全文获取类型
收费全文 | 510篇 |
免费 | 7篇 |
国内免费 | 1篇 |
专业分类
化学 | 361篇 |
晶体学 | 4篇 |
力学 | 13篇 |
数学 | 100篇 |
物理学 | 40篇 |
出版年
2023年 | 6篇 |
2022年 | 16篇 |
2021年 | 12篇 |
2020年 | 13篇 |
2019年 | 7篇 |
2018年 | 8篇 |
2017年 | 6篇 |
2016年 | 8篇 |
2015年 | 3篇 |
2014年 | 17篇 |
2013年 | 26篇 |
2012年 | 33篇 |
2011年 | 35篇 |
2010年 | 24篇 |
2009年 | 13篇 |
2008年 | 36篇 |
2007年 | 26篇 |
2006年 | 27篇 |
2005年 | 23篇 |
2004年 | 16篇 |
2003年 | 25篇 |
2002年 | 20篇 |
2001年 | 9篇 |
2000年 | 7篇 |
1999年 | 11篇 |
1998年 | 10篇 |
1997年 | 6篇 |
1996年 | 9篇 |
1995年 | 2篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1989年 | 2篇 |
1985年 | 2篇 |
1984年 | 5篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 4篇 |
1968年 | 3篇 |
1912年 | 2篇 |
1903年 | 1篇 |
1899年 | 1篇 |
1897年 | 2篇 |
1894年 | 1篇 |
1892年 | 1篇 |
1889年 | 2篇 |
1888年 | 1篇 |
1882年 | 1篇 |
排序方式: 共有518条查询结果,搜索用时 15 毫秒
511.
Beatriz Martín-García María del Carmen Razola-Díaz Ana María Gmez-Caravaca Guillermo Benítez Vito Verardo 《Molecules (Basel, Switzerland)》2021,26(15)
Hawthorn leaves are a rich source of phenolic compounds that possess beneficial activities for human health. Ultrasonic-assisted extraction (UAE) is an extraction technique frequently used for the isolation of phenolic compounds in plants. Thus, in this study, a Box–Behnken design was used to optimize UAE conditions such as the percentage of acetone, the extraction time and solvent-to-solid ratio (v/w) in order to obtain the maximum content of total compounds by Folin–Ciocalteu and the maximum in vitro antioxidant activity by DPPH, ABTS and FRAP assays in Crataegus monogyna leaves. The optimum conditions to obtain the highest total phenolic content and antioxidant activities were 50% acetone, 55 min and 1/1000 (w/v). A total of 30 phenolic compounds were identified and quantified in C. monogyna leaf extract obtained at these optimum UAE conditions. HPLC-MS allows the identification and quantification of 19 phenolic compounds and NP-HPLC-FLD analyses showed the presence of 11 proanthocyanidins. According to the results, the most concentrated phenolic compounds in C. monogyna leaf extract obtained at optimum UAE conditions were phenolic acid derivatives such as protocatechuic acid-glucoside, dihydroxy benzoic acid pentoside and chlorogenic acid, flavones such as 2″-O-rhamnosyl-C-hexosyl-apigenin, flavonols such as hyperoside and isoquercetin and proanthocyanidins such as monomer and dimer. As a result, the optimized UAE conditions could be used to obtain an extract of C. monogyna leaves enriched with phenolic compounds. 相似文献
512.
Vito Lampret 《Central European Journal of Mathematics》2012,10(2):775-787
An asymptotic approximation of Wallis’ sequence W(n) = Π
k=1
n
4k
2/(4k
2 − 1) obtained on the base of Stirling’s factorial formula is presented. As a consequence, several accurate new estimates
of Wallis’ ratios w(n) = Π
k=1
n
(2k−1)/(2k) are given. Also, an asymptotic approximation of π in terms of Wallis’ sequence W(n) is obtained, together with several double inequalities such as, for example,
W(n) ·(an + bn ) < p < W(n) ·(an + b¢n )W(n) \cdot (a_n + b_n ) < \pi < W(n) \cdot (a_n + b'_n ) 相似文献
513.
We analyze the efficiency as thermoelectric energy converter of a silicon–germanium alloy with composition and temperature dependent heat conductivity. The dependency on composition is determined by a non-linear regression method (NLRM), while the dependency on temperature is approximated by a first-order expansion in the neighborhood of three reference temperatures. The differences with respect to the case of thermal conductivity depending on composition only are pointed out. The efficiency of the system is analyzed under the assumption that the optimal energy conversion corresponds to the minimum rate of energy dissipated. The values of composition and temperature which minimize such a rate are calculated as well. 相似文献
514.
María del Carmen Razola-Díaz Eduardo Jesús Guerra-Hernndez Beln García-Villanova Vito Verardo 《Molecules (Basel, Switzerland)》2022,27(23)
Fruits and vegetables are a source of a wide range of nutrients, including bioactive compounds. These compounds have great biological activity and have been linked to the prevention of chronic non-communicable diseases. Currently, the food industry is developing new products to introduce these compounds, whereby smoothies are becoming more popular among consumers. The aim of this study was to evaluate the nutritional quality and the polyphenol and vitamin C content of smoothies available on the Spanish market. An evaluation of the nutritional information and ingredients was carried out. The phenolic compounds were determined by HPLC-ESI-TOF-MS; the vitamin C content was quantified using HPLC-UV/VIS; and the antioxidant activity was analyzed by DPPH and FRAP. Among all of the ingredients of the smoothies, coconut and banana have shown a negative impact on the polyphenol content of the smoothies. In contrast, ingredients such as orange, mango, and passion fruit had a positive correlation with the vitamin C content. Moreover, apple and red fruits showed the highest positive correlations with most of the phenolic acids, flavonoids, total phenolic compounds, and antioxidant activities. In addition, a clustering analysis was performed, and four groups were clearly defined according to the bioactive composition determined here. This research is a precious step for the formulation of new smoothies and to increase their polyphenol quality. 相似文献
515.
