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   8301篇
  免费   185篇
  国内免费   633篇
化学   8130篇
晶体学   329篇
力学   32篇
综合类   20篇
数学   142篇
物理学   466篇
  2024年   6篇
  2023年   57篇
  2022年   146篇
  2021年   125篇
  2020年   210篇
  2019年   244篇
  2018年   221篇
  2017年   289篇
  2016年   271篇
  2015年   170篇
  2014年   240篇
  2013年   486篇
  2012年   1442篇
  2011年   399篇
  2010年   324篇
  2009年   409篇
  2008年   505篇
  2007年   553篇
  2006年   411篇
  2005年   395篇
  2004年   310篇
  2003年   280篇
  2002年   200篇
  2001年   143篇
  2000年   148篇
  1999年   152篇
  1998年   115篇
  1997年   101篇
  1996年   99篇
  1995年   110篇
  1994年   85篇
  1993年   72篇
  1992年   63篇
  1991年   50篇
  1990年   42篇
  1989年   26篇
  1988年   15篇
  1987年   20篇
  1986年   24篇
  1985年   12篇
  1984年   12篇
  1982年   8篇
  1981年   14篇
  1980年   16篇
  1979年   22篇
  1978年   11篇
  1977年   18篇
  1976年   16篇
  1974年   7篇
  1973年   9篇
排序方式: 共有9119条查询结果,搜索用时 0 毫秒
31.
Phosphorane Iminato-Trichloroselenates(II): Syntheses and Crystal Structures of [SeCl(NPPh3)2]+SeCl3? and [Me3SiN(H)PMe3]2+[Se2Cl6]2? [SeCl(NPPh3)2]+SeCl3? has been synthesized by the reaction of Se2Cl2 with Me3SiNPPh3 in acetonitrile solution, forming orangered crystals, whereas red crystals of [Me3SiN(H)PMe3]2+[Se2Cl6]2? were obtained by the reaction of Me3SiNPMe3 with SeOCl2 in acetonitrile solution. Both complexes were characterized by X-ray structure determinations. [SeCl(NPPh3)2]+SeCl3?: Space group P21/n, Z = 4, structure solution with 7 489 observed unique reflections, R = 0.057. Lattice dimensions at ?60°C: a = 1 117.0; b = 2 241, c = 1 407.5 pm, β = 95.61°. In the cation [SeCl(NPPh3)2]+ the selenium atom is φ-tetrahedrally coordinated by the chlorine atom and by the nitrogen atoms of the phosphorane iminato ligands, whereas the anion SeCl3? has a T-shaped structure with φ-trigonal-bipyramidale surrounding of the selenium atom. [Me3SiN(H)PMe3]2+[Se2Cl6]2?: Space group P21/c, Z = 4, structure solution with 2 093 observed unique reflections, R = 0.080. Lattice dimensions at ?70°C: a = 956, b = 828, c = 1 973 pm, β = 93.80°. The structure consists of [Me3SiN(H)PMe3]+ ions and planar [Se2Cl6]2? anions, in which the selenium atoms are bridged nearly symmetrically by two chlorine atoms.  相似文献   
32.
Commercially available copper(II) tetrafluoroborate hydrate was found to be a highly efficient catalyst for chemoselective N-tert-butoxycarbonylation of amines with di-tert-butyl dicarbonate under solvent-free conditions and at room temperature. Various aromatic amines were protected as their N-tert-butyl carbamates in high yields and in short times. No competitive side reactions such as isocyanate, urea, and N,N-di-t-Boc formation was observed. Chemoselective N-tert-butoxycarbonylation was achieved with substrates bearing OH and SH groups. Chiral α-amino acid esters afforded the corresponding N-t-Boc derivatives in excellent yields.  相似文献   
33.
Four new Schiff base functionalized 1,2,3-triazolylidene nickel complexes, [Ni-(L1NHC)2](PF6)2; 3, [Ni-(L2NHC)2](PF6)2; 4, [Ni-(L3NHC)](PF6)2; 7 and [Ni-(L4NHC)](PF6)2; 8, (where L1NHC = (E)-3-methyl-1-propyl-4-(2-(((2-(pyridin-2-yl)ethyl)imino)methyl)phenyl)-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 1, L2NHC = (E)-3-methyl-4-(2-((phenethylimino)methyl)phenyl)-1-propyl-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 2, L3NHC = 4,4′-(((1E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 5, and L4NHC = 4,4′-(((1E)-(butane-1,4-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 6), were synthesised and characterised by a variety of spectroscopic methods. Square planar geometry was proposed for all the nickel complexes. The catalytic potential of the complexes was explored in the oxidation of styrene to benzaldehyde, using hydrogen peroxide as a green oxidant in the presence of acetonitrile at 80 °C. All complexes showed good catalytic activity with high selectivity to benzaldehyde. Complex 3 gave a conversion of 88% and a selectivity of 70% to benzaldehyde in 6 h. However, complexes 4 and 7–8 gave lower conversions of 48–74% but with higher (up to 90%) selectivity to benzaldehyde. Results from kinetics studies determined the activation energy for the catalytic oxidation reaction as 65 ± 3 kJ/mol, first order in catalyst and fractional order in the oxidant. Results from UV-visible and CV studies of the catalytic activity of the Ni-triazolylidene complexes on styrene oxidation did not indicate any clear possibility of generation of a Ni(II) to Ni(III) catalytic cycle.  相似文献   
34.
