全文获取类型
收费全文 | 1907篇 |
免费 | 85篇 |
国内免费 | 8篇 |
专业分类
化学 | 1386篇 |
晶体学 | 19篇 |
力学 | 74篇 |
数学 | 290篇 |
物理学 | 231篇 |
出版年
2023年 | 20篇 |
2022年 | 37篇 |
2021年 | 42篇 |
2020年 | 55篇 |
2019年 | 40篇 |
2018年 | 31篇 |
2017年 | 25篇 |
2016年 | 55篇 |
2015年 | 49篇 |
2014年 | 68篇 |
2013年 | 117篇 |
2012年 | 127篇 |
2011年 | 169篇 |
2010年 | 74篇 |
2009年 | 77篇 |
2008年 | 132篇 |
2007年 | 130篇 |
2006年 | 106篇 |
2005年 | 109篇 |
2004年 | 93篇 |
2003年 | 95篇 |
2002年 | 103篇 |
2001年 | 21篇 |
2000年 | 15篇 |
1999年 | 21篇 |
1998年 | 25篇 |
1997年 | 26篇 |
1996年 | 21篇 |
1995年 | 14篇 |
1994年 | 12篇 |
1993年 | 10篇 |
1992年 | 9篇 |
1991年 | 7篇 |
1989年 | 9篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 9篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1895年 | 1篇 |
1887年 | 2篇 |
排序方式: 共有2000条查询结果,搜索用时 15 毫秒
81.
Nada Marquise Philip J. Harford Floris Chevallier Thierry Roisnel Vincent Dorcet Anne-Laure Gagez Sophie Sablé Laurent Picot Valérie Thiéry Andrew E.H. Wheatley Philippe C. Gros Florence Mongin 《Tetrahedron》2013
The efficiency of the deprotocupration–aroylation of 2-chloropyridine using lithiocuprates prepared from CuX (X=Cl, Br) and LiTMP (TMP=2,2,6,6-tetramethylpiperidido, 2 equiv) was investigated. CuCl was identified as a more suitable copper source than CuBr for this purpose. Different diaryl ketones bearing a halogen at the 2 position of one of the aryl groups were synthesized in this way from azines and thiophenes. These were then involved in palladium-catalyzed ring closure: substrates underwent expected CH-activation-type arylation to afford fluorenone-type compounds, and were also subjected to cyclization reactions leading to xanthones, notably in the presence of oxygen-containing substituents or reagents. 相似文献
82.
Dr. Chih‐Kai Liang Dr. Galina V. Dubacheva Dr. Thierry Buffeteau Dr. Dominique Cavagnat Dr. Philippe Hapiot Dr. Bruno Fabre Prof. James H. R. Tucker Dr. Dario M. Bassani 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12748-12758
The synthesis of an anthracene‐bearing photoactive barbituric acid receptor and its subsequent grafting onto azide‐terminated alkanethiol/Au self‐assembled monolayers by using an CuI‐catalyzed azide–alkyne reaction is reported. Monolayer characterization using contact‐angle measurements, electrochemistry, and spectroscopic ellipsometry indicate that the monolayer conversion is fast and complete. Irradiation of the receptor leads to photodimerization of the anthracenes, which induces the open‐to‐closed gating of the receptor by blocking access to the binding site. The process is thermally reversible, and polarization‐modulated IR reflection–absorption spectroscopy indicates that photochemical closure and thermal opening of the surface‐bound receptors occur in 70 and 100 % conversion, respectively. Affinity of the open and closed surface‐bound receptor was characterized by using force spectroscopy with a barbituric‐acid‐modified atomic force microscope tip. 相似文献
83.
