全文获取类型
收费全文 | 1496篇 |
免费 | 66篇 |
国内免费 | 7篇 |
专业分类
化学 | 914篇 |
晶体学 | 7篇 |
力学 | 72篇 |
数学 | 362篇 |
物理学 | 214篇 |
出版年
2023年 | 10篇 |
2022年 | 19篇 |
2021年 | 46篇 |
2020年 | 54篇 |
2019年 | 21篇 |
2018年 | 32篇 |
2017年 | 24篇 |
2016年 | 69篇 |
2015年 | 62篇 |
2014年 | 79篇 |
2013年 | 83篇 |
2012年 | 99篇 |
2011年 | 124篇 |
2010年 | 85篇 |
2009年 | 64篇 |
2008年 | 100篇 |
2007年 | 89篇 |
2006年 | 65篇 |
2005年 | 67篇 |
2004年 | 54篇 |
2003年 | 44篇 |
2002年 | 36篇 |
2001年 | 20篇 |
2000年 | 11篇 |
1999年 | 15篇 |
1998年 | 9篇 |
1997年 | 14篇 |
1996年 | 16篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 6篇 |
1988年 | 9篇 |
1987年 | 7篇 |
1986年 | 8篇 |
1985年 | 11篇 |
1984年 | 7篇 |
1983年 | 8篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1875年 | 3篇 |
1873年 | 2篇 |
1870年 | 3篇 |
1869年 | 2篇 |
1868年 | 2篇 |
1858年 | 3篇 |
排序方式: 共有1569条查询结果,搜索用时 15 毫秒
71.
72.
73.
Organic‐acid mediated bulk polymerization of ε‐caprolactam and its copolymerization with ε‐caprolactone 下载免费PDF全文
Ana Sanchez‐Sanchez Andere Basterretxea Daniele Mantione Agustin Etxeberria Cristina Elizetxea Amaia de la Calle Sonia García‐Arrieta Haritz Sardon David Mecerreyes 《Journal of polymer science. Part A, Polymer chemistry》2016,54(15):2394-2402
Polyamides (PA) constitute one of the most important classes of polymeric materials and have gained strong position in different areas, such as textiles, fibers, and construction materials. Whereas most PA are synthesized by step‐growth polycondensation, PA 6 is synthesized by ring opening polymerization (ROP) of ε‐caprolactam (ε‐CLa). The most popular ROP methods involve the use of alkaline metal catalyst difficult to handle at large scale. In this article, we propose the use of organic acids for the ROP of ε‐CLa in bulk at 180 °C (below the polymer's melting point). Among evaluated organic acids, sulfonic acids were found to be the most effective for the polymerization of ε‐CLa , being the Brønsted acid ionic liquid: 1‐(4‐sulfobutyl)?3‐methylimidazolium hydrogen sulfate the most suitable due to its higher thermal stability. End‐group analysis by 1H nuclear magnetic resonance and model reactions provided mechanistic insights and suggested that the catalytic activity of sulfonic acids was a function of not only the acid strength, but of the nucleophilic character of conjugate base as well. Finally, the ability of sulfonic acid to promote the copolymerization of ε‐CLa and ε‐caprolactone is demonstrated. As a result, poly(ε‐caprolactam‐co‐ε‐caprolactone) copolymers with considerably randomness are obtained. This benign route allows the synthesis of poly(ester amide)s with different thermal and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2394–2402 相似文献
74.
75.
76.
77.
Roger Fosdick Pilade Foti Aguinaldo Fraddosio Mario Daniele Piccioni 《Continuum Mechanics and Thermodynamics》2010,22(2):77-97
We determine lower bound estimates for the critical load for hyperelastic solids under monotonic dead load processes. By considering
the Hadamard criterion of infinitesimal stability, we first determine a lower bound for the Hadamard stability functional;
then, we develop a procedure for optimal lower bound estimates for the critical load. As examples, we apply our procedure
to generalized Blatz-Ko solids under simple extension, simple compression and rectilinear shear, and compare our results with
other proposals contained in the literature. 相似文献
78.
