全文获取类型
收费全文 | 603篇 |
免费 | 12篇 |
国内免费 | 4篇 |
专业分类
化学 | 312篇 |
晶体学 | 3篇 |
力学 | 33篇 |
数学 | 127篇 |
物理学 | 144篇 |
出版年
2023年 | 13篇 |
2022年 | 16篇 |
2021年 | 18篇 |
2020年 | 15篇 |
2019年 | 21篇 |
2018年 | 11篇 |
2017年 | 11篇 |
2016年 | 27篇 |
2015年 | 20篇 |
2014年 | 27篇 |
2013年 | 46篇 |
2012年 | 29篇 |
2011年 | 43篇 |
2010年 | 24篇 |
2009年 | 19篇 |
2008年 | 27篇 |
2007年 | 33篇 |
2006年 | 33篇 |
2005年 | 28篇 |
2004年 | 24篇 |
2003年 | 20篇 |
2002年 | 14篇 |
2001年 | 5篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 9篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1982年 | 3篇 |
1980年 | 2篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 7篇 |
1938年 | 2篇 |
1930年 | 1篇 |
1911年 | 1篇 |
1910年 | 1篇 |
1907年 | 1篇 |
1906年 | 2篇 |
1905年 | 1篇 |
1903年 | 1篇 |
1877年 | 1篇 |
1868年 | 1篇 |
排序方式: 共有619条查询结果,搜索用时 296 毫秒
611.
This contribution reports the results obtained in the definition of a catalytic method for the nucleophilic ring opening of epoxides by activated methylenes promoted by a polymer-supported base. The attention has been focused on the use of polymer supported bases and the best results have been obtained by using 4-(dimethylamino)pyridine (PS-DMAP) and 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorine both on polystyrene (PS-BEMP). Solvent-free conditions has been essential for reaching a sufficient reactivity to realize this process, in fact when a reaction medium is used, the processes are almost unfeasible. 相似文献
612.
N-acyl-homoserine-lactones (AHSLs) are widely conserved signal molecules present in quorum sensing systems of Gram-negative bacteria such as Pseudomonas aeruginosa. We present here the results obtained with a hybrid linear trap/Fourier transform ion cyclotron resonance (LTQ-FTICR) mass spectrometer used to investigate the occurrence of AHSLs and cognate N-acyl-homoserines (AHSs) in bacterial isolates of P. aeruginosa (strain PAO1). Two hydrolysed AHSs were found in significant amounts, most likely formed through the lactone opening of N-3-oxo-decanoyl-L-homoserine-lactone (3OC10-HSL) and N-3-oxo-dodecanoyl-L-homoserine-lactone (3OC12-HSL). Structure elucidation of these ring-opened molecules, i.e. N-3-oxo-decanoyl-L-homoserine (3OC10-HS), and N-3-oxo-dodecanoyl-L-homoserine (3OC12-HS), which are not detected by bacterial biosensors, was performed by high-resolution and accurate mass measurements upon liquid chromatography (LC) and confirmed by tandem MS in the LTQ analyser. Assignment of chemical formula, with mass spectra in the form of [M+H]+, was significantly expedited by extracted ion chromatograms (XICs) because the number of potentially plausible formulae for each protonated signalling molecule was considerably reduced a priori by the LC behaviour, the high mass measurement accuracy available in FTICR mass spectra and the isotopic patterns. At least two concentration levels were observed in spent culture supernatants of P. aeruginosa: compounds at a relatively high content (5-15 microM) that is C4-HSL, 3OC10-HS, and 3OC12-HS and those occurring at a lower content (<0.2 microM) that is C6-HSL and C8-HSL. The implications of this work extend to a great variety of Gram-negative bacteria. 相似文献
613.
614.
Every 1‐rotational solution of a classic or twofold Oberwolfach problem (OP) of order n is generated by a suitable 2‐factor (starter) of or , respectively. It is shown that any starter of a twofold OP of order n gives rise to a starter of a classic OP of order (doubling construction). It is also shown that by suitably modifying the starter of a classic OP, one may obtain starters of some other OPs of the same order but having different parameters. The combination of these two constructions leads to lots of new infinite classes of solvable OPs. Still more classes can be obtained with the help of a third construction making use of the possible gracefulness of a graph whose connected components are cycles and at most one path. As one of the many applications, Hilton and Johnson's [J London Math Soc, 64 (2001) 513–522] bound about the solvability of OP is improved to in the case of r even. © 2012 Wiley Periodicals, Inc. J. Combin. Designs 20: 483‐503, 2012 相似文献
615.
