全文获取类型
收费全文 | 4254篇 |
免费 | 465篇 |
国内免费 | 350篇 |
专业分类
化学 | 2846篇 |
晶体学 | 31篇 |
力学 | 219篇 |
综合类 | 23篇 |
数学 | 508篇 |
物理学 | 1442篇 |
出版年
2023年 | 69篇 |
2022年 | 148篇 |
2021年 | 138篇 |
2020年 | 158篇 |
2019年 | 131篇 |
2018年 | 118篇 |
2017年 | 119篇 |
2016年 | 147篇 |
2015年 | 161篇 |
2014年 | 192篇 |
2013年 | 258篇 |
2012年 | 337篇 |
2011年 | 316篇 |
2010年 | 230篇 |
2009年 | 200篇 |
2008年 | 264篇 |
2007年 | 218篇 |
2006年 | 194篇 |
2005年 | 164篇 |
2004年 | 130篇 |
2003年 | 113篇 |
2002年 | 102篇 |
2001年 | 89篇 |
2000年 | 102篇 |
1999年 | 73篇 |
1998年 | 66篇 |
1997年 | 55篇 |
1996年 | 75篇 |
1995年 | 56篇 |
1994年 | 60篇 |
1993年 | 52篇 |
1992年 | 54篇 |
1991年 | 36篇 |
1990年 | 28篇 |
1989年 | 41篇 |
1988年 | 37篇 |
1987年 | 31篇 |
1986年 | 41篇 |
1985年 | 30篇 |
1984年 | 35篇 |
1983年 | 26篇 |
1982年 | 20篇 |
1981年 | 14篇 |
1980年 | 22篇 |
1979年 | 12篇 |
1978年 | 11篇 |
1977年 | 15篇 |
1976年 | 17篇 |
1975年 | 17篇 |
1973年 | 9篇 |
排序方式: 共有5069条查询结果,搜索用时 15 毫秒
21.
The ultraviolet photolysis of low concentrations of CH(2)XI (X = Cl, Br, I) were investigated in water and saltwater solutions by photochemistry and picosecond time-resolved resonance Raman spectroscopy. Photolysis in both kinds of solutions formed mostly CH(2)(OH)(2) and HI and HX products. However, photolysis of the CH(2)XI molecules in saltwater resulted in production of some CH(2)XCl products not observed in aqueous solutions without salt present. The appearance of these new products in saltwater solutions is accompanied by a decrease in the amount of CH(2)(OH)(2), HI, and HX products compared to photolysis in aqueous solutions without salt present. The possible implications for photolysis of CH(2)XI and other polyhalomethanes in seawater and other salt aqueous environments compared to nonsaltwater solvated environments is briefly discussed. 相似文献
22.
A rapid method for the derivatization of phenolic antioxidants using microwave irradiation has been developed. Six antioxidatively active phenolic components of wines and fruits, namely gallic acid, gentisic acid, vanillic acid, caffeic acid, ferulic acid and p-coumaric acid were used in the model study. The solution of phenolic acids was evaporated to dryness on a rotary evaporator followed by further drying under microwave irradiation (600 W, 30 s). The resultant residue was dissolved in pyridene and treated with bis(trimethylsilyl)acetamide while irradiated by microwave using high power for 30 s. Controlled reaction was carried out employing bis(trimethylsilyl)trifluoroacetamide under conventional heating for 30 min. The trimethylsilyl derivatives were identified and quantified on a gas chromatography/mass selective detector. The mass spectral fragmentation patterns of the derivatives obtained by microwave irradiation were identical to those prepared by heating. The yields of microwave-assisted silylation were comparable to those from conventional heating. The rsd were less than 8% for six replicates. The linearity in wine matrix was nearly perfect. This method is a useful protocol to examine the phenolic constituents in wines and agricultural products. 相似文献
23.
使用TPR和H2-TPD技术对镍铝系催化剂的还原和氢脱附性能进行了研究,并与其催化性能相关联。结果发现,镍铝系催化剂的氢脱附能力与其催化性能之间有一定联系,脱附氢能力越强,催化剂的甲烷部分氧化反应性能就越好,但催化性能与还原性能无直接关联。 相似文献
24.
25.
FTIR-ATR has been used for understanding the interaction between bacteria and surfaces in the adsorption progress. 相似文献
26.
Synthesis of six new triorganosiloxybenzaldehydes, two m-methoxy-(triorganosiloxy)benzaldehydes, and seven methoxy(triorganosiloxy)benzenes are reported. From comparison of the stability of these compounds in the atmosphere, it is concluded that formyl group shows unfavorable influence and methoxy group shows favorable influence on the stability of these compounds. The oposite influences of these two groups on phenoxysilane linkage seems to connect with the oposite directiones of inductive effect of formyl group and resonance effect of methoxy group on the benzene ring. 相似文献
27.
