全文获取类型
收费全文 | 1913篇 |
免费 | 74篇 |
国内免费 | 206篇 |
专业分类
化学 | 1584篇 |
晶体学 | 9篇 |
力学 | 125篇 |
综合类 | 1篇 |
数学 | 100篇 |
物理学 | 374篇 |
出版年
2024年 | 4篇 |
2023年 | 36篇 |
2022年 | 31篇 |
2021年 | 29篇 |
2020年 | 26篇 |
2019年 | 25篇 |
2018年 | 28篇 |
2017年 | 48篇 |
2016年 | 54篇 |
2015年 | 49篇 |
2014年 | 90篇 |
2013年 | 121篇 |
2012年 | 90篇 |
2011年 | 120篇 |
2010年 | 105篇 |
2009年 | 145篇 |
2008年 | 123篇 |
2007年 | 161篇 |
2006年 | 129篇 |
2005年 | 107篇 |
2004年 | 100篇 |
2003年 | 56篇 |
2002年 | 38篇 |
2001年 | 44篇 |
2000年 | 39篇 |
1999年 | 26篇 |
1998年 | 31篇 |
1997年 | 25篇 |
1996年 | 23篇 |
1995年 | 35篇 |
1994年 | 31篇 |
1993年 | 25篇 |
1992年 | 25篇 |
1991年 | 18篇 |
1990年 | 14篇 |
1989年 | 19篇 |
1988年 | 22篇 |
1987年 | 12篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 21篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 5篇 |
1980年 | 9篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 3篇 |
排序方式: 共有2193条查询结果,搜索用时 15 毫秒
21.
Gallium metal is effective in mediating the allylation of various carbonyl compounds and imines under solvent-free conditions, with the application of sonic energy, affording the corresponding homoallylic alcohols and amines. The imines themselves were also prepared under solventless conditions in high yield, thereby establishing a two-step solvent-free synthesis of homoallylic amines. In comparison, indium metal produced a mixture of the desired homoallylic secondary amine and the bis-allylated species via an iminium ion intermediate. 相似文献
22.
Keiichi Satoh Zhang Xiang-Yu Masashi Miya-iri Akiko Honma Kiyoshi Sawada 《Monatshefte für Chemie / Chemical Monthly》2006,137(11):1375-1383
Summary. The ion-pair solvent extraction behavior of ethylenediaminetetraacetate (EDTA) anion by various tetraalkylammonium ions was investigated at 25.0 ± 0.1°C. The extraction of EDTA exceeded 90% from the basic aqueous solution into the organic solvents such as n-hexane and benzene derivatives containing tri-n-octylmethylammonium chloride, but EDTA was hardly extracted from acidic solution. Among the chemical species of EDTA in aqueous solution, edta
4− is the most extractable one. On the other hand, the extraction of EDTA was less than 1% into chloroform and 1,2-dichloroethane even from the basic aqueous solution. The effect of the structure
of alkylammonium ion was also examined. Tetra-n-hexylammonium and tetra-n-octylammonium ions could not extract EDTA even from the basic aqueous solution, while the use of tri-n-octylmethylammonium and di-n-lauryldimethylammonium ions enhances the extraction of EDTA. These results suggest that the steric hindrance in the ion-pair of alkylammonium and EDTA anion in the organic phase affects the extractability of EDTA containing ion-pair. The solution structure of ion-pair in the organic phase was calculated by MMFF force field and the steric
effect in the ion-pair was also suggested. From the extraction constants obtained, the possibility of the extraction separation
of EDTA has been shown.
Present address: Chemistry Department, Heilongjiang University, Harbin, China 相似文献
23.
Jan S. Jaworski 《Monatshefte für Chemie / Chemical Monthly》1984,115(4):415-418
A two parameter approach to solvent variations in the electroreduction rate constants of cobalt complexes and europium cations is presented and discussed in terms of solvent—solute and solvent—solvent interactions.
Ein Zwei-Parameter Donor-Acceptor-Ansatz für Lösungsmitteleffekte bei der Elektrodenkinetik von Kationen (Kurze Mitteilung)
Zusammenfassung Es wird eine Zwei-Parameter-Annäherung der Lösungsmitteleinflüsse auf die Geschwindigkeitskonstanten der Elektroreduktion von Kobalt-Komplexen und Europium-Kationen präsentiert und auf der Basis von Lösungsmittel—gelöster Stoff- und Lösungsmittel—Lösungsmittel-Wechselwirkung diskutiert.相似文献
24.
