全文获取类型
收费全文 | 29440篇 |
免费 | 103篇 |
国内免费 | 275篇 |
专业分类
化学 | 10751篇 |
晶体学 | 261篇 |
力学 | 1411篇 |
综合类 | 12篇 |
数学 | 9213篇 |
物理学 | 8170篇 |
出版年
2021年 | 45篇 |
2020年 | 42篇 |
2019年 | 31篇 |
2018年 | 1202篇 |
2017年 | 1454篇 |
2016年 | 732篇 |
2015年 | 572篇 |
2014年 | 498篇 |
2013年 | 687篇 |
2012年 | 3146篇 |
2011年 | 2328篇 |
2010年 | 1836篇 |
2009年 | 1563篇 |
2008年 | 582篇 |
2007年 | 625篇 |
2006年 | 606篇 |
2005年 | 4438篇 |
2004年 | 3912篇 |
2003年 | 2314篇 |
2002年 | 503篇 |
2001年 | 294篇 |
2000年 | 107篇 |
1999年 | 189篇 |
1998年 | 125篇 |
1997年 | 80篇 |
1996年 | 54篇 |
1995年 | 48篇 |
1994年 | 54篇 |
1993年 | 31篇 |
1992年 | 184篇 |
1991年 | 159篇 |
1990年 | 142篇 |
1989年 | 111篇 |
1988年 | 107篇 |
1987年 | 65篇 |
1986年 | 45篇 |
1985年 | 43篇 |
1984年 | 40篇 |
1983年 | 31篇 |
1979年 | 33篇 |
1976年 | 81篇 |
1975年 | 42篇 |
1974年 | 44篇 |
1973年 | 48篇 |
1972年 | 40篇 |
1970年 | 38篇 |
1969年 | 39篇 |
1968年 | 37篇 |
1967年 | 31篇 |
1966年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
331.
Solid Phase Extraction and Flame Atomic Absorption Spectrometric Determination of Trace Amounts of Zinc and Cobalt Ions in Water Samples 总被引:1,自引:0,他引:1
A simple and rapid method for the preconcentration of Co2+ and Zn2+ as their 2-guanidino-benzimidazole chelates is proposed using an octadecyl silica cartridge. The retained analytes were recovered with a mixture of 5mL of 0.01M HNO3 and 5mL of methanol. The metal ions in the effluent were determined by flame atomic absorption spectrometry. The effect of different parameters, such as sample matrix, amount of ligand, type of eluent for elution of ions from cartridge, flow rates of sample solution and eluent, breakthrough volume, and limit of detection, were evaluated. The effects of various cationic and anionic interferences on the percent recovery of Co2+ and Zn2+ were also studied. Quantitative extraction efficiencies were obtained by elution of the cartridge with a minimal amount of solvent. Hence, with a typical preconcentration factor of 50, the limits of detections of the proposed method are 0.26 and 1.62ngmL–1 for Zn2+ and Co2+, respectively. The method was applied to the determination of zinc and cobalt ions in different water samples. 相似文献
332.
Darja?Rudan-Tasic Cveto?KlofutarEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(7):773-784
Summary. The freezing temperatures of dilute aqueous solutions of some poly(oxyethylene) glycols (PEG, HO–(CH2CH2O)
n
–H, n varying from 4 to 117) were measured over a solute to solvent mass ratio from 0.0100 to 0.3900. The second and third osmotic virial coefficient (A
22 and A
222) of poly(oxyethylene) glycols in aqueous solution were determined. The molecular weight dependence of the second virial coefficient can be described by a simple relation A
22=2×10–5
M
n
1.86, and the third virial coefficient is A
222=0.038A
22
2. The activity coefficients of the solute were calculated using the Gibbs-Duhem equation as applied by Bjerrum. From the osmotic and activity coefficients the excess Gibbs energies of solution, as well as the respective partial molar functions of solute and solvent and the virial pair interaction coefficients for the excess Gibbs energies were estimated. The second and the third osmotic virial coefficients are correlated with the Mc-Millan-Mayer virial coefficients. 相似文献
333.
Thirty-five chemical solutions, acids, bases, complexing, argentometric, reducing, oxidising, salts and eluent mixtures, were studied continuously over a 7.5-month period. Twenty-seven remained reasonably stable and had acceptable expiration dates, which were equal to or more than 2 months longer than the established average deviation of ±2% relative to the initial value. Exceptions were made for potassium permanganate (0.1 M), perchloric acid (0.1 M) and disodium hydrogen phosphate (10%) solutions, as well as for HPLC eluent mixtures, which showed stability with expiration dates equal to stated values or shorter by 1 month. The eight chemical solutions presenting expiration dating higher than 6 months were hydrochloric acid (0.1 and 1 M), sulphuric acid (0.5 and 1.5 M), ethylenediamine tetraacetic acid (EDTA) (0.1 M), silver nitrate (0.1 M), ammonium thiocyanate (0.1 M) and iodine (0.1 M). The present data is a suitable guideline for the date of several chemical solutions routinely used in the analytical laboratories. 相似文献
334.
Ayfer?Kalkan Zehra A.?BayirEmail author 《Monatshefte für Chemie / Chemical Monthly》2003,134(12):1555-1560
Summary. Unsymmetrical porphyrazines bearing a single peripheral bis(hydroxyethylthio) moiety were synthesised by mixed condensation of bis(2-hydroxyethylthio)maleonitrile and phthalonitrile. Complexation of the thioether groups of metal-free porphyrazine with PdCl2 further lowered the intensity of the Q-band absorption of the porphyrazine core. The new compounds were characterised by elemental analyses, IR, 1H NMR, UV-Vis, and mass spectra. 相似文献
335.
