全文获取类型
收费全文 | 5425篇 |
免费 | 171篇 |
国内免费 | 25篇 |
专业分类
化学 | 3430篇 |
晶体学 | 24篇 |
力学 | 308篇 |
数学 | 1066篇 |
物理学 | 793篇 |
出版年
2023年 | 37篇 |
2022年 | 81篇 |
2021年 | 171篇 |
2020年 | 125篇 |
2019年 | 129篇 |
2018年 | 104篇 |
2017年 | 83篇 |
2016年 | 213篇 |
2015年 | 157篇 |
2014年 | 191篇 |
2013年 | 307篇 |
2012年 | 355篇 |
2011年 | 360篇 |
2010年 | 237篇 |
2009年 | 208篇 |
2008年 | 282篇 |
2007年 | 302篇 |
2006年 | 277篇 |
2005年 | 248篇 |
2004年 | 219篇 |
2003年 | 140篇 |
2002年 | 163篇 |
2001年 | 55篇 |
2000年 | 58篇 |
1999年 | 50篇 |
1998年 | 41篇 |
1997年 | 47篇 |
1996年 | 54篇 |
1995年 | 40篇 |
1994年 | 41篇 |
1993年 | 47篇 |
1992年 | 49篇 |
1991年 | 33篇 |
1990年 | 17篇 |
1989年 | 24篇 |
1988年 | 24篇 |
1987年 | 36篇 |
1986年 | 19篇 |
1985年 | 36篇 |
1984年 | 39篇 |
1983年 | 38篇 |
1982年 | 39篇 |
1981年 | 50篇 |
1980年 | 48篇 |
1979年 | 42篇 |
1978年 | 26篇 |
1977年 | 33篇 |
1976年 | 23篇 |
1975年 | 19篇 |
1967年 | 13篇 |
排序方式: 共有5621条查询结果,搜索用时 46 毫秒
1.
Dr. Joaquim Torra Dr. Felipe Viela Dr. Diego Megías Dr. Begoña Sot Prof. Cristina Flors 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(19):e202200026
CRANAD-2 is a fluorogenic curcumin derivative used for near-infrared detection and imaging in vivo of amyloid aggregates, which are involved in neurodegenerative diseases. We explore the performance of CRANAD-2 in two super-resolution imaging techniques, namely stimulated emission depletion (STED) and single-molecule localization microscopy (SMLM), with markedly different fluorophore requirements. By conveniently adapting the concentration of CRANAD-2, which transiently binds to amyloid fibrils, we show that it performs well in both techniques, achieving a resolution in the range of 45–55 nm. Correlation of SMLM with atomic force microscopy (AFM) validates the resolution of fine features in the reconstructed super-resolved image. The good performance and versatility of CRANAD-2 provides a powerful tool for near-infrared nanoscopic imaging of amyloids in vitro and in vivo. 相似文献
2.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
3.
Condeixa Lucas Dias Silva Pierry Moah Diego Farias Brenda Leiras Adriana 《Central European Journal of Operations Research》2022,30(3):921-940
Central European Journal of Operations Research - Societal awareness and legislation changes concerning sustainability have affected how organizations generate value for stakeholders, as well as... 相似文献
4.
Dr. Carla Carrera Dr. Eleonora Cavallari Dr. Giuseppe Digilio Dr. Oksana Bondar Prof. Silvio Aime Dr. Francesca Reineri 《Chemphyschem》2021,22(11):1042-1048
An efficient synthesis of vinyl-[1-13C]pyruvate has been reported, from which 13C hyperpolarized (HP) ethyl-[1-13C]pyruvate has been obtained by means of ParaHydrogen Induced Polarization (PHIP). Due to the intrinsic lability of pyruvate, which leads quickly to degradation of the reaction mixture even under mild reaction conditions, the vinyl-ester has been synthesized through the intermediacy of a more stable ketal derivative. 13C and 1H hyperpolarizations of ethyl-[1-13C]pyruvate, hydrogenated using ParaHydrogen, have been compared to those observed on the more widely used allyl-derivative. It has been demonstrated that the spin order transfer from ParaHydrogen protons to 13C, is more efficient on the ethyl than on the allyl-esterdue to the larger J-couplings involved. The main requirements needed for the biological application of this HP product have been met, i. e. an aqueous solution of the product at high concentration (40 mM) with a good 13C polarization level (4.8 %) has been obtained. The in vitro metabolic transformation of the HP ethyl-[1-13C]pyruvate, catalyzed by an esterase, has been observed. This substrate appears to be a good candidate for in vivo metabolic investigations using PHIP hyperpolarized probes. 相似文献
5.
Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine 下载免费PDF全文
Diego García‐Gómez Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez 《Biomedical chromatography : BMC》2015,29(8):1190-1196
In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
6.
We report studies on the structure of the metallic core and the alkyl cap layer in monolayer protected gold nanoparticles having sizes down to 1.6 nm. These particles are obtained by laser ablating gold targets in alkane-thiol solutions at different concentrations. The electronic structure of gold core and the vibrational properties of the capping hydrocarbon chains reveal effects connected with the nanosized nature of the particles. 相似文献
7.
We apply here the harmonic and Cartan decomposition techniques to piezoelectric material symmetries classification. We show in particular that we shall reduce from 19 to 17 the number of symmetry classes corresponding to the piezoelectric phenomenon. To cite this article: G. Geymonat, T. Weller, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 847–852. 相似文献
8.
Nicolò Giovannelli Giuseppe Rao Calogero Vetro 《Rendiconti del Circolo Matematico di Palermo》2005,54(3):443-450
In this paper we consider a definition of essentialK-variation for real functions which gives information on the absolute integrability of its approximate derivate on a measurable
set. 相似文献
9.
Vincenzo Santagada Ferdinando FiorinoElisa Perissutti Beatrice SeverinoSara Terracciano Giuseppe CirinoGiuseppe Caliendo 《Tetrahedron letters》2003,44(6):1145-1148
A novel and convenient microwave-assisted dimerization of an active peptide compound using the DKPs as scaffold is described. The key reaction giving rise to the diketopiperazine scaffold is the intermolecular coupling. No epimerization was detected in the reactions used. Conventional and microwave heating of the reactions are compared. Synthesis by microwave irradiation gave the desired compounds in higher yields and in shorter reaction times than those obtained by conventional heating. 相似文献
10.
Giuseppe Coppola Andrea Irace Giovanni Breglio Mario Iodice Luigi Zeni Antonello Cutolo Pasqualina M. Sarro 《Optics and Lasers in Engineering》2003,39(3):317-332
In this paper we describe two different kind of optoelectronic devices both based on a three terminals active device and exploit the plasma dispersion effect to achieve the desired working. The first device exploits this effect in order to obtain an optical modulation. The second device is an optoelectronic router based on the mode-mixing principle together with the injection-induced optical phase shift. Both devices are integrated into a Silicon on Silicon optical channel waveguide which can be realized using a standard bipolar process. The possibility of using standard, well-known technology presents several advantages with respect to III–V Optoelectronics. The active three terminal device used is a Bipolar Mode Field Effect Transistor (BMFET). Numerical simulation results are presented on both devices. 相似文献