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   72804篇
  免费   7749篇
  国内免费   14208篇
化学   65125篇
晶体学   2650篇
力学   1337篇
综合类   593篇
数学   5085篇
物理学   19971篇
  2024年   155篇
  2023年   1209篇
  2022年   1977篇
  2021年   2391篇
  2020年   2628篇
  2019年   2439篇
  2018年   1999篇
  2017年   2671篇
  2016年   2748篇
  2015年   2436篇
  2014年   3225篇
  2013年   6530篇
  2012年   4599篇
  2011年   5070篇
  2010年   4302篇
  2009年   5112篇
  2008年   4956篇
  2007年   5031篇
  2006年   4708篇
  2005年   4191篇
  2004年   3961篇
  2003年   3240篇
  2002年   2803篇
  2001年   2241篇
  2000年   2147篇
  1999年   1691篇
  1998年   1460篇
  1997年   1290篇
  1996年   1094篇
  1995年   1042篇
  1994年   972篇
  1993年   788篇
  1992年   686篇
  1991年   519篇
  1990年   352篇
  1989年   322篇
  1988年   276篇
  1987年   182篇
  1986年   156篇
  1985年   164篇
  1984年   127篇
  1983年   62篇
  1982年   104篇
  1981年   135篇
  1980年   105篇
  1979年   110篇
  1978年   74篇
  1977年   76篇
  1976年   50篇
  1973年   42篇
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
991.
以(S)-2-氨基丙醇为手性源与α-溴-3-氯苯丙酮反应, (R)-2-氨基丙醇为手性源与6-甲氧基-2-(2-溴丙酰基)萘反应, 分别合成了手性纯化合物(2R,3R,5S)-3,5-二甲基-2-(3-氯苯基)-2-吗啉醇盐酸盐(4a)和(2S,3S,5R)-3,5-二甲基-2-(6-甲氧基-2-萘基)-2-吗啉醇盐酸盐(4b), 利用X射线单晶衍射仪测定了两化合物的晶体结构和两化合物的空间结构, 并初步分析两化合物空间结构, 化合物4a晶体属正交晶系, 空间群为P21212, 晶胞参数为: a=0.8718(2) nm, b=0.7883(2) nm, c=2.0247(6) nm, Z=4, V=1.3915(7) nm3, Dc=1.328 g/cm3, F(000)=584, R1=0.0399, wR2=0.0797, S=1.042. 化合物4b晶体属正交晶系, 空间群为P212121, 晶胞参数为: a=0.71035 (9) nm, b=0.77703(10) nm, c=2.9820(4) nm, Z=4, V=1.6318(4) nm3, Dc=1.318 g/cm3, F(000)=688, R1=0.0520, wR2=0.1108, S=0.994.  相似文献   
992.
In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba0.77Ca0.23TiO3 nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis, morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy. In summary, Ba0.77Ca0.23TiO3 nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution (30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the chelation in higher pHs.  相似文献   
993.
Gamma radiolysis of oxygenated 1–10 mM azide solutions was carried out at various pH values. In oxygenated 10 mM azide solutions, H2O2 and NO 2 were observed as radiolytic products while NH3 was not. The concentration of H2O2 reached its maximum level at a dose of 1 kGy, whereas NO 2 yield increased non-linearly beyond 2 kGy in this system. Both in aerated and oxygenated systems, G(NO 2 ) and G(H2O2) were found to vary with N 3 concentration. The yield of NO 2 was found to be dependent on both dose rate and pH. On pulse radiolysis, NO 2 was found as a radiolytic product in aerated 1 mM azide solution at pH 6.8. In this system the intermediate generated exhibits absorbance around 250 nm. The overall results obtained during the present study reveal that in presence of both reducing radical (mainly e aq ) and oxygen, N 3 produced an intermediate possibly NH2O 2 radical, which is the prime source for NO 2 generation.  相似文献   
994.
Cerium-doped terbium aluminum garnet phosphors, Tb3Al5O12:Ce3+ (TAG:Ce3+), were prepared with different methods: co-precipitation (CP), half dry-half wet (HDHW), sol-combustion (SC) and Pechini method plus conventional solid state reaction (SS) method. Comparative study on the phase-formation, particle size, morphologies and luminescent characteristics of the phosphors synthesized with different methods was carried out by means of XRD, FE-SEM and photoluminescence (PL) analysis and SC method was confirmed by the comparison of the results to be an easy and an effective process for preparing efficient and nano-sized Tb3Al5O12:Ce3+ phosphors. Various factors influencing particle size, morphology and PL of the phosphors, such as precursor preparation, reaction temperature and heating time, were also investigated. Light-emitting diodes (LEDs) were fabricated with each phosphor and a ∼460 nm emitting InGaN chip. The LEDs from SS, HDHW and CP exhibit strong white emission while those from SC and Pechini emit yellow, revealing that the emission characteristics of LEDs are influenced not only by the morphology and the particle size of the phosphors, but also by the preparing process of the phosphors.  相似文献   
995.
