全文获取类型
收费全文 | 2642篇 |
免费 | 101篇 |
国内免费 | 6篇 |
专业分类
化学 | 2161篇 |
晶体学 | 14篇 |
力学 | 25篇 |
数学 | 275篇 |
物理学 | 274篇 |
出版年
2024年 | 3篇 |
2023年 | 26篇 |
2022年 | 75篇 |
2021年 | 83篇 |
2020年 | 60篇 |
2019年 | 57篇 |
2018年 | 29篇 |
2017年 | 31篇 |
2016年 | 83篇 |
2015年 | 92篇 |
2014年 | 94篇 |
2013年 | 155篇 |
2012年 | 188篇 |
2011年 | 209篇 |
2010年 | 124篇 |
2009年 | 115篇 |
2008年 | 207篇 |
2007年 | 209篇 |
2006年 | 163篇 |
2005年 | 160篇 |
2004年 | 110篇 |
2003年 | 103篇 |
2002年 | 70篇 |
2001年 | 19篇 |
2000年 | 36篇 |
1999年 | 22篇 |
1998年 | 13篇 |
1997年 | 19篇 |
1996年 | 17篇 |
1995年 | 12篇 |
1994年 | 9篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 7篇 |
1990年 | 10篇 |
1989年 | 3篇 |
1988年 | 9篇 |
1987年 | 12篇 |
1986年 | 12篇 |
1985年 | 18篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 6篇 |
1981年 | 8篇 |
1980年 | 5篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 2篇 |
排序方式: 共有2749条查询结果,搜索用时 15 毫秒
101.
Patrick Achenbach Sebastian Bleser Josef Pochodzalla Alicia Sanchez Lorente Marcel Steinen 《Hyperfine Interactions》2012,208(1-3):99-104
Samples obtained as a result of the valleriite synthesis process under different conditions (temperature and proportion Cu:Fe:Mg in the initial mixture) were investigated by 57Fe M?ssbauer spectroscopy with attraction data of X-ray diffraction. Parameters of hyperfine interactions for valleriite were determined and crystal chemical identification of 57Fe subspectra was carried out. It was found that valleriite was formed in samples synthesized at 150°C and 180°C and not formed in samples synthesized at 250°C. 相似文献
102.
Elionai Cassiana de Lima Gomes Izabella Ercole de Carvalho Silvia Ligório Fialho Jamile Barbosa Maria Irene Yoshida Armando da Silva Cunha Júnior 《Journal of Thermal Analysis and Calorimetry》2018,131(3):2123-2128
Most of the pharmaceutical products are formulated as solid dosage form, which may present drug–excipient interactions that lead to changes in the chemical nature of the drug, such as solubility and bioavailability and may compromise its safety and effectiveness. Differential scanning calorimetry (DSC) is a widely used method for the rapid evaluation of the drug-excipient compatibility and the stability of the mixture formed; however, there is no consensus on the preparation methods of the drug–excipient mixtures. The aim of this study was to investigate the influence of the mixing method on the drug–excipient compatibility studies by means of DSC analysis, using tenofovir disoproxil fumarate as a drug model. Statistical analysis revealed significant differences in the heat of fusion of the drug in the mixtures prepared by several mixing methods. Vortex Mixer with a Pop-Off Cup used for 3 min proved to be very satisfactory for these studies. A polymorphic transition was observed in the mixture prepared with the mortar and pestle. Therefore, this method should be avoided since it may induce errors in the interpretation of DSC results. In this way, the mixing method used to prepare a mixture for studies of interactions between the API and the excipients in a pharmaceutical formulation has a great influence on the results and it must be chosen carefully. 相似文献
103.
Roberta Seraglia Giovanni Sartore Raffaella Marin Silvia Burlina Enzo Manzato Eugenio Ragazzi Pietro Traldi Annunziata Lapolla 《Journal of mass spectrometry : JMS》2013,48(1):105-110
Increased oxidation of low density lipoprotein (LDL) is characteristic of atherosclerosis. In this frame, high density lipoproteins (HDL) play an important role, being able to remove lipid peroxides (LPOs) and cholesterol from oxidized LDL, so exhibiting a protective role against atherosclerosis. A wide range of reactive compounds lead to the oxidation of methionine (Met) residues with the formation of methionine sulphoxide (MetO) in apolipoprotein A‐I (ApoA‐I). Consequently, the determination of MetO level can give both an evaluation of oxidative stress and the reduced capability of ApoA‐I in LPOs and cholesterol transport. For these reasons, the development of analytical methods able to determine the MetO level is surely of interest, and we report here the results obtained by MALDI mass spectrometry. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
104.
Nora Jannsen Dr. Stefano Diodati Nicola Dengo Francesca Tajoli Dr. Nicola Vicentini Dr. Giacomo Lucchini Prof. Adolfo Speghini Prof. Denis Badocco Prof. Paolo Pastore Prof. Silvia Gross 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(59):13624-13634
The aim of this work was i) to develop a hydrothermal, low-temperature synthesis protocol affording the upconverting hexagonal phase NaYF4 with suitable dopants while adhering to the “green chemistry” standards and ii) to explore the effect that different parameters have on the products. In optimizing the synthesis protocol, short reaction times and low temperatures (below 150 °C) were considered. Yb3+ and Er3+ ions were chosen as dopants for the NaYF4 material. Within the context of the second goal, parameters including nature of the precursors, treatment temperature, and treatment time were investigated to afford a pure hexagonal crystalline phase, both in the doped and undoped materials. To fully explore the synthesis results, the prepared materials were characterized from a structural (XRD), compositional (XPS, ICP-MS), and morphological (SEM) point of view. The upconverting properties of the compounds were confirmed by photoluminescence measurements. 相似文献
105.
