全文获取类型
收费全文 | 4979篇 |
免费 | 696篇 |
国内免费 | 281篇 |
专业分类
化学 | 3647篇 |
晶体学 | 30篇 |
力学 | 38篇 |
综合类 | 25篇 |
数学 | 128篇 |
物理学 | 2088篇 |
出版年
2024年 | 12篇 |
2023年 | 34篇 |
2022年 | 91篇 |
2021年 | 105篇 |
2020年 | 117篇 |
2019年 | 119篇 |
2018年 | 132篇 |
2017年 | 152篇 |
2016年 | 153篇 |
2015年 | 159篇 |
2014年 | 162篇 |
2013年 | 414篇 |
2012年 | 352篇 |
2011年 | 254篇 |
2010年 | 201篇 |
2009年 | 258篇 |
2008年 | 276篇 |
2007年 | 367篇 |
2006年 | 308篇 |
2005年 | 296篇 |
2004年 | 267篇 |
2003年 | 240篇 |
2002年 | 203篇 |
2001年 | 193篇 |
2000年 | 180篇 |
1999年 | 172篇 |
1998年 | 132篇 |
1997年 | 104篇 |
1996年 | 101篇 |
1995年 | 78篇 |
1994年 | 64篇 |
1993年 | 68篇 |
1992年 | 49篇 |
1991年 | 40篇 |
1990年 | 25篇 |
1989年 | 21篇 |
1988年 | 12篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 5篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1977年 | 3篇 |
1974年 | 5篇 |
1972年 | 1篇 |
1971年 | 2篇 |
1957年 | 1篇 |
排序方式: 共有5956条查询结果,搜索用时 15 毫秒
81.
82.
A simple procedure for the determination of manganese in different sections of human brain samples by graphite furnace atomic absorption spectrometry has been developed. Brain sections included cerebellum, hypothalamus, frontal cortex, vermix and encephalic trunk. Two sample preparation procedures were evaluated, namely, slurry sampling and microwave-assisted acid digestion. Brain slurries (2% w/v) could be prepared in distilled, de-ionized water, with good stability for up to 30 min. Brain samples were also digested in a domestic microwave oven using 5 ml of concentrated HNO3. A mixed palladium+magnesium nitrate chemical modifier was used for thermal stabilization of the analyte in the electrothermal atomizer up to pyrolysis temperatures of 1300 °C, irrespective of the matrix. Quantitation of manganese was conducted in both cases by means of aqueous standards calibration. The detection limits were 0.3 and 0.4 ng ml−1 for the slurry and the digested samples, respectively. The accuracy of the procedure was checked by comparing the results obtained in the analysis of slurries and digested brain samples, and by analysis of the NIST Bovine Liver standard reference material (SRM 1577a). The ease of slurry preparation, together with the conventional set of analytical and instrumental conditions selected for the determination of manganese make such methodology suitable for routine clinical applications. 相似文献
83.
E. Yu. Mikhteeva E. G. Savchuk E. A. Tararako E. B. Merkulov V. K. Goncharuk 《Journal of Structural Chemistry》2005,46(6):1082-1085
Images of cleaved surfaces were obtained for 53ZrF4-20BaF2-4LaF3-3AlF3-20NaF (ZBLAN) glasses and fused quartz using an NTMDT atomic force microscope. It is shown that the scatter of particle size depends on the cooling rate and is 21–48.5 Å for the cleaved surface of ZBLAN glass obtained by very fast cooling and 68–172 Å for the cleaved surface of ZBLAN after slow cooling. For cleaved fused quartz, the range is 25-18 Å. 相似文献
84.
This paper proposes a quick, novel method for tin determination in organotin chemicals by slurry nebulization inductively coupled plasma atomic emission (ICP-AES) spectrometry. The method was tested by the measurement of five organotin carboxylate complexes of known composition for obtaining simple stoichiometric data. The slurries were prepared by first dissolving the organotins in an adequate solvent (methanol, pyridine or acetone) well miscible with water and then adding this solution drop-by-drop to a 0.005% TX-100 tenzide solution while maintaining intensive mixing. Dynamic laser light scattering experiments showed that the average equivalent particle size in the resulting slurry was ≈0.3 μm for all samples and solvents. Under suitable ICP-AES measuring conditions, the signal recoveries were found to be between 101.8 and 106.6%, which allowed direct nebulization and calibration against aqueous solutions. Typically, 70 μg l−1 detection limit and 1–5% relative S.D. on five replicates can be achieved by the described method. 相似文献
85.
An inductively coupled plasma atomic emission spectrometry (ICP-AES) procedure has been developed and examined for the determination of boron content (0.01 up to about 2% B) in boron-alloyed steels such as POLDI ATA BOR (65% Fe, 19%Cr, 12% Ni, 1.5% Mn, 1% B), POLDI ATA BOR EXTRA (62% Fe, 18% Cr, 13% Ni, 2.5% Mo, 1.5% Mn, 1% B) and POLDI ATA BOR-R (75% Fe, 18% Cr, 3.5% Ti, 1.8% B). The steel sample is dissolved with a mixture of hydrochloric, nitric, sulfuric and phosphoric acids in a quartz vessel. Borides of alloyed metals, especially of iron and chromium, are quantitatively decomposed. The presence of phosphoric acid in a sample solution reduces the volatility of boric acid with water vapour.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria 相似文献
86.
