全文获取类型
收费全文 | 4133篇 |
免费 | 599篇 |
国内免费 | 463篇 |
专业分类
化学 | 2985篇 |
晶体学 | 40篇 |
力学 | 233篇 |
综合类 | 35篇 |
数学 | 474篇 |
物理学 | 1428篇 |
出版年
2024年 | 15篇 |
2023年 | 101篇 |
2022年 | 125篇 |
2021年 | 164篇 |
2020年 | 193篇 |
2019年 | 174篇 |
2018年 | 146篇 |
2017年 | 112篇 |
2016年 | 185篇 |
2015年 | 188篇 |
2014年 | 175篇 |
2013年 | 290篇 |
2012年 | 293篇 |
2011年 | 303篇 |
2010年 | 215篇 |
2009年 | 215篇 |
2008年 | 244篇 |
2007年 | 196篇 |
2006年 | 194篇 |
2005年 | 195篇 |
2004年 | 179篇 |
2003年 | 121篇 |
2002年 | 116篇 |
2001年 | 111篇 |
2000年 | 113篇 |
1999年 | 101篇 |
1998年 | 86篇 |
1997年 | 81篇 |
1996年 | 84篇 |
1995年 | 62篇 |
1994年 | 72篇 |
1993年 | 50篇 |
1992年 | 44篇 |
1991年 | 34篇 |
1990年 | 41篇 |
1989年 | 25篇 |
1988年 | 24篇 |
1987年 | 25篇 |
1986年 | 18篇 |
1985年 | 22篇 |
1984年 | 13篇 |
1983年 | 3篇 |
1982年 | 9篇 |
1981年 | 10篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1969年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有5195条查询结果,搜索用时 15 毫秒
101.
F. Yang J. Mao X. W. He L. X. Chen Y. K. Zhang 《Analytical and bioanalytical chemistry》2013,405(21):6639-6648
In this study, a boronate-silica hybrid affinity monolith was prepared for specific capture of glycoproteins at neutral pH condition. The monolith was synthesized via a facile one-pot procedure in a stainless steel column by concurrently mixing hydrolyzed alkoxysilanes tetramethoxysilane and vinyltrimethoxysilane, organic monomer 3-acrylamidophenylboronic acid and initiator 2,2′-azobisisobutyronitrile together. The polycondensation of alkoxysilanes and copolymerization of organic monomer and vinyl-silica monolith were carried out successively by reacting at different temperatures. After optimizing the preparation conditions, the resulting hybrid affinity monolith was systematically characterized and exhibited excellent affinity to both cis-diol-containing small molecules and glycoproteins at neutral and physiological pH, including adenosine, horseradish peroxidase, transferrin and ovalbumin. The binding capacity of ovalbumin on monolith was measured to be 2.5 mg g?1 at pH 7.0. Furthermore, the hybrid affinity monolith was applied to the separation of transferrin from bovine serum sample at a physiological condition. Good repeatability was obtained and the relative standard deviations of retention time were 1.15 and 4.77 % (n?=?5) for run-to-run and column-to-column, respectively. 相似文献
102.
Mediated by samarium diiodide, 1-(benzotriazole-1-yl)alkyl esters 1 underwent cross-coupling with aldehydes or ketones to afford β-(benzotriazole-1-yl)alcohols 2 exclusively with the selective removal of acyloxy over benzotriazolyl. 相似文献
103.
Liping Zhao Zhenghong Guo Zhenhu Cao Tao Zhang Zhengping Fang Mao Peng 《Polymer Degradation and Stability》2013
Fullerene (C60)/high density polyethylene (HDPE) composites were studied in order to understand for their behaviors on thermal and thermo-oxidative degradation. Under different atmosphere, the influences of C60 on the thermal stability of HDPE are different. Thermogravimetric analysis coupled to Fourier transform infrared spectroscopy (TG-FTIR) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) demonstrate that in N2 the addition of C60 increases the onset decomposition temperature by about 10 °C with more heavy compounds (more than 34 carbon). Also the thermal stability of HDPE in air is remarkably improved with the addition of C60. When the content of C60 is 2.5 wt% the onset decomposition temperature increases by about 91 °C. The results of viscoelastic behavior and gel content reveal that C60 can trap the alkyl radicals and alkyl peroxide radicals to inhibit hydrogen abstraction to suppress the chain scission and preserve the long chain structure. However, in the absence of C60 or with low C60 concentration, hydrogen abstraction occurs, resulting in the formation of a series of alkyl radicals and alkyl peroxide radicals, which accelerates the chain scission and plays a leading role in the thermal oxidative degradation. 相似文献
104.
Mao Chen Ting Zhao Zhong‐Xin Zhu Chao Niu Dan‐dan Ruan Mao‐Wei Ni Xuan Zhou Li‐Tai Jin 《Electrophoresis》2013,34(24):3277-3286
An improved Stains‐All (ISA) staining method for phosphoproteins in SDS‐PAGE was described. Down to 0.5–1 ng phosphoproteins (α‐casein, β‐casein, or phosvitin) can be successfully selectively detected by ISA stain, which is approximately 120‐fold higher than that of original Stains‐All stain, but is similar to that of commonly used Pro‐Q Diamond stain. Furthermore, unlike the original Stains‐All protocol that was time consuming and light unstable, ISA stain could be completed within 60 min without resorting to protect the gels from light during the whole staining procedure. According to the results, it is concluded that ISA stain is a rapid, sensitive, specific, and economic staining method for a broad application to the research of phosphoproteins. 相似文献
105.
