全文获取类型
收费全文 | 1920篇 |
免费 | 71篇 |
国内免费 | 8篇 |
专业分类
化学 | 1385篇 |
晶体学 | 19篇 |
力学 | 74篇 |
数学 | 290篇 |
物理学 | 231篇 |
出版年
2023年 | 19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1999条查询结果,搜索用时 0 毫秒
991.
Anne J. Rüger Joshua Kramer Stefan Seifermann Mark Busch Thierry Muller Stefan Brse 《Chemie in Unserer Zeit》2012,46(5):294-301
We may “live in a material world” as claimed by Madonna but we definitely evolve in a chiral one. As we are born into a chiral environment, where a lot of objects are not identical with their mirror images, we most naturally and often unconsciously adapt to it. It is only when one exchanges for example the corkscrewer by its left‐handed counterpart that we actually notice that something is not as usual. We will – supported by six practical experiments – explain to you and guide you through the fascinating world of chirality. 相似文献
992.
Elisabeth Nagaradja Floris Chevallier Thierry Roisnel Viatcheslav Jouikov Florence Mongin 《Tetrahedron》2012,68(14):3063-3073
The deprotonation of 2-methoxypyridine was attempted using putative (TMP)3FeLi prepared from different iron sources. Using iodine to intercept the metalated 2-methoxypyridine, the best result was obtained from FeBr2 (1 equiv) using THF at room temperature; nevertheless, in addition to the expected iodide, the corresponding 2,2′-dimer was obtained (86% total yield). The origin of the competitive formation of the 2,2′-dimer was not identified but mechanisms were suggested to explain its formation. It was observed that the nature of the electrophile employed to trap the 3-metalated 2-methoxypyridine has a strong impact on this dimer formation, the latter being favored using iodine (35% yield), but also benzophenone (28%), benzoyl chloride (22%), methyl iodide (27%), allyl bromide (15%), benzyl bromide (41%), and tetramethylthiuram disulphide (36%); for this reason, the yields of the expected derivatives were only 51, 15, 62, 0, <5, 18, and 0%, respectively. In contrast, using aldehydes readily led to the expected pyridine alcohols without dimerization (59% yield using 3,4,5-trimethoxybenzaldehyde and 66% yield using pivalaldehyde). 2,6-Dimethoxypyridine (in 68% yield), anisole (47%), 2,4-dimethoxypyrimidine (50% at C5 and 3% at C6), 2-fluoropyridine (64%), and thiophene (49%) were similarly converted into the corresponding alcohols after subsequent trapping with pivalaldehyde. Using iodine to trap the 2-metalated anisole did not lead to dimer formation, and 2-iodoanisole was isolated in 71% yield. 相似文献
993.
Jacquemet A Mériadec C Lemiègre L Artzner F Benvegnu T 《Langmuir : the ACS journal of surfaces and colloids》2012,28(20):7591-7597
The relative stereochemistry (cis or trans) of a 1,3-disubstituted cyclopentane unit in the middle of tetraether archaeal bipolar lipid analogues was found to have a dramatic influence on their supramolecular self-assembly properties. SAXS studies of two synthetic diastereomeric archaeal lipids bearing two lactosyl polar head groups at opposite ends revealed different lyotropic behaviors. The cis isomer led to L(c)-L(α)-Q(II) transitions whereas the trans isomer retained an L(α) phase from 20 to 100 °C. These main differences originate from the conformational equilibrium (pseudorotation) of 1,3-disubstituted cyclopentanes. Indeed, this pseudorotation exhibits quite similar orientations of the two substituents in a trans isomer whereas several orientations of the two alkyl chains are expected in a cis-1,3-dialkyl cyclopentane, thus authorizing more conformational flexibility in the lipid packing. 相似文献
994.