纳米TiO2膜用于光催化氧化测定化学需氧量的研究   总被引:4,自引:0,他引:4  
A photocatalytic oxidation method for determination of chemical oxygen demand (COD) using nano-TiO2 film, based on the use of a nano-TiO2-Ce(SO4)2 system and electrochemical detection, was proposed. The technique was originated from the direct determination of the Ce(Ⅲ) concentration change resulting from photocatalytic oxidation of organic compounds. Ce(Ⅲ), which was produced by photocatalytic reduction of Ce(SO4)2, could be measured at a multi-walled carbon nanotubes (MWNT) chemically modified electrode (CME). The COD values by this method were calculated from the differential pulse voltammetry (DPV) current of Ce(Ⅲ) at the CME. Under the optimal operation conditions, the detection limit of 0.5 mg·L^-1 COD with the linear range of 1-600 mg·L^-1 was achieved. This method was also applied to determination of various COD of ground water and wastewater samples. The resuits were in good agreement with those from the conventional COD methods, i.e., permanganate and dichromate ones.  相似文献   
996.
Summary Single reverse water-gas shift (RWGS) and dehydrogenation of propane with CO2(DH-CO2) reactions in the presence and absence of the CrOx/SiO2 catalyst have been studied between 673 and 873 K. It was found that the CrOx/SiO2 catalyst is active both in the dehydrogenation of propane and in the RWGS reactions. The obtained results suggest that the dehydrogenation of propane to propene in the presence of CO2on CrOx/SiO2can be facilitated by the RWGS reaction.</o:p>  相似文献   
997.
Photocleavable protecting groups are important in synthesis and caging. Among many such groups, 2-nitrobenzyl and related groups have been found useful in many applications. However, most of the known 2-nitrobenzyl-based caging chromophores show either low quantum yield or the photolysis wavelength is not suitable for various applications. In this paper, we report 2-nitro-3-naphthalenemethanol (NNM) as an efficient photocleavable protecting group for molecules containing a carboxylic function. NNM possesses photochemical properties better than the 2-nitrobenzyl chromophores as it is photoactivatable at 380 nm in aqueous medium (CH3CN/H2O, 3:2 v/v) showing the desired photochemistry. The carboxylic acids are efficiently photoreleased from NNM-based esters in almost quantitative yield.  相似文献   
998.
Factors (reaction temperature, reaction time, flow rate of oxygen, amount of catalyst, etc.) influencing the catalytic properties of Co3O4/SiO2catalyst in the oxidation octadecan-1-ol to octadecanoic acid were investigated. The catalysts were characterized by means of XRD, FT-IR and N2-adsorption. The experimental results indicate that under the optimal condition the selectivity to octadecanoic acid reached 97.5 % over 5 % Co3O4/SiO2 catalyst.This revised version was published online in December 2005 with corrections to the Cover Date.  相似文献   
999.
The reactions of substituted 3-cyanopyridine-2(1H)-thiones and 3-cyano-2-(methylthio)pyridines with lithium aluminum hydride in anhydrous diethyl ether afforded the corresponding 3-aminomethyl derivatives, which were used in the synthesis of the corresponding amides.  相似文献   
1000.
Sol-gel Cu//MgOSiO2 catalysts were prepared gelling tetraethoxysilane (TEOS), magnesium ethoxide and copper acetylacetonate at pH 3 and pH 9. The catalysts shown specific surface areas ca. 500 m2/g and 140 m2/g for pH 9 and pH 3 preparations respectively. Si(OH) and Si(OH)2 hydroxy groups were observed by MAS-RMN spectroscopy in both preparations. CO2-TPD and NH3-TPD desorption thermograms showed that acid and basic sites were formed on the catalysts surface. It has been found that the catalysts having the highest density of basic sites were the catalysts showing the highest activity for the CO oxidation. It is proposed that the catalytic activity depends of the relative Cu=1/Cu=2 stability given by the support acidity.  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