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   5326篇
  免费   1071篇
  国内免费   820篇
化学   4023篇
晶体学   69篇
力学   418篇
综合类   75篇
数学   584篇
物理学   2048篇
  2024年   13篇
  2023年   106篇
  2022年   147篇
  2021年   202篇
  2020年   271篇
  2019年   238篇
  2018年   198篇
  2017年   211篇
  2016年   264篇
  2015年   286篇
  2014年   355篇
  2013年   410篇
  2012年   504篇
  2011年   523篇
  2010年   364篇
  2009年   355篇
  2008年   336篇
  2007年   279篇
  2006年   252篇
  2005年   243篇
  2004年   209篇
  2003年   170篇
  2002年   184篇
  2001年   190篇
  2000年   127篇
  1999年   120篇
  1998年   99篇
  1997年   73篇
  1996年   99篇
  1995年   64篇
  1994年   73篇
  1993年   42篇
  1992年   32篇
  1991年   29篇
  1990年   24篇
  1989年   22篇
  1988年   23篇
  1987年   19篇
  1986年   17篇
  1985年   9篇
  1984年   4篇
  1983年   5篇
  1982年   10篇
  1981年   3篇
  1980年   3篇
  1979年   2篇
  1975年   1篇
  1965年   2篇
  1964年   3篇
  1963年   2篇
排序方式: 共有7217条查询结果,搜索用时 703 毫秒
131.
Wan J  Wang J  Cheng H  Yu Y  Xing G  Oiu Z  Qian X  He F 《Electrophoresis》2001,22(14):3026-3037
The irreversible destiny of apoptosis in its early stage might play a critical role in the apoptosis of human acute promyelocytic leukemia (APL) cell line induced by all-trans retinoic acid (ATRA). To characterize protein alterations during the apoptosis-initiation phase and to understand the metabolic status at that time, we investigated the protein profiles in the apoptosis-initiation phase of APL cell line HL-60 by proteomic analysis. ATRA-withdrawal was conducted to demonstrate that there was committed initiation phase of apoptosis triggered by 10(-6) M ATRA at day 3. Only after that time point, ATRA-treated cells irreversibly went to apoptosis. Also at that time point, the positive regulators of apoptosis such as STAT3 increased at protein level, whereas negative regulators (Bcl-2 and p-STAT3) decreased. In addition, caspase-3 also increased after that time. Furthermore, comparative proteomic analysis was utilized to examine the protein expression profiles during the initiation stage of apoptosis. Our results showed 12 upregulated and 7 downregulated proteins experiencing twofold alteration, including key regulators of signal transduction such as G-proteins and nucleic receptors, proteins related with metabolism, oxidation and reduction, proteins associated with the nucleus and cytoskeleton-related proteins. Some of them could be positive modulators to trigger apoptosis, whereas others could contribute to intracellular defense against apoptosis induced by exogenous triggers. The results above suggest that there is a subtle balance between apoptosis and the intracellular defense against apoptosis. Once the balance is disturbed, cells would irreversibly initiate to undergo the execution of apoptosis.  相似文献   
132.
Eight new benzoylated gentisyl alcohol (=2‐(hydroxymethyl)benzene‐1,4‐diol) glucosides, itosides A–H ( 1 – 8 ), together with the new pyrocatechol (=benzene‐1,2‐diol) glycoside itoside I ( 9 ) were isolated from the bark and twigs of Itoa orientalis (Flacourtiaceae). In itosides B–D ( 2 – 4 ), the gentisyl alcohol moiety was esterified by 1‐hydroxy‐6‐oxocyclohex‐2‐ene‐1‐carboxylic acid, while itosides E–H ( 5 – 8 ) contained instead an additional 2‐hydroxybenzoic acid moiety. The compounds were accompanied by the known derivatives 4‐hydroxytremulacin ( 10 ), poliothyrsoside ( 11 ), poliothyrsin ( 12 ), homaloside D ( 13 ), tremulacin, and pyrocatechol β‐D ‐glucopyranoside. The structures of the new compounds were elucidated by spectral and chemical methods.  相似文献   
133.