Three kinds of novel aromatic diamine-based benzoxazines containing naphthalene, propane-2,2-diyldibenzene and neopentyl groups in the backbone, respectively (designated as BAPNCP, BAPBACP and BAPNPGCP, respectively), were synthesized and characterized. In addition, the effects of backbone structures on curing behaviors of the monomers and thermal and flammability properties of the resulting polymers were systematically studied. The results indicated that BAPNPGCP displayed the highest enthalpy of the curing reaction associated with the ring-opening of benzoxazine, which was due to the effect of benzoxazine ring content per unit mass. Interestingly, the 5 wt% weight loss temperature and char residue after thermogravimetric test for poly(BAPNPGCP) were 8 °C and 7% higher than those of poly(BAPBACP). Meanwhile, the total heat release of poly(BAPNPGCP) was less than half of that for poly(BAPBACP), indicating the substantial effect of benzoxazine ring content on flammability and char formation. Furthermore, it was found that poly(BAPNCP) gave the best thermal stability and flame retardancy, which was due to the synergistic effect between naphthalene group and benzoxazine ring content. This study provides new insight into the curing behavior of benzoxazine and further understanding on the high performance of polybenzoxazine. 相似文献
106.
Binglian Bai Xiyue Mao Zhanhu Xi Jie Ma Xiaolong Lin Haitao Wang 《Liquid crystals》2013,40(2):214-221
Two series of dissymmetric hydrazide derivatives containing alkoxyazobenzene with nitro terminal group and octyloxy terminal group, N-4-alkoxyphenyl-N′-4-((4-nitrophenyl)azophenyl) benzohydrazide (Bn-NO2, n indicates the number of carbon atoms) and N-4-octyloxyphenyl-N′-4-((4-octyloxyphenyl)azophenyl) benzohydrazide (B8-B8), were designed and synthesised, and their liquid crystalline properties were investigated by means of differential scanning calorimetry, polarised optical microscopy and wide-angle X-ray diffraction. It was found that B8-B8 with octyloxy terminal chains displayed monolayer smectic C phase, whereas Bn-NO2 with nitro terminal group displayed SmAd phase, and intermolecular hydrogen bonding was confirmed as the driving force. In addition, the effect of hydrogen bonding, dipole–dipole interactions and steric hindrance effect on the liquid crystalline structures were also discussed. 相似文献
107.
Takuya Adachi Yasuhisa Yamamura Mafumi Hishida Mao Ueda Shunji Ito 《Liquid crystals》2013,40(11):1340-1344
Molecular dynamics in the soft crystal, E phase of 6-octyl-2-phenylazulene was studied by X-ray diffraction, and dielectric and Fourier transform infrared spectroscopies. Clear dielectric dispersion is observed due to the head-to-tail disordering in a kHz range around 400 K. The CH stretching frequencies exhibit more pronounced shifts at the phase transition point from the high-temperature ordered crystal to the E phase than that at the melting from the E phase to the isotropic liquid. The results are discussed in comparison with a typical E series, 4-n-alkyl-4′-isothiocyanatobiphenyl (n being the number of carbon atoms in the alkyl group). 相似文献
108.
Jia Mao Anayancy Osorio-Madrazo Marie-Pierre Laborie 《Cellulose (London, England)》2013,20(4):1829-1840
Cellulose I nanowhiskers were prepared in relatively high yield (48 ± 2 %) by single-stage hydrolysis of microcrystalline cellulose with an aqueous solution of 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO4). This reaction occurred under mildly acidic reaction conditions with an [H+]/[AGU] ratio of 0.24 mol/mol, i.e., 2 orders of magnitude lower than with concentrated sulfuric acid. The nanowhiskers exhibited small width and width distribution and also smaller length than nanowhiskers obtained with concentrated acid. With a relatively low content of sulfur they also exhibited higher thermal stability than whiskers obtained with concentrated sulfuric acid. The lower solvating power of the aqueous ionic liquid compared to that of concentrated sulfuric acid likely contributes to the greater hydrolysis efficiency in the present system. 相似文献
109.
110.
Jing Liu Fangjun Wang Jun Zhu Jiawei Mao Zheyi Liu Kai Cheng Hongqiang Qin Hanfa Zou 《Analytical and bioanalytical chemistry》2014,406(13):3103-3109
Conventional N-glycoproteome analysis usually applies C18 reversed-phase (RP) adsorbent for sample purification, which will lead to unavoidable sample loss due to the high hydrophilicity of N-glycopeptides. In this study, a porous graphitized carbon (PGC) absorbent was combined with a C18 adsorbent for N-glycopeptide purification in comprehensive N-glycoproteome analysis based on the hydrophobic and polar interactions between carbon and N-glycans. It was observed that the small hydrophilic N-glycopeptides that cannot retain onto C18 adsorbent can be captured by the graphitized carbon, while the large hydrophobic N-glycopeptides that cannot retain onto the graphitized carbon can be feasibly captured by the C18 adsorbent. Comparing with sample purification by using C18 adsorbent only, 28.5 % more N-glycopeptides were identified by combining both C18 and PGC adsorbents. The C18-PGC strategy was further applied for both sample purification and pre-fractionation of a complex protein sample from HeLa cell. After hydrophilic interaction chromatography enrichment, 1,484 unique N-glycopeptides with 1,759 unique N-glycosylation sites were finally identified. Online Abstract Figure
The overlap of identified N-glycosylation sites by different SPE strategies 相似文献