Dr. Gaëlle Malik Dr. Anna Natangelo Prof. Jaime Charris Dr. Laurent Pouységu Prof. Stefano Manfredini Dr. Dominique Cavagnat Dr. Thierry Buffeteau Dr. Denis Deffieux Prof. Stéphane Quideau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(29):9063-9074
C‐glucosidic ellagitannins constitute a subclass of bioactive polyphenolic natural products with strong antioxidant properties, as well as promising antitumoral and antiviral activities that are related to their capacity to interact with both functional and structural proteins. To date, most synthetic efforts toward ellagitannins have concerned glucopyranosic species. The development of a synthetic strategy to access C‐glucosidic ellagitannins, whose characteristic structural feature includes an atropoisomeric hexahydroxydiphenoyl (HHDP) or a nonahydroxyterphenoyl (NHTP) unit that is linked to an open‐chain glucose core by a C‐aryl glucosidic bond, is described herein. The total synthesis of the biarylic HHDP‐containing 5‐O‐desgalloylepipunicacortein A ( 1 β ) was achieved by either using the natural ellagic acid bis‐lactone as a precursor of the requested HHDP unit or by implementing an atroposelective intramolecular oxidative biarylic coupling to forge this HHDP unit. Both routes converged in the penultimate step of this synthesis to enable a biomimetic formation of the key C‐aryl glucosidic bond in the title compound. 相似文献
995.
Erwann Bocquillon Vincent Freulon François D. Parmentier Jean‐Marc Berroir Bernard Plaçais Claire Wahl Jérome Rech Thibaut Jonckheere Thierry Martin Charles Grenier Dario Ferraro Pascal Degiovanni Gwendal Fève 《Annalen der Physik》2014,526(1-2):1-30
The edge channels of the quantum Hall effect provide one dimensional chiral and ballistic wires along which electrons can be guided in an optics‐like setup. Electronic propagation can then be analyzed using concepts and tools derived from optics. After a brief review of electron optics experiments performed using stationary current sources which continuously emit electrons in the conductor, this paper focuses on triggered sources, which can generate on‐demand a single particle state. It first outlines the electron optics formalism and its analogies and differences with photon optics and then turns to the presentation of single electron emitters and their characterization through the measurements of the average electrical current and its correlations. This is followed by a discussion of electron quantum optics experiments in the Hanbury‐Brown and Twiss geometry where two‐particle interferences occur. Finally, Coulomb interactions effects and their influence on single electron states are considered. 相似文献
996.
Recent literature shows that the arrival and discharge processes in hospital intensive care units do not satisfy the Markovian property, that is, interarrival times and length of stay tend to have a long tail. In this paper we develop a generalised loss network framework for capacity planning of a perinatal network in the UK. Decomposing the network by hospitals, each unit is analysed with a GI/G/c/0 overflow loss network model. A two-moment approximation is performed to obtain the steady state solution of the GI/G/c/0 loss systems, and expressions for rejection probability and overflow probability have been derived. Using the model framework, the number of required cots can be estimated based on the rejection probability at each level of care of the neonatal units in a network. The generalisation ensures that the model can be applied to any perinatal network for renewal arrival and discharge processes. 相似文献
997.
Five-membered ring lactones have been synthesized using a straightforward three-component reaction among in situ-generated arylzinc reagents, dimethyl itaconate and aromatic aldehydes. This Barbier-like procedure, which is characterized by its simplicity, allows the concise synthesis of a range of highly functionalized 4,5-substituted γ-butyrolactones. 相似文献
998.
