全文获取类型
收费全文 | 2370篇 |
免费 | 68篇 |
国内免费 | 366篇 |
专业分类
化学 | 2279篇 |
晶体学 | 40篇 |
力学 | 22篇 |
综合类 | 1篇 |
数学 | 2篇 |
物理学 | 460篇 |
出版年
2024年 | 7篇 |
2023年 | 36篇 |
2022年 | 38篇 |
2021年 | 41篇 |
2020年 | 41篇 |
2019年 | 46篇 |
2018年 | 45篇 |
2017年 | 44篇 |
2016年 | 69篇 |
2015年 | 50篇 |
2014年 | 96篇 |
2013年 | 154篇 |
2012年 | 136篇 |
2011年 | 144篇 |
2010年 | 138篇 |
2009年 | 156篇 |
2008年 | 167篇 |
2007年 | 162篇 |
2006年 | 156篇 |
2005年 | 135篇 |
2004年 | 146篇 |
2003年 | 110篇 |
2002年 | 79篇 |
2001年 | 69篇 |
2000年 | 59篇 |
1999年 | 63篇 |
1998年 | 54篇 |
1997年 | 47篇 |
1996年 | 49篇 |
1995年 | 50篇 |
1994年 | 42篇 |
1993年 | 37篇 |
1992年 | 31篇 |
1991年 | 22篇 |
1990年 | 14篇 |
1989年 | 21篇 |
1988年 | 13篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 4篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1974年 | 3篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有2804条查询结果,搜索用时 0 毫秒
11.
Sodium tridecafluorohexanesulfinate (1a) and sodium 1-chloro-2,2,2-trifluoroethanesulfinate (1b) were prepared by the treatment of 1-iodo-tridecafluorohexane and 1-bromo-1-chloro-2,2,2-trifluoroethane with sodium dithionite in a water-acetonitrile solution. Prolonged reaction of 1a with allyl bromide in DMF afforded tridecafluorohexane 1-propenyl sulfone 2 as the only product in good yield. A similar treatment of 1b gave exclusively 1-chloro-2,2,2-trifluoroethane 3-propenyl sulfone 4. Bromination of 4 followed by dehydrobromination with Et3N resulted in a mixture of 1-chloro-2,2,2-trifluoroethane 3-bromo-1-propenyl sulfone 6 and 1-chloro-2,2,2-trifluoroethane 2-bromo-3-propenyl sulfone 7, while dehydrobromination with pyridine gave sulfone 6 practically as the only product. α,β-Unsaturated sulfones 2 and 6 were shown to be active dienophiles. 相似文献
12.
W Schoner 《Angewandte Chemie (International ed. in English)》1971,10(12):882-889
The transport of Na+ out of the cell and K+ into the cell against a concentration gradient is catalyzed by a (Na+ + K+)-activated ATPase. The way in which the cations pass through the cell membrane has not yet been elucidated. Studies on the ATP hydrolysis revealed a Na+-dependent phosphorylation of the enzyme protein; the conformation of the enzyme also appears to change. The energy required for transport of the cations against their concentration gradients is probably provided by K+-dependent hydrolysis of the enzyme-bound phosphate. The enzyme can synthesize ATP from inorganic phosphate and ADP on reversal of the cation concentration gradient. By keeping the enzyme in a particular conformation, the cardiac glycoside ouabain specifically inhibits the Na+ pump. 相似文献
13.
Yue Liu Congmin Wang Rong Guo Juexiu Li Quan Zhao Weiqiang Wang Fei Qi Haifang Liu Yang Li Huifan Zheng 《Molecules (Basel, Switzerland)》2022,27(15)
Iron–manganese silicate (IMS) was synthesized by chemical coprecipitation and used as a catalyst for ozonating acrylic acid (AA) in semicontinuous flow mode. The Fe-O-Mn bond, Fe-Si, and Mn-Si binary oxide were formed in IMS on the basis of the results of XRD, FTIR, and XPS analysis. The removal efficiency of AA was highest in the IMS catalytic ozonation processes (98.9% in 15 min) compared with ozonation alone (62.7%), iron silicate (IS) catalytic ozonation (95.6%), and manganese silicate catalytic ozonation (94.8%). Meanwhile, the removal efficiencies of total organic carbon (TOC) were also improved in the IMS catalytic ozonation processes. The IMS showed high stability and ozone utilization. Additionally, H2O2 was formed in the process of IMS catalytic ozonation. Electron paramagnetic resonance (EPR) analysis and radical scavenger experiments confirmed that hydroxyl radicals (•OH) were the dominant oxidants. Cl−, HCO3−, PO43−, Ca2+, and Mg2+ in aqueous solution could adversely affect AA degradation. In the IMS catalytic ozonation of AA, the surface hydroxyl groups and Lewis acid sites played an important role. 相似文献
14.
N. A. Weir 《辐射效应与固体损伤》2013,168(1):23-27
The effect of self-irradiation of β-tritiated polystyrene under high vacuum at 25°C was studied, and simultaneous random chain scission and cross-linking were observed. Analyses of the gaseous products and the colored polymer residue showed that hydrogen was the only volatile product, while spectroscopic measurements indicated that the coloration was associated with the presence of main-chain double bonds. G values for hydrogen formation GH2, cross-linking, G XL and chain scission, G CS were obtained as follows: GH2=0.031; G CS=0.044; G XL=0.061. Possible mechanisms of radiation damage are discussed. 相似文献
15.
探讨了环境光的存在,对谷氨酸钠溶液的激光拉曼光谱的影响。研究表明,不同的环境光,自然光和室内荧光灯光,会对拉曼光谱产生不同的干扰效应,存在着特征谱峰、负峰或尖锐正峰, 干扰的影响不能忽略。建议在进行溶液激光拉曼光谱检测时,需在暗室或暗罩中进行,以完全隔离环境光的影响。 相似文献
16.
