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   1071篇
  免费   48篇
  国内免费   6篇
化学   705篇
晶体学   10篇
力学   53篇
数学   107篇
物理学   250篇
  2024年   8篇
  2023年   4篇
  2022年   67篇
  2021年   44篇
  2020年   35篇
  2019年   22篇
  2018年   40篇
  2017年   26篇
  2016年   48篇
  2015年   52篇
  2014年   48篇
  2013年   89篇
  2012年   72篇
  2011年   70篇
  2010年   46篇
  2009年   55篇
  2008年   50篇
  2007年   39篇
  2006年   25篇
  2005年   21篇
  2004年   20篇
  2003年   25篇
  2002年   18篇
  2001年   20篇
  2000年   18篇
  1998年   7篇
  1997年   3篇
  1996年   5篇
  1995年   10篇
  1994年   4篇
  1993年   11篇
  1992年   6篇
  1991年   8篇
  1990年   10篇
  1989年   7篇
  1988年   8篇
  1987年   7篇
  1986年   7篇
  1985年   10篇
  1984年   4篇
  1983年   4篇
  1982年   11篇
  1981年   4篇
  1980年   3篇
  1979年   6篇
  1977年   3篇
  1976年   7篇
  1975年   5篇
  1973年   3篇
  1969年   2篇
排序方式: 共有1125条查询结果,搜索用时 15 毫秒
21.
Summary A simple, rapid, selective, and sensitive method for the spectrophotometric determination of palladium is developed based on the reaction of Pd(II) with 1-amino-4-hydroxyanthraquinone (AMHA). The reaction is carried out atpH 3.8 in 50% (v/v) ethanol-water medium. The molar absorptivity of the complexed ligand is 1.1 · 104 l mol–1 cm–1 at 620 nm. Calibration plots are linear up to 17 µg Pd cm–3. The optimum concentration range (Ringbom plot) is between 3–14.5 µg cm–3. The spectral study of the reaction in solutions containing equimolar concentrations or an excess of one component, in thepH range 0.3–6.5, indicate the possible complex transitions that occur in solution. Complete graphical and logarithmic analysis of the absorbance-pH graphs was performed to demonstrate and characterize the complexation equilibria in solution. Under the optimum conditions, palladium can be determined as the noncharged complex Pd(AMHA)2 in the presence of a large number of foreign ions. Interferences caused by zirconium(IV) could be masked with fluoride ions.
Eine neue spektrophotometrische Methode für die Bestimmung von Palladium in Spuren
Zusammenfassung Eine einfache, schnelle und empfindliche Methode für die spektrophotometrische Bestimmung von Palladium wurde auf der Basis der Reaktion von Pd(II) mit 1-Amino-4-hydroxyanthrachinon (AMHA) entwickelt. Die Reaktion wird in 50% (v/v) Ethanol/Wasser beipH 3.8 ausgeführt. Die molare Absorption des komplexierten Liganden beträgt 1.1 · 104 l mol–1 cm–1 bei 620 nm. Kalibrierungskurven verlaufen bis zu 17 µg Pd cm–3 linear. Der optimale Konzentrationsbereich (Ringbom-Plot) liegt zwischen 3 und 14.5 µg cm–3. Spektroskopische Untersuchungen der Reaktion in Lösungen, entweder mit equimolaren Konzentrationen oder mit einem Überschuß an einer Komponente impH-Bereich 0.3–6.5, lassen Rückschlüsse auf mögliche Komplex-Übergänge in Lösung zu. Es wurde eine vollständige graphische, logarithmische Analyse der Absorptions-pH-Graphen durchgeführt, um die Komplexgleichgewichte in Lösung aufzuklären und zu charakterisieren. Unter den Optimalbedingungen kann Palladium als nichtgeladener Komplex Pd(AMHA)2 in Gegenwart einer großen Anzahl an Fremd-Ionen bestimmt werden. Schwierigkeiten mit Zirkonium(IV) konnte durch Maskierung mit Fluorid-Ionen umgangen werden.
  相似文献   
22.
The hydrodistilled oils from the aerial parts of Ferula latisecta and Mozaffariania insignis, which is endemic to Iran, were analyzed by GC and GC/MS. (Z)-Ocimenone (32.4%), (E)-ocimenone (20.3%), and cis-pinocarvone (11.4%) were the main components among the 22 constituents characterized in the oil of F. latisecta, representing 87.7% of the total components detected. Twenty-five compounds were identified in the oil of M. insignis, representing 99.0% of the total oil, with octyl acetate (41.1%), β-pinene (30.3%), and α-pinene (23.9%) as the main constituents. The essential oils were examined for their potential antimicrobial activities. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 561–563, November–December, 2006.  相似文献   
23.
The nitrosoarenes ArNO (Ar = C6H5, 2-MeC6H4, 2,4,6- Me3C6H2 and C6F5) have been condensed with 4-(dichloroamino)- tetrafluoropyridine to provide the azoxy-compounds pyFNN+(N-)Ar (pyF = 2,3,5,6-tetrafluoro-4-pyridyl); de-oxygenation of the first three with triphenylphosphine or triethyl phosphite gave the corresponding azo-compounds, and the reverse reaction was achieved in the case of pyFNNC6H2Me3-2,4,6 using peroxytrifluoroacetic acid. Thermolysis of 4-azidotetrafluoropyridine in the presence of pentafluoronitrosobenzene provided the perfluorinated azoxy-compound pyFNN+(O-)C6F5. X-Ray methods have been used to determine the molecular geometry of pyFNN+(O-)C6H2Me3-2,4,6.  相似文献   
24.