Volkringer C Loiseau T Guillou N Férey G Haouas M Taulelle F Elkaim E Stock N 《Inorganic chemistry》2010,49(21):9852-9862
A new porous metal-organic framework (MOF)-type aluminum pyromellitate (MIL-121 or Al(OH)[H(2)btec]·(guest), (guest = H(2)O, H(4)btec = pyromellitic acid) has been isolated by using a high-throughput synthesis method under hydrothermal conditions. Its structure was determined from powder X-ray diffraction analysis using synchrotron radiation (Soleil, France) and exhibits a network closely related to that of the MIL-53 series. It is a three-dimensional (3D) framework containing one-dimensional (1D) channels delimited by infinite trans-connected aluminum-centered octahedra AlO(4)(OH)(2) linked through the pyromellitate ligand. Here the organic ligand acts as tetradendate linker via two of the carboxylate groups. The two others remain non-bonded in their protonated form, and this constitutes a rare case of the occurrence of both bonding and non-bonding organic functionalities of the MOF family. The non-coordinated -COOH groups points toward the channels to get them an open form configuration. Within the tunnels are located unreacted pyromellitic acid and water species, which are evacuated upon heating, and a porous MIL-121 phase is obtained with a Brunauer-Emmett-Teller (BET) surface area of 162 m(2) g(-1). MIL-121 has been characterized by IR, thermogravimetry (TG) analyses, and solid state NMR spectroscopy employing a couple of two-dimensional (2D) techniques such as (1)H-(1)H SQ-DQ BABA, (1)H-(1)H SQ-SQ RFDR, (27)Al{(1)H} CPHETCOR and (27)Al MQMAS. 相似文献
999.
Dalila Sicupira Karol Campos Thierry Vincent Versiane Leao Eric Guibal 《Adsorption》2010,16(3):127-139
Two chitosan hydrogels (prepared by NaOH neutralization and by polyphosphate ionotropic gelation) have been tested in the
dry state for Pd(II) and Pt(IV) sorption at pH 2. Similar sorption isotherms with maximum sorption capacities close to 190 mg Pd g−1 and 235 mg Pt g−1 were achieved. The sorption mechanism involves electrostatic attraction of the chloro-anionic species onto protonated amine
groups; the drastic decrease of sorption capacity with the addition of chloride ions supports this hypothesis. SEM-EDAX analysis
suggests that sorption proceeds, in kinetic terms, through a shrinking core mechanism. Metal ions can diffuse throughout all
the sorbent volume. The main differences between the sorbents are revealed by kinetics. The hydrogels prepared by ionotropic
gelation in polyphosphate (C-PPh) allows reaching equilibrium much faster than the hydrogels prepared by the neutralization
process (C-NaOH). While for C-PPh sorbent the chemical reaction rate seems to control sorption profiles, in the case of C-NaOH
a combination of mechanisms including intraparticle diffusion resistance controls uptake kinetics. Metal desorption from loaded
sorbents is possible using thiourea alone or in association with HCl solutions. The recycling of the sorbents is possible
but for a limited number of cycles. 相似文献
1000.
Chekri R Noël L Vastel C Millour S Kadar A Guérin T 《Journal of AOAC International》2010,93(6):1888-1896
This paper describes a validation process in compliance with the NFIEN ISO/IEC 17025 standard for the determination of the macrominerals calcium, magnesium, sodium, and potassium in foodstuffs by microsampling with flame atomic absorption spectrometry after closed-vessel microwave digestion. The French Standards Commission (Agence Francaise de Normalisation) standards NF V03-110, NF EN V03-115, and XP T-90-210 were used to evaluate this method. The method was validated in the context of an analysis of the 1322 food samples of the second French Total Diet Study (TDS). Several performance criteria (linearity, LOQ, specificity, trueness, precision under repeatability conditions, and intermediate precision reproducibility) were evaluated. Furthermore, the method was monitored by several internal quality controls. The LOQ values obtained (25, 5, 8.3, and 8.3 mg/kg for Ca, Mg, Na, and K, respectively) were in compliance with the needs of the TDS. The method provided accurate results as demonstrated by a repeatability CV (CVr) of < 7% and a reproducibility CV (CVR) of < 12% for all the elements. Therefore, the results indicated that this method could be used in the laboratory for the routine determination of these four elements in foodstuffs with acceptable analytical performance. 相似文献