35.
The selective determination of metals in waste solutions is a very important aspect of the industry and environmental protection. Knowledge of the contents and composition of the waste can contribute to design an efficient process separation and recovery of valuable metals. The problematic issue is primarily the correct determination of metals with similar properties such as palladium and platinum. Thus this paper focuses on the development of a selective method that enables Pd(II) determination in the presence of Pt(IV) ions using the azo-dye tropaeolin OO (TR). For this purpose, the process of the metalorganic complex formation and Pd(II) ions determination were studied by using UV–Vis spectrophotometry under different conditions: solvents (water and B-R buffer), pH (2.09–6.09), temperature (20–60 °C), anions and cations concentrations. The formed metalorganic complex between Pd and tropaeolin OO allows for distinguishing Pd(II) ions from both platinum complexes, i.e. Pt(II), Pt(IV). Moreover, the proposed method can be applied to solutions containing both chloride and chlorate ions. The obtained characteristic spectrum with two maxima allows the determination of palladium even in the presence of other cations (Na, K, Mg, Zn, Co, Ni, Al) and changed concentrations of Pt(IV) ions. Furthermore, the developed spectrophotometric method for the Pd(II) ions determination using tropaeolin OO is characterized by high selectivity towards palladium ions.  相似文献   
36.
COVID-19 has expanded across the world since its discovery in Wuhan (China) and has had a significant impact on people’s lives and health. Long COVID is a term coined by the World Health Organization (WHO) to describe a variety of persistent symptoms after acute SARS-CoV-2 infection. Long COVID has been demonstrated to affect various SARS-CoV-2-infected persons, independently of the acute disease severity. The symptoms of long COVID, like acute COVID-19, consist in the set of damage to various organs and systems such as the respiratory, cardiovascular, neurological, endocrine, urinary, and immune systems. Fatigue, dyspnea, cardiac abnormalities, cognitive and attention impairments, sleep disturbances, post-traumatic stress disorder, muscle pain, concentration problems, and headache were all reported as symptoms of long COVID. At the molecular level, the renin-angiotensin system (RAS) is heavily involved in the pathogenesis of this illness, much as it is in the acute phase of the viral infection. In this review, we summarize the impact of long COVID on several organs and tissues, with a special focus on the significance of the RAS in the disease pathogenesis. Long COVID risk factors and potential therapy approaches are also explored.  相似文献   
37.
A convenient and general method of synthesis of binuclear ruthenium(II) pyridazine complex was reported. The synthesized complex was characterized by analytical and spectral methods. The structure of the complex was confirmed by X-ray diffraction technique and was found to be an efficient catalyst for the transfer hydrogenation of ketones with excellent conversions in the presence of isopropanol/KOH at 82 °C. The effect of solvents, bases, and different catalyst/substrate ratio for the reaction was also investigated.  相似文献   
38.
A rapid,sensitive,selective and reliable strip assay based on DNA-functionalized gold nanoparticles for Hg2+ detection has been developed,with a detection limit 5 nmol/L.The measurement principle was based on thymine-Hg2+-thymine(T-Hg2+-T) coordination chemistry and streptavidin-biotin interaction.The major advantages of this assay are that results can be read visually without any instrument in less than 10 min and that it does not require any sample pretreatment.  相似文献   
39.
《Analytical letters》2012,45(14):1743-1748
Abstract

The chromatographic behaviour of 32 metal ions has been studied on paper Impregnated with Zirconium(IV) antimonate in aqueous HCI and mixed solvent system containing dimethyisul phoxide and dioxane. Several Important binary and ternary separations have been achieved. Quantitative separation of Hg(ll) from Ni2+, Pb2+, Pd2+, Ru3+, Rh3+, Bi3+, Co2+, Cd2+ and Gd3+ is described.  相似文献   
40.
Lead(II) 4,4,4-trifluoro-1-naphthyl-1,3-butanedione (Htfnb) complexes of 1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy), [Pb2(bpy)2(tfnb)2] (1) and [Pb2(phen)2(tfnb)2] (2), have been synthesized and characterized by elemental analysis, IR, spectroscopy and X-ray crystallography. The self-assembly of 1 and 2 is likely to be caused by C–H ··· F–C, C–H ··· O and π–π stacking interactions.  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