全文获取类型
收费全文 | 2558篇 |
免费 | 438篇 |
国内免费 | 189篇 |
专业分类
化学 | 2639篇 |
晶体学 | 9篇 |
力学 | 3篇 |
综合类 | 7篇 |
数学 | 9篇 |
物理学 | 117篇 |
无线电 | 401篇 |
出版年
2024年 | 7篇 |
2023年 | 28篇 |
2022年 | 48篇 |
2021年 | 67篇 |
2020年 | 87篇 |
2019年 | 95篇 |
2018年 | 89篇 |
2017年 | 112篇 |
2016年 | 159篇 |
2015年 | 166篇 |
2014年 | 187篇 |
2013年 | 229篇 |
2012年 | 200篇 |
2011年 | 229篇 |
2010年 | 180篇 |
2009年 | 222篇 |
2008年 | 196篇 |
2007年 | 143篇 |
2006年 | 145篇 |
2005年 | 100篇 |
2004年 | 133篇 |
2003年 | 106篇 |
2002年 | 68篇 |
2001年 | 35篇 |
2000年 | 22篇 |
1999年 | 24篇 |
1998年 | 19篇 |
1997年 | 13篇 |
1996年 | 13篇 |
1995年 | 11篇 |
1994年 | 12篇 |
1993年 | 14篇 |
1992年 | 9篇 |
1991年 | 3篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1988年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有3185条查询结果,搜索用时 11 毫秒
1.
Naoto Takase Junpei Kuwabara Seong Jib Choi Takeshi Yasuda Liyuan Han Takaki Kanbara 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):536-542
The Pd‐catalyzed polycondensation of 4‐octylaniline with various dibromoarylenes was carried out under microwave heating. Microwave heating led to a decrease in the reaction time and an increase in the molecular weight of the polymers as compared to conventional heating. Microwave heating also allowed the catalyst loading to be reduced to 1 mol %, yielding polymerization results that were comparable to those under conventional heating and 5 mol % catalyst. Investigations regarding field‐effect transistors and organic photovoltaic cells using the obtained poly(arylamine) with azobenzene units revealed that increasing the molecular weight of the polymer led to improved device performance, including hole mobility and power conversion efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 536–542 相似文献
2.
Effect of additive length and chemistry on the morphology of blends of conjugated thiophenes and fullerene derivative acceptor molecules 下载免费PDF全文
Small molecule additives have been shown to increase the device efficiency of conjugated polymer (donor) and fullerene derivative (acceptor) based organic solar cells by modifying the morphology of the device active layer. In this paper we conduct a systematic study of how additives affect the donor‐acceptor morphology using molecular dynamics simulations of blends of thiophene‐based oligomers, mimicking poly(3‐dodecylthiophene) (P3DDT) or poly(2,2′:5′,2”‐3,3”‐didocyl‐terthiophene) (PTTT), and fullerene derivatives with additives of varying length and chemical functionalization, mimicking experimentally used additives like methyl ester additives, diiodooctane, and alkanedithiols. We find that functionalization of additives with end groups that are attracted to acceptor molecules are necessary to induce increased donor‐acceptor macrophase separation. In blends where acceptors intercalate between oligomer alkyl side chains, functionalized additives decrease acceptor intercalation. Functionalized additives with shorter alkyl segments increase acceptor macrophase separation more than additives with same chemical functionalization but longer alkyl segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1046–1057 相似文献
3.
Yimei Wang Yi Qiao Xiaomin Xu Xiaohong Ding Weiwei Li Bo Yuan Haiyan Xu 《Biomedical chromatography : BMC》2019,33(8)
A sensitive and reliable LC–MS/MS method was developed and validated for simultaneous quantification of the major components of Huangqi–Honghua extact in rat plasma, including hydroxysafflor yellow A (HSYA), astragaloside IV (ASIV), calycosin‐7‐O‐β‐d ‐glucoside (CAG), calycosin, calycosin‐3′‐O‐glucuronide (C‐3′‐G) and calycosin‐3′‐O‐sulfate (C‐3′‐S). After extraction by protein precipitation with acetonitrile and methanol from plasma, the analytes were separated on a Hypersil BDS C18 column by gradient elution with acetonitrile and 5 mM ammonium acetate. The detection was carried out on a triple quadrupole tandem mass spectrometer equipped with electrospray ionization source switched between negative and positive modes. HSYA was monitored in negative ionization mode from 0 to 4.9 min, and ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S were determined in positive ionization mode from 4.9 to 10 min. The lower limits of quantification of the analytes were 6.25 ng/mL for HSYA, 0.781 ng/mL for CAG and 1.56 ng/mL for ASIV and calycosin. The intra‐ and inter‐assay precision (RSD) values were within 13.43%, and accuracy (RE) ranged from ?8.75 to 9.92%. The validated method was then applied to the pharmacokinetic study of HSYA, ASIV, CAG, calycosin, C‐3′‐G and C‐3′‐S in rat after an oral administration of Huangqi–Honghua extract. 相似文献
4.
