全文获取类型
收费全文 | 22347篇 |
免费 | 2169篇 |
国内免费 | 6326篇 |
专业分类
化学 | 28246篇 |
晶体学 | 372篇 |
力学 | 128篇 |
综合类 | 182篇 |
数学 | 101篇 |
物理学 | 1813篇 |
出版年
2024年 | 10篇 |
2023年 | 201篇 |
2022年 | 306篇 |
2021年 | 587篇 |
2020年 | 824篇 |
2019年 | 684篇 |
2018年 | 703篇 |
2017年 | 773篇 |
2016年 | 1094篇 |
2015年 | 1072篇 |
2014年 | 1351篇 |
2013年 | 2287篇 |
2012年 | 1585篇 |
2011年 | 1637篇 |
2010年 | 1376篇 |
2009年 | 1580篇 |
2008年 | 1633篇 |
2007年 | 1713篇 |
2006年 | 1729篇 |
2005年 | 1645篇 |
2004年 | 1583篇 |
2003年 | 1347篇 |
2002年 | 871篇 |
2001年 | 561篇 |
2000年 | 463篇 |
1999年 | 414篇 |
1998年 | 364篇 |
1997年 | 406篇 |
1996年 | 314篇 |
1995年 | 327篇 |
1994年 | 288篇 |
1993年 | 275篇 |
1992年 | 260篇 |
1991年 | 138篇 |
1990年 | 93篇 |
1989年 | 88篇 |
1988年 | 73篇 |
1987年 | 41篇 |
1986年 | 28篇 |
1985年 | 36篇 |
1984年 | 28篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1978年 | 2篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Yan Zhang 《Numerical Functional Analysis & Optimization》2019,40(11):1268-1290
G-frames generalize frames in Hilbert spaces. The literatures show that g-frames and frames share many similar properties, while they behave differently in redundancy and perturbation properties. Interestingly, g-frames have been extensively studied, but g-frame sequences have not. This problem is nontrivial since a g-frame and a frame both involve all vectors in the same Hilbert space, while a g-frame sequence and a frame sequence do not. They involve different linear spans. Using the synthesis and Gram matrix methods, we in this paper characterize g-frame sequences and g-Riesz sequences; obtain the Pythagorean theorem for g-orthonormal systems. These results recover several known results and lead to some new results on g-frames. 相似文献
82.
83.
Pengfei Xie Jiao Wang Jianbo Li Qian Cheng Keyu Zhou Jie Ren 《Journal of polymer science. Part A, Polymer chemistry》2019,57(7):814-826
The miktoarm star‐shaped poly(lactic acid) (PLA) copolymer, (PLLA)2‐core‐(PDLA)2, was synthesized via stepwise ring‐opening polymerization of lactide with dibromoneopentyl glycol as the starting material. 1H NMR and FTIR spectroscopy proved the feasibility of synthetic route and the successful preparation of star‐shaped PLA copolymers. The results of FTIR spectroscopy and XRD showed that the stereocomplex structure of the copolymer could be more perfect after solvent dissolution treatment. Effect of chain architectures on crystallization was investigated by studying the nonisothermal and isothermal crystallization of the miktoarm star‐shaped PLA copolymer and other stereocomplexes. Nonisothermal differential scanning calorimetry and polarizing optical microscopy tests indicated that (PLLA)2‐core‐(PDLA)2 exhibited the fastest formation of a stereocomplex in a dynamic test due to its special structure. In isothermal crystallization tests, the copolymer exhibited the fast crystal growth rate and the most perfect crystal morphology. The results reveal that the unique molecular structure has an important influence on the crystallization of the miktoarm star‐shaped PLA copolymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 814–826 相似文献
84.
Lianghao Song Tiantian Xu Daowei Gao Prof. Xun Hu Prof. Cuncheng Li Prof. Shun Li Prof. Guozhu Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6621-6627
CeO2-based catalysts are widely studied in catalysis fields. Developing one novel synthetic approach to increase the intimate contact between CeO2 and secondary species is of particular importance for enhancing catalytic activities. Herein, an interfacial reaction between metal–organic framework (MOF)-derived carbon and KMnO4 to synthesize CeO2−MnO2, in which carbon is derived from the pyrolysis of Ce-MOFs under an inert atmosphere, is described. The MOF-derived carbon is found to restrain the growth of CeO2 crystallites under a high calcination temperature and, more importantly, intimate contact within CeO2/C is conveyed to CeO2/MnO2 after the interfacial reaction; this is responsible for the high catalytic activity of CeO2−MnO2 towards CO oxidation. 相似文献
85.
Dr. Markus Zegke Hannah L. M. Spencer Dr. Rianne M. Lord 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(53):12275-12280
A range of oxobis(phenyl-1,3-butanedione) vanadium(IV) complexes have been successfully synthesized from cheap starting materials and a simple and solvent-free one-pot dry-melt reaction. This direct, straightforward, fast and alternative approach to inorganic synthesis has the potential for a wide range of applications. Analytical studies confirm their successful synthesis, purity and solid-state coordination, and we report the use of such complexes as potential drug candidates for the treatment of cancer. After a 24 hour incubation of A549 lung carcinoma cells with the compounds, they reveal cytotoxicity values elevenfold greater than cisplatin and remain non-toxic towards normal cell types. Additionally, the complexes are stable over a range of physiological pH values and show the potential for interactions with bovine serum albumin. 相似文献
86.