A polyaluminum chloride (PAC) sample was prepared using a slow alkaline titration method. The Bio-Gel P-100 gel column chromatographic
technique was used to separate and characterize the various forms of aluminum present in the prepared PAC solution. The effluents
from a gel column were monitored using online chemical method: Al-Ferron timed complexation spectrophotometry and by 27Al nuclear magnetic resonance (NMR) spectroscopy. Effects of different experimental conditions such as eluent flow rate, ionic
strength and pH on separation of Al13 were investigated. Experimental results indicated that molecule size exclusion was not the only parameter affecting the column
chromatographic separation efficiency of Al13 but molecule charge as well. Reducing the eluent flow rate, increasing the ionic strength and suitable pH resulted in increase
in the separation efficiency. Experimental results clearly indicated that by varying the experimental conditions, it is possible
to produce pure Al13 species using a gel column chromatographic technique. 相似文献
28.
A polyaluminum chloride (PAC) sample was prepared using a slow alkaline titration method. The Bio-Gel P-100 gel column chromatographic technique was used to separate and characterize the various forms of aluminum present in the prepared PAC solution. The effluents from a gel column were monitored using online chemical method: Al-Ferron timed complexation spectrophotometry and by 27Al nuclear magnetic resonance (NMR) spectroscopy. Effects of different experimental conditions such as eluent flow rate, ionic strength and pH on separation of Al13 were investigated. Experimental results indicated that molecule size exclusion was not the only parameter affecting the column chromatographic separation efficiency of Al13 but molecule charge as well. Reducing the eluent flow rate, increasing the ionic strength and suitable pH resulted in increase in the separation efficiency. Experimental results clearly indicated that by varying the experimental conditions, it is possible to produce pure Al13 species using a gel column chromatographic technique. 相似文献
29.
The repression of glucose oxidase (GOD) biosynthesis by catabolites during fermentation can be alleviated through membrane dialysis fermentation (MDF). The results show that the volumetric enzyme productivity of MDF was two times higher than that of the control (fermentation without dialysis), and its total enzyme activity was increased by 30–50%. The operation conditions of MDF, such as pore size of the membrane, initiating time for membrane dialysis, and volume of dialysate used, were optimized. The content of amino acids and organic acids in the fermentation broth and the dialysate in the reservoir were assessed by amino acid analyzer and ionic chromatography, respectively. The relationship among the contents of pyruvic acid, gluconic acid, and enzyme activity during fermentation was analyzed quantitatively. Furthermore, the effect of membrane dialysis technology applied to the low-yield strain was found to be more effective than that applied to the high-yield strain. 相似文献
30.
James Elver Johnson Joanne A. Maia Karen Tan Abdolkarim Ghafouripour Patrice De Meester Shirley S. C. Chu 《Journal of heterocyclic chemistry》1986,23(6):1861-1868
O-Methyl-α-ketophenylacetohydroximoyl chloride ( 1 ) was prepared by the reaction of O-methyl-α-methoxyphenylacetohydroximoyl chloride ( 5 ) with N-bromosuccinimide and concentrated hydrobromic acid. Reaction of 1 with ethylenediamine gave 3-phenyl-5,6-dihydro-2(1H)-pyrazinone-O-methyloxime ( 6 ). 3-Phenyl-5,6-cyclohexano-5,6-dihydro-2(1H)-pyrazininone-O-methyloxime ( 7 ) was prepared by reaction of 1 with trans-1,2-diaminocyclohexane. The X-ray structure of 6 has been determined. The crystals are orthorhombic, space group Pbca with a = 10.264(3), b = 18.262(4), c = 23.530(4)Å, V = 4411(2)Å3, and Z = 16. The structure, which was refined to R = 0.038 using 1652 observed reflections, shows the amidoxime moiety to be the Z configuration. Reaction of benzohydroximoyl chloride with aziridine gave (Z)-aziridinylbenzaldoxime ( 16a ). Ultraviolet irradiation of a benzene solution of 16a gave a mixture of the Z and E isomers 16a and 16b . The E isomer 16b underwent thermal isomerization to 16a at 100°. Reaction of 16a with dimethyl sulfate in sodium hydroxide solution gave (Z)-O-methylaziridinylbenzaldoxime ( 17a ). Photoisomerization of a hexane solution of 17a gave a mixture of the Z and E isomers 17a and 17b which were separated by preparative glc. The isomers 17a and 17b are resistant to thermal Z = E isomerization. The mechanisms of thermal isomerization of benzamidoximes are discussed. 相似文献