Antonio Monopoli Giovanni Ventura Andrea Aloia Fulvio Ciriaco Angelo Nacci Tommaso R. I. Cataldi Cosima D. Calvano 《Molecules (Basel, Switzerland)》2022,27(8)
A significant area of study and upgrading for increasing sensitivity and general performances of matrix-assisted laser-desorption ionization (MALDI) mass spectrometry (MS) is related to matrix design. Several efforts have been made to address the challenge of low-mass-region interference-free for metabolomics analysis and specifically for lipidomics. To this aim, rationally designed matrices as 4-chloro-α-cyanocinnamic acid (ClCCA) were introduced and reported to provide enhanced analytical performances. We have taken this rational design one step further by developing and optimizing new MALDI matrices with a range of modifications on the CHCA core, involving different functionalities and substituents. Of particular interest was the understanding of the electron-withdrawing (e.g., nitro-) or donating (e.g., methoxy-) effects along with the extent of conjugation on the ionization efficiency. In the present work, ten matrices were designed on a reasonable basis, synthesized, and characterized by NMR and UV spectroscopies and laser desorption ionization. With the assistance of these putative MALDI matrices, samples containing phospholipids (PL), and neutral di-/tri-acylglycerols (DAG, TAG) were investigated using milk, fish, blood, and human plasma extracts. In comparison with CHCA and ClCCA, four of them, viz. [(2E,4E)-2-cyano-5-(4-methoxyphenyl)penta-2,4-dienoic acid] (1), [(2E,4E)-2-cyano-5-(4-nitrophenyl)penta-2,4-dienoic acid] (2), [(E)-2-cyano-3-(6-methoxynaphthalen-2-yl)acrylic acid] (6) and [(E)-2-cyano-3-(naphthalen-2-yl)acrylic acid] (7) displayed good to even excellent performances as MALDI matrices in terms of ionization capability, interference-free spectra, S/N ratio, and reproducibility. Especially compound 7 (cyano naphthyl acrylic acid, CNAA) was the election matrix for PL analysis and matrix 2 (cyano nitrophenyl dienoic acid, CNDA) for neutral lipids such as DAG and TAG in positive ion mode. 相似文献
616.
Dr. Kumar Bhaskar Pal Dr. Ester Maria Di Tommaso Dr. A. Ken Inge Prof. Berit Olofsson 《Angewandte Chemie (International ed. in English)》2023,62(20):e202301368
We report an efficient radical-mediated C−C coupling through photoredox-catalyzed reactions of 4-alkyl-dihydropyridines (DHPs) and vinylbenziodoxol(on)es (VBX, VBO). This transition-metal-free and mild photocatalytic method has excellent functional group tolerance and affords vinylated products in good yields, with complete retention of the alkene configuration. The utility of the methodology is demonstrated by the diastereoselective synthesis of C-vinyl glycosides. Preliminary mechanistic studies suggest that the C−C bond formation is stereospecific and proceeds through a concerted radical coupling transition state. 相似文献
617.
Dr. Sara Cuadros Dr. Giulio Goti Giorgia Barison Alfredo Raulli Tommaso Bortolato Prof. Giorgio Pelosi Dr. Paolo Costa Prof. Luca Dell'Amico 《Angewandte Chemie (International ed. in English)》2023,62(31):e202303585
Here, we report a general approach to the synthesis of the difluoroalkyl bicycloalkanes (CF2-BCAs), as structural surrogates of aryl ketones and ethers. The chemistry is driven by a dihydrobenzoacridine photocatalyst, that engages in a catalytic electron-donor acceptor (EDA) complex, or directly reduces the fluorinated substrate. These two convergent manifolds lead to the generation of the R-CF2 radical, that reacts with the [1.1.1]- or [3.1.1.]-propellane. The method is extremely general, and extendable to complex bioactive molecules (30 examples, up to 87 % yield). The structural features of the CF2-BCP hybrid bioisostere were investigated by single crystal X-ray. Finally, we synthesised a CF2-BCP analogue of a Leukotriene A4 hydrolase inhibitor, replacing the original aryl ether motif. In silico docking studies indicated that this new analogue maintains the same arrangement within the enzyme pocket, profiling the use of the CF2-BCA hybrid bioisostere in medicinal chemistry settings. 相似文献
618.
619.
Tommaso Rigon 《商业与工业应用随机模型》2023,39(2):232-250
There is an increasingly rich literature about Bayesian nonparametric models for clustering functional observations. Most recent proposals rely on infinite-dimensional characterizations that might lead to overly complex cluster solutions. In addition, while prior knowledge about the functional shapes is typically available, its practical exploitation might be a difficult modeling task. Motivated by an application in e-commerce, we propose a novel enriched Dirichlet mixture model for functional data. Our proposal accommodates the incorporation of functional constraints while bounding the model complexity. We characterize the prior process through a urn scheme to clarify the underlying partition mechanism. These features lead to a very interpretable clustering method compared to available techniques. Moreover, we employ a variational Bayes approximation for tractable posterior inference to overcome computational bottlenecks. 相似文献