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   1998篇
  免费   139篇
  国内免费   414篇
化学   1852篇
晶体学   28篇
力学   124篇
综合类   39篇
数学   144篇
物理学   364篇
  2024年   3篇
  2023年   14篇
  2022年   45篇
  2021年   66篇
  2020年   78篇
  2019年   59篇
  2018年   55篇
  2017年   103篇
  2016年   101篇
  2015年   79篇
  2014年   98篇
  2013年   192篇
  2012年   118篇
  2011年   109篇
  2010年   103篇
  2009年   114篇
  2008年   128篇
  2007年   123篇
  2006年   106篇
  2005年   128篇
  2004年   87篇
  2003年   80篇
  2002年   79篇
  2001年   64篇
  2000年   47篇
  1999年   55篇
  1998年   44篇
  1997年   43篇
  1996年   43篇
  1995年   20篇
  1994年   32篇
  1993年   17篇
  1992年   30篇
  1991年   17篇
  1990年   18篇
  1989年   15篇
  1988年   13篇
  1987年   5篇
  1986年   6篇
  1985年   1篇
  1984年   1篇
  1982年   6篇
  1981年   2篇
  1980年   1篇
  1978年   1篇
  1977年   1篇
  1975年   1篇
排序方式: 共有2551条查询结果,搜索用时 312 毫秒
71.
A marine isolate of fluorescent Pseudomonas sp. having the ability to produce the pyoverdine type of siderophores under low iron stress (up to 10 μM iron in the succinate medium) was identified as Pseudomonas aeruginosa by using BIOLOG Breathprint and siderotyping. Pyoverdine production was optimum at 0.2% (w/v) succinate, pH 6.0, in an iron-deficient medium. Studies carried out in vitro revealed that purified siderophores and Pseudomonas culture have good antifungal activity against the plant deleterious fungi, namely, Aspergillus niger, Aspergillus flavus, Aspergillus oryzae, Fusarium oxysporum, and Sclerotium rolfsii. Siderophore-based maximum inhibition was observed against A. niger. These in vitro antagonistic actions of marine Pseudomonas against phytopathogens suggest the potential of the organism to serve as a biocontrol agent.  相似文献   
72.
The effect of the nature of organic electron transfer agents and of PtII, PdII, RhII, CoII, NiII, CuII, CrIII, MnII, TiIII, VIII, ZnII, and AgI metal ions on the kinetics of the homogeneous reduction ofgem-dichlorocyclopropanes has been studied. PtII, PdII, RhIII, CoII, and NiII ions accelerate this process, VIII and AgI ions exert practically no effect on the reduction rate, and the rest of the metal ions exhibit inhibitor properties.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1407–1410, August, 1993.  相似文献   
73.
Isomerization at the Complexation of 3-Acetyltetramic Acid: Structure and Magnetic Properties of the CuII- and NiII-Complex of 2,7-Bis (1′, 5′, 5′ -trimethylpyrrolidin-2′,4′ -dion-3′ -yl)-3,6-diazaocta-2,6-dien 2,7-Bis(1′, 5′, 5′ -trimethylpyrrolidin-2′, 4′ -dion-3′ -yl)-3,6-diazaoctadien formes CuII and NiII complexes with different constitutions (because of the Z/E isomerization). Results of X-ray analysis of N,N′ -ethylenbis(1′, 5′, 5′ -trimethylpyrrolidin-2′, 4′ -dion-3′ -acetiminato)nickel(II) 1 respectively -copper(II) 2 shows, that the complexing agent in 1 occurs in the E-form, whereas the ligand of the CuII complex forms the Z-form. Magnetic susceptibility and shift effects of the 13C-NMR signals point to a weak paramagnetism of the NiII complex. ESR-spectra are obtained from 2 only. Furthermore, the CuII complex reduces the relaxation times T1 and T2 of 1H and 17O nuclei spins from water. From the temperature dependence of the shortening of the relaxation times an activation energy is calculated which describes the reorientation of the copper complex in the “water matrix”.  相似文献   
74.
Four tetradentate nitrogen ligands, viz. dichloro{[N,N-diphenyl-N,N-di(quinoline-2-methyl)]-1,2-ethylene diamine} (1), {[N,N-dioctyl-N,N-di(quinoline-2-methyl)]-1,2-ethylene diamine} (2), {[N,N-dibenzyl-N,N-di(quinoline-2-methyl)]-1,2-ethylene diamine} (3), and (1R,2R)-(−)-N,N-di(quinoline-2-methyl) di-iminocyclohexane (4), were investigated as novel complexing ligands in iron-mediated atom transfer radical polymerization (ATRP) of methyl methacrylate where ethyl-2-bromoisobutyrate was the initiator in o-xylene at 90 °C. With ligands 1 and 2 the experimental molecular weights increased gradually with monomer conversion. High to moderate conversions (87%, 43%) were obtained in relatively short times (90 min for 1 and 30 min for 2), which indicates an efficient catalyst system, but after these times a dramatic increase in viscosity of the polymerization medium led to loss of control. It is noteworthy that polymerization proceeded in a controlled manner with ligand 1, which has two rather bulky substituents on the N-atom. Such bulky ligands did not work for a copper-based system, where they led to excessive terminations or other side reactions. When the bulkiness of the substituents was significantly increased, as in ligand 3, a decrease in polymerization rate and loss of control occurred. Ligand 4 was less efficient than the other ligands, probably because the ethylene bridge was replaced by cyclohexane bridge.  相似文献   
75.
