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   4246篇
  免费   111篇
  国内免费   30篇
化学   2905篇
晶体学   58篇
力学   79篇
数学   699篇
物理学   646篇
  2022年   63篇
  2021年   42篇
  2020年   66篇
  2019年   63篇
  2018年   34篇
  2017年   44篇
  2016年   74篇
  2015年   75篇
  2014年   101篇
  2013年   189篇
  2012年   204篇
  2011年   267篇
  2010年   141篇
  2009年   126篇
  2008年   207篇
  2007年   253篇
  2006年   229篇
  2005年   237篇
  2004年   210篇
  2003年   177篇
  2002年   189篇
  2001年   78篇
  2000年   54篇
  1999年   58篇
  1998年   44篇
  1997年   53篇
  1996年   61篇
  1995年   51篇
  1994年   68篇
  1993年   50篇
  1992年   43篇
  1991年   50篇
  1990年   39篇
  1989年   34篇
  1988年   32篇
  1987年   31篇
  1986年   32篇
  1985年   39篇
  1984年   41篇
  1983年   33篇
  1982年   48篇
  1981年   51篇
  1980年   30篇
  1979年   44篇
  1978年   33篇
  1977年   27篇
  1976年   28篇
  1975年   32篇
  1974年   26篇
  1973年   30篇
排序方式: 共有4387条查询结果,搜索用时 16 毫秒
991.
The current study discusses application of the lanthanum ions (La3+) as an activating agent incorporated /immobilized into coconut shell–based granular activated carbon (GAC) for porosity development; subsequently, the carbon material is used for the adsorption of phenol from aqueous solutions. The new carbons were characterized using FTIR, XRD, CHNO, burn off, and carbon yield. The surface functional groups were determined by Boehm titration. The Brunauer–Emmett–Teller (BET) surface area of the carbons is 953 m2 g−1 (GACLa1073), 997 m2 g−1 (GAC383), and 973 m2 g−1 (GACO383). Langmuir, Freundlich, Dubinin–Radushkevich, and John–Sivanandan Achari (J-SA) isotherm models on the equilibrium isotherm data were examined for the new carbon-phenol system. It is found that the Langmuir isotherm fits better with a monolayer adsorption capacity, highest for GACLa1073 (387.59 mg g−1) followed by GAC383 (303.03 mg g−1) and GACO383 (197.62 mg g−1). Kinetic studies reveal that the adsorption system follows the pseudo–second-order kinetic model. Isotherm analysis by the phase change method of John-Sivanandan Achari (J-SA) isotherm gives a better insight into adsorption phenomena, which is accompanied by regeneration studies of carbon with >75% for GACLa1073 after three cycles.  相似文献   
992.
The electrophilic character of free diamidocarbenes (DACs) allows them to activate inert bonds in small molecules, such as NH3 and P4. Herein, we report that metal coordinated DACs also exhibit electrophilic reactivity, undergoing attack by Zn and Cd dialkyl precursors to afford the migratory insertion products [(6‐MesDAC‐R)MR] (M=Zn, Cd; R=Et, Me; Mes=mesityl). These species were formed via the spectroscopically characterised intermediates [(6‐MesDAC)MR2], exhibiting barriers to migratory insertion which increase in the order MR2 = ZnEt2 < ZnMe2 < CdMe2. Compound [(6‐MesDAC‐Me)CdMe] showed limited stability, undergoing deposition of Cd metal, by an apparent β‐H elimination pathway. These results raise doubts about the suitability of diamidocarbenes as ligands in catalytic reactions involving metal species bearing nucleophilic ligands (M‐R, M‐H).  相似文献   
993.
994.
995.
BACKGROUND: To prepare for a possible major radiation disaster involving large numbers of potentially exposed people, it is important to be able to rapidly and accurately triage people for treatment or not, factoring in the likely conditions and available resources. To date, planners have had to create guidelines for triage based on methods for estimating dose that are clinically available and which use evidence extrapolated from unrelated conditions. Current guidelines consequently focus on measuring clinical symptoms (e.g., time-to-vomiting), which may not be subject to the same verification of standard methods and validation processes required for governmental approval processes of new and modified procedures. Biodosimeters under development have not yet been formally approved for this use. Neither set of methods has been tested in settings involving large-scale populations at risk for exposure. OBJECTIVE: To propose a framework for comparative evaluation of methods for such triage and to evaluate biodosimetric methods that are currently recommended and new methods as they are developed. METHODS: We adapt the NIH model of scientific evaluations and sciences needed for effective translational research to apply to biodosimetry for triaging very large populations following a radiation event. We detail criteria for translating basic science about dosimetry into effective multi-stage triage of large populations and illustrate it by analyzing 3 current guidelines and 3 advanced methods for biodosimetry. CONCLUSIONS: This framework for evaluating dosimetry in large populations is a useful technique to compare the strengths and weaknesses of different dosimetry methods. It can help policy-makers and planners not only to compare the methods' strengths and weaknesses for their intended use but also to develop an integrated approach to maximize their effectiveness. It also reveals weaknesses in methods that would benefit from further research and evaluation.  相似文献   
996.
We clarify the explicit structure of the Hurwitz quaternion order, which is of fundamental importance in Riemann surface theory and systolic geometry.  相似文献   
997.
Abstract

α-Hydroxyiminophosphonic acid derivatives are widely known not only as intermediates in the synthesis of the important aminophosphonic acids,1,2 but also as phosphorylating agents,3 potential metalloenzyme inhibitors,4 and as compounds having fungicidal activity.5 In this work the scope of these compounds has been extended considerably by the synthesis of a number of novel dialkyl derivatives. Novel lanthanide (LaIII, PrIII, NdIII, GdIII and DyIII) and transition metal (CoII and NiIII) complexes of dialkyl α-hydroxyiminophosphonates (RO)2P(O)C(R')N(OH) where R = Et. Pri and R′ = Me, Et have been prepared and the NMR shift properties of the PrIII complex (R = Et; R′ = Et) indicate the potential of these compounds as NMR shift reagents for the analysis of geometric isomers.6,7 X-ray crystal structure analysis of [Ni(L1)2C12] (L1: R = Et; R′ = Et) shows a distorted cis octahedral coordination at the nickel atom giving two symmetry related diethyl-(E)-α-hydroxyiminopropanephosphonate ligands and two chlorine donors, and those of [Pr(L2)3Cl3] and [Nd(L2)2(NO3)3(H2O)] (L2: R = Pri; R′ = Et) show nine-coordination geometries with asymmetric bidentate and monodentate L2 bonding respectively. Thus the metal complexes show unusual coordination ambivalence, changing from symmetrically bidentate to asymmetrically bidentate and then to monodentate bonding modes, to accommodate the different steric requirements of the coordinating anions in facilitating neutral complex formation.  相似文献   
998.
999.
1000.
The polycyclic title compound {systematic name: (1S,16S,17S,31S)‐3,20‐diazatetracyclo[15.15.01,17.13,31.116,20]tetratriaconta‐6,8,23,25‐tetraene}, C32H52N2, has recently been isolated and characterized structurally, in solution by NMR spectroscopy and in the solid state by X‐ray crystallography. At 130 K the structure is monoclinic (P21, Z = 4) and comprises two molecules in the asymmetric unit with distinctly different conformations in the twelve‐C‐atom bridging chains. We report that, at 250 K, a phase change from monoclinic to orthorhombic (P22121, Z = 4) occurs. The higher‐temperature phase is structurally characterized herein at 293 K. The two different conformers resolved in the monoclinic low‐temperature form merge to give a single disordered molecule in the asymmetric unit of the high‐temperature phase.  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