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   7703篇
  免费   1227篇
  国内免费   991篇
化学   4179篇
晶体学   42篇
力学   445篇
综合类   33篇
数学   757篇
物理学   2456篇
无线电   2009篇
  2024年   12篇
  2023年   196篇
  2022年   185篇
  2021年   246篇
  2020年   253篇
  2019年   276篇
  2018年   210篇
  2017年   220篇
  2016年   328篇
  2015年   358篇
  2014年   370篇
  2013年   464篇
  2012年   656篇
  2011年   679篇
  2010年   491篇
  2009年   430篇
  2008年   534篇
  2007年   467篇
  2006年   450篇
  2005年   408篇
  2004年   329篇
  2003年   238篇
  2002年   227篇
  2001年   191篇
  2000年   164篇
  1999年   192篇
  1998年   165篇
  1997年   163篇
  1996年   168篇
  1995年   161篇
  1994年   102篇
  1993年   96篇
  1992年   87篇
  1991年   74篇
  1990年   77篇
  1989年   60篇
  1988年   45篇
  1987年   28篇
  1986年   35篇
  1985年   29篇
  1984年   14篇
  1983年   10篇
  1982年   13篇
  1981年   6篇
  1980年   7篇
  1979年   1篇
  1976年   2篇
  1974年   1篇
  1957年   3篇
排序方式: 共有9921条查询结果,搜索用时 31 毫秒
121.
A sensitive amperometric glucose biosensor based on platinum nanoparticles (PtNPs) combined aligned carbon nanotubes (ACNTs) electrode was investigated. PtNPs which can enhance the electrocatalytic activity of the electrode for electrooxidating hydrogen peroxide by enzymatic reaction were electrocrystallized on 4‐aminobenzene monolayer‐grafted ACNTs electrode by potential‐step method. These PtNPs combined ACNTs' (PtNPs/ACNTs) surfaces were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The highly dispersed PtNPs on ACNTs can be obtained. The enzyme electrode exhibits excellent response performance to glucose with linear range from 1×10?5–7×10?3 mol L?1 and fast response time within 5 s. Furthermore, this glucose biosensor also has good reproducibility. It is demonstrated that the PtNPs/ACNTs electrode with high electrocatalytic activity is a suitable basic electrode for preparing enzyme electrodes.  相似文献   
122.
采用低湿溶液缩聚的方法合成了对苯二甲酰氯,二甲基联苯胺和己二醇为单体的芳酯族液晶聚酯酰胺。用DSC,X光衍射分析和偏光显微镜等手段研究了该系列聚酯酰胺的热致液晶行为,确认了二甲基联苯胺单体用量在20%(mol)的情况下,所得聚酯酰胺仍为向列型液晶聚合物。由于聚酯酰胺分子间聚酰胺链段之间的氢键作用,随着二甲基联苯胺用量增加至60mol%时,所得的聚酯酰胺己无液晶转变温度,其液晶区间即从熔融温度直至分  相似文献   
123.
The methylation of tin(II) [Sn(II)] by iodomethane (CH3I) under environmental conditions has been further demonstrated by a 13C carbon isotope tracer method. Methylation products are mainly monomethyltin, and very small amounts of dimethyltin. The reaction of Sn(II) and CH3I was investigated at pH 2, 4, 6, 8, 10 and salinity (S) 8, 15, 22, 28, 35%; it has been found the reaction was affected by pH and salinity, the tin methylation activity being highest at about pH 6 and S = 28% . The methylation reaction is first-order for both CH3I and Sn(II), and the rate equation has been obtained as follows: .  相似文献   
124.
The mechanism of cell death by pheophorbide a (Pba) which has been established to be a potential photosensitizer was examined in experimental photodynamic therapy (PDT) on Jurkat cells, a human lymphoid tumor cell line. In 30-60 min after irradiation, Pba treated cells exhibited apoptotic features including membrane blebbing and DNA fragmentation. Pba/PDT caused a rapid release of cytochrome c from mitochondria into the cytosol. Sequentially, activation of caspase-3 and the cleavage of poly ADP-ribose polymerase (PARP) were followed. Meanwhile, no evidence of activation of caspase-8 was indicated in the cells. In experiments with caspase inhibitors, it was found that caspase-3 alone was sufficient initiator for the Pba-induced apoptosis of the cells. Pba specific emission spectra were confirmed in the mitochondrial fraction and the light irradiation caused a rapid change in its membrane potential. Thus, mitochondria were entailed as the crucial targets for Pba as well as a responsible component for the cytochrome c release to initiate apoptotic pathways. Taken together, it was concluded that the mode of Jurkat cell death by Pba/PDT is an apoptosis, which is initiated by mitochondrial cytochrome c release and caspase-3-pathways.  相似文献   
125.
