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11.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis
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Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
12.
Synthesis of Small‐Sized,Porous, and Low‐Toxic Magnetite Nanoparticles by Thin POSS Silica Coating
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Dr. Swee Kuan Yen D. Prathyusha Varma Wei Mei Guo Dr. Vincent H. B. Ho Dr. Vimalan Vijayaragavan Dr. Parasuraman Padmanabhan Prof. Kishore Bhakoo Prof. Subramanian Tamil Selvan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3914-3918
In this communication, we report the synthesis of small‐sized (<10 nm), water‐soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS‐coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51–53 emu g?1) comparable to silica‐coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF‐7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging. 相似文献
13.
Development of biocompatible porous supports is a promising strategy in the field of tissue engineering for the repair and regeneration of bone tissues with severe damage. Graphene oxide aerogels (GOAs) are excellent candidates for the manufacture of these systems due to their porosity, ability to imitate bone structure, and mechanical resistance, and according to their surface chemical reactivity, they can facilitate osseointegration, osteogenesis, osteoinduction and osteoconduction. In this review, synthesis of GOAs from the most primary source is described, and recent studies on the use of these functionalized carbonaceous foams as scaffolding for bone tissue regeneration are presented. 相似文献
14.
Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones
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Behrooz Maleki Samaneh Barat Nam Chalaki Samaneh Sedigh Ashrafi Esmail Rezaee Seresht Farid Moeinpour Amir Khojastehnezhad Reza Tayebee 《应用有机金属化学》2015,29(5):290-295
A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni0.5Zn0.5Fe2O4 magnetic nanoparticles (Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni0.5Zn0.5Fe2O4@HAP‐Cs2CO3 could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
15.
煤直接液化油中混合酚的分离研究 《燃料化学学报》2019,47(11):1298-1304
利用分子筛择形特点,对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物,采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变,分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响,以获得高性能固相吸附剂,并将其应用于180-190℃馏分段混合酚分离。结果表明,当分子筛硅铝比为25、粒径为3-5 μm时,分子筛的孔口结构调节效果最优;当正硅酸乙酯的最小用量为0.2 mL/g时,固相吸附剂的吸附量为0.03 g/g,对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化,导致对甲酚选择性的提高。进一步采用HZSM-5(1)吸附剂对真实煤直接液化油混合酚的分离中发现,苯酚和对甲酚的选择性均达到100%。 相似文献
16.
Active anodes, especially those consisting of metal mixed oxides (MMOs) containing Ru and/or Ir oxides, have been applied in the treatment of wastewater, especially when chloride ions are present. Their characteristics continuously drive the study of applications of these materials, be they in the degradation of different organic molecules, the preparation of new electrode materials and in the association of various processes to increase pollutant removal. Thus, this brief review aims to present some of the recent advances in the application of active anode materials in environmental electrochemistry. Focussing on the 2018–2020 period, it is possible to note many applied studies, using commercially available materials, covering a wide range of target pollutants. Still other studies aim to modify the catalyst surfaces to increase the mineralization capacity, and the use of these anodes in the production of free chlorine species to mediate indirect organic reduction is observed. 相似文献
17.
Given an ‐vertex pseudorandom graph and an ‐vertex graph with maximum degree at most two, we wish to find a copy of in , that is, an embedding so that for all . Particular instances of this problem include finding a triangle‐factor and finding a Hamilton cycle in . Here, we provide a deterministic polynomial time algorithm that finds a given in any suitably pseudorandom graph . The pseudorandom graphs we consider are ‐bijumbled graphs of minimum degree which is a constant proportion of the average degree, that is, . A ‐bijumbled graph is characterised through the discrepancy property: for any two sets of vertices and . Our condition on bijumbledness is within a log factor from being tight and provides a positive answer to a recent question of Nenadov. We combine novel variants of the absorption‐reservoir method, a powerful tool from extremal graph theory and random graphs. Our approach builds on our previous work, incorporating the work of Nenadov, together with additional ideas and simplifications. 相似文献
18.
19.
近年来深度卷积神经网络在可见光船舶检测方面取得了显著的进展,然而,大多数相关研究是通过改进大型的网络结构来提高检测性能,因此加大了对更高计算机性能的需求。此外,可见光图像难以在云、雾、海杂波、黑夜等复杂场景检测到船舶。针对以上问题,提出了一种融合红(red, R)、绿(green, G)、蓝(blue, B)和近红外(NIR)4个波段光谱信息的由粗到精细的轻量型船舶检测算法。与现有的方法中根据光谱特性利用水体检测算法提取水体区域不同之处是该算法是利用改进的水体检测算法来提取船舶候选区域。为获取更准确的候选区域,对船舶、厚云、薄云、平静海面、杂波海面5种场景中4个波段的像素值进行了统计分析,选取近红外大于阈值作为辅助判断,并以其中心点获取候选区域32×32大小的切片,并对切片进行非极大值抑制,由此获得了船舶粗检测结果。随后构建了轻量级LSGFNet网络对船舶候选区域切片进行精细识别。构建的网络融合了1×1卷积提取的波谱特征与3×3的提取几何特征,为防止光谱特征与几何特征的信息在融合时“信息不流通”,在LSGFNet网络中引入了ShuffleNet中的通道打乱机制,并减小了模型结构,与典型的轻量级网络相比具有更好的效果且模型较小。最后,利用Sentinel-2卫星多光谱10 m分辨率数据构建了512×512大小的1 120组数据进行粗检测,以及32×32大小的6 014组数据进行精细网络训练,其中候选区域粗提取的查全率为98.99%,精细识别网络精确度为96.04%,不同场景下的平均精确度为92.98%。实验表明该算法在抑制云层、海浪杂波等干扰的复杂背景下具有较高的检测效率,且训练时间短、计算机性能需求低。 相似文献
20.
The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by 1H- and 13C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C2 symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a Cs transition state with a calculated relative free energy of 11.0 kcal mol−1. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol−1 at 298 K. 相似文献