Xing WL  He XW 《Talanta》1997,44(6):959-965
A single piezoelectric quartz crystal coated with one kind of crown ether was applied to the simultaneous determination of binary acid and amine vapor mixtures. From the adsorption and desorption curves of analytes, which were somewhat different in shape, frequency shifts from ten time windows were taken as inputs for artificial neural networks (ANN). Prediction results were satisfactory for ANN in both sample sets. The average relative errors, for formic acid and acrylic acid were 5%, for n-butylamine and aniline, they were 3% with ANN respectively. The effects of number of neurons in the hidden layer of ANN on the performance of the network are also discussed.  相似文献   
134.
The absorption spectra of 4f electron transitions of the complexes of neodymium and erbium with 8-hydroxyquinoline-5-sulphonic acid in the presence of diethylamine and ethanol have been measured by normal and third-derivative spectrophotometry. Their molar absorptivities are 70.7 l.mol~(-1).cm~(-1) for Nd and 62.5 l.mol~(-1).cm~(-1) for Er. They are 7.6 times and 14.9 times greater than those of corresponding chlorides, respectively. Use of the third-derivative spectra both eliminates the interference of Ce(Ⅳ) and increases the sensitivity for Nd and Er. Beer,s Law was obeyed from 0-10 ug/ml of Nd and Er. The method has been applied to the determination of neodymium and erbium in rare earth mixtures.  相似文献   
135.
Xing W  Ingman F 《Talanta》1982,29(8):707-711
The complexation reaction between Alizarin complexan ([3-N,N-di(carboxymethyl)aminomethyl]-1,2-dihydroxyanthraquinone; H(4)L) and zinc(II), nickel(II), lead(II), cobalt(II) and copper(II) has been studied by a spectrophotometric method. All these metal ions form 1:1 complexes with HL; 2:1 metal:ligand complex were found only for Pb(II) and Cu(II). The stability constants are (ionic strength I = 0.1, 20 degrees C): Zn(2+) + HL(3-) right harpoon over left harpoon ZnHL(-) log K +/- 3sigma(log K) = 12.19 +/- 0.09 (I = 0.5) Ni(2+) + HL(3-) right harpoon over left harpoon NiHL(-) log K +/- 3sigma(log K) = 12.23 +/- 0.21 Pb(2+) + HL(3-) right harpoon over left harpoon PbHL(-) log K +/- 3sigma(log K) = 11.69 +/- 0.06 PbHL(-) + Pb(2+) right harpoon over left harpoon Pb(2)L + H(+) log K approximately -0.8 Co(2+) + HL(3-) right harpoon over left harpoon CoHL(-) log K 3sigma(log K) = 12.25 + 0.13 Cu(2+) + HL(3-) right harpoon over left harpoon CuHL(-) log K 3sigma(log K) = 14.75 +/- 0.07 Cu(2+) + CuHL(-) right harpoon over left harpoon Cu(2)L + H(+) log K approximately 3.5 The solubility and stability of both the reagent and the complexes and the closenes of the values of the stability constants make this reagent suitable for the photometric detection of several metal ions in the eluate from an ion-exchange column.  相似文献   
136.
聚苯乙烯磺酸掺杂聚苯胺的合成   总被引:7,自引:1,他引:7  
以苯胺(An)为单体,过硫酸铵(APS)为氧化剂,在聚苯乙烯磺酸(PSSA)的水溶液中,合成了可完全溶于水的PSSA掺杂PAn。研究了An浓度,PSSA浓度,APS浓度,APS的滴加时间,反应时间及温度对An聚合反应及其产物的水溶性,导电性及特性粘度[η]的影响。结果表明:在比较宽的实验条件下,都可以合成出具有良好导电性的可溶于水的PSSA掺杂PAn;其中当An:PSSA:APS的摩尔比为1.7:2.5:1,APS溶液的滴加时间为3h,反应时间为1h,反应温度为14℃时,得到的掺杂PAn导电率最高达0.156S/cm。  相似文献   
137.
