全文获取类型
收费全文 | 3476篇 |
免费 | 149篇 |
国内免费 | 7篇 |
专业分类
化学 | 2732篇 |
晶体学 | 15篇 |
力学 | 84篇 |
数学 | 327篇 |
物理学 | 474篇 |
出版年
2023年 | 33篇 |
2022年 | 79篇 |
2021年 | 87篇 |
2020年 | 105篇 |
2019年 | 93篇 |
2018年 | 47篇 |
2017年 | 42篇 |
2016年 | 126篇 |
2015年 | 114篇 |
2014年 | 126篇 |
2013年 | 201篇 |
2012年 | 251篇 |
2011年 | 311篇 |
2010年 | 181篇 |
2009年 | 151篇 |
2008年 | 235篇 |
2007年 | 257篇 |
2006年 | 204篇 |
2005年 | 174篇 |
2004年 | 161篇 |
2003年 | 101篇 |
2002年 | 97篇 |
2001年 | 35篇 |
2000年 | 43篇 |
1999年 | 26篇 |
1998年 | 23篇 |
1997年 | 15篇 |
1996年 | 22篇 |
1995年 | 18篇 |
1994年 | 14篇 |
1993年 | 15篇 |
1992年 | 21篇 |
1991年 | 12篇 |
1990年 | 8篇 |
1989年 | 12篇 |
1988年 | 13篇 |
1986年 | 9篇 |
1985年 | 17篇 |
1984年 | 14篇 |
1983年 | 16篇 |
1982年 | 10篇 |
1981年 | 10篇 |
1980年 | 13篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1977年 | 6篇 |
1976年 | 11篇 |
1974年 | 6篇 |
1973年 | 8篇 |
1972年 | 6篇 |
排序方式: 共有3632条查询结果,搜索用时 15 毫秒
1.
2.
The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time. 相似文献
3.
Amphiphilic block copolymer self‐assemblies of poly(NVP)‐b‐poly(MDO‐co‐vinyl esters): Tunable dimensions and functionalities 下载免费PDF全文
Guillaume G. Hedir A. Pitto‐Barry Andrew P. Dove Rachel K. O'Reilly 《Journal of polymer science. Part A, Polymer chemistry》2015,53(23):2699-2710
Functional, degradable polymers were synthesized via the copolymerization of vinyl acetate (VAc) and 2‐methylene‐1,3‐dioxepane (MDO) using a macro‐xanthate CTA, poly(N‐vinylpyrrolidone), resulting in the formation of amphiphilic block copolymers of poly(NVP)‐b‐poly(MDO‐co‐VAc). The behavior of the block copolymers in water was investigated and resulted in the formation of self‐assembled nanoparticles containing a hydrophobic core and a hydrophilic corona. The size of the resultant nanoparticles was able to be tuned with variation of the hydrophilic and hydrophobic segments of the core and corona by changing the incorporation of the macro‐CTA as well as the monomer composition in the copolymers, as observed by Dynamic Light Scattering, Static Light Scattering, and Transmission Electron Microscopy analyses. The concept was further applied to a VAc derivative monomer, vinyl bromobutanoate, to incorporate further functionalities such as fluorescent dithiomaleimide groups throughout the polymer backbone using azidation and “click” chemistry as postpolymerization tools to create fluorescently labeled nanoparticles. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2699–2710 相似文献
4.
5.
Thermodynamic study of transthyretin association (wild‐type and senile forms) with heparan sulfate proteoglycan: pH effect and implication of the reactive histidine residue 下载免费PDF全文
Ambre Geneste Claire André Nadine Magy‐Bertrand Lydie Lethier Gharbi Tijani Yves Claude Guillaume 《Biomedical chromatography : BMC》2015,29(4):514-522
The tetramer destabilization of transthyretin into monomers and its fibrillation are phenomena leading to amyloid deposition. Heparan sulfate proteoglycan (HSPG) has been found in all amyloid deposits. A chromatographic approach was developed to compare binding parameters between wild‐type transthyretin (wtTTR) and an amyloidogenic transthyretin (sTTR). Results showed a greater affinity of sTTR for HSPG at pH 7.4 compared with wtTTR owing to the monomeric form of sTTR. Analysis of the thermodynamic parameters showed that van der Waals interactions were involved at the complex interface for both transthyretin forms. For sTTR, results from the plot representing the number of protons exchanged vs pH showed that the binding mechanism was pH‐dependent with a critical value at a pH 6.5. This observation was due to the protonation of a histidine residue as an imidazolium cation, which was not accessible when TTR was in its tetrameric structure. At pH >6.5, dehydration at the binding interface and several contacts between nonpolar groups of sTTR and HSPG were also coupled to binding for an optimal hydrogen‐bond network. At pH <6.5, the protonation of the His residue from sTTR monomer when pH decreased broke the hydrogen‐bond network, leading to its destabilization and thus producing slight conformational changes in the sTTR monomer structure. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
6.
Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters 下载免费PDF全文
Dr. Sophie M. Guillaume Dr. Evgueni Kirillov Dr. Yann Sarazin Prof. Dr. Jean‐François Carpentier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):7988-8003
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted. 相似文献
7.
Patricia D. Morrell Camille Wainwright Lawrence Flick 《School science and mathematics》2004,104(5):199-213
The purposes of this study were to observe the teaching practices occurring in student teachers' science and mathematics K‐12 classrooms, compare the student teachers' perceptions of their teaching with what was actually occurring in their classrooms, and determine which college faculty members and courses these student teachers felt contributed to the teaching methods they used. Data on each student teacher were gathered via field notes of three classes, an observation protocol completed after each lesson, and an interview. Composites were written for each of the students. The total data set of all composites was examined to see if any patterns generalizable to the whole were evident. Differences between and among grade levels and content areas surfaced and are discussed. 相似文献
8.
Belting, a vocal technique typically cultivated in musical theatre singing, differs timbrally from operatic singing in many interesting respects. The underlying phonatory differences have not been previously investigated in detail. Yet, belting is frequently associated with disturbances of voice function. Articulatory and phonatory characteristics are investigated in a female subject who is a professional singer (co-author JL) trained in both the operatic and belting styles and in an intermediate vocal technique (“mixed”). This article presents data obtained from this subject by video-fiberoptic observation of the pharynx, inverse filtering of airflow, and measurement of subglottal pressure. The results reveal that belting was characterized by very high subglottal pressures and sound levels, and apparently also by a comparatively high degree of glottal adduction. Comparisons with other investigations of related aspects of belting and operatic singing support the assumption that the data obtained from our subject are representative for these vocal techniques. 相似文献
9.
Wing-Sum Cheung Patricia J.Y. Wong 《Journal of Mathematical Analysis and Applications》2007,329(2):851-869
We consider a system of focal boundary value problems where the nonlinearities may be singular in the independent variable and may also be singular in the dependent arguments. Using Schauder fixed point theorem, we establish criteria such that the system of boundary value problems has at least one fixed-sign solution. 相似文献
10.
Patricia Smichowski María Beatriz de la Calle Guntiñas Carmen Cámara 《Fresenius' Journal of Analytical Chemistry》1994,348(5-6):380-384
Summary A method is described for antimony preconcentration based on retention on a column of activated alumina. Recovery is 80% when no pH-control and 4 mol/l HCl as eluent are used. The preconcentration factor is 400. The method was applied to the determination of antimony in spiked tap and sea water. The analytical performance of the method is discussed. 相似文献