全文获取类型
收费全文 | 1001篇 |
免费 | 37篇 |
国内免费 | 23篇 |
专业分类
化学 | 673篇 |
晶体学 | 8篇 |
力学 | 8篇 |
综合类 | 8篇 |
数学 | 63篇 |
物理学 | 301篇 |
出版年
2024年 | 2篇 |
2023年 | 8篇 |
2022年 | 37篇 |
2021年 | 33篇 |
2020年 | 22篇 |
2019年 | 14篇 |
2018年 | 12篇 |
2017年 | 13篇 |
2016年 | 27篇 |
2015年 | 22篇 |
2014年 | 21篇 |
2013年 | 61篇 |
2012年 | 25篇 |
2011年 | 37篇 |
2010年 | 23篇 |
2009年 | 41篇 |
2008年 | 41篇 |
2007年 | 58篇 |
2006年 | 48篇 |
2005年 | 33篇 |
2004年 | 26篇 |
2003年 | 46篇 |
2002年 | 187篇 |
2001年 | 41篇 |
2000年 | 24篇 |
1999年 | 19篇 |
1998年 | 19篇 |
1997年 | 9篇 |
1996年 | 10篇 |
1995年 | 7篇 |
1994年 | 7篇 |
1993年 | 14篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 9篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 2篇 |
1981年 | 2篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1975年 | 4篇 |
1972年 | 1篇 |
1970年 | 2篇 |
1969年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1061条查询结果,搜索用时 0 毫秒
241.
Klaus Ruthenberg 《Foundations of Chemistry》2009,11(2):79-91
Immanuel Kant has built up a dualistic epistemology that seems to fit to the peculiarities of chemistry quite well. Friedrich
Paneth used Kant’s concept and characterised simple and basic substances which refer to the empirical and to the transcendental
world, respectively. This paper takes account of the Kantian influences in Paneth’s philosophy of chemistry, and discusses
pertinent topics, like observables, atomism and realism.
相似文献
Klaus RuthenbergEmail: |
242.
Céline Claveranne-Lamolère Gaëtane Lespes Stéphane Dubascoux Jean Aupiais Fabien Pointurier Martine Potin-Gautier 《Journal of chromatography. A》2009,1216(52):9113-9119
The aim of this study was to characterize colloids associated with uranium by using an on-line fractionation/multi-detection technique based on asymmetrical flow field-flow fractionation (As-Fl-FFF) hyphenated with UV detector, multi angle laser light scattering (MALLS) and inductively coupling plasma-mass spectrometry (ICP-MS). Moreover, thanks to the As-Fl-FFF, the different colloidal fractions were collected and characterized by a total organic carbon analyzer (TOC). Thus it is possible to determine the nature (organic or inorganic colloids), molar mass, size (gyration and hydrodynamic radii) and quantitative uranium distribution over the whole colloidal phase. In the case of the site studied, two populations are highlighted. The first population corresponds to humic-like substances with a molar mass of (1500 ± 300) g mol−1 and a hydrodynamic diameter of (2.0 ± 0.2) nm. The second one has been identified as a mix of carbonated nanoparticles or clays with organic particles (aggregates and/or coating of the inorganic particles) with a size range hydrodynamic diameter between 30 and 450 nm. Each population is implied in the colloidal transport of uranium: maximum 1% of the uranium content in soil leachate is transported by the colloids in the site studied, according to the depth in the soil. Indeed, humic substances are the main responsible of this transport in sub-surface conditions whereas nanoparticles drive the phenomenon in depth conditions. 相似文献
243.
H. Raissi A. F. Jalbout M. Yoosefian Mustapha Fazli A. Nowroozi M. Shahinin A. De Leon 《International journal of quantum chemistry》2010,110(4):821-830
The molecular structure and intramolecular hydrogen bond energies of 44 conformers of 2‐Amino methylene malonaldehyde were investigated at MP2 and B3LYP levels of theory using the standard 6‐311++G** basis set and AIM and NBO analysis. The calculated geometrical parameters and conformational analysis in gas phase show that the closed ring via intramolecular hydrogen bonded conformers of this compound are more stable than the other ones. Hydrogen bond energies for H‐bonded conformers were obtained from the related rotamers method (RRM) and Schuster method, and also the nature of H‐bonding of them has been investigated by means of the Bader theory of atoms in molecules, which is based on topological properties of the electron density. Delocalization effects can be identified from the presence of off diagonal elements of the Fock matrix in the NBO basis. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
244.