Dr. Alyssa F. Schneider Prof. Michael A. Brook 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(67):15367-15374
Arylsilicones are widely exploited for their thermal and optical properties. The creation of phenylsilicone elastomers with specific physical properties is typically done by a “one-off” formulation and test process. Herein, it is demonstrated that high-throughput synthesis methods can be used to rapidly prepare a series of arylsilicone elastomers and then the relative impact of different aryl groups on their physical properties is assessed. Aromatic groups were incorporated into polydimethylsiloxane (PDMS) elastomers by exploiting the relative reactivity of different functional groups in the Piers–Rubinsztajn reaction. To analyze trends in the silicone mechanical properties as a function of increasing aryl concentration—structure/property relationships—libraries of elastomers were both quickly synthesized and characterized by using high-throughput suites starting from low viscosity silicone oils/monomers in 96-well plates. Liquid handling parameters were optimized to effectively work with the silicones. Incorporating aryl instead of alkyl crosslinkers into the PDMS backbone increased the silicone elastomer modulus by approximately 50 % (at a crosslink density of 6 %); elastomers prepared with an aromatic crosslinker with three contact points led to much higher moduli compared with those with one contact point at the same crosslink density. When located at precise rather than random points on the silicone chains, diphenylsilicones had lower moduli than analogous monophenylsilicones. 相似文献
87.
In this work, a simple and green method is reported for the biosynthesis of Cu/bone nanocomposite using Cordyline fruticosa extract as a stabilizer and reductant. Animal bone was used as a natural support to prevent the accumulation of Cu nanoparticles. The catalytic activity of Cu/bone nanocomposite was assessed in the synthesis of 1‐substituted 1H‐1,2,3,4‐tetrazoles and reduction of various organic dyes, including 4‐nitrophenol (4‐NP), nigrosin (NS), congo red (CR) and methylene blue (MB). The best catalytic performance in the synthesis of 1‐substituted tetrazoles was achieved using 0.05 g of Cu/bone nanocomposite at 120°C. In addition, under optimal conditions, the absorption bands corresponding to 4‐NP, CR, NS and MB completely disappeared after about 6 min, 3 min, 50 s and 7 s, respectively. The biosynthesis protocol used in the preparation of Cu/bone nanocomposite offers a very attractive area for further research. 相似文献
88.
Three multinuclear Cu (II), Zn (II) and Cd (II) complexes, [Cu2(L)(μ‐OAc)]·CHCl2 ( 1 ), [Zn2(L)(μ‐OAc)(H2O)]·3CHCl3 ( 2 ) and [{Cd2(L)(OAc)(CH3CH2OH)}2]·2CH3CH2OH ( 3 ) with a single‐armed salamo‐like dioxime ligand H3L have been synthesized, and characterized by FT‐IR, UV–vis, X‐ray crystallography and Hirshfeld surfaces analyses. The ligand H3L has a linear structure and C‐H···π interactions between the two molecules. The complex 1 is a dinuclear Cu (II) complex, Cu1 and Cu2 are all five‐coordinate possessing distorted square pyramidal geometries. The complex 2 also forms a dinuclear Zn (II) structure, and Zn1 and Zn2 are all five‐coordinate bearing distorted trigonal bipyramidal geometries. The complex 3 is a symmetrical tetranuclear Cd (II) complex, and Cd1 is a hexa‐coordinate having octahedral configuration and Cd2 is hepta‐coordinate with a pentagonal bipyramidal geometry, and it has π···π interactions inside the molecule. In addition, fluorescence properties of the ligand and its complexes 1 – 3 have also been discussed. 相似文献
89.
Hailing Liu Nuverah Mohsin Sundol Kim Hoyong Chung 《Journal of polymer science. Part A, Polymer chemistry》2019,57(20):2121-2130
This work reports a new direction of natural lignin valorization, which utilizes lignin to produce crosslinked polycaprolactone (PCL) via a straightforward synthesis. Lignin's hydroxyl groups of its multibranched phenolic structure allow lignin to serve as crosslinkers, whereas the aromatic groups serve as hard segments. The modified natural lignin containing alkene terminals is crosslinked with a thiol‐terminal PCL via Ru‐catalyzed photoredox thiol‐ene reaction. The high rate of gel contents measured for all crosslinked polymers, with the least being 84% of gel content, indicates efficient crosslinking. The prepared flat rectangular shape lignin‐crosslinked PCL sample demonstrates rapid thermal responsive shape memory behavior at 10 °C and 80 °C showing interconversion between a permanent and temporary shape. The melting temperature of the lignin‐crosslinked PCL is tunable by varying the percent weight of lignin. The 11, 21, and 30 wt % lignin demonstrated Tm of 42 °C, 35 °C, and 26 °C, respectively. The role of lignin as a crosslinker presented in this work suggests that lignin can serve as an efficient biomass‐based functional additive to polymers. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2121–2130 相似文献
90.
Braulio Aranda Sergio A. Moya Andres Vega Gonzalo Valdebenito Sofia Ramirez‐Lopez Pedro Aguirre 《应用有机金属化学》2019,33(4)
Aminocarbonylation of aryl halides, homogeneously catalysed by palladium, is an efficient method that can be employed for obtaining amides for pharmaceutical and synthetic applications. In this work, palladium (II) complexes containing P^N ligands were studied as catalysts in the aminocarbonylation of iodobenzene in the presence of diethylamine. Two types of systems were used: a palladium (II) complex formed in situ; and one prepared prior to the catalytic reaction. In general, the palladium complexes studied achieved high conversions in an average reaction time of less than 2 hr, which is less than that for the standard system (Pd (II)/PPh3) used. The pre‐synthesized complexes were faster than their in situ counterparts, as the latter require an induction time to form the Pd/P^N species. The structure and electronic properties of the ligand P^N can influence both the activity and the selectivity of the reaction, stabilizing the acyl‐palladium intermediates formed in a better manner. 相似文献