全文获取类型
收费全文 | 473篇 |
免费 | 18篇 |
国内免费 | 3篇 |
专业分类
化学 | 242篇 |
晶体学 | 2篇 |
力学 | 18篇 |
数学 | 132篇 |
物理学 | 100篇 |
出版年
2023年 | 3篇 |
2022年 | 5篇 |
2021年 | 10篇 |
2020年 | 10篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2017年 | 6篇 |
2016年 | 23篇 |
2015年 | 14篇 |
2014年 | 24篇 |
2013年 | 31篇 |
2012年 | 32篇 |
2011年 | 47篇 |
2010年 | 33篇 |
2009年 | 21篇 |
2008年 | 25篇 |
2007年 | 25篇 |
2006年 | 24篇 |
2005年 | 22篇 |
2004年 | 21篇 |
2003年 | 9篇 |
2002年 | 15篇 |
2001年 | 6篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 7篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有494条查询结果,搜索用时 15 毫秒
281.
Mutai C Abatis D Vagias C Moreau D Roussakis C Roussis V 《Molecules (Basel, Switzerland)》2007,12(5):1035-1044
Three new pentacyclic triterpenoids: (20R)-3-oxolupan-30-al (1), (20S)-3-oxolupan-30-al (2) and (20R)-28-hydroxylupen-30-al-3-one (3), along with (20S)-3beta-hydroxylupan-30-al (4), the latter previously described as a constituent of an epimeric mixture, were isolated from Acacia mellifera. In addition, the known metabolites 30-hydroxylup-20-(29)-en-3-one (5), 30-hydroxylup-20-(29)-en-3beta-ol (6), atranorin, methyl 2,4-dihydroxy-3,6 dimethyl benzoate, sitosterol-3beta-O-glucoside and linoleic acid were found in the analyzed plant species for the first time. The structures of the new metabolites were elucidated by extensive spectroscopic analyses and their relative stereochemistry was determined by NOESY experiments. The new metabolite 3 exhibited significant cytotoxic activity against the NSCLC-N6 cell line, derived from a human non-small-cell bronchopulmonary carcinoma. 相似文献
282.
Mohammad Khorasani Luca Lampani Rossana Dimitri Francesco Tornabene 《Molecules (Basel, Switzerland)》2021,26(21)
Due to the widespread use of sandwich structures in many industries and the importance of understanding their mechanical behavior, this paper studies the thermomechanical buckling behavior of sandwich beams with a functionally graded material (FGM) middle layer and two composite external layers. Both composite skins are made of Poly(methyl methacrylate) (PMMA) reinforced by carbon-nano-tubes (CNTs). The properties of the FGM core are predicted through an exponential-law and power-law theory (E&P), whereas an Eshelby–Mori–Tanaka (EMT) formulation is applied to capture the mechanical properties of the external layers. Moreover, different high-order displacement fields are combined with a virtual displacement approach to derive the governing equations of the problem, here solved analytically based on a Navier-type approximation. A parametric study is performed to check for the impact of different core materials and CNT concentrations inside the PMMA on the overall response of beams resting on a Pasternak substrate and subjected to a hygrothermal loading. This means that the sensitivity analysis accounts for different displacement fields, hygrothermal environments, and FGM theories, as a novel aspect of the present work. Our results could be replicated in a computational sense, and could be useful for design purposes in aerospace industries to increase the tolerance of target productions, such as aircraft bodies. 相似文献
283.
Synthesis of All‐Carbon Disubstituted Bicyclo[1.1.1]pentanes by Iron‐Catalyzed Kumada Cross‐Coupling
Jeremy Nugent Bethany R. Shire Dimitri F. J. Caputo Helena D. Pickford Frank Nightingale Ian T. T. Houlsby James J. Mousseau Edward A. Anderson 《Angewandte Chemie (International ed. in English)》2020,59(29):11866-11870
1,3‐Disubstituted bicyclo[1.1.1]pentanes (BCPs) are important motifs in drug design as surrogates for p‐substituted arenes and alkynes. Access to all‐carbon disubstituted BCPs via cross‐coupling has to date been limited to use of the BCP as the organometallic component, which restricts scope due to the harsh conditions typically required for the synthesis of metallated BCPs. Here we report a general method to access 1,3‐C‐disubstituted BCPs from 1‐iodo‐bicyclo[1.1.1]pentanes (iodo‐BCPs) by direct iron‐catalyzed cross‐coupling with aryl and heteroaryl Grignard reagents. This chemistry represents the first general use of iodo‐BCPs as electrophiles in cross‐coupling, and the first Kumada coupling of tertiary iodides. Benefiting from short reaction times, mild conditions, and broad scope of the coupling partners, it enables the synthesis of a wide range of 1,3‐C‐disubstituted BCPs including various drug analogues. 相似文献
284.
