全文获取类型
收费全文 | 22852篇 |
免费 | 4029篇 |
国内免费 | 2781篇 |
专业分类
化学 | 11291篇 |
晶体学 | 247篇 |
力学 | 928篇 |
综合类 | 153篇 |
数学 | 1663篇 |
物理学 | 6595篇 |
无线电 | 8785篇 |
出版年
2024年 | 109篇 |
2023年 | 557篇 |
2022年 | 764篇 |
2021年 | 986篇 |
2020年 | 979篇 |
2019年 | 897篇 |
2018年 | 825篇 |
2017年 | 800篇 |
2016年 | 1073篇 |
2015年 | 1197篇 |
2014年 | 1404篇 |
2013年 | 1769篇 |
2012年 | 2183篇 |
2011年 | 2103篇 |
2010年 | 1599篇 |
2009年 | 1644篇 |
2008年 | 1646篇 |
2007年 | 1491篇 |
2006年 | 1309篇 |
2005年 | 1072篇 |
2004年 | 832篇 |
2003年 | 635篇 |
2002年 | 573篇 |
2001年 | 493篇 |
2000年 | 434篇 |
1999年 | 405篇 |
1998年 | 260篇 |
1997年 | 221篇 |
1996年 | 240篇 |
1995年 | 163篇 |
1994年 | 166篇 |
1993年 | 135篇 |
1992年 | 124篇 |
1991年 | 95篇 |
1990年 | 100篇 |
1989年 | 73篇 |
1988年 | 54篇 |
1987年 | 46篇 |
1986年 | 31篇 |
1985年 | 35篇 |
1984年 | 36篇 |
1983年 | 23篇 |
1982年 | 21篇 |
1981年 | 14篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1974年 | 6篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
141.
SynthesesandStudiesofPEG┐b┐PNIPABlockPolymersCAOWei-xiao**andZHANGTao(ColegeofChemistryandMolecularEnginering,PekingUniversit... 相似文献
142.
Lijun Kong 《European Polymer Journal》2006,42(12):3171-3179
In order to increase the biocompatibility and bioactivity of chitosan, hydroxyapatite had been in situ combined into chitosan scaffolds. The bioactivity of the composite scaffolds was studied by examining the apatite formed on the scaffolds by incubating in simulated body fluid and the activity of preosteoblasts cultured on them. The apatite layer was assessed using scanning electronic microscope (SEM), X-ray diffraction (XRD), Fourier-Transformed Infrared spectroscopy (FTIR) and weight measurement. Composite analysis showed that after incubation in simulated body fluid on both of the scaffolds carbonate hydroxyapatite was formed. With increasing nano-hydroxyapatite content in the composite, the quantity of the apatite formed on the scaffolds increased. Compared with pure chitosan, the composite with nano-hydroxyapatite could form apatite more readily during the biomimetic process, which suggests that the composite possessed better mineralization activity. Furthermore, preosteoblast cells cultured on the apatite-coated scaffolds showed different behavior. On the apatite-coated composite scaffolds cells presented better proliferation than on apatite-coated chitosan scaffolds. In addition, alkaline phosphatase activities of cells cultured on the scaffolds in conditioned medium were assessed. The cells on composite scaffolds showed a higher alkaline phosphatase activity which suggested a higher differentiation level. The results indicated that the addition of nano-hydroxyapatite improved the bioactivity of chitosan/nano-hydroxyapatite composite scaffolds. On the other hand, that is to say composition of substrates could affect the apatite formation on them, and pre-loaded hydroxyapatite can enhance the apatite-coating. It will also be significant in preparation of apatite-coating polymer scaffolds for bone tissue engineering. 相似文献
143.
The first total synthesis of penicimutanin A (1) was achieved within 10 steps (LLS). Key innovations in this synthesis consist of (1) a highly efficient electro-oxidative dearomatization; (2) an unprecedented bisoxirane-directed intermolecular aldol reaction from the sterically hindered face of the ketone and (3) the diastereoselective one-step Meerwein–Eschenmoser–Claisen rearrangement enabling the construction of vicinal quaternary stereocenters. Related family members e.g. penicimutanolone (3) and penicimutatin (5) have also been synthesized alongside, elucidating their absolute configurations, hence the absolute configuration of 1.The first total synthesis of penicimutanin A (1) was achieved within 10 steps (LLS). 相似文献
144.
A novel capsule composed of an azo dye, Congo red (CR), and different polymers, including poly(styrenesulfonate, sodium salt) (PSS), poly(allylamine hydrochloride) (PAH), and poly(diallyldimethylammonium chloride) (PDDA), have been successfully fabricated by the layer-by-layer self-assembly technique. The stepwise linear deposition process was monitored by means of UV-visible absorption measurements. The formation of hollow capsules was verified by confocal laser scanning microscopy (CLSM) and scanning force microscopy (SFM). The resulting hollow PSS/PAH/CR/PDDA capsules displayed a sensitive response to visible light. Optical changes of the hollow capsules prior to and after the photoreaction were investigated in detail by means of UV-visible spectroscopy, CLSM, and SFM. It was found that the photochemical reaction of the assembled hollow capsules depends strongly on the matrix. Qualitative results on the permeability of the hollow capsule walls with CR as one component indicate that the permeability of the walls can be easily photo-controlled at varying irradiation time intervals without addition of external chemicals. 相似文献
145.
