全文获取类型
收费全文 | 5516篇 |
免费 | 225篇 |
国内免费 | 54篇 |
专业分类
化学 | 3318篇 |
晶体学 | 85篇 |
力学 | 246篇 |
综合类 | 16篇 |
数学 | 1094篇 |
物理学 | 1036篇 |
出版年
2023年 | 39篇 |
2022年 | 75篇 |
2021年 | 124篇 |
2020年 | 145篇 |
2019年 | 142篇 |
2018年 | 184篇 |
2017年 | 182篇 |
2016年 | 255篇 |
2015年 | 205篇 |
2014年 | 248篇 |
2013年 | 517篇 |
2012年 | 379篇 |
2011年 | 393篇 |
2010年 | 348篇 |
2009年 | 246篇 |
2008年 | 336篇 |
2007年 | 284篇 |
2006年 | 218篇 |
2005年 | 188篇 |
2004年 | 162篇 |
2003年 | 126篇 |
2002年 | 150篇 |
2001年 | 107篇 |
2000年 | 88篇 |
1999年 | 54篇 |
1998年 | 58篇 |
1997年 | 49篇 |
1996年 | 49篇 |
1995年 | 24篇 |
1994年 | 33篇 |
1993年 | 22篇 |
1992年 | 18篇 |
1991年 | 23篇 |
1990年 | 26篇 |
1989年 | 19篇 |
1988年 | 10篇 |
1986年 | 17篇 |
1985年 | 14篇 |
1984年 | 19篇 |
1983年 | 20篇 |
1982年 | 11篇 |
1981年 | 22篇 |
1980年 | 19篇 |
1979年 | 14篇 |
1978年 | 15篇 |
1977年 | 15篇 |
1976年 | 16篇 |
1975年 | 14篇 |
1974年 | 15篇 |
1964年 | 8篇 |
排序方式: 共有5795条查询结果,搜索用时 15 毫秒
101.
Van Hoof F Van Wiele P Bruchet A Schmitz I Bobeldiji I Sacher F Ventura F Marti I Morecos Do Monte MH Sa Da Costa M 《Journal of AOAC International》2001,84(5):1420-1429
As part of a project funded by the European Commission (EC) for the development and evaluation of multiresidue methods for analysis of drinking and related waters, 15 European laboratories evaluated a method using styrene-divinylbenzene co-polymer solid-phase extraction followed by gas chromatography/mass spectrometry. The main aim of the study was to evaluate whether the method meets the requirements of EC Directive 98/83 in terms of accuracy, precision, and detection limit for 22 pesticides according to the following requirements: limit of detection, < or = 0.025 microg/L; accuracy, expressed as recovery between 75 and 125%; and precision, expressed as repeatability relative standard deviation of the method of < 12.5% and as reproducibility relative standard deviation of the method of < 25%. Analyses for unknown concentrations were performed with fortified commercial bottled and tap waters. All laboratories were able to achieve detection limits of 0.01 microg/L for all pesticides except dimethoate and desisopropylatrazine (0.02 microg/L). The criteria for repeatability were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and chlorpyrifos, dimethoate, and lindane in tap water. The criteria for reproducibility were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and pendimethalin, chlorpyrifos, dimethoate, terbutryn, and lindane in tap water. In terms of accuracy, the method meets the requirements for all pesticides in both matrixes, except for lindane in bottled water and lindane and chlorpyrifos in tap water. 相似文献
102.
Heteroleptic copper complexes containing an acetylacetonato ligand and a thioether derivatized dipyrrinato ligand are shown to form oligomers and polymers in the solid state. 相似文献
103.
The object of this paper has been to determine the effect of water of crystallization on magnetic properties of MgSO4. Changes in the magnetic properties of MgSO4 in depenedence on the number of waters of crystallization have been established from the magnetic susceptibility changes. The value obtained by measurement differs from that calculated by the additivity law. This disagreement can be explained by the presence of the thermally independent Van Vleck's polarization paramagnetism
p
.The paper brings forward calculations of p values for the individual hydrates of MgSO4.i H2O fori=0, 1, ..., 7. Besides, it examines what portion of the polarization paramagnetism
pi
of the overall values of
pci is due to the effect of water of crystallization. On the basis of this information the deviation from the spherical symmetry, caused by hydration of the MgSO4 molecule, has been interpreted. 相似文献
104.
A new melamine based polymeric sequestering resin was prepared for preconcentration and separation of hexavalent chromium from water, and its sequestering action was investigated. The water-insoluble, cross-linked sequestering resin was formed by reaction with bromosuccinic acid and cross-linking of melamine. The active sequestering group on the resin is NH-(Succinic acid) or salt thereof. The resulting chelating resin was characterized by infrared spectra. The newly prepared resin quantitatively retained Cr(VI) at pH 2.0-4.0 when the flow rate was maintained between 1 and 5 ml min−1. The retained Cr(VI) was instantaneously eluted with 25 ml of 0.1 M NaOH. The chromium species were determined by a flame atomic absorption spectrometer. The limits of detection for Cr(VI) and Cr(III) were found to be 5.3 and 4.2 μg l−1, respectively. The precision and accuracy of the proposed procedure was checked by the use synthetic and reference steel samples. The established preconcentration method was successfully applied to the determination and selective separation of Cr(VI) in electroplating industry wastewater. Total concentrations determined by the spectrophotometric method (110.3±0.6 g l−1 Cr(VI) and 1.2±0.3 g l−1 Cr(III)) are compared with those found by FAAS and the obtained results (110.4±1.8 g l−1 Cr(VI) and 1.4±0.5 g l−1 Cr(III)) show good agreement. 相似文献
105.