R. ZielińskaE. Mulik A. MichalskaS. Achmatowicz M. Maj-?urawska 《Analytica chimica acta》2002,451(2):243-249
All-solid-state ion-selective electrodes with plastic membrane (poly(vinyl chloride) (PVC), bis(2-ethylhexyl) sebacate (DOS), methyltri-n-tetradecylammonium chloride (MTTACl)), a conducting poly(pyrrole) (PPy) film doped either with chloride ions (PPyCl) or hexacyanoferrate(II) ions (PPyFeCN), and glassy carbon (GC) or screen-printed graphite layer (S-PG) as an inner electric contact were investigated. All the electrodes show close to Nernstian response, but their lifetimes vary. The at least 2-months lifetime of screen-printed electrodes is only achieved for the electrodes containing PPyFeCN (cation-exchanging film). Shorter lifetime of other screen-printed electrodes, i.e. without PPy, or with PPyCl (anion-exchanging film), was attributed to the diffusion of anionic products of the hydrolysis of organic components of the graphite paste used to prepare the electric contact. The properties of miniature, screen-printed electrodes comprising PPyFeCN solid contact, were comparable to those ion-selective electrodes with PPy solid contact (regardless the ion-exchanging characteristic of the polymer) deposited on GC electric contact. 相似文献
336.
Boron-doped diamond (BDD) electrodes were used to investigate the possibility of detecting aniline by linear-sweep cathodic stripping voltammetry. It was found that the dimeric species (p-aminodiphenylamine and benzidine) formed by anodic oxidation of aniline during the accumulation period are involved in electrochemically reversible redox processes and, in acidic media, the shape of the stripping voltammetric response is suitable for aniline detection in the micromolar concentration range. The low background current of conductive diamond is an advantage compared to other electrode materials and allows a detection limit of 1 μM. Weak adsorption properties and the extreme electrochemical stability are additional advantages of BDD and it was found that, even after long-time measurements, the electrode surface can regain its initial activity by an anodic polarization in the potential region of water decomposition. 相似文献
337.
Renata Toczy?owska 《Analytica chimica acta》2005,540(1):167-172
Back-side contact Au and Ag microelectrodes were used as transducers to construct planar all-solid-state electrodes suitable for flow-through analysis. The microsensors were based on plasticized PVC potassium-selective membranes containing ion-electron conducting polymer—polypyrrole doped with di(2-ethylhexyl) sulfosuccinate. The proposed technique allowed simple construction of microsensors in one step, by membrane solution casting directly on the surface of the planar metallic transducers. The performance of the microsensors based on Au and Ag transducers were determined and compared with planar sensors based on internal electrolyte immobilized in polyHEMA. The addition of the polypyrrole to the membrane composition did not influence on the selectivity, reproducibility and long-term stability of the microsensors but improved their standard potential stability in time in comparison with coated-wire type sensors. Moreover, all-solid-state microsensors based on Au transducers exhibited better signal stability than Ag based sensors. 相似文献
338.
A miniaturized liquid chromatographic system with electrochemical detection (LC-ED) was developed and applied to the analysis of dopamine and its metabolites in dialysate samples collected from the rat brain in vivo. An existing LC-ED system was down-scaled using a 1 mm I.D. small-bore column operated at a reduced flow-rate and with an injection volume of 1 microliter. With the small-bore system the limit of detection for dopamine of ca. 0.06 pg was almost 50 times less than with the conventional system, which represents a two-fold improvement in concentration sensitivity. Miniaturization was accomplished with negligible loss in resolution by using a conventional commercial amperometric detector with minor modifications. The results indicate that a number of useful advantages could be realized by the combination of this small-bore LC-ED system and the in vivo brain dialysis method. 相似文献
339.
Shigendo?Enomoto Ken-ichi?Kumagai Taro?Tamura Miki?Hasegawa Kyoko?Nakada Toshihiko?Hoshi Michio?KobayashiEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(5):471-481
Summary. Fluoranthene (FA) forms a 1:1 van der Waals complex with benzene in cyclohexane. The 1H NMR spectrum of this complex shows that the FA moiety in the complex state has five kinds of hydrogen atoms and that the 1H NMR peaks assigned to the protons attached to the naphthalene skeleton are largely shifted to higher magnetic field on complex formation with benzene. These observations indicate that the complex takes the structure of CS symmetry, in which the benzene molecule mainly interacts with the electronic system localized on the naphthalene moiety of FA. The present ab initio calculations reproduce well the 1H NMR spectral shifts mentioned above and the experimentally predicted CS structure of the complex. According to the PPP calculations for the electronic absorption spectral changes on the complex formation, the FA-benzene complex is considered to take a sandwich type structure. 相似文献
340.
Mass spectrometric identification and characterization of steroids using electrospray ionization and tandem mass spectrometry has advantages in drug testing and doping control analysis attributable to limitations of gas chromatography followed by electron ionization mass spectrometry. Steroids with an androstadiene-17beta-ol-3-one nucleus and double bonds located either at C-1 and C-4, C-4 and C-9, or C-4 and C-6 were used to determine characteristic fragmentation pathways. Diagnostic dissociation routes are proposed using deuterium labeling, MS3 experiments, and analyses of structurally closely related compounds. Steroids such as boldenone (androst-1,4-diene-17beta-ol-3-one) produced characteristic product ions at m/z 121, 135, and 147. Compounds with double bonds at C-4 and C-9 generated abundant product ions at m/z 145 and 147. Conjugated double bonds at C-4 and C-6 gave rise to an intense and characteristic signal at m/z 133. Stereochemical differentiation between 5alpha- and 5beta-isomers of androstan-17beta-ol-3-ones was possible because of significant differences in relative abundance of product ions generated by elimination of acetone from alpha,beta-saturated 3-keto steroids. 相似文献