Crystallization behavior and biodegradation of poly(3-hydroxybutyrate) and poly(ethylene glycol) multiblock copolymers 总被引:1,自引:0,他引:1
Block copolymerization by using isocyanates is an effective method for incorporating PHB and PEG because it can prepare copolymers with good properties, such as toughness, strength, and so on. In this study, we adopted soil suspension system to estimate the biodegradability of a series of PHB/PEG multiblock copolymers with different compositions and block lengths. In the degradation process, the changes in weight loss, molecular weight, and tensile strength were periodically measured to determine the biodegradability, and the surface morphology was also observed by SEM. In contrast to pure PHB, the weight loss of the copolymer was relatively lower. On the other hand, the tensile strength and molecular weight experienced apparent decrease, and for BHG1000-3-1, they reached 46.7% and 77.7% of the initial value, respectively. SEM observation showed that the surface was covered with numerous erosion pits. All these indicate that the degradation indeed took place and long-chain molecules have been hydrolyzed into shorter ones. The crystallization behavior was also investigated by DSC and WAXD. The results showed that both the segments, PEG and PHB, can form crystalline phases at lower PHB contents ranging from 29% to 44%, and when PHB component was more than 60%, only PHB phase can crystallize. 相似文献
146.
Zr0.5Ti0.5O2(ZT) and Zr0.25Ti0.25Al0.5O2(ZTA) mixed oxides were prepared by co-precipitation method and characterized by low temperature adsorption-desorption, XRD and NH3-TPD. The activity of Pt/Zr0.5Ti0.5O2 and Pt/ Zr0.5Ti0.5Al0.5O2 catalysts was evaluated using the simulated gases. The results show that ZTA samples exhibit higher specific surface area, larger pore volume and proper surface acidic amount and acidity in comparison with ZT. The results of the catalytic test indicate that Pt/ZT and Pt/ZTA catalysts exhibit excellent low-temperature catalytic activity and lower light-off temperatures of hydrocarbon, carbon monoxide and nitrogen oxides, especially better conversion for nitrogen oxides (NOx). The addition of Al2O3 into ZT enhanced the anti-aging property of Pt/ ZTA catalysts due to the excellent textural, structural, surface acidity and thermal stability. 相似文献
147.
Xi-Shang Sun Xing-Heng Wang Hai-Yan Tao Liang Wei Chun-Jiang Wang 《Chemical science》2020,11(40):10984
In this study, we developed an efficient Ir-catalyzed cascade umpolung allylation/2-aza-Cope rearrangement of tertiary α-trifluoromethyl α-amino acid derivatives for the preparation of a variety of quaternary α-trifluoromethyl α-amino acids in high yields with excellent enantioselectivities. The umpolung reactivity empowered by the activation of the key isatin-ketoimine moiety obviates the intractable enantioselectivity control in Pd-catalyzed asymmetric linear α-allylation. In combination with quasi parallel kinetic resolution or kinetic resolution, the generality of this method is further demonstrated by the first preparation of enantioenriched quaternary trifluoromethyl β-, γ-, δ- and ε-amino acid derivatives.In this study, we developed an efficient Ir-catalyzed cascade umpolung allylation/2-aza-Cope rearrangement for the preparation of a variety of quaternary trifluoromethyl α-ε-amino acids in high yields with excellent enantioselectivities. 相似文献
148.
Ben-zhong Tang Xiang-xing Kong Xin-de Feng Department of Chemistry Hong Kong University of Science & Technology Clear Water Bay Kowloon Hong Kong China Department of Polymer Science & Engineering College of Chemistry Peking University Beijing China 《高分子科学》1999,(3):289-294
A new liquid crystalline polyacetylene containing a phenyl benzoate mesogen (5) is synthesized,whose mesomorphic properties are found to be easily "tunab1e" by simple mechanical perturbation. Thepolymerization of 10- [ 4 - (4' -methoxyphenoxycarbonyl )phenoxycarbonyl] - 1 -decyne (4 ) in itiated by theWCl_6-Ph_4Sn/dioxane complex yields polymer 5 with a M_w of 28400. The molecular structure of 5 ischaracterized by NMR, IR, and UV spectroscopy and its liquid crystalline behavior is investigated by DSC,POM, and XRD analysis. Upon mechanical perturbation, 5 exhibits unusual agitation-induced high-strengthdisclinations, shear-induced inversion walls, and solidification-induced banded textures. Such phenomenahave been observed in the main-chain liquid crystalline polymers with rigid backbones, but have seldom beenreported for the side-chain liquid crystalline polymers with flexible backbones, suggesting that the rigidpolyacetylene backbone of 5 plays a constructive role in inducing the novel molecular alignments. 相似文献
149.
V. A. Dorokhov L. S. Vasil'ev N. Kyu Khoa N. Kong Hao V. S. Bogdanov 《Russian Chemical Bulletin》1997,46(11):1967-1969
A method for the synthesis of 2,2′-bipyridin-4-one from 4-amino-4-(2-pyridyl)-but-3-en-2-onevia its diphenylboron, chelates was proposed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2071–2073, November, 1997. 相似文献
150.
Aromatization of methane over different Mo-supported catalysts in the absence of oxygen 总被引:2,自引:0,他引:2
Tan Pinglian Xu Zhusheng Zhang Tao Chen Liayuan Lin Liwu 《Reaction Kinetics and Catalysis Letters》1997,61(2):391-396
Both acidity and structure of the support are important factors in converting methane to aromatics. Lower SiO2/Al2O3 ratio seems to favor the aromatization of methane over the Mo/HZSM-5 catalyst. When Pt is added as a modifier the activity
of Mo/HZSM-5 catalyst will decrease slightly, but coke formation will enhanced. 相似文献