245.
为了进行硫代反义寡核苷酸药物FT19的质量控制研究,建立了用阴离子交换高效液相色谱(AX-HPLC)和毛细管凝胶电泳(CGE)分析自行合成的FT19有关物质的方法。设计合成了FT19的硫代不完全序列(P=O)1和短序列(n-x)并将它们作为已知杂质。在AX-HPLC上,使用的分析柱为DNA Pac PA-100 (4 mm×250 mm);流动相A为10 mmol/L NaOH-0.1 mol/L NaCl,流动相B为10 mmol/L NaOH-3 mol/L NaCl;梯度洗脱条件为流动相B液在8 min内从60%升至100%;流速1 mL/min;柱温40 ℃;检测波长为260 nm。CGE所用毛细管规格为内径100 μm,总长度为31 cm,有效长度为20 cm;电泳缓冲溶液为三羟甲基氨基甲烷(Tris)-硼酸-7 mol/L尿素,pH 8.5;采用电动进样,进样电压-10 kV;分离胶为250 g/L的聚丙烯酰胺;检测波长为254 nm。结果表明,FT19与硫代不完全的(P=O)1序列在AX-HPLC上能够达到基线分离,与短序列(n-1)在CGE上能达到基线分离。说明AX-HPLC和CGE联合应用能够很好地分析FT19中的有关物质。 相似文献
246.
Ieva Jokubauskaite Kristina Amaleviciute Viia Lepane Alvyra Slepetiene Jonas Slepetys Inga Liaudanskiene 《International journal of environmental analytical chemistry》2015,95(6):508-519
High-performance liquid chromatography (HPLC) with size exclusion (SEC) separation function was used to isolate and examine the molecular mass (MM) distributions and polydispersity of humic substances (HSs) and dissolved organic matter (DOM) from mineral soils and peats. The aim was to improve their detailed characterisation and to inform of their soil carbon (C) sequestration and environmental quality. This is the first study conducted in Lithuania in which HSs and DOM, separated from two soil types, have been used to characterise soil at the molecular level. The HPLC-SEC, as a separation method, was coupled with diode-array detection (DAD), thus enabling the separation of molecular fractions. Results showed that HPLC-SEC can be used to determine the MM of HSs in soil, provided that the relation between retention time and MM is known and a suitable method for fitting the HS peak is available. The UV-spectra analysis showed that DOM has a larger MM (Mw = 2439–3436 Da), which contains more aliphatic C. The HS fraction has a smaller MM (Mw = 2776 Da), with aromatic structures that reflect a higher aromaticity. Separated fractions had characteristic MMs of humic acid (HA) and fulvic acid (FA) and DOM. The HSs separated from peat samples were characterised by higher aromaticity, humification and stability. The HSs extracted from mineral soil samples showed a higher degradability level. The results also show the MM distribution and polydispersity of HS and DOM fractions (Mw/Mn = 1.009–1.252) are relatively homogenous in both soil types. Findings confirm that chromatographic and spectrometric parameters can be used for characterisation of both HSs and DOM, and for detecting changes in organic matter quality. Moreover, they can also be used for a further understanding the C-cycle and could be applied for enhancing soil C-sequestration and informing environmental quality management. 相似文献
247.
膜生物反应器(membrane bioreactor, MBR)作为一种高效的污水处理及回用工艺,比传统的活性污泥法具有更多优势。然而,膜污染问题是限制其广泛应用的关键性问题。众多研究者已证实Fe3+能有效的改善MBR中混合液的可滤性及减缓膜污染。本文简述了MBR污泥混合液中主要污染物—胞外聚合物(extracellular polymeric substances, EPSs),并总结Fe3 在去除混合液中污染物、减缓膜污染方面的效能及其对污泥混合液的影响。最后,对Fe3 在减缓MBR膜污染的未来研究方向进行展望。 相似文献
248.
