stability of colour parameters of pork with normal (NOR) and abnormal course of autolysis in the CIE Lab colour space. The mechanism of stabilisation of the colour of meat is attributed to donor–acceptor bonds of metmyoglobin (MetMb). The accumulation of excessive number of free electrons in the medium are capable of activating MetMb. This reduces the activity of meat, when the native participants of the metmyoglobin reductase system and their own antioxidant systems of meat are depleted.Based on the additive calculation of deviations (increase / decrease) by the coordinates L*, a*, b* in the CIE Lab system, and the total colour difference (ΔE) in control and experimental samples, recommendations were developed. To optimize the colour characteristics of all types of meat, both on the surface and in the thickness of the meat, the preliminary activation of a 3% brine in a low-frequency submersible ultrasonic unit is recommended. Moreover, preliminary cavitation activation of a 3% is more preferable to stabilise the colour of PSE – meat (pale, soft, exudative (watery),) brine in a flow-through installation.  相似文献   
59.
When dealing with simple phenols such as caffeic acid (CA) and ferulic acid (FA), found in a variety of plants, it is very important to have control over the most important factors that accelerate their degradation reactions. This is the first report in which the stabilities of these two compounds have been systematically tested by exposure to various different factors. Forced degradation studies were performed on pure standards (trans-CA and trans-FA), dissolved in different solvents and exposed to different oxidative, photolytic and thermal stress conditions. Additionally, a rapid, sensitive, and selective stability-indicating gas chromatographic-mass spectrometric method was developed and validated for determination of trans-CA and trans-FA in the presence of their degradation products. Cis-CA and cis-FA were confirmed as the only degradation products in all the experiments performed. All the compounds were perfectly separated by gas chromatography (GC) and identified using mass spectrometry (MS), a method that additionally elucidated their structures. In general, more protic solvents, higher temperatures, UV radiation and longer storage times led to more significant degradation (isomerization) of both trans-isomers. The most progressive isomerization of both compounds (up to 43%) was observed when the polar solutions were exposed to daylight at room temperature for 1 month. The method was validated for linearity, precision as repeatability, limit of detection (LOD) and limit of quantitation (LOQ). The method was confirmed as linear over tested concentration ranges from 1−100 mg L−1 (r2s were above 0.999). The LOD and LOQ for trans-FA were 0.15 mg L−1 and 0.50 mg L−1, respectively. The LOD and LOQ for trans-CA were 0.23 mg L−1 and 0.77 mg L−1, respectively.  相似文献   
60.
Quinones are electroactive species that have shown great promise for redox flow batteries due to the ability to tune their properties and to act as both negative and positive electrolytes. The following review outlines highlights of work in the last couple of years working to provide materials with higher stability, solubility, and performance. Developments toward stable negolytes have provided opportunities for potential commercial opportunities when paired with alternate chemistries. However, the stability of quinones in high potential electrolytes is still not sufficient and the number of potential quinones limited.  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