全文获取类型
收费全文 | 1088篇 |
免费 | 64篇 |
国内免费 | 10篇 |
专业分类
化学 | 747篇 |
晶体学 | 2篇 |
力学 | 22篇 |
数学 | 202篇 |
物理学 | 189篇 |
出版年
2023年 | 19篇 |
2022年 | 41篇 |
2021年 | 46篇 |
2020年 | 47篇 |
2019年 | 42篇 |
2018年 | 36篇 |
2017年 | 27篇 |
2016年 | 59篇 |
2015年 | 41篇 |
2014年 | 37篇 |
2013年 | 63篇 |
2012年 | 85篇 |
2011年 | 75篇 |
2010年 | 33篇 |
2009年 | 44篇 |
2008年 | 47篇 |
2007年 | 71篇 |
2006年 | 45篇 |
2005年 | 48篇 |
2004年 | 33篇 |
2003年 | 20篇 |
2002年 | 22篇 |
2001年 | 15篇 |
2000年 | 19篇 |
1999年 | 12篇 |
1998年 | 12篇 |
1997年 | 12篇 |
1996年 | 11篇 |
1995年 | 11篇 |
1994年 | 11篇 |
1993年 | 7篇 |
1992年 | 4篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 11篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1980年 | 3篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1971年 | 2篇 |
1969年 | 5篇 |
1963年 | 2篇 |
1959年 | 2篇 |
1952年 | 1篇 |
1938年 | 1篇 |
排序方式: 共有1162条查询结果,搜索用时 15 毫秒
41.
42.
Chargaff’s second parity rule (CSPR) asserts that the frequencies of short polynucleotide chains are the same as those of
the complementary reversed chains. Up to now, this hypothesis has only been observed empirically and there is currently no
explanation for its presence in DNA strands. Here we argue that CSPR is a probabilistic consequence of the reverse complementarity
between paired strands, because the Gibbs distribution associated with the chemical energy between the bonds satisfies CSPR.
We develop a statistical test to study the validity of CSPR under the Gibbsian assumption and we apply it to a large set of
bacterial genomes taken from the GenBank repository. 相似文献
43.
Felipe Wodtke Fernando R. Xavier Samuel R. Mendes Alfredo R.M. de Oliveira Rogério A. Gariani 《Tetrahedron letters》2017,58(3):231-234
A novel application of the highly stable niobium oxide phosphate (NbOPO4) as an efficient catalyst for the synthesis of β-enamino ketones under solvent-free conditions is described. This protocol, exhibits attractive yields, short reaction periods, lower loading of catalyst and high chemoselectivity. 相似文献
44.
45.
Rita de Cássia da Silva Felipe Silva Semaan Csaba Novák Eder Tadeu Gomes Cavalheiro 《Journal of Thermal Analysis and Calorimetry》2013,111(3):1933-1937
Data from theoretical, thermal, and spectroscopic methods were compared in order to map a possible mechanism for the thermal decomposition of furosemide, a diuretic compound, in solid state. TG/DTG curves suggested a two-stage decomposition process. The first product of decomposition is water (m/z = 18), released due to a dimerization resulting in the formation of an amide. Then carbon dioxide (m/z = 44), nitroxide (m/z = 30), and 2-methyl-furanyl ion (m/z = 81) are released in the second stage. The chlorine substituted benzene ring, due to the double bond conjugated system, being the last fraction to decompose. Theoretical calculations presented are in agreement with experimental results. 相似文献
46.
Dr. Ulrich Hintermair Dr. Giancarlo Franciò Prof. Dr. Walter Leitner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(14):4538-4547
A continuous‐flow process based on a chiral transition‐metal complex in a supported ionic liquid phase (SILP) with supercritical carbon dioxide (scCO2) as the mobile phase is presented for asymmetric catalytic transformations of low‐volatility organic substrates at mild reaction temperatures. Enantioselectivity of >99 % ee and quantitative conversion were achieved in the hydrogenation of dimethylitaconate for up to 30 h, reaching turnover numbers beyond 100 000 for the chiral QUINAPHOS–rhodium complex. By using an automated high‐pressure continuous‐flow setup, the product was isolated in analytically pure form without the use of any organic co‐solvent and with no detectable catalyst leaching. Phase‐behaviour studies and high‐pressure NMR spectroscopy assisted the localisation of optimum process parameters by quantification of substrate partitioning between the IL and scCO2. Fundamental insight into the molecular interactions of the metal complex, ionic liquid and the surface of the support in working SILP catalyst materials was gained by means of systematic variations, spectroscopic studies and labelling experiments. In concert, the obtained results provided a rationale for avoiding progressive long‐term deactivation. The optimised system reached stable selectivities and productivities that correspond to 0.7 kg L ?1 h?1 space–time yield and at least 100 kg product per gram of rhodium, thus making such processes attractive for larger‐scale application. 相似文献
47.
Dr. Jacorien Coetzee Dr. Deborah L. Dodds Prof. Jürgen Klankermayer Sandra Brosinski Prof. Walter Leitner Prof. Alexandra M. Z. Slawin Prof. David J. Cole‐Hamilton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):11039-11050
Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4‐pentanedione), triphos [1,1,1‐tris‐ (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)3], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ1O)2(H2O)(triphos)], [Ru(OAc‐κ2O,O′)(CH3SO3‐κ1O)(triphos)], [Ru(CH3SO3‐κ1O)2(H2O)(triphos)] and [Ru2(μ‐CH3SO3)3(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc‐κ1O)(OAc‐κ2O,O′)(triphos)], [Ru(CH3SO3‐κ1O)(CH3SO3‐κ2O,O′)(triphos)], H[Ru(CH3SO3‐κ1O)3(triphos)], [RuH(CH3SO3‐κ1O)(CO)(triphos)] and [RuH(CH3SO3‐κ2O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed. 相似文献
48.
49.
50.
Microextraction by packed sorbent liquid chromatography with time‐of‐flight mass spectrometry of triazines employing a molecularly imprinted polymer†
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Felipe Nascimento Andrade Álvaro José Santos‐Neto Fernando Mauro Lanças 《Journal of separation science》2014,37(21):3150-3156
Molecularly imprinted polymers for the determination of triazines were synthesized by precipitation using atrazine as template, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslinker, and 2,2′‐azobisisobutrynitrile as initiator. The polymers were characterized by infrared spectroscopy and scanning electron microscopy and packed in a device for microextraction by packed sorbent aiming for the preconcentration/cleanup of herbicides, such as atrazine, simazine, simetryn, ametryn, and terbutryn in corn samples. Liquid chromatography coupled with time‐of‐flight mass spectrometry was used for the separation and determination of the herbicides. The selectivity coefficient of molecularly imprinted polymers was compared with that of nonimprinted polymer for the binary mixtures of atrazine/propanil and atrazine/picloram, and the values obtained were 15.6 and 2.96, respectively. The analytical curve ranged from 10 to 80 μg/kg (r = 0.989) and the limits of detection and quantification in the corn matrices were 3.3 and 10 μg/kg, respectively. Intra‐ and interday precisions were < 14.8% and accuracy was better than 90.9% for all herbicides. Polymer synthesis was successfully applied to the cleanup and preconcentration of triazines from fortified corn samples with 91.1–109.1% of recovery. 相似文献