全文获取类型
收费全文 | 1319篇 |
免费 | 20篇 |
国内免费 | 103篇 |
专业分类
化学 | 1035篇 |
晶体学 | 2篇 |
力学 | 1篇 |
综合类 | 4篇 |
数学 | 5篇 |
物理学 | 395篇 |
出版年
2024年 | 8篇 |
2023年 | 83篇 |
2022年 | 26篇 |
2021年 | 25篇 |
2020年 | 24篇 |
2019年 | 18篇 |
2018年 | 14篇 |
2017年 | 29篇 |
2016年 | 23篇 |
2015年 | 39篇 |
2014年 | 35篇 |
2013年 | 133篇 |
2012年 | 133篇 |
2011年 | 106篇 |
2010年 | 54篇 |
2009年 | 60篇 |
2008年 | 48篇 |
2007年 | 81篇 |
2006年 | 74篇 |
2005年 | 54篇 |
2004年 | 62篇 |
2003年 | 34篇 |
2002年 | 44篇 |
2001年 | 35篇 |
2000年 | 23篇 |
1999年 | 19篇 |
1998年 | 13篇 |
1997年 | 15篇 |
1996年 | 17篇 |
1995年 | 24篇 |
1994年 | 19篇 |
1993年 | 6篇 |
1992年 | 13篇 |
1991年 | 6篇 |
1990年 | 8篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 7篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有1442条查询结果,搜索用时 491 毫秒
111.
Epoxy resins made from vegetable oils are an alternative to synthesize epoxy resins from renewable sources. Tung oil is rich in α -eleostearic fatty acid, which contains three double bonds producing epoxy resins with up to three epoxy groups per fatty acid. This work studied the production of tung oil epoxy resin using hydrogen peroxide as an oxidizing agent and acetic and formic acid as percarboxylic acid precursors, applying low frequency high power ultrasound. This study evaluated the effects of ultrasound power density, hydrogen peroxide concentration, acetic acid concentration, and formic acid concentration on the yield into epoxy resin, selectivity, and by-products formation. Application of ultrasound was carried out using a 19 kHz probe ultrasound (horn ultrasound) with a 1.3 cm diameter titanium probe, 500 W nominal power, 2940 W L−1 maximum effective power density applied to the reaction mixture. Ultrasound technology yielded up to 85% of epoxy resin in 3 h of reaction. The use of formic acid resulted in a slightly lower oil conversion than acetic acid but with a much higher selectivity towards epoxidized tung oil. However, using acetic acid resulted in the production of high-value by-products, such as 2-heptenal and 2,4-nonadienal. The ultrasound-assisted epoxidation showed to be particularly efficient when applied to oils containing conjugated double-bonds. 相似文献
112.
Hongbo Zhu Ziping Cao Xin Meng Laijin Tian Guang Chen Xuejun Sun Jinmao You 《Tetrahedron》2017,73(24):3310-3315
Acid-mediated domino reaction of ortho-carbonylated alkynyl-substituted arylaldehydes with phenols is described. The implement of this reaction can provide directly a variety of tetracyclic indeno[2,1-c]chromen-7-one products in good yields. The mechanism was proposed to be a domino indanone ring formation/ortho-alkylation of phenols/dehydrated cyclization for the formation of polycyclic skeleton. In addition, several interesting dimeric products containing a pentacyclic scaffold were also afforded stereoselectively albeit in moderate yields. The present transformations feature the use of simple acid catalyst, short reaction time and good substrate scope. 相似文献
113.
Sergey Miltsov Vladimir Karavan Alexandr Misharev Galina Starova Julian Alonso-Chamarro Mar Puyol 《Tetrahedron letters》2017,58(34):3353-3357
meso-Bromosubstituted indodicarbocyanine dyes produce dimeric molecules, together with the debrominated species, under acid catalysis. The relationship between the dimerization and hydrodebromination routes depends on the aryl substitution of the dyes. A possible reaction mechanism is also proposed. 相似文献
114.
115.
Fardis Nakhaei 《Journal of Dispersion Science and Technology》2017,38(12):1755-1763
Iron ore tailings have become one kind of the most hazardous solid waste. Beneficiation of iron ore tailings is a significant issue in the world steel industries, from the point of view of both pollution control and secondary resources. This investigation addressed the processing of tailings with high sulphur content from an iron ore concentrator to produce pellet feed fines and to prevent acid mine drainage. This study was the lab-scale testing of an integrated method consisting of froth flotation combined with gravity and magnetic separation. Reverse flotation located at the end of the primary treatment circuit (high- and low-intensity magnetic separation) will lower a large amount of the sulphur from magnetic separator concentrate. The effects of various operating parameters such as concentrations of collector, frother, depressant and activator, pH, solid-in-pulp concentration have been studied on the sulphur removal using reverse flotation. According to the data presented in this study, the maximum recovery of total sulphur was obtained when the operational parameters were set to the PAX dosage160?gr/t, MIBC dosage 140?gr/t, CuSo4 100?gr/t, air flow rate 10?l/min, pH 8.5, and pulp density 30%. With these optimum parameters, final concentrate with the grade of 63.7% Fe and 0.085% S was obtained. The results of this study indicated that, with this method, a great amount of iron concentrate is produced and, simultaneously, the sulphidic fraction is separated that can later be managed more easily owing to the reduced volume. 相似文献
116.