Farzaneh Fayazpour Bart Lucas Roosmarijn E. Vandenbroucke Stefaan Derveaux Jan Tavernier Sam Lievens Joseph Demeester Stefaan C. De Smedt 《Advanced functional materials》2008,18(18):2716-2723
To obtain more biologically relevant data there is a growing interest in the use of living cells for assaying the biological activity of unknown chemical compounds. Density ‘multiplex’ cell‐based assays, where different cell types are mixed in one well and simultaneously investigated upon exposure to a certain compound are beginning to emerge. To be able to identify the cells they should be attached to microscopic carriers that are encoded. This paper investigates how digitally encoded microparticles can be loaded with cells while keeping the digital code in the microcarriers readable. It turns out that coating the surface of the encoded microcarriers with polyelectrolytes using the layer‐by‐layer (LbL) approach provides the microcarriers with a ‘highly functional’ surface. The polyelectrolyte layer allows the growth of the cells, allows the orientation of the cell loaded microcarriers in a magnetic field, and does not hamper the reading of the code. It has further been shown that the cells growing on the polyelectrolyte layer can become transduced by adenoviral particles hosted by the polyelectrolyte layer. It is concluded that the digitally encoded microparticles are promising materials for use in biomedical and pharmaceutical in‐vitro research where cells are used as tools. 相似文献
5.
Mao‐Chuan Yuan Ping‐I Shih Chen‐Han Chien Ching‐Fong Shu 《Journal of polymer science. Part A, Polymer chemistry》2007,45(14):2925-2937
We have synthesized a blue‐light‐emitting polyfluorene (PF) derivative ( PF‐CBZ‐OXD ) that presents bulky hole‐transporting carbazole and electron‐transporting oxadiazole pendent groups functionalized at the C‐9 positions of alternating fluorene units. The results from photoluminescence and electrochemical measurements indicate that both the side chains and the PF main chain retain their own electronic characteristics in the copolymer. An electroluminescent device incorporating this polymer as the emitting layer was turned on at 4.5 V; it exhibited a stable blue emission with a maximum external quantum efficiency of 1.1%. Moreover, we doped PF‐CBZ‐OXD and its analogue PF‐TPA‐OXD with a red‐light‐emitting iridium phosphor for use as components of phosphorescent red‐light emitters to investigate the effect of the host's HOMO energy level on the degree of charge trapping and on the electrophosphorescent efficiency. We found that spectral overlap and individual energy level matching between the host and guest were both crucial features affecting the performance of the electroluminescence devices. Atomic force microscopy measurements indicated that the dipolar nature of PF‐CBZ‐OXD , in contrast to the general nonpolarity of polydialkylfluorenes, provided a stabilizing environment that allowed homogeneous dispersion of the polar iridium triplet dopant. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2925–2937, 2007 相似文献
6.
Liang Liao Yi Pang Liming Ding Frank E. Karasz 《Journal of polymer science. Part A, Polymer chemistry》2003,41(20):3149-3158
A soluble cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative ( 9 ) was synthesized and characterized. Comparison between 9 and its model compound ( 10 ) showed that the chromophore in 9 remained to be well defined as a result of a π‐conjugation interruption at adjacent m‐phenylene units. The attachment of a cyano substituent only at the β position of the vinylene allowed the maximum electronic impact of the cyano group on the optical properties of the poly(p‐phenylene vinylene) material. At a low temperature (?108 or ?198 °C), the vibronic structures of 9 and 10 were partially resolved. The absorption and emission spectra of a film of 9 were less temperature‐dependent than those of a film of 10 , indicating that the former had a lower tendency to aggregate. A light‐emitting diode (LED) based on 9 emitted yellow light (λmax ≈ 578 nm) with an external quantum efficiency of 0.03%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3149–3158, 2003 相似文献
7.