Kate Lauder Silvia Anselmi Dr. James D. Finnigan Dr. Yuyin Qi Dr. Simon J. Charnock Dr. Daniele Castagnolo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(46):10422-10426
The enantioselective synthesis of α-thiocarboxylic acids by biocatalytic dynamic kinetic resolution (DKR) of nitrile precursors exploiting nitrilase enzymes is described. A panel of 35 nitrilase biocatalysts were screened and enzymes Nit27 and Nit34 were found to catalyse the DKR of racemic α-thionitriles under mild conditions, affording the corresponding carboxylic acids with high conversions and good-to-excellent ee. The ammonia produced in situ during the biocatalytic transformation favours the racemization of the nitrile enantiomers and, in turn, the DKR without the need of any external additive base. 相似文献
106.
Numerical Algorithms - This paper describes a new MATLAB software package of iterative regularization methods and test problems for large-scale linear inverse problems. The software package, called... 相似文献
107.
Prof. Dr. Mateo Alajarin Dr. Raul‐Angel Orenes Prof. Dr. Judith A. K. Howard Dr. Elinor C. Spencer Prof. Dr. Jonathan W. Steed Dr. Aurelia Pastor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(8):2389-2397
Tris(2‐ and 3‐ureidobenzyl)amines with Cs symmetry self‐assemble in solution forming mixtures of regioisomeric capsular aggregates, one of which is chiral and the other centrosymmetric. Under certain conditions, a predominance of the centrosymmetric regioisomer is found before equilibrium, that is, a mixture close to the statistical ratio of the two species is reached. In the solid state, there is a preference for the centrosymmetric capsules. Molecular models of both regioisomeric aggregates have been built and analyzed for comparison. Guests inside capsules formed by self‐assembly of desymmetrized tris(3‐ureidobenzyl)amines feel different magnetic environments, depending on whether they are inside a chiral or an achiral regioisomeric container. Of special significance are the experiments with a more flexible triurea endowed with an ureidopropylic arm, which self‐assembles with the same efficiency as the more rigid tris(ureidobenzyl)amines. 相似文献
108.
Abstract The ability of macrocyclic polyethers to activate enolates has been studied in the alkylation of de-oxybenzoin (1) with butyl derivatives nBuY (Y = Br, I, OMes) catalyzed by crown ether PHDB18C6 (7) or cryptand [2.2.2,C10] (8) under phase-transfer catalysis (PTC) and homogeneous (chlorobenzene) conditions. The enolate reactivity is mainly determined by the ligand (cryptand > crown ether) and solvent (increasing with the polarity, in the order: toluene < chlorobenzene < 1,2dichlorobenzene). Regioselectivity of the reaction is also remarkably affected by ligand and alkylating agent. 相似文献
109.
Dendrimers are macromolecules characterized by high controlled size, shape and architecture, presence of inner cavities able to accommodate small molecules and many peripheral functional groups to bind target entities. They are of eminent interest for biomedical applications, including gene transfection, tissue engineering, imaging, and drug delivery. The well-known pharmacological activities of ursolic and oleanolic acids are limited by their small water solubility, non-specific cell distribution, low bioavailability, poor pharmacokinetics, and their direct administration could result in the release of thrombi. To overcome such problems, in this paper we described their physical incorporation inside amino acids-modified polyester-based dendrimers which made them highly water-soluble. IR, NMR, zeta potential, mean size of particles, buffer capacity and drug release profiles of prepared materials were reported. The achieved water-soluble complexes harmonize a polycationic character and a buffer capacity which presuppose efficient cell penetration and increased residence time with a biodegradable cell respectful scaffold, thus appearing as a promising team of not toxic prodrugs for safe administration of ursolic and oleanolic acids. 相似文献
110.
Development of a syn‐Selective Mannich Reaction of Aldehydes with Propargylic Imines by Dual Catalysis: Asymmetric Synthesis of Functionalized Propargylic Amines
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Irati Lapuerta Dr. Silvia Vera Prof. Mikel Oiarbide Prof. Claudio Palomo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(21):7229-7237
Direct coupling of enolizable aldehydes with C‐alkynyl imines is realized affording the corresponding propargylic Mannich adducts of syn configuration, thus complementing previous methods that gave access to the anti‐isomers. The combination of proline and a urea Brønsted base cocatalyst is key for the reactions to proceed under very mild conditions (3–10 mol % catalyst loading, dichloromethane as solvent, ?20 °C, 1.2 molar equivalents of aldehyde) and with virtually total stereocontrol (syn/anti ratio up to 99:1; ee up to 99 %). Some possibilities of further chemical elaboration of adducts are also briefly illustrated. 相似文献