建立了同时检测血样中3,4-亚甲二氧基甲卡西酮(Methylone)、3,4-亚甲二氧基乙卡西酮(Ethylone)、4-氯甲卡西酮(4-CMC)、4-氯乙卡西酮(4-CEC)4种卡西酮类新精神活性物质的超高效液相色谱-四极杆飞行时间质谱法(UHPLC-QTOF MS/MS)。取0.5 mL血液,按体积比5∶2∶13将血液、水和乙腈混合,涡旋振荡1 min,以12 000 r/min离心15 min将蛋白沉淀,取上清液待测。采用Acquity UPLC?BEH C18色谱柱(2.1 mm×100 mm,1.7μm)分离,0.1%甲酸-水(5 mmol/L乙酸铵)和乙腈作为流动相进行梯度洗脱,采用多反应监测(MRM)模式,正离子[M+H]+扫描检测。结果表明,4种目标药物在5~500 ng/mL质量浓度范围内线性关系良好,检出限为2 ng/mL,定量下限为5 ng/mL,回收率为87.3%~111%,日内和日间相对标准偏差分别不大于8.1%和8.6%。该方法可同时检测血样中4种卡西酮类新精神活性物质,满足实际检验需要。 相似文献
249.
An on-line sample stacking method, namely field-amplified sample injection, has been developed for the separation and determination of carnosine, anserine, and homocarnosine by capillary electrophoresis. Using electrokinetic injection, about 130- to 160-fold improvement of sensitivity was achieved without loss of separation efficiency when compared to conventional sample injection. For conventional injection, the samples were dissolved in running buffer and then hydrodynamically injected for 10 s (3.45 kPa). Various parameters affecting separation and sample stacking were optimized. Under optimum conditions, linear responses were obtained over two orders of magnitude and the detection limits (defined as S/N = 3) of carnosine, anserine, and homocarnosine were 1.5 x 10(-8) to 1.6 x 10(-8) mol/L. 相似文献
250.
Summary The following compounds were chosen as reference substances for HPLC investigations on 4-(6-bis(2-chloro-ethyl)amino-3-methylbenzimidazoyl(2))butyric acid (bendamustin), an antineoplastic agent of the N-lost type (synthesized or isolated from crude bendamustin): 4-(6-((2-chloroethyl)(2-hydroxyethyl)amino)-3-methylbenzimidazoyl(2))butyric acid (HP1), 4-(6-bis(2-hydroxyethyl)amino-3-methylbenzimidazoyl(2))butyric acid (HP2), ethyl-4-(6-bis(2-hydroxyethyl)amino-3-methylbenzimidazoyl(2))butyrate (dihydroxyester), and ethyl-4-(6-bis(2-chloroethyl)amino-3-methylbenzimidazoyl(2))butyrate (dichloroester). Furthermore, the so far unidentified side product 4-(7,8-dihydro-6-(2-chloroethylamino)-3-methyl-1,4-thiazino[3,2-g]benzimidazoyl(2))-butyric acid (NP1), formed in the last step of the synthesis, was isolated and identified.
Untersuchungen zur Stabilität von Bendamustin, einem Cytostatikum vom N-Lost-Typ, 1. Mitt.: Synthese, Isolierung und Charakterisierung von Vergleichssubstanzen
Zusammenfassung Die folgenden Verbindungen wurden als Vergleichssubstanzen für HPLC-analytische Untersuchungen von 4-(6-Bis(2-chlorethyl)amino-3-methylbenzimidazoyl(2))buttersäure (Bendamustin), einem Antitumormittel des N-lost-Typs, synthetisiert oder aus Bendamustin-Rohstoff vor der Endreinigung isoliert: (4-(6-((2-Chlorethyl)(2-hydroxyethyl)amino)-3-methylbenzimidazoyl(2))buttersäure (HP1), 4-(6-Bis(2-hydroxyethyl)amino-3-methylbenzimidazoyl(2))buttersäure (HP2), 4-(6-Bis(2-hydroxyethyl)amino-3-methylbenzimidazoyl(2))buttersäureethylester (Dichlorester). Weiterhin konnte das bislang unbekannte Nebenprodukt 4-(7,8-Dihydro-6-(2-chlorethylamino)-3-methyl-1,4-thiazino[3,2-g]benzimidazoyl(2))buttersäure (NP1), welches sich im letzten Schritt der Synthese bildet, isoliert und identifiziert werden.相似文献