Peixiang Xing Gilles P. Robertson Michael D. Guiver Serguei D. Mikhailenko Serge Kaliaguine 《Journal of polymer science. Part A, Polymer chemistry》2004,42(12):2866-2876
A series of sulfonated poly(aryl ether ketone)s (SPAEKs) were prepared by aromatic nucleophilic polycondensation of 2,6‐dihydroxynaphthalene with 5,5′‐carbonyl‐bis(2‐fluorobenzenesulfonate) and 4,4′‐difluorobenzophenone. The structure and degree of sulfonation (DS) of the SPAEKs were characterized using 1H NMR spectroscopy. The experimentally observed DS values were close to the expected values derived from the starting material ratios. The thermal stabilities of the SPAEKs were characterized by thermogravimetric analysis, which showed that in acid and sodium salt forms they were thermally stable in air up to about 240 and 380 °C, respectively. Transparent membranes cast from the directly polymerized SPAEKs exhibited good mechanical properties in both dry and hydrated states. The dependence of water uptake and of membrane swelling on the DS at different temperatures was studied. SPAEK membranes with a DS from 0.72 to 1.60 maintained adequate mechanical properties after immersion in water at 80 °C for 24 h. The proton conductivity of SPAEK membranes with different degrees of sulfonation was measured as a function of temperature. The proton conductivity of the SPAEK films increased with increased DS, and the highest room temperature conductivity (4.2 × 10?2 S/cm) was recorded for a SPAEK membrane with a DS of 1.60, which further increased to 1.1 × 10?1 S/cm at 80 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2866–2876, 2004 相似文献
8.
Dmitry S. Zimnitsky Tatiana L. Yurkshtovich Pavel M. Bychkovsky 《Journal of polymer science. Part A, Polymer chemistry》2004,42(19):4785-4791
Samples of oxidized cellulose (OC) with various carboxyl contents and degrees of crystallinity were obtained by the oxidation of native and mercerized cellulose with a solution of nitrogen(IV) oxide in CCl4. A detailed characterization of these OC samples was performed. The effect of oxidation conditions (concentration of N2O4 in the solution and oxidation time) and starting cellulose material on OC characteristics (carboxyl, carbonyl and nitrogen content, degree of crystallinity and polymerization, surface area and swelling, and acidic properties) was investigated. Reactivity in the oxidation process was higher in mercerized cellulose than in native cellulose. The action of dilute solutions (10–15%) of N2O4 did not affect the degree of crystallinity of cellulose samples. Under these conditions, the oxidation took place mainly in amorphous regions and on the surface of crystallites. Oxidation in a concentrated (40%) N2O4 solution led to the destruction of crystallites, which increased the surface area and swelling of cellulose in water. The surface area and the swelling of OC samples increased with a decrease in the index of crystallinity. The acidic properties of OC were shown to increase with an increase of swelling in water. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4785–4791, 2004 相似文献
9.
Thomas Pautzsch Elisabeth Klemm 《Journal of polymer science. Part A, Polymer chemistry》2004,42(12):2911-2919
Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by 1H and 13C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004 相似文献
10.
Ecaterina Stela Dragan Simona Schwarz 《Journal of polymer science. Part A, Polymer chemistry》2004,42(10):2495-2505
The formation and characterization of some interpolyelectrolyte complex (IPEC) nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate) (NaPAMPS), as a function of the polycation structure, polyanion molar mass, and polyion concentration, were followed in this work. Poly(diallyldimethylammonium chloride) and two polycations (PCs) containing (N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride) units in the backbone (PCA5 and PCA5D1) were used as starting polyions. The complex stoichiometry, (n?/n+)iso, was pointed out by optical density at 500 nm (OD500), polyelectrolyte titration, and dynamic light scattering. IPEC nanoparticle sizes were influenced by the polycation structure and polyanion molar mass only before the complex stoichiometry, which was higher for the more hydrophilic polycations (PCA5 and PCA5D1) and for a higher NaPAMPS molar mass, and were almost independent of these factors after that, at a flow rate of the added polyion of about 0.28 mL × (mL PC)?1 × h?1. The IPEC nanoparticle sizes remained almost constant for more than 2 weeks, both before and after the complex stoichiometry, at low concentrations of polyions. NIPECs as stable colloidal dispersions with positive charges in excess were prepared at a ratio between charges (n?/n+) of 0.7, and their storage colloidal stability, as a function of the polycation structure and polyion concentration (from 0.8 to ca. 7.8 mmol/L), was demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2495–2505, 2004 相似文献