S. Korhammer Rolf Herzig Peter Schramel Jorma Kumpulainen Bernd Markert Herbert Muntau Philippe Quevauviller 《Accreditation and quality assurance》2000,5(6):238-242
Cabbage is frequently used in environmental monitoring and food control, and, hence, cabbage reference materials (RMs) are
required for ensuring quality assurance. A cabbage RM was prepared in view of certification of specific elements from the
"black list" of high toxicological interest and nutritive importance. All tasks of the RM production (production of the plant
material, cutting and freeze-drying, determination of the residual water content, preparation of the RM, homogeneity testing,
stability testing, certification measurements) are described in detail.
Received: 12 November 1999 / Accepted: 29 January 2000 相似文献
25.
The adverse effects of injection solvent strength on microbore packed column SFC band broadening are demonstrated and a solventless injection system that eliminates these effects is introduced. The injection system removes solvent in a GC-like manner using a retention gap and an on-column capillary GC syringe. The analyte is delivered to the analytical column in a solvent-free plug of supercritical fluid mobile phase. 相似文献
26.
Summary In this study, a rapid and efficient semi-micro extraction procedure is presented for the extraction of some higher n-alkanes
from water and soil samples. In the case of water samples n-hexane was used as the organic phase in a phase volume ratio (volume
of aqueous phase/volume of organic phase) higher than 285, while in the case of soil samples, extraction with n-hexane was
carried out in the presence of an excess of 2 M NaCl solution. The extraction rate from soil samples is very high and is better
than Soxhlet extraction, comparable with supercritical fluid extraction. High preconcentration factor in water samples allows
the limits of detection to be in the ng.mL−1 level with the use of gas chromatographic analysis. Flame ionization detector was used for monitoring the analytes. The obtained
recoveries of all studied compounds from both water and soil samples are higher than 90%. This method was successfully used
to determine some n-alkanes in municipal wastewater and contaminated soil. 相似文献
27.
Varughese M. Alexander 《Tetrahedron letters》2005,46(40):6957-6959
Bismuth(III) nitrate pentahydrate is found to be an efficient catalyst for the Pechmann condensation reaction of phenols and β-ketoesters under solvent-free conditions. The reaction protocol is simple and is followed by aqueous work-up leading to the formation of the corresponding coumarin derivatives in good yield and high purity. 相似文献
28.
G.A. Groß 《Thermochimica Acta》2005,432(2):229-240
A silicon chip device with two types of integrated platinum thin film resistors was applied for microcaloric measurements. It was shown that the device is capable of fast characterization of liquid evaporation behaviour and allows the determination of evaporation enthalpies for pure liquids and mixtures. The applicability was demonstrated for a wide range of solvents from nonpolar aliphatic solvents over polar organics to protic solvents (e.g. iso-octane, toluene, acetone, ethanol, methanol and water). The sample volumes were in the range of about 2-5 μL. The determination of transient times, in case of constant power mode, or the power integral over time was used for the fast estimation of binary liquid mixtures. Thermo-resistive measurements of 5 μL droplets of solvent mixtures like methanol/iso-propanol, ethanol/water, iso-octane/iso-propanol and iso-octane/1,4-dioxane showed significant changes in temperature characteristics and evaporation enthalpies in dependence on composition. The applied heating power was about 1 W, which corresponds to measurement times between a few seconds and a minute. 相似文献
29.
Yasuyuki Takeda Chihiro Takagi 《Journal of inclusion phenomena and macrocyclic chemistry》1994,17(1):93-97
The theory is derived to determine the dimer-formation constant,K
2, of a crown ethermetal salt 111 complex in organic solvents of low dielectric constant by solvent extraction. The theoretical predictions are verified experimentally by extraction of sodium picrate (NaA) with 15-crown-5 (15C5) into carbon tetrachloride. All the experiments were conducted at 25°C. The logK
2 value of the Na(15C5)A complex in carbon tetrachloride has been determined to be 4.05±0.11. Moreover, the partition constant of the complex is calculated. 相似文献
30.
The performance of a PTV injector operated in the solvent venting mode with Tenax in the glass insert was evaluated with synthetic mixtures containing 5 to 50 ng of n-alkanes, ethyl esters, n-alcohols, and carboxylic acids. The influence of the sampled amount, the injected volume, and the nature of the solvent on accuracy and precision were studied. Coefficients of variation of relative (normalized) peak areas and absolute peak area ratios of each compound to the standard are of the order of 5 %. 相似文献