Dr. Stéphane Le Gac Dr. Btissam Najjari Dr. Vincent Dorcet Dr. Thierry Roisnel Dr. Luca Fusaro Prof. Dr. Michel Luhmer Dr. Eric Furet Dr. Jean‐François Halet Dr. Bernard Boitrel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):11021-11038
Overhanging carboxylic acid porphyrins have revealed promising ditopic ligands offering a new entry in the field of supramolecular coordination chemistry of porphyrinoids. Notably, the adjunction of a so‐called hanging‐atop (HAT) PbII cation to regular PbII porphyrin complexes allowed a stereoselective incorporation of the N‐core bound cation, and an allosterically controlled Newton’s cradle‐like motion of the two PbII ions also emerged from such bimetallic complexes. In this contribution, we have extended this work to other ligands and metal ions, aiming at understanding the parameters that control the HAT PbII coordination. The nature of the N‐core bound metal ion (ZnII, CdII), the influence of the deprotonation state of the overhanging COOH group and the presence of a neutral ligand on the opposite side (exogenous or intramolecular), have been examined through 1H NMR spectroscopic experiments with the help of radiocrystallographic structures and DFT calculations. Single and bis‐strap ligands have been considered. They all incorporate a COOH group hung over the N‐core on one side. For the bis‐strap ligands, either an ester or an amide group has been introduced on the other side. In the presence of a base, the mononuclear ZnII or CdII complexes incorporate the carbonyl of the overhanging carboxylate as apical ligand, decreasing its availability for the binding of a HAT PbII. An allosteric effector (e.g., 4‐dimethylaminopyridine (DMAP), in the case of a single‐strap ligand) or an intramolecular ligand (e.g., an amide group), strong enough to compete with the carbonyl of the hung COO?, is required to switch the N‐core bound cation to the opposite side with concomitant release of the COO?, thereby allowing HAT PbII complexation. In the absence of a base, ZnII or CdII binds preferentially the carbonyl of the intramolecular ester or amide groups in apical position rather than that of the COOH. This better preorganization, with the overhanging COOH fully available, is responsible for a stronger binding of the HAT PbII. Thus, either allosteric or acid–base control is achieved through stereoselective metalation of ZnII or CdII. In the latter case, according to the deprotonation state of the COOH group, the best electron‐donating ligand is located on one or the other side of the porphyrin (COO?>CONHR>COOR>COOH): the lower affinity of COOH for ZnII and CdII, the higher for a HAT PbII. These insights provide new opportunities for the elaboration of innovative bimetallic molecular switches. 相似文献
84.
On doubling metric measure spaces endowed with a strongly local regular Dirichlet form, we show some characterisations of pointwise upper bounds of the heat kernel in terms of global scale-invariant inequalities that correspond respectively to the Nash inequality and to a Gagliardo–Nirenberg type inequality when the volume growth is polynomial. This yields a new proof and a generalisation of the well-known equivalence between classical heat kernel upper bounds and relative Faber–Krahn inequalities or localised Sobolev or Nash inequalities. We are able to treat more general pointwise estimates, where the heat kernel rate of decay is not necessarily governed by the volume growth. A crucial role is played by the finite propagation speed property for the associated wave equation, and our main result holds for an abstract semigroup of operators satisfying the Davies–Gaffney estimates. 相似文献
85.
