全文获取类型
收费全文 | 2975篇 |
免费 | 95篇 |
国内免费 | 3篇 |
专业分类
化学 | 2358篇 |
晶体学 | 15篇 |
力学 | 31篇 |
数学 | 304篇 |
物理学 | 365篇 |
出版年
2023年 | 18篇 |
2022年 | 77篇 |
2021年 | 100篇 |
2020年 | 74篇 |
2019年 | 54篇 |
2018年 | 55篇 |
2017年 | 49篇 |
2016年 | 121篇 |
2015年 | 113篇 |
2014年 | 112篇 |
2013年 | 193篇 |
2012年 | 210篇 |
2011年 | 290篇 |
2010年 | 184篇 |
2009年 | 137篇 |
2008年 | 200篇 |
2007年 | 151篇 |
2006年 | 152篇 |
2005年 | 148篇 |
2004年 | 80篇 |
2003年 | 80篇 |
2002年 | 81篇 |
2001年 | 33篇 |
2000年 | 19篇 |
1999年 | 39篇 |
1998年 | 32篇 |
1997年 | 23篇 |
1996年 | 23篇 |
1995年 | 15篇 |
1994年 | 10篇 |
1993年 | 10篇 |
1992年 | 17篇 |
1991年 | 7篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1986年 | 10篇 |
1985年 | 8篇 |
1984年 | 16篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 10篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1977年 | 10篇 |
1976年 | 7篇 |
1974年 | 7篇 |
1973年 | 5篇 |
排序方式: 共有3073条查询结果,搜索用时 0 毫秒
41.
Alessandra Gentili Fulvia Caretti Giuseppe D’Ascenzo Lucia Mainero Rocca Stefano Marchese Stefano Materazzi Daniela Perret 《Chromatographia》2007,66(9-10):669-676
Two new methods of analysis, based on liquid chromatography–tandem mass spectrometry, for simultaneous determination of trichothecenes A, B, and D in maize flour and oil have been developed and validated in accordance with European Commission decision 2002/657/EC (recovery, CCα, CCβ, and precision). The trichothecenes were extracted from maize flour by matrix solid-phase dispersion, with recoveries ≥79%, and from maize oil by liquid–liquid extraction, with recoveries ≥78%. Limits of quantitation ranged between 0.03 and 50 μg kg?1, depending on the electrospray response to each analyte and on the matrix. Monitoring of flour and oil samples with this HPLC–MS–MS method revealed the presence of deoxynivalenol, T-2 toxin, and diacetoxyscirpenol at very low concentrations. 相似文献
42.
Trávníček Zdeněk Machala Viktor Szüčová Lucie Maloň Michal Marek Jaromír 《Transition Metal Chemistry》2004,29(4):352-357
A series of new [NiX(S2P{O-c-Hex}2)(PPh3)](X = Cl–, Br–, I– and NCS–)(1)–(4) and [Ni(NCS)(S2P{OR}2)(PPh3)][R =n-Pr (5), i-Pr (6)] complexes has been synthesized and characterized by elemental analyses, f.i.r., i.r., u.v.–vis., 1H-, 13C{1H}- and 31P{1H}-n.m.r. spectra, magnetochemical and conductivity measurements. A single crystal X-ray analysis of [Ni(NCS)(S2P{O-n-Pr}2)(PPh3)](5) reveals the molecular structure of the complex and confirms a square-planar geometry around the central atom of nickel with the NCS anion coordinated via the nitrogen atom. 相似文献
43.
Daniela Walterová Zdeně;K Stránský Vladimír Preininger Prof. Dr. Vilím Šimánek 《Electrophoresis》1985,6(3):128-132
The isotachophoretic behavior of quaternary benzo/c/phenanthridine, protoberberine and aporphine alkaloids in different electrolyte systems is described. The concentration of the leading ion and the pH value of the leading electrolyte affect the relative effective mobilities of the alkaloids. The system of pH 4.7, containing the leading ion K+ (0.005 M) counter ion acetate, and the terminating ion β-alanine (0.02 M), has been selected for the quantitative determination of the studied alkaloids in model mixtures and plant extracts. 相似文献
44.
Marchese S Curini R Gentili A Perret D Rocca LM 《Rapid communications in mass spectrometry : RCM》2004,18(3):265-272
A simple and rapid method using reversed-phase liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the simultaneous determination of the urinary metabolites of benzene, toluene, xylene and styrene in human urine specimens and standard solutions is described. A hybrid quadrupole/time-of-flight (QqTOF) mass spectrometer was compared for the determination of metabolite of aromatic solvents in urine samples. The metabolites selected were: trans,trans-muconic acid, hippuric acid, o-, m- and p-methylhippuric acid and phenylglyoxylic acid. The compounds were well separated from each other on narrow-bore 1-mm i.d. reversed-phase LC C-18 columns. Average recoveries for loading 100 microL of urine samples varied from 88-110% and the quantification limits were less than 30 ng/mL for each analyte (3 ng/mL for trans,trans-muconic acid). The qualitative information obtained (mass accuracy, resolution and full-scan spectra) with the QqTOF mass spectrometer allows a secure identification of analytes in biological matrices. 相似文献
45.