A methodology for the determination of bismuth, based on under-potential deposition-stripping voltammetry (UPD-SV), was investigated. It makes use of mesoporous platinum microelectrodes (Pt-MEs) prepared by a liquid crystal templating technique. The mesoporous microelectrodes, which are characterised by a very high surface area, allowed the accumulation of relatively large amounts of bismuth at under-potential without saturation of the electrode surface. Calibration plots for quantification of bismuth at micromolar levels were constructed by using the charge involved in either the anodic or cathodic peak recoded by cyclic voltammetry that ensued the accumulation of bismuth at the electrode surface. During the anodic scan, the oxidation of metallic bismuth occurred; the cathodic scan involved irreversibly adsorbed bismuth species, which are retained on to the electrode surface. The reproducibility of the proposed UPD-SV procedure (which was within 5 %) was assured by the application to the Pt-MEs of a suitable potential waveform, properly designed to avoid memory effect due to the irreversibly deposited bismuth. The latter phenomenon along with UPD allowed to overcome interference due to copper, which is normally observed when quantification of bismuth is performed by anodic stripping voltammetry at solid electrodes involving bulk metal deposits. The usefulness of the proposed method for the determination of bismuth in real samples was demonstrated by the analysis of a tablet of a pharmaceutical preparation, which is used for curing ulcers. 相似文献
79.
Marco Vincenti Daniele Cavanna Enrico Gerace Valentina Pirro Michele Petrarulo Daniele Di Corcia Alberto Salomone 《Analytical and bioanalytical chemistry》2013,405(2-3):863-879
Forensic investigations involving acute or lethal intoxication, drug-facilitated sexual assault, driving or workplace impairment frequently require the analysis of fresh or postmortem blood samples to check out a wide variety of pharmaceutical and illicit drugs, even after single-dose consumption. A sensitive and selective ultrahigh-performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) screening method was developed for fast screening of 88 psychoactive drugs and metabolites in blood samples, including the ones most frequently involved in acute intoxications and forensic investigations in Italy. The new method allows short sample processing and analysis time (the whole procedure can be accomplished in less than 30 min) together with the simultaneous monitoring of a large number of pharmaceutical substances. These features represent crucial factors in the approach of acute intoxications, when the patient requires urgent and appropriate therapy. Blood sample treatment was limited to protein precipitation. Two UHPLC–MS/MS runs in positive and negative electrospray ionization modes were performed. The data were acquired at unit mass resolution in the selected reaction monitoring mode. According to international guidelines, linearity range, precision, trueness, detection and quantification limits, recovery, selectivity, specificity, carryover, and matrix effect phenomena were determined. Despite the limited sample purification and the inherent decreased chance of eliminating any potential interference, the present multiresidue screening method proved extremely effective and sensitive, allowing the detection of all tested drugs, even those belonging to structurally different classes of substances. Moreover, the developed method is easily susceptible to further expansion to encompass more drugs, either new or those becoming important for criminal investigation. This protocol was also applied to the analysis of authentic blood samples collected from victims of various crimes in routine casework, whose relevance in forensic investigations is presented in five cases. 相似文献
80.
Patrizia Scafato Francesca Caprioli Laura Pisani Daniele Padula Fabrizio Santoro Giuseppe Mazzeo Sergio Abbate France Lebon Giovanna Longhi 《Tetrahedron》2013
Three forms of chiroptical spectroscopies, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and optical rotatory dispersion (ORD) have been employed to study the configuration and conformational properties of the three molecules: (S)-3-phenylcyclopentanone, (S)-3-phenylcyclohexanone, and (S)-3-phenylcycloheptanone (including (S)-3-phenylcyclopentanone-2,2,5,5-d4 and (S)-3-phenylcyclohexanone-2,2,6,6-d4). ECD and VCD spectra in the mid-IR for the three molecular systems are marginally dependent on fine conformational details, as interpreted in terms of standard DFT computational methods, with common spectroscopic features to the three systems clearly identified. Accounting for vibronic coupling mechanisms reproduces the structuring of ECD n→π∗ band. The ORD curves are quite similar for the three types of molecules, but their interpretation highlights a crucial role played by conformations of the cycloalkanone ring in the case of (S)-3-phenylcycloheptanone. The same conclusions are reached by considering the VCD spectra in the CH-stretching region. 相似文献