The search for new efficient sensitizers for photodynamic therapy (PDT) points to improve photophysical properties like absorption in the red region and singlet oxygen quantum yield as well as to control the localization of the sensitizer within the tumour cell. Depending on their physicochemical properties and their uptake mechanism, sensitizers can reach different intracellular concentrations and localize in different subcellular compartments. Moreover, the preferential localization of a sensitizer in target organelles, like mitochondria or lysosomes, could determine the cell death mechanism after PDT. This study aimed to investigate the influence of substitutions on dihydroxychlorins with regard to intracellular uptake, subcellular localization and cell death pathway. Moreover, the effect of a liposome-based delivery system was tested. The intracellular uptake was found to be strictly dependent on the sensitizer molecular structure and the means of its delivery. The most polar sensitizer in this study (compound 3) had, depending on incubation time, an intracellular concentration 2-8 times higher than the unsubstituted chlorin 1. All investigated photosensitizers localize predominantly in lysosomes but after longer incubation times weak fluorescence intensity was also detected in mitochondria and Golgi apparatus. The cell death pathway was found to be influenced by the sensitizer intracellular concentration and the applied light doses. In general, the increasing amphiphilicity of the sensitizer molecules is correlated with an increased sensitizer uptake and an increased rate of necrotic cells after irradiation.  相似文献   
25.
The reactions between strontium and iron nitrates have been studied in an open atmosphere system using three different molar ratios, 1:1 (I), 1:2 (II) and 2:1 (III) at different temperatures as pointed out from the DTA data. The reaction mechanism was discussed based on the chemical composition characterized by means of thermal analysis, X‐ray diffraction patterns, infrared spectra and magnetic susceptibility. It was found that the reaction products depend on both temperature of reaction and the ratio between reactants. The reaction products were found to be composed of a variety of iron compounds that possess different valences: SrFeO2.86, SrFeO2.97, SrFe2O4, SrFe12O19, Sr2Fe2O5 and Sr7Fe10O22 in addition to some accessory reaction products namely α‐Fe2O3 and FeO(OH).  相似文献   
26.
Murty in a recent paper has shown that the computational effort required to solve a linear complementarity problem (LCP), by either of the two well known complementary pivot methods is not bounded above by a polynomial in the size of the problem. In that paper, by constructing a class of LCPs—one of ordern forn 2—he has shown that to solve the problem of ordern, either of the two methods goes through 2 n pivot steps before termination.However that paper leaves it as an open question to show whether or not the same property holds if the matrix,M, in the LCP is positive definite and symmetric. The class of LCPs in whichM is positive definite and symmetric is of particular interest because of the special structure of the problems, and also because they appear in many practical applications.In this paper, we study the computational growth of each of the two methods to solve the LCP, (q, M), whenM is positive definite and symmetric and obtain similar results.This research is partially supported by Air Force Office of Scientific Research, Air Force Number AFOSR-78-3646. The United States Government is authorized to reproduce and distribute reprints for governmental purposes notwithstanding any copyright notation thereon.  相似文献   
27.
The motivation behind the present work is to synthesize some nonionic surfactants containing heterocyclic nucleus with intermediate fatty compounds for improving their surfactants properties. 2‐Cyano‐N‐octadecylacetamide was utilized as key intermediate for the synthesis of some new thiazole, pyrazole, oxazole, pyrimidine, 1,3‐dithiolane, thiophene, coumarin, oxazine and pyridazine derivatives. The newly synthesized compounds undergo propoxylation using propylene oxide to afford nonionic surface active agents. The antimicrobial and surface activities were evaluated and characterized through investigations of their spreading behavior in monolayer on water.  相似文献   
28.
The shift of the Q-band of sodium zinc(II)-2,9,16,23-phthalocyanine tetracarboxylate (ZnPc(COONa)4) to about 800 nm is attributed to the influence of the electron-donating property of the carboxylate groups substituted in the β–position. ZnPc(COONa)4 which was found to have a symmetry of D 2h characterized by a splitting of the Q transition. This splitting was interpreted by the formation of dianionic symmetric ZnPc(COONa)4 resulting from the dissociation of the pyrrole protons as well as the possibility of Na+ dissolution of ZnPc(COONa)4 in the aqueous solution of NaOH.  相似文献   
29.
This study has presented a performance investigation of an advanced tracked prime mover for the operation of agricultural goods and other operations on peat terrain. The maximum and continuous traction torque of the prime mover has been developed by designing an advanced controller for controlling the intelligent system. The prime mover’s mobility is studied with ultrasonic displacement sensor, torque transducer, National Instrument cRIO-9004 Compact-RIO Real-time Controller Unit (RCU), a National Instrument TPC 2106T Touch Panel Control (TPC), a Trimble AG132 GPS antenna and receiver unit, and a Dlink DIR-655 router. The fuzzy logic controller (FLC) has been equipped with the prime mover hydraulic system to increase the traction torque of the hydraulic motor when the prime mover’s sinkage is more than or equal to 70 mm. The prime mover’s design demonstrates good potential in traversing peat terrain as the measured tractive effort was found to be 48% of the vehicle’s gross weight while the recommended tractive effort is in the range of 30–36% of the vehicle’s gross weight.  相似文献   
30.
In an environmentally benign system, alcohols are rapidly oxidized to carbonyl compounds using CrO 3 supported onto wet silica gel as an oxidant under microwave irradiation.  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