Andrea Francesca Quivelli Federico Vittorio Rossi Chiara Alario Francesco Sannicol Paola Vitale Joaquín García-lvarez Filippo Maria Perna Vito Capriati 《Molecules (Basel, Switzerland)》2022,27(21)
Dimethindene is a selective histamine H1 antagonist and is commercially available as a racemate. Upon analyzing the synthetic pathways currently available for the industrial preparation of dimethindene, we set up a sustainable approach for the synthesis of this drug, switching from petroleum-based volatile organic compounds (VOCs) to eco-friendly solvents, such as 2-methyltetrahydrofuran (2-MeTHF) and cyclopentyl methyl ether (CPME) belonging to classes 3 and 2, respectively. Beyond decreasing the environmental impact of the synthesis (E-factor: 24.1–54.9 with VOCs; 12.2–22.1 with 2-MeTHF or CPME), this switch also improved the overall yield of the process (from 10% with VOCs to 21–22% with 2-MeTHF or CPME) and remarkably simplified the manual operations, working under milder conditions. Typical metrics applied at the first and second pass, according to the CHEM21 metrics toolkit, were also calculated for the whole synthetic procedure of dimethindene, and the results were compared with those of the classical procedure. 相似文献
516.
Franco Cristiani Francesco A. Devillanova Francesco Isaia Vito Lippolis Gaetano Verani Francesco Demartin 《Heteroatom Chemistry》1993,4(6):571-578
1,4,7-Trithiacyclononane ([9]aneS3) reacts with molecular diiodine in CH2Cl2 to form a 1:1 adduct. The formation constant and the thermodynamic parameters of this adduct have been determined by UV-visible spectra of several solutions at the temperatures of 15, 20, 25, 30, and 35°C. The 13C NMR spectra show that adducts with higher ligand/diiodine molar ratios are formed. Two neutral charge-transfer molecular compounds having formula 2[9]aneS3 · 4I2 ( I ) and [9]aneS3 · 3I2 · ( II ) have been obtained as crystals. The crystals of I are triclinic (a = 8.498(2) Å, b = 13.984(4) Å, c = 14.898(6) Å, α = 65.57(2)°, γ = 89.19(2)°, γ = 81.26(2)°, Z = 2, space group P1; R = 0.025) and contain units formed by two [9]aneS3 molecules connected by a diiodine molecule; one [9]aneS3 binds two other diiodine molecules, while the second binds only one other diiodine molecule. The crystals of II are monoclinic (a = 13.810(2) Å, b = 9.829(4) Å, c = 16.198(6) Å, β = 113.41(2)°, Z = 4, space group P21/c; R = 0.019) and contain molecules of [9]aneS3 binding three diiodine molecules. FT-Raman spectra in the characteristic v(I–I) region, carried out on the solid adducts, are discussed in comparison with the structural parameters. 相似文献
517.
Dr. Giuseppe Dilauro Dr. Cosimo Luccarelli Dr. Andrea F. Quivelli Prof. Paola Vitale Prof. Filippo M. Perna Prof. Vito Capriati 《Angewandte Chemie (International ed. in English)》2023,62(30):e202304720
Advancing the development of perfecting the use of polar organometallics in bio-inspired solvents, we report on the effective generation in batch of organosodium compounds, by the oxidative addition of a C−Cl bond to sodium, a halogen/sodium exchange, or by direct sodiation, when using sodium bricks or neopentylsodium in hexane as sodium sources. C(sp3)-, C(sp2)-, and C(sp)-hybridized alkyl and (hetero)aryl sodiated species have been chemoselectively trapped (in competition with protonolysis), with a variety of electrophiles when working “on water”, or in biodegradable choline chloride/urea or L-proline/glycerol eutectic mixtures, under hydrous conditions and at room temperature. Additional benefits include a very short reaction time (20 s), a wide substrate scope, and good to excellent yields (up to 98 %) of the desired adducts. The practicality of the proposed protocol was demonstrated by setting up a sodium-mediated multigram-scale synthesis of the anticholinergic drug orphenadrine. 相似文献
518.
Dr. Giuseppe Dilauro Dr. Luciana Cicco Prof. Paola Vitale Prof. Filippo Maria Perna Prof. Vito Capriati 《European journal of organic chemistry》2023,26(3):e202200814
A Deep Eutectic Solvent, choline chloride/glycerol (1 : 2 mol mol−1), proved to be an effective and sustainable reaction medium to promote telescoped, one-pot Mizoroki-Heck cross-coupling/reduction processes between 2,3-dihydrofuran or 3,4-dihydro-2H-pyran and several (hetero)aryl halides to easily access valuable 2-(hetero)aryl tetrahydrofuran (THF) or tetrahydropyran derivatives in up to 95 % yield. Notably, the whole transformation takes place under aerobic conditions, in the absence of additional ligands, and with a good substrate scope. The practicability of the method is also exemplified by the sustainable synthesis of two key THF derivatives, which are side chains of pharmacologically relevant inhibitors of Kv1.2 channel. 相似文献
|