Bernard Leyh Dimitri Hautot 《Journal of the American Society for Mass Spectrometry》1995,6(11):1019-1029
The dissociation mechanisms of dichlorocarbene dications following collisional activation have been investigated via tandem mass spectrometric techniques and semi-empirical calculations. Three channels appear to be significant: {fx1019-1} The second channel becomes dominant at high internal energy. Production of ground state fragments (channel 1) involves a transition driven by spin—orbit coupling from the CCl 2 2+ $CCl_2^2 \tilde X^1 \Sigma _g^ + $ state to the CCl 2 2? ā3Σ u ? state en route to the fragments. The dissociation barrier for the production of ground state fragments from the ground electronic state of CCl 2 2+ via the spin—orbit-induced transition is equal to 420 kJ mol?1. The dissociation pathway that corresponds to channel 3 includes a first isomerization step from the linear Cl-C-Cl2+ structure to a bent Cl-Cl-C2+ connectivity. The calculated isomerization barrier amounts to 550 kJ mol?1. The calculated reverse activation barriers are compatible with the measured kinetic energy released on the fragments. 相似文献
285.
Olivier Braun Clment Coquery Johann Kieffer Frdric Blondel Cdrick Favero Cline Besset Julien Mesnager Franois Voelker Charlne Delorme Dimitri Matioszek 《Molecules (Basel, Switzerland)》2022,27(1)
Humankind is facing a climate and energy crisis which demands global and prompt actions to minimize the negative impacts on the environment and on the lives of millions of people. Among all the disciplines which have an important role to play, chemistry has a chance to rethink the way molecules are made and find innovations to decrease the overall anthropic footprint on the environment. In this paper, we will provide a review of the existing knowledge but also recent advances on the manufacturing and end uses of acrylamide-based polymers following the “green chemistry” concept and 100 years after the revolutionary publication of Staudinger on macromolecules. After a review of raw material sourcing options (fossil derivatives vs. biobased), we will discuss the improvements in monomer manufacturing followed by a second part dealing with polymer manufacturing processes and the paths followed to reduce energy consumption and CO2 emissions. In the following section, we will see how the polyacrylamides help reduce the environmental footprint of end users in various fields such as agriculture or wastewater treatment and discuss in more detail the fate of these molecules in the environment by looking at the existing literature, the regulations in place and the procedures used to assess the overall biodegradability. In the last section, we will review macromolecular engineering principles which could help enhance the degradability of said polymers when they reach the end of their life cycle. 相似文献
286.
287.
288.
Meenu Murali Dimitri Berne Dr. Christine Joly-Duhamel Dr. Sylvain Caillol Dr. Eric Leclerc Dr. Eric Manoury Dr. Vincent Ladmiral Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(61):e202202058
Vitrimers are 3D “covalent adaptable networks” (CANs) with flow properties thanks to thermally activated associative exchange reactions. This contribution introduces coordination adaptable networks, or CooANs, that are topologically related to metal–organic frameworks with octahedral Zr6 clusters as secondary building units in a carboxylic acid-functionalized acrylate-methacrylate copolymer matrix. A series of Zr-CooAN-x materials (x=percent of Zr6 loading relative to maximum capacity) was synthesized with x=5, 10, 15, 20, 25, 50 and 100. The mechanical and rheological investigations demonstrate vitrimer-like properties for x up to 50, the crosslink migration being ensured by carboxylate ligand exchange, with relaxation becoming slower as the Zr6 content is increased. The flow activation energy of Zr-CooAN-10 is 92.9±3.6 kJ mol−1. Rapid (30 min) hot-press reshaping occurs at temperatures in the 50–100 °C range under a 3-ton pressure and does not significantly alter the material properties. 相似文献
289.
290.
Jānis Lejnieks Dr. Xiaomin Zhu Jingbo Wang Dr. Ahmed Mourran Dr. Helmut Keul Prof. Martin Möller Dr. Denis V. Anokhin Dr. Dimitri A. Ivanov 《Chemphyschem》2010,11(17):3638-3644
Herein, we describe the synthesis of a low‐symmetry monodendron, 3,4‐bis(dodecyloxy)‐5‐[3,4,5‐tris(dodecyloxy)benzyloxy]benzoic acid, following a simple route which starts from gallic acid ethyl ester and does not require any protecting groups. The self‐assembled structures formed by the compound in 3D and 2D were investigated by synchrotron X‐ray scattering and scanning force microscopy (SFM). In 3D, the compound forms a stable crystalline phase with an orthorhombic lattice in which the alkyl chains connected to different benzene rings form crystalline and amorphous domains. Upon cooling from the isotropic melt the compound exhibits a monotropic smectic mesophase. In 100‐nm‐thick films on a neutral substrate the structure loses its biaxiality, adopting a hexagonal columnar structure with the columns oriented parallel to the substrate. By contrast, in ultrathin films on graphite the SFM likely reveals two crystal orientations, which can develop due to the epitaxial adsorption on the substrate of the alkyl chains pertinent to different benzene rings. 相似文献