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

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 β^2,3,3‐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.     

Trends in the detection of pharmaceuticals and endocrine-disrupting compounds by Field-Effect Transistors (FETs)

Field-effect transistors (FETs) are one of the most widely-used electronic sensors for continuous monitoring and detection of contaminants such as pharmaceuticals and endocrine-disrupting compounds at low concentrations. FETs have been successfully utilized for the rapid analysis of these environmental pollutants due to their advantageous material properties like the disposability, rapid responses and simplicity. This paper presented an up-to-date overview of applied strategies with different bio-based materials in order to enhance the analytical performances of the designed sensors. Comparison and discussion were made between characteristics of recently engineered FET bio-sensors used for the detection of famous and selected pharmaceutical compounds in the literature. The recent progress in environmental research applications, comments on interesting trends, current challenge for future research in endocrine-disrupting chemicals’ (EDCs) detection using FETs biosensors were highlighted.     

Strategies for Improving the Catalytic Performance of 2D Covalent Organic Frameworks for Hydrogen Evolution and Oxygen Evolution Reactions

Hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have been deemed as clean and sustainable strategies to solve the energy crisis and environmental problems. Various catalysts have been developed to promote the process of HER and OER. Among them, two-dimensional covalent organic frameworks (2D COFs) have received great attention due to their diverse and designable structure. In this minireview, we mainly summarize the diverse linkages of 2D COFs and strategies for enhancing the catalytic performance of 2D COFs for HER and OER, such as introducing active building blocks, metal ions and tailored linkages. Furthermore, a brief outlook for the development directions of COFs in the field of HER and OER is provided, expecting to stimulate new opportunities in future research.     

稳定分层湍流中逆梯度输运的关联分析研究

本文采用关联分析方法研究了稳定温度分层湍流中的结构特性、输运特性，以及热量、动量逆梯度输运现象的尺度效应及其参数演化．首先采用大涡模拟方法对稳定分层湍流中的结构特性和输运特性进行了分析，将逆梯度输运发生的时间尺度作为已知条件，结合关联量分析方法在波数空间中的解析解，对逆梯度输运现象的尺度效应进行了分析研究．结果发现，稳定分层强度较大的流动中发生垂向热量及动量逆梯度输运现象，发生的结构尺度与关联分析所发现垂向热量、动量逆梯度输运的波数形成了呼应．随着分层强度增加，热量、动量的输运强度均受抑制，与逆梯度输运关联的流场结构尺度减小，同样的效应也发生在流场结构向下游演化的过程中．     

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

A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni_0.5Zn_0.5Fe₂O₄ magnetic nanoparticles (Ni_0.5Zn_0.5Fe₂O₄@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, Ni_0.5Zn_0.5Fe₂O₄@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.     

Time dependent Schrödinger equation for black hole evaporation: No information loss

In 1976 S. Hawking claimed that “Because part of the information about the state of the system is lost down the hole, the final situation is represented by a density matrix rather than a pure quantum state”. ¹ This was the starting point of the popular “black hole (BH) information paradox”.     

Local linear convergence analysis of Primal–Dual splitting methods

In this paper, we study the local linear convergence properties of a versatile class of Primal–Dual splitting methods for minimizing composite non-smooth convex optimization problems. Under the assumption that the non-smooth components of the problem are partly smooth relative to smooth manifolds, we present a unified local convergence analysis framework for these methods. More precisely, in our framework, we first show that (i) the sequences generated by Primal–Dual splitting methods identify a pair of primal and dual smooth manifolds in a finite number of iterations, and then (ii) enter a local linear convergence regime, which is characterized based on the structure of the underlying active smooth manifolds. We also show how our results for Primal–Dual splitting can be specialized to cover existing ones on Forward–Backward splitting and Douglas–Rachford splitting/ADMM (alternating direction methods of multipliers). Moreover, based on these obtained local convergence analysis result, several practical acceleration techniques are discussed. To exemplify the usefulness of the obtained result, we consider several concrete numerical experiments arising from fields including signal/image processing, inverse problems and machine learning. The demonstration not only verifies the local linear convergence behaviour of Primal–Dual splitting methods, but also the insights on how to accelerate them in practice.     

煤直接液化油中混合酚的分离研究

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%。