Luminescence enhancement of Eu-doped calcium magnesium silicate blue phosphor for UV-LED application 总被引:1,自引:0,他引:1
(Ca1−x,Eux)MgSi2yO6+δ blue phosphor was prepared by spray pyrolysis and the photoluminescence properties were optimized by controlling concentration of Si element and the activator content. At y=1.0, the concentration quenching in the luminescent intensity appeared when the Eu2+ content (x) was 0.01 (1 at%). Such quenching concentration was changed with the concentration of silicon (y), which was increased with an increase in the quantity of excess Si (y>1.0). The highest luminescent intensity was achieved when the Eu2+ content (x) and the Si concentration (y) were 0.04 and 1.3, respectively. According to X-ray diffraction (XRD) analysis, the tetragonal SiO2 phase was formed as a minor phase when the y value was larger than 1.3. The formation of SiO2 phase, however, did not reduce but increased the luminescent intensity when the Eu2+ content was optimized again. As a result, the luminescent intensity of the phosphor particles optimized in the content of both Si and Eu2+ was about 150% improved compared with that of the CaMgSi2O6:Eu sample (x=0.01, y=1.0). 相似文献
17.
We have used vibrational spectroscopy to study the formula and molecular structure of the mineral penkvilksite Na 2TiSi 4O 11·2H 2O. Penkvilksite is a mineral which may be used in the uptake of radioactive elements. Both Raman and infrared spectroscopies identify a band at ~3638 cm?1 attributed to an OH-stretching vibration of hydroxyl units. The inference is that OH units are involved in the structure of penkvilksite. The formula may be well written as Na 2TiSi 4O 10(OH)2·H 2O. The mineral is characterised by a very intense Raman band at 1085 cm?1 and a broad infrared band at 1080 cm?1 assigned to SiO-stretching vibrations. Raman bands at 620, 667 and 711 cm?1 are attributed to SiO and TiO chain bonds. Water-stretching vibrations are observed as Raman bands at 3197, 3265, 3425 and 3565 cm?1. Vibrational spectroscopy enables aspects of the molecular structure of the mineral penkvilksite to be ascertained. Penkvilksite is a mineral which can incorporate actinides and lanthanides from radioactive waste. 相似文献
18.
19.
The collagen type I segment long spacing (SLS) crystallite is a well-ordered rod-like molecular aggregate, ∼300 nm in length, which is produced in vitro under mildly acidic conditions (pH 2.5–3.5) in the presence of 1 mM ATP. The formation of the SLS crystallite amplifies the inherent linear structural features of individual collagen heterotrimers, due to the punctate linear distribution and summation of the bulkier amino acid side chains along the length of individual collagen heterotrimers. This can be correlated structurally with the 67 nm D-banded collagen fibril that is found in vivo, and formed in vitro. Although first described many years ago, the range of conditions required for ATP-induced SLS crystallite formation from acid-soluble collagen have not been explored extensively. Consequently, we have addressed biochemical parameters such as the ATP concentration, pH, speed of formation and stability so as to provide a more complete structural understanding of the SLS crystallite. Treatment of collagen type I with 1 mM ATP at neutral and higher pH (6.0–9.0) also induced the formation of D-banded fibrils. Contrary to previous studies, we have shown that the polysulphonated diazo dyes Direct red (Sirius red) and Evans blue, but not Congo red and Methyl blue, can also induce the formation of SLS-like aggregates of collagen, but under markedly different ionic conditions to those employed in the presence of ATP. Specifically, pre-formed D-banded collagen fibrils, prepared in a higher than the usual physiological NaCl concentration (e.g. 500 mM NaCl, 20 mM Tris-HCl pH7.4 or x3 PBS), readily form SLS aggregates when treated with 0.1 mM Direct red and Evans blue, but this did not occur at lower NaCl concentrations. These new data are discussed in relation to the anion (Cl−) and polyanion (phosphate and sulphonate) binding by the collagen heterotrimer and their likely role in collagen fibrillogenesis and SLS formation. 相似文献
20.
Pradip B. SarawadeJong-Kil Kim Askwar HilongaDang Viet Quang Hee Taik Kim 《Applied Surface Science》2011,258(2):955-961
The conventional drying (oven drying) method used for the preparation of precipitated mesoporous silica with low surface area (>300 m2/g) and small pore volume is often associated with a high production cost and a time consuming process. Therefore, the main goal of this study was to develop a cost-effective and fast drying process for the production of precipitated mesoporous silica using inexpensive industrial grade sodium silicate and spray drying of the precipitated wet-gel silica slurry. The precipitated wet-gel silica slurry was prepared from an aqueous sodium silicate solution through the drop-wise addition of sulfuric acid. Mesoporous precipitated silica powder was prepared by drying the wet-gel slurry with different drying techniques. The effects of the oven drying (OD), microwave drying (MD), and spray drying (SD) techniques on the physical (oil, water absorption, and tapping density), and textural properties (specific BET surface area, pore volume, pore size, and % porosity) of the precipitated mesoporous silica powder were studied. The dried precipitated mesoporous silica powders were characterized with field-emission scanning electron microscopy; Brunauer, Emmett and Teller and BJH nitrogen gas adsorption/desorption methods; Fourier-transform infrared spectroscopy; thermogravimetric and differential analysis; N2 physisorption isotherm; pore size distribution and particle size analysis. There was a significant effect of drying technique on the textural properties, such as specific surface area, pore size distribution and cumulative pore volume of the mesoporous silica powder. Additionally, the effect of the microwave-drying period on the physicochemical properties of the precipitated mesoporous silica powder was investigated and discussed. 相似文献