A new (E,E)-dioxime, (6Z,7Z)-15,16-dihydro-14H-dibenzo[b,h][1,10,4, 7]dithiadiazacyclotride-cine-6,7(5H,8H)-dionedioxime (H
2
L) has been synthesized by reacting cyanogen-di-N-oxide (2) with 2,2′-[propane-1,3-diylbis(thio)]dianiline (1). Mononuclear complexes (4) and (5) of this ligand have been synthesized by reacting the vic-dioxime (H2L) with NiCl2 · 6H2O and CoCl2 · 6H2O, respectively. The BF
2
+
capped Ni(II) and Co(III) complexes (6) and (7) of the dioxime have been synthesized from (4) and (5). The new compounds were characterized by a combination of elemental analysis, 1H- and 13C-n.m.r, i.r. and m.s. spectral data. 相似文献
106.
Nebojša Banjac Gordana Ušćumlić Nataša Valentić Dušan Mijin 《Journal of solution chemistry》2007,36(7):869-878
Absorption spectra of eight 3-substituted-5,5-diphenylhydantoins have been recorded in fourteen solvents in the range 200–400 nm.
The effect of solvent dipolarity/polarizability and solvent/solute hydrogen bonding interactions are analyzed by means of
the linear solvation energy relationship (LSER) concept proposed by Kamlet and Taft. The lipophilic activity of the investigated
hydantoins was estimated by the calculation of log 10
P values with the Advanced Chemistry Development Software. The calculated values of log 10
P were correlated with the ratio of the contributions of specific solvent interactions, and, by employing the linear dependence
thus obtained, the pharmacological activity of the studied hydantoin derivatives is discussed. 相似文献
107.
An application of tissue-based electrodes aimed at eliminating interferences from co-existing electroactive constituents is described. The concept is illustrated using a zucchini-containing carbon paste electrode. The presence of the enzyme ascorbic acid oxidase (AAO) in the zucchini tissue effectively eliminates contributions from ascorbic acid, thus allowing selective measurement of dopamine or norepinephrine. In comparison with analogous enzyme-based AAO electrodes, the tissue “eliminator” electrode offers high biocatalytic stability and activity and extremely low cost. The effects of various experimental variables are studied using pulse voltammetry, chronoamperometry and flow-injection amperometry. The electrode has a useful lifetime of 4 weeks. Simultaneous elimination of uric acid interferences is obtained via the co-immobilization of uricase. Oxygen background currents are eliminated in the presence of ascorbic acid. 相似文献
108.
N. K. Tunali H. N. Erten S. Kinikoğlu Ş. Gümüş 《Journal of Radioanalytical and Nuclear Chemistry》1979,49(2):225-237
The extraction of iodine and bromine under various conditions from their saturated aqueous solutions by CCl4, C6H6 and o-xylene has been studied. The data obtained from the experiments carried out at various temperatures, for H2O(I2)−CCl4 and H2O(I2)−C6H6 systems, exhibit an Arrhenius behaviour. The overall activation energy calculated for the extraction in the H2O(I2)−CCl4 system, 650±50 cal·mol−1 is lower than that of H2O(I2)−C6H6, 3600±300 cal·mol−1. The use of the solubility parameter for the interpretation of the data in the extraction of iodine is investigated. The
data obtained in multiple extractions are treated by using the analogy between extraction and radioactive decay. The half
number of extraction for each system is determined. The complex curves obtained in the H2O(I2)−CCl4 and H2O(I2) −Br2)−CCl4 systems are resolved into two components. 相似文献
109.
Marija Vojnovi Draan Jozi Gerald Giester Berislav Peri Pavica Planini Nevenka Brni
evi 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m219-m220
The novel title compound, [(CH3)4N]2[Ta6Br12(H2O)6]Br4·2H2O, with a [Ta6Br12]2+ cluster unit, has been prepared and structurally characterized. The compound crystallizes in space group C2/c, with a twofold axis passing through the cluster and the centre of symmetry located between the clusters. The nearest neighbouring cluster units are aligned along the crystallographic c axis, forming a one‐dimensional chain pattern. 相似文献
110.
The method developed in this work for the separation and preconcentration of Cr(III) is based on its retention by an Amberlite XAD-2 copolymer resin functionalized with 5-palmitoyl-8-hydroxyquinoline (oxine), abbreviated XAD-POx, with the ligand covalently bound to the copolymer. Cr(III) sorption was quantitative within the pH range 4.5–7.0 and Cr(VI) was not retained. The Cr(III) held by the resin column was eluted with a hot solution of H2O2 in pH9.0 aqueous NH3–NH4Cl buffer, and Cr oxidized to CrO42– was rejected by the chelating cation-exchanger column. Any Cr(VI) originally present with Cr(III) could be reduced with an acidic solution of H2O2, and retained by the column yielding total Cr results, Cr(VI) being determined from the difference. The resin showed a maximal preconcentration factor of 60 for Cr(III), the LOD and LOQ being 9.3 and 30.1 nmol L–1, respectively. The developed preconcentration-speciation analysis was finished with a diphenylcarbazide (DPC) spectrophotometric procedure suitable for conventional laboratories. The resin showed excellent salt tolerance, enabling Cr analysis in seawater, and was stable over extended use. All the interferents of this procedure that normally occur in an electroplating effluent, a blended coal CRM, and a standard steel sample could be removed by the recommended procedure, by use of partial and total selectivity at the adsorption and desorption stages, respectively, enabling preconcentration and colorimetric determination of chromium in various complex matrices. 相似文献