In the present work, scandium was determined in sediment slurry samples (from three different rivers) by electrothermal atomic absorption spectrometry (ETAAS). Slurries were prepared by weighting 100 mg of dry sediment samples (≤53 μm particle sizes) and adding 6 ml of HCl:HNO3:HF (3:1:2, v/v). Accurate results were only possible due to the synergetic effect between Rh as permanent chemical modifier and acetylacetone (Acac) as complexing agent. The same platform was used for 400 heating cycles. The performance of the chemical modification was evaluated by using scanning electron microscopy (SEM), synchrotron radiation X-ray fluorescence (SRXRF) and some figures of merit (precision and detectability). The best analytical conditions were attained using 1500 and 2550 °C as pyrolysis and atomization temperatures. The scandium content in the liquid phase of the slurries ranged from 61 to 73%, thus indicating, in this study, that both liquid and solid phases play an important role in slurry analyses. An amount of 5.0–20.0 μg l−1 Sc linear range as well as LOD and LOQ of 0.19 and 0.62 μg l−1, respectively, were obtained under these conditions. The accuracy was checked by using microwave-assisted decomposition, and the results compared to those obtained with the proposed methodology (slurry analysis). By checking both sets of the results, there is no statistical difference at the 95% confidence levels.  相似文献   
76.
用杂交方法培育新作物品种是农业增产的重要措施。与常规杂交育种方法相比,采用化学杀雄法(Chemical induction lf male sterility)育种具有程序简单,节省劳力,时间缩短等优点,可以诱导产生非遗传性的雄性不育母本,与另一品种的文本杂交而得优化组合的良种,国外在小麦上已试验成功但在水稻上尚在探索,美国Rohm and Haas公司曾报道一些哒嗪酮类  相似文献   
77.
申书昌  彭程  王荻 《应用化学》2019,36(6):717-725
通过酸洗、硅烷偶联剂表面活化、键合苯甲酰异硫氰酸酯对蒙脱土进行改性,制得新型固相萃取(SPE)材料。 采用红外光谱、扫描电子显微镜、X射线光电子能谱表征了改性蒙脱土的结构和形貌。 考察了制备的SPE填料对水中As3+、Bi3+、Cu2+、Sb3+、Sn2+和Pb2+的吸附性能,确定了最佳固相萃取条件,对6种金属离子吸附容量分别为10.83、11.92、12.67、10.43、10.01及10.54 mg/g。 通过SPE与电感耦合等离子体质谱联用测定了样品中As3+、Bi3+、Cu2+、Sb3+、Sn2+和Pb2+ 6种重金属离子的含量,检出限分别为0.024、0.013、0.075、0.037、0.011和0.064 μg/L。  相似文献   
78.
采用多拷贝同时搜寻法(MCSS), 并结合现有微管抑制剂的SAR及3D-QSAR对β微管蛋白中Taxol(紫杉醇)结合腔的性质进行了分析. 结构研究结果表明, Taxol结合腔以疏水性质为主, 并指出官能团分布的具体位置: 在Phe270上方(Leu361-Pro272-Leu273-Leu228之间)的弧形区域、Asp26羧基下方及其与Glu22羧基之间、M-loop的中部, 以及Asp224内侧且靠近Arg276的胍基的位置. 而Asp224的内侧又是新提出的结合位点. 研究结果符合现有微管抑制剂的SAR, 为现有抗肿瘤药物的结构改造以及小分子微管抑制剂设计提供了理论依据.  相似文献   
79.
应用高分子铂络合物催化合成硅烷偶联剂   总被引:1,自引:0,他引:1  
以二氧化硅为载体的侧链上含有配位基团和-COOH的聚硅氧烷(1-5)分别与氯铂酸反应制备了五种聚硅氧烷-铂络合物(“St-Pt-l”—“St-Pt-5”).这些高分子铂络合物,用于催化环氧丙基烯丙基醚与三甲及基氢硅烷反应具有很高的催化活性,在温和的条件下(80℃,30min),反应以72—98%的产率生成了硅烷偶联剂γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷.通过对含,配位基的高分子铂络合物“Si-Pt-1”的稳定性研究,发现它可以重复使用多次而不降低其催化活性.  相似文献   
80.
纳米级TiO2粉体的制备研究——Ⅱ.絮凝剂及其浓度的影响   总被引:9,自引:0,他引:9  
采用溶胶-凝胶-超临界流体干燥(SCFD)法制备纳米级TiO2超细粉,详细考察了不同絮凝剂及其浓度对TiO2织构和结构性质的影响。结果表明,利用强碱溶液作为絮凝剂,浓度为5 mol·L-1是制备大孔高比表面TiO2超细粉较为适宜的条件。  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