Petra Krystek Jutta Tentschert Yacine Nia Benedicte Trouiller Laurent Noël Mario E. Goetz Arnaud Papin Andreas Luch Thierry Guérin Wim H. de Jong 《Analytical and bioanalytical chemistry》2014,406(16):3853-3861
Nanosized titanium dioxide (TiO2) is one of the most interesting and valuable nanomaterials for the construction industry but also in health care applications, food, and consumer goods, e.g., cosmetics. Therefore, the properties associated with this material are described in detail. Despite its widespread use, the analytical determination and characterization of nanosized metal oxides is not as straightforward as the comparatively easy-to-detect metallic nanoparticles (e.g., silver or gold). This study presents the method development and the results of the determination of tissue titanium (Ti) levels after treatment of rats with the nanosized TiO2. Total Ti levels were chosen to evaluate the presence and distribution of TiO2 nanoparticles. A procedure consisting of incubation with a mixture of nitric acid (HNO3) and hydrofluoric acid (HF), and heating was developed to digest tissues and TiO2 nanomaterials in order to determine the total Ti content by inductively coupled plasma mass spectrometry (ICPMS). For the inter-laboratory comparison, altogether four laboratories analyzed the same samples upon digestion using the available ICPMS equipment. A major premise for any toxicokinetic study is the possibility to detect the chemical under investigation in biological samples (tissues). So, the study has to be performed with a dose high enough to allow for subsequent tissue level measurement of the chemical under investigation. On the other hand, dose of the chemical applied should not induce over toxicity in the animal as this may affect its absorption, distribution, metabolism, and excretion. To determine a non-toxic TiO2 dosage, an acute toxicity study in rats was performed, and the organs obtained were evaluated for the presence of Ti by ICPMS. Despite the differences in methodology and independent of the sample preparation and the ICPMS equipment used, the results obtained for samples with Ti concentrations >4 μg Ti/g tissue agreed well. Figure
Major Ti concentrations in micrograms per gram of organ as determined by different laboratories. 相似文献
86.
87.
88.
Thierry Moreno 《Journal of synchrotron radiation》2015,22(5):1163-1169
Synchrotron infrared beamlines are powerful tools on which to perform spectroscopy on microscopic length scales but require working with large bending‐magnet source apertures in order to provide intense photon beams to the experiments. Many infrared beamlines use a single toroidal‐shaped mirror to focus the source emission which generates, for large apertures, beams with significant geometrical aberrations resulting from the shape of the source and the beamline optics. In this paper, an optical layout optimized for synchrotron infrared beamlines, that removes almost totally the geometrical aberrations of the source, is presented and analyzed. This layout is already operational on the IR beamline of the Brazilian synchrotron. An infrared beamline design based on a SOLEIL bending‐magnet source is given as an example, which could be useful for future IR beamline improvements at this facility. 相似文献
89.
Camille Flament Joël Ribis Jérôme Garnier Thierry Vandenberghe Jean Henry Alexis Deschamps 《哲学杂志》2015,95(8):906-917
The age hardening 6061-T6 aluminium alloy has been chosen as structural material for the core vessel of the material testing Jules Horowitz nuclear reactor. The alloy contains incoherent Al(Cr, Fe, Mn)Si dispersoids whose characterization by energy-filtered transmission electron microscopy (EFTEM) analysis shows a core/shell organization tendency where the core is (Mn, Fe) rich, and the shell is Cr rich. The present work studies the stability of this organization under irradiation. TEM characterization on the same particles, before and after 1 MeV electron irradiation, reveals that the core/shell organization is enhanced after irradiation. It is proposed that the high level of point defects, created by irradiation, ensures a radiation-enhanced diffusion process favourable to the unmixing forces between (Fe, Mn) and Cr. Shell formation may result in the low-energy interface segregation of Cr atoms within the (Fe, Mn) system combined with the unmixing of Cr, Fe and Mn components. 相似文献
90.
Contribution of Cytosine‐Containing Cyclobutane Dimers to DNA Damage Produced by Photosensitized Triplet–Triplet Energy Transfer 下载免费PDF全文
Dr. Thierry Douki Izabel Bérard Aude Wack Sigrid Andrä 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(19):5787-5794
Mutagenic cyclobutane pyrimidine dimers (CPDs) can be induced in DNA through either direct excitation or photosensitized triplet–triplet energy transfer (TTET). In the latter pathway, thymines are expected to receive the excitation energy from the photosensitizer and react with adjacent pyrimidines. By using state‐of‐the art analytical tools, we provide herein additional information on the formation of cytosine‐containing CPDs. We thus determined the yield of all possible CPDs upon TTET in a series of natural DNAs with various base compositions. We show that the distribution of CPDs cannot be explained only by excitation of individual thymines. We propose that the mechanism for TTET involves at least dinucleotides as the minimal targets. The observation of the formation of cytosine–cytosine CPDs also suggests that additional pathways are involved in this photosensitized reaction. 相似文献