通过简单的一锅两步法制备了三氟金属(铝,钛,锆)接枝介孔SBA-15 (AlTf/S,TiTf/S,ZrTf/S)固体酸材料,并通过XRD,N2吸附,TGA,FTIR,原位吡啶FTIR和元素分析对这些材料进行了详细的表征.其中,ZrTf/S能够高效催化环氧化物温和条件下被胺或醇开环生成对应β-氨基醇或β-烷氧基醇,并且催化剂能循环利用.ZrTf/S相较于AlTf/S和TiTf/S酸性最强,因而催化活性也最高. 相似文献
117.
Cocos nucifera L. water as green corrosion inhibitor for acid corrosion of aluminium in HCl solution
<正>The ability of Cocos nucifera L.water(CW) as non-toxic corrosion inhibitor for acid corrosion of aluminium in 0.5 mol/L HCl has been studied using chemical technique.CW shows significant inhibition as corrosion inhibitor,with 93%efficiency at the highest concentration of the inhibitor.The inhibitive action is attributed to the adsorption of the inhibitor molecules on metal surface following Langmuir adsorption isotherm. 相似文献
118.
The quantitative determination of boldine alkaloid in boldo leaf extracts by employing cyclic voltammetry, at a liquid/liquid interface as well as the validation of this methodology against the reference method, high performance liquid chromatography (HPLC), are reported in the present paper. The voltammetric analysis was performed successfully and economically using two kinds of liquid/liquid interfaces: water/1,2-dicholoroethane and water/PVC (polyvinyl chloride)-gelled 1,2-dichloroethane. Linear calibration curves in the concentration range of 1.04 × 10−5 mol L−1 to 5.19 × 10−4 mol L−1 were obtained with a detection limit equal to (6.1 ± 0.7) × 10−5 mol L−1 and the quantitative determination of this alkaloid, in complex matrixes such as boldo leaf extracts, by the electrochemical technique proposed was found to be equal to the values obtained using the standard HPLC method. The validation analysis of this methodology against HPLC demonstrated that accuracy, linearity, limit of detection (LOD), limit of quantification (LOQ), specificity and precision are acceptable. The electroanalytical technique proposed is economical and selective, involves simple equipment and can be applied for the quantitative determination of boldine alkaloid in complex matrixes such as leaf extracts without special drug separation. Moreover, cyclic voltammetry (CV) experiments applied at the liquid/liquid interface under different experimental conditions allowed us to study the transfer mechanism of boldine, and determine a value of pKaw = 6.90 for protonated boldine, from the variation of voltammetric peak current with pH. 相似文献
119.
Gloria Brusotti Tatiana Adrienne Ngueyem Raffaela Biesuz Gabriele Caccialanza 《Journal of separation science》2010,33(11):1692-1697
Euphorbiaceae barks are known to contain an appreciable amount of polyphenolic compounds responsible for several biological activities. Preliminary extraction from Bridelia grandis stem bark afforded high content of polyphenols, determined by spectrophotometric methods such as Folin–Ciocalteu (for total phenols, TP) and n‐butanol‐HCl (for condensed tannins, CT). A preliminary Plackett–Burman screening design was used to identify the key factors that influence the TP and CT extraction. Between all the variables known to influence the extraction from vegetable matrixes, six were selected; maceration was chosen as traditional extraction methodology. To investigate the effect of solvents and extraction method, methanol, acetone 70% (v/v in water), centrifugation and ultrasound were chosen. A full factorial design 23 was applied to optimize the extraction procedure. The responses were obtained analyzing the extracts for their TP and CT contents determined by the above‐mentioned spectrophotometric methods. The results confirm that, within the explored domain, the optimum solvent is methanol and the optimum method is one‐cycle centrifugation. Finally, it was also compared with the effect of maceration on the considered responses. It has never given results better than centrifugation, whereas in the case of CT it represents an advantage to employ a three‐cycle centrifugation instead of one. 相似文献
120.
Acid/base modifiers are sometimes used as additives in normal phase elution on columns packed with CHIRALPAK® AD®. These modifiers affect enantioseparations in ways that are not yet fully understood for the lack of systematic studies. Shifts of the selectivity of certain pairs of enantiomers upon exposure of the column to these modifiers is amply documented. Furthermore, once the modifier has been removed from the mobile phase, the modified selectivity remains, which has been named the Memory Effect. After a column has been exposed to an eluent stream containing acidic/basic modifiers, this particular column no longer separates certain enantiomeric pairs with the same selectivity as a modifier naive column. This makes the transfer of developed methods from one to other CHIRALPAK AD columns difficult to predict, if the selectivity needs to be similar between the two columns. We selected four enantiomeric pairs for a systematic study of this Memory Effect. The selectivity of 4-chlorophenylalanine ethyl ester improves after a solution of ethanesulfonic acid (ESA) is percolated through the column. The selectivity of Propranolol and Tröger's base increases after a solution of Diiospropylamine is percolated through the column. The selectivity of Propranolol and Tröger's base enantiomers is inversely affected by percolation of the acid solution. The 4-chlorophenylalanine ethyl ester enantiomers is inversely affected by percolation of the base solution. In contrast, the selectivity of trans-stilbene oxide (TSO) is not affected by either modifier. Analytical studies of the stationary phase suggest that slow protonation/deprotonation of water molecules attached to the carbamate moiety may be responsible for the acid/base Memory Effect. To further the understanding of the effect of water on the Memory Effect, mobile phases – spiked with water (0.01–0.43%) – were used to measure changes in the Memory Effect. Finally, we showed that the influence of water on the Memory Effect can be minimized by percolating through the column a sufficiently concentrated solution of the appropriate base while using dried mobile phases. 相似文献