Poly(vinyl chloride) supported tetraethylenepentamine (PVC-TEPA) has been found to be an efficient catalyst for the Knoevenagel condensation. A wide range of aromatic aldehydes easily undergo condensations with ethyl cyanoacetate and malononitrile in the commercial 95% ethanol in refluxing using PVC-TEPA as catalyst to afford the desired products of good purity in moderate to excellent yields. A recycling study confirmed that the catalyst could be reused, the yield of the desired condensation product were not reduced. The merits of this protocol are environmentally benign, simple operation, convenient work-up and good yields. Furthermore, the catalyst can easily be recovered and reused at five times with comparable yields.  相似文献   
126.
High-yield solvothermal formation of magnetic CoPt alloy nanowires   总被引:4,自引:0,他引:4  
One-dimensional (1D) magnetic nanomaterials have attracted much attention recently because of their applications in magnetic recording and spintronics. Nevertheless, it remains a challenge to prepare free-standing magnetic nanowires in high yield. This Communication reports the successful high-yield synthesis of an interesting 1D ferromagnetic CoPt alloy by direct decomposition of platinum acetylacetonate and cobalt carbonyl compound in ethylenediamine solvent through a solvothermal reaction. The CoPt alloy nanowires obtained have a tunable diameter of 10-50 nm and a length along the longitudinal axis of up to several microns, depending on crystallization temperature and reaction time. A unique formation mechanism involving coarsening and ripening under solvothermal conditions was discovered. This research opens new opportunities in synthesizing nanomaterials through low-temperature solvothermal processes.  相似文献   
127.
使用双沸点仪测定了丙酮、乙酸乙酯、对二氧六环、乙腈或三乙胺与甲醇或1,2→二氯乙烷以及二者混合物等十一组二元体系在99.3 kPa下的汽液平衡数据(T,x,p), 计算了有关体系的过量吉布斯自由能。结果表明, 六种非质子溶剂与甲醇组成的二元系GE>0; 乙腈或三乙胺与1,2-二氯乙烷组成的二元系GE>0, 而丙酮、乙酸乙酯或对二氧六环与1,2-二氯乙烷的二元混合物GE<0。从同种分子间或不同种分子间的缔合作用对上述结果进行了讨论。本文还在固定极性非质子溶剂(第三组分)物质的量浓度的条件下, 测定了非质子溶剂+1,2-二氯乙烷+甲醇三元混合物的汽液平衡数据, 考察了非质子溶剂的加入对甲醇+1,2-二氯乙烷二元系GE的影响。  相似文献   
128.
本文编制了一个简易计算机程序,测定了氟氯烷溶液沉淀聚合体系中四氟乙烯-乙烯共聚竞聚率:40℃:γC_2H_4=0.156±0.001,γC_2F_4=0.022±0.01670℃:γC_2H_4=0.197±0.001,γC_2F_4=0.055±0.020在此聚合体系中,聚合温度和共聚物组成比对链的规整性都有明显影响。当乙烯在45~55mol%范围内时,共聚物的IR随组成比而变化,利用此规律可简便地测定共聚物的组成比。  相似文献   
129.
Dai Q  Ran C  Harvey RG 《Organic letters》2005,7(6):999-1002
[structure: see text] The first syntheses of the adducts formed in the reactions of o-quinone metabolites of carcinogenic polycyclic aromatic hydrocarbons (BPQ and BAQ) at 2'-deoxyadenosine and 2'-deoxyguanosine sites in DNA are reported. These syntheses entail Pd-catalyzed coupling of protected amine derivatives of catechols with suitably protected halopurine analogues of 2'-deoxyribonucleosides.  相似文献   
130.
A series of novel two-dimensional (2D) and three-dimensional (3D) praseodymium coordination polymers, namely, {[Pr3(PDA)4(HPDA)(H2O)8] x 8H2O}n (2), {[Pr2(PDA)3(H2O)3] x H2O}n (3), {[Pr(PDA)(H2O)4] x ClO4}n (4), and { [Pr2(PDA)2(H2O)5SO4] x 2H2O}n (5) (PDA = pyridine-2,6-dicarboxylic anion), was designed and synthesized under hydrothermal conditions. Complexes 1-3 (chainlike polymer, {[Pr(PDA)(HPDA)(H2O)2] x 4H2O}n (1) was also obtained independently by us, although it has been reported recently by Ghosh et al.) were fabricated successfully by simply tuning the Pr/PDA ratio and exhibited various and intriguing topological structures from a 1D chain to a 3D network. While the synthetic strategy of 5 was triggered and further performed only after 1 was structurally characterized. The complexes were characterized by X-ray single-crystal determination, spectroscopic, and variable-temperature magnetic susceptibility analyses. In complex 2 an unusual nanosized square motif as a building block constructed by eight Pr ions was further assembled into a highly ordered 2D grid compound. In complex 3 the decanuclear Pr metal-based structure as a repeat unit interpenetrated to form a novel 3D polymer. Complex 4 was a 3D network polymer fabricated through a hexanuclear Pr ring as a building block, and ClO4- anions as guests were trapped in the cavity. In complex 5 six Pr atoms, two SO4(2-) anions, and carboxylic oxygen bridges constructed an intriguing rectangle structure as a repeat unit in the grid to form a 2D coordination polymer in which the unique bi-bidentate coordination mode of SO4(2-) anion was observed.  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