A simple accurate and precise analytical method for the determination of platinum, ruthenium, and molybdenum in Pt, PtRu, and PtMo nanoparticles catalysts deposited on high-surface area carbon by flame atomic absorption spectrometry (FAAS) and graphite furnace atomic absorption spectrometry (GFAAS) is described. The complete digestion of samples (0.010-0.020 g), which contain noble metals (NMs) in the range between 0 and 30% in combination among them or with other non-NMs, is obtained under mild conditions using both concentrated HCl and HCl+HNO3 (1+1 (v/v)) mixture to boiling for 30 min in an open vessel. Carbon is separated from the solution by filtering it. Under optimized conditions of the flame, the poor sensitivity of platinum is enhanced 50-fold in presence of 1% (m V−1) ascorbic acid, whereas the analytical signal of ruthenium increased by the presence of co-existing platinum. Any kind of interference is observed on the analytical signal of molybdenum. Recovery test obtained by analyzing commercial powder catalysts ranged from 99 to 101%. The precision, expressed as relative standard deviation of five measurements, is better than 1%. Electrode catalysts, made by using the carbon-supported platinum-based powder catalysts, have been analyzed for the metal loadings onto the electrode by GFAAS after dissolution under the same conditions used for the powder catalysts. The precision, expressed as relative standard deviation of three measurements, is better than 2%. 相似文献
87.
Determination of trace elements in biological materials using tetramethylammonium hydroxide for sample preparation 总被引:1,自引:0,他引:1
Patrícia Martins Dirce Pozebon Valderi L. Dressler Gisele A. Kemieciki 《Analytica chimica acta》2002,470(2):62-204
A method to prepare milk powder, bovine liver and bovine muscle samples for analysis by electrothermal atomic absorption spectrometry (ETAAS) is proposed. Samples are mixed with a small amount of tetramethylammonium hydroxide (TMAH) and a stable and homogeneous slurry is produced in ca. 2 h with heating at 60–70 °C. After such sample preparation and dilution with water, trace elements are determined in certified reference materials. Pyrolysis and atomisation temperatures are optimised for each element, and several modifiers are investigated. External calibration is used for every analyte. Limits of detection (LODs), precision and accuracy are reported for Cd, Pb, Ni, Cr, Cu and Ag and compared with those obtained after conventional acid digestion. The main advantages of the proposed method are the simplicity of sample preparation and the longer lifetime of the graphite tube. 相似文献
88.
Fused-sphere surfaces can be used to mimic a molecular boundary associated with a constant value of the electron density. The simplest of such fused-sphere models are constructed by using the atomic radii for the spherical isodensity surfaces of individual atoms. In this work, we discuss the extension of this model to molecules containing atoms beyond the second row. In these many- electron systems, the computation of electron densities is usually simplified by adopting a pseudopotential (or effective-core potential) approach. Here, we discuss the performance of large- and small-core pseudo-potential calculations as a tool to derive atomic radii. Our results provide an optimum set of variable radii that can be used to build fused-sphere surfaces. This continuum of surfaces provides a simple approximation to the low-electron-density regions around molecules with heavy atoms. 相似文献
89.
Dolores Bellido-Milla Anabel Oñate-Jaén Jose M. Palacios-Santander Dolores Palacios-Tejero María P. Hernández-Artiga 《Mikrochimica acta》2004,144(1-3):183-190
Many standard and official sample digestion procedures for trace metal determination are carried out in open vessels on hot plates. A new procedure for the determination of trace metals by flame atomic absorption spectrometry or inductively coupled plasmaatomic emission spectrometry in beer samples was developed to be performed in closed reactors assisted by microwaves. The results are compared with the ones obtained by other procedures by means of the analysis of the variance. The differences between the procedures are attributed to residual organic matter. Voltammetry, absorption molecular spectrophotometry and high pressure liquid chromatography with a photodiode array detector are used to study the nature of these residues. Nitrobenzoic acids, phenolic acids and other organic compounds are often present after digestion. The results obtained are related to the precision in metal determination by atomic spectrometry. The need for elaboration of certified reference materials for trace metals in beer is suggested. 相似文献
90.
Othman A. Farghaly 《Microchemical Journal》2003,75(2):119-131
Tap water samples (Assiut city, lie in the middle north of upper Egypt, approx. 370 km from Cairo, January-March, 2002) were taken from the eight sampling sites of different locations at Assiut city. The samples are analyzed to determine the total content of cadmium, copper, lead and zinc by differential pulse anodic stripping voltammetry (DPASV) while nickel and cobalt are determined by a new simple differential pulse adsorptive stripping voltammetry (DPAdSV), using dimethylglyoxime (DMG) as the complexing agent. This method uses sodium sulfite as the supporting electrolyte, which facilitates the removal of oxygen interference without the traditional necessity of purging with inert gas. The effect of various parameters was studied using DPASV (for Cd, Pb, Cu and Zn) and AdSV (for Ni and Co) methods. Subsequently, under the so found experimental conditions, the stability of calibration curves and the detection limits (μg/l) have been determined. The data achieved (for all metals utility) are comparable to those measured by the graphite furnace atomic absorption spectrophotometric (GF-AAS) method. The effects of the interferences between these metal ions have been investigated. Moreover, the effect of storage was discussed and the obtained results were compared favorably with standard official methods. Statistical analysis of the database exhibits applicability and the accuracy of the techniques. The results obtained from the two techniques (Voltammetry and GF-AAS) are in very good agreements in the most tap water samples. 相似文献