N,N''''-硝基苯酰基取代苯酰氨基硫脲的合成与生物活性   总被引:6,自引:0,他引:6  
酰氨基硫脲类化合物不仅具有广谱抗菌性能 ,还具有极好的杀虫和植物生长调节活性 [1~ 3] ,因而引起许多国内外学者对硫脲类化合物的合成及其化学结构与生物活性关系方面的研究 [4~ 8] .为了进一步研究不同的取代基团对此类化合物生物活性的影响 ,作者用硝基苯酰基异硫氰酸酯与芳基酰肼加成制得相应的 N ,N -硝基苯酰基取代苯酰氨基硫脲 ( ) ,并初步测定了它们抑制大肠杆菌和枯草杆菌生长的生物活性 .这些化合物尚未见文献报道 .Ar— COCl KSCN Ar—CONCS a~ cAr CONHNH2 ( 1 ~ 7) Ar—CONHC( S) NHNHCOAr Ar:a.o-N…  相似文献   
138.
Synthesis and properties of liquid crystalline polyurethanes   总被引:1,自引:0,他引:1  
1,4-Bis(p-hydroxybenzoate)phenylene was prepared using 1,4-bis(trimethylsiloxy)benzene and p-hydroxybenzoyl chloride as starting materials. A series of novel 1,4-bis(p-hydroxyalkoxybenzoate)phenylene were synthesized by reaction of 1,4-bis(p-hydroxybenzoate) phenylene with 3-brompropanol and 4-bromobutanol, respectively. The liquid crystal polyurethanes were prepared by 1,4-bis(p-hydroxyalkoxybenzoate)phenylene with MDI (p-methylene diphenylenediisocyanate) and 2,4-TDI(2,4-toluenediisocyanate), respectively. The thermotropic properties, the melting point (T m) and the isotropization temperature (T i) of the synthesized polyurethanes were characterized by DSC, IR and POM. It showed that all of the polyurethane polymers exhibited thermotropic liquid crystalline properties between 144°C and 260°C. The transition temperature (T m and T i) decreased with an increase in the length of the methylene spacer. __________ Translated from Journal of Qingdao University of Science and Technology, 2006, 27(1) (in Chinese)  相似文献   
139.
The rate constants for the gas-phase reactions of isopropyl- and tert-butylperoxy radicals with nitric oxide (NO) have been studied at 298 +/- 2 K and a total pressure of 3-4 Torr (He buffer) using a laser flash photolysis technique coupled with a time-resolved negative-ionization mass spectrometry. The alkyl peroxy radicals were generated by the reaction of alkyl radicals with excess O(2), where alkyl radicals were prepared by laser photolysis of several precursor molecules. The rate constants were determined to be k(i-C(3)H(7)O(2) + NO) = (8.0 +/- 1.5) x 10(-12) and k(t-C(4)H(9)O(2) + NO) = (8.6 +/- 1.4) x 10(-12) cm(3) molecule(-1) s(-1). The results in combination with our previous studies are discussed in terms of the systematic reactivity of alkyl peroxy radicals toward NO.  相似文献   
140.
链酚胺型配体锌(Ⅱ)配合物模拟碳酸酐酶研究   总被引:1,自引:2,他引:1  
合成了酚胺型链状配体,N,N'-二(2-羟基苄基)丙二胺(H~2L)及其Zn(Ⅱ)配合物(ZnL),通过元素分析、IR和^1HNRM等手段进行了表征。采用pH电位滴定法,在25℃±0.1℃,I=0.1mol·dm^-^3(KNO~3)条件下,测定了配体的质子化常数以及配体与金属离子Zn(Ⅱ)配位反应平衡常数。讨论了配体与金属离子Zn(Ⅱ)的配位情况,得到了配位酚羟基的解离常数。运用分光光度法,在25℃±0.1℃,I=0.1mol·dm^-^3(KNO~3)条件下,在pH=5.5~9.0(50mmol·dm^-^3缓冲溶液)范围内,研究了配合物作为碳酸酐酶模拟物催化对-硝基苯酚乙酸酯(NA)水解动力学,得到了NA酯水解的配合物催化速率常数k~N~P。实验结果表明,ZnHL^+的配位酚羟基的解离常数pK~a为6.83;催化速率常数k~N~P与pH之间不存在Sigmoidal型曲线关系,而是在pH值中性附近有最大值,ZnHL^+对NA酯水解有很好的催化效果,并且采取双重催化机理,是碳酸酐酶很好的模拟物。  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