Versatile Near-Infrared Super-Resolution Imaging of Amyloid Fibrils with the Fluorogenic Probe CRANAD-2

CRANAD-2 is a fluorogenic curcumin derivative used for near-infrared detection and imaging in vivo of amyloid aggregates, which are involved in neurodegenerative diseases. We explore the performance of CRANAD-2 in two super-resolution imaging techniques, namely stimulated emission depletion (STED) and single-molecule localization microscopy (SMLM), with markedly different fluorophore requirements. By conveniently adapting the concentration of CRANAD-2, which transiently binds to amyloid fibrils, we show that it performs well in both techniques, achieving a resolution in the range of 45–55 nm. Correlation of SMLM with atomic force microscopy (AFM) validates the resolution of fine features in the reconstructed super-resolved image. The good performance and versatility of CRANAD-2 provides a powerful tool for near-infrared nanoscopic imaging of amyloids in vitro and in vivo.     

烧结温度对Cao.9(NaCe)0.05Bi2Nb2O9无铅压电陶瓷性能的影响

采用传统固相反应法制备了Ca0.9(NaCe)0.05Bi2 Nb2 O9铋层状无铅压电陶瓷.采用XRD、SEM、EDS及相关电学性能测试系统表征了样品的晶体结构、断面形貌、元素组成以及介电、压电、铁电等性能,探究不同烧结温度对于陶瓷性能的影响.结果表明:当烧结温度为1150℃时,样品的晶体结构单一均匀,呈现片层状结构,致密性较好,压电常数高达17 pC/N,介电损耗仅为0.42;,居里温度为908℃,并且具有很好的温度稳定性,说明固相反应法制备的Ca0.9(NaCe)0.05Bi2Nb2O9压电陶瓷最佳烧结温度为1150℃.     

Influence of Polarity and Activation Energy in Microwave–Assisted Organic Synthesis (MAOS)

The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol⁻¹ and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.     

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.     

考虑非结构性的多级生产流程调度方法

针对智能化柔性制造过程存在的再制造过程,对中小型设备生产车间及其仓储转运的模型构建、分析方法、以及参量相关性提出了新的解决思路.为了最大限度的减少建设周期、合理化投资成本、以及优化生产流程,建立了考虑非结构性的多级生产流程的数学模型,以完成度、完工时间和调度频次为目标函数分析生产要素间的相关性.实验结果表明,融合再加工过程的智能化柔性制造单元中,生产要素为非线性相关,个别要素具备对称性,为实际工况中的生产改进及优化提供了一定理论基础.