Cocchi M Faeti V Manfredini M Manzini D Marchetti A Sighinolfi S 《Journal of AOAC International》2005,88(2):393-398
The presence of some essential and toxic metals in fat supplements for swine diet was investigated. Collected samples represented a relevant production of the Italian industry. In particular, some samples were enriched with antioxidants or waste cooking oils. The method for the determination of Ca, Cu, Cd, Fe, Mg, Mn, Ni, Pb, and Zn in fat samples was developed by means of a certified reference material (CRM 186) and a representative fatty sample (RFS). All samples were digested in closed vessels in a microwave oven and then analyzed by flame atomic absorption or graphite furnace atomic absorption spectrometry. The entire analytical method provided a satisfactory repeatability and reproducibility confirmed by agreement between the experimental recovery data obtained for the CRM 186 sample and, with the method of standard additions, for the RFS material. The samples generally showed a small amount of metals compared with the recommended daily intake for the essential elements. On the other hand, some samples contained a significant concentration, from an analytical point of view, of Cd, Ni, and Pb. Principal component analysis (PCA) was applied to inspect the experimental data obtained from samples analysis. Basically no differences were detected in terms of metal concentration among the fat supplements analyzed. 相似文献
46.
Saturnino C Buonerba M Boatto G Pascale M Moltedo O de Napoli L Montesarchio D Lancelot JC de Caprariis P 《Chemical & pharmaceutical bulletin》2003,51(8):971-974
The therapy of human cancer is one of the more pursued goals by medicinal chemistry research. Most of the compounds clinically used as a treatment owe their efficacy to their cytotoxic interaction (direct or indirect) with nuclear DNA. This interaction results in the inhibition of DNA synthesis and the degradation of nucleic strands. Ellipticine is a naturally occurring 6H-pyrido[4,3-b]carbazole alkaloid endowed with antitumor activity, and several ellipticine derivatives have been used in clinical trials. We previously reported some 1,4-dimethyl-9H-carbazole derivatives structurally related to ellipticine. The purpose of our research was to transform the pyridocarbazole in a prodrug so that it would have more penetration in the tumor cells and block their replication. Our prodrug is slowly hydrolyzed in human plasma in the corresponding acid. From these preliminary results, we deduce that our compound can block cellular replication. Our hypothesis is that the antitumoral activity is probably related to the induction of damage to DNA, without cellular lysis in the short term. 相似文献
47.
Stefan Motiu Daniela Dogaru Valentin Gogonea 《International journal of quantum chemistry》2007,107(5):1248-1252
This work puts forth a reaction pathway for the reactivation of exogenous ligand inhibited H‐cluster, the active site of Fe‐only hydrogenases. The H‐cluster is a dimetal complex, Fe–Fe, with the metal centers bridged by di(thiomethyl)amine. Exogenous ligands, H2O, and OH?, are bound to the distal iron (Fed). Density functional theory (DFT) calculations on the native and ruthenium‐modified H‐cluster have been performed using the B3LYP functional with 6‐31+G** and 6‐311+G** basis sets. We have ascertained that there is a thermodynamically favorable pathway for the reactivation of the OH? inhibited H‐cluster, which proceeds by an initial protonation of the Fed–OH? complex. The proposed reaction pathway has all its intermediate reactions ensue exothermically. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
48.
A stereoselective total synthesis of (S)-Virol C and (S)-1-dehydroxyvirol A has been developed, based upon the selective and sequential substitution of the two trimethylsilyl groups of readily available 1,4-bis(trimethylsilyl)-1,3-butadiyne. 相似文献
49.
Mixed gels of starch and bentonite are investigated in the interval 0.056–0.089 of total solids/water ratio and 0-100% starch in the solids. The bentonite was a sodium calcium bentonite with a Na/Ca ratio of 1.76. In water it forms gels consisting of a network of band-type structures. Starch forms gels through hydrogen bonds between granules and/or amylose and amylopectin present on the external surfaces of granules and/or in fully stretched form. Mixed gels of bentonite and starch were obtained by adding corn starch granules to the already formed bentonite gels and heating the mixture above the Kofler gelatinization temperature. Amylose and amylopectin were adsorbed on strands of band-type structures of mont-morillonite lamellae. Starch gellation, e.g. diffusion of amylose out of the granule, was facilitated in the presence of bentonite. On the other hand, the presence of starch favored delamination of the montmorillonite particle into thinner lamellae. Maximum gelatinization and polymer adsorption were observed for gels with 20% starch and 80% bentonite. Montmorillonite networks formed the continuous phase for 0-80% starch. At higher starch concentrations, montmorillonite flakes were dispersed within the polymer network. Increase in the water content of the gels caused segregation of the bentonite and starch. 相似文献
50.
A comparison of sequential extraction techniques for determining arsenic fractionation in synthetic mineral mixtures 总被引:6,自引:0,他引:6
The sequential extraction methods according to Tessier et al. [1], Borovec et al. [2], Zhang and Moore [3] and Hall et al. [4] have been tested for their suitability for arsenic fractionation in samples of artificially prepared mineral mixtures. Mixtures containing different amounts of As-containing phases were prepared so that their compositions corresponded to weathering products on As-bearing ore deposits. A comparison of different procedures on simple mineral mixtures containing calcium arsenate (CaHAsO4·H2O), As-bearing goethite (FeOOH) and arsenopyrite (FeAsS) showed that only the results of the Hall method satisfactorily correspond to the expected arsenic distribution. A detailed verification of the Hall method was subsequently carried out on most complex synthetic mineral mixtures with varying amounts of As-containing kaolinite and carbonate, calcium arsenate, As-bearing goethite and arsenopyrite. The results confirm that the Hall method cannot be fully employed for an accurate As speciation but may be applied for a route identification of As distribution between "labile", "medium-labile" and "residual" forms in heavily polluted soils. 相似文献