Multivariate optimization and comparison between conventional extraction (CE) and ultrasonic-assisted extraction (UAE) of carotenoid extraction from cashew apple

Carotenoids are an essential component of cashew and can be used in pharmaceuticals, cosmetics, natural pigment, food additives, among other applications. The present work focuses on optimizing and comparing conventional and ultrasound-assisted extraction methods. Every optimization step took place with a 1:1 (w:w) mixture of yellow and red cashew apples lyophilized and ground in a cryogenic mill. A Simplex-centroid design was applied for both methods, and the solvents acetone, methanol, ethanol, and petroleum ether were evaluated. After choosing the extractor solvent, a central composite design was applied to optimize the sample mass (59–201 mg) and extraction time (6–34 min). The optimum conditions for the extractor solvent were 38% acetone, 30% ethanol, and 32% petroleum ether for CE and a mixture of 44% acetone and 56% methanol for UAE. The best experimental conditions for UAE were a sonication time of 19 min and a sample mass of 153 mg, while the CE was 23 min and 136 mg. Comparing red and yellow cashews, red cashews showed a higher carotenoid content in both methodologies. The UAE methodology was ca. 21% faster, presented a more straightforward composition of extracting solution, showed an average yield of superior carotenoid content in all samples compared to CE. Therefore, UAE has demonstrated a simple, efficient, fast, low-cost adjustment methodology and a reliable alternative for other applications involving these bioactive compounds in the studied or similar matrix.     

On the Nature of Functional Differentiation: The Role of Self-Organization with Constraints

The focus of this article is the self-organization of neural systems under constraints. In 2016, we proposed a theory for self-organization with constraints to clarify the neural mechanism of functional differentiation. As a typical application of the theory, we developed evolutionary reservoir computers that exhibit functional differentiation of neurons. Regarding the self-organized structure of neural systems, Warren McCulloch described the neural networks of the brain as being “heterarchical”, rather than hierarchical, in structure. Unlike the fixed boundary conditions in conventional self-organization theory, where stationary phenomena are the target for study, the neural networks of the brain change their functional structure via synaptic learning and neural differentiation to exhibit specific functions, thereby adapting to nonstationary environmental changes. Thus, the neural network structure is altered dynamically among possible network structures. We refer to such changes as a dynamic heterarchy. Through the dynamic changes of the network structure under constraints, such as physical, chemical, and informational factors, which act on the whole system, neural systems realize functional differentiation or functional parcellation. Based on the computation results of our model for functional differentiation, we propose hypotheses on the neuronal mechanism of functional differentiation. Finally, using the Kolmogorov–Arnold–Sprecher superposition theorem, which can be realized by a layered deep neural network, we propose a possible scenario of functional (including cell) differentiation.     

使用稀疏贝叶斯学习的水声多途信道盲估计

提出了一种使用稀疏贝叶斯学习(SBL)的多途信号盲解卷积方法对水声多途信道的信道脉冲响应(CIR)进行盲估计。该方法利用垂直阵和多频SBL获得宽带舰船声源在不同垂直到达角上的复数域多频点信号,取其相位对垂直阵接收信号匹配滤波,得到每条路径上的CIR,将多路径CIR相干叠加得到最终的多途CIR结果。仿真与海试数据处理结果表明,相比于原有的基于交替投影的多途信号盲解卷积方法,所提出方法有以下几个好处:(1)无需准确预估多途信号数目;(2)分离的多途信号的方位更准确且信号相位更可靠;(3)有效获取了舰船与阵列之间的CIR.并且将弱路径CIR的平均时间估计误差从4.7 ms缩小到1.0 ms.显著提高了弱路径CIR的时间估计精度。使用稀疏贝叶斯学习的多途信号盲解卷积方法能够有效提高多途环境下水声信道盲估计的性能。     

磁刺激穴位复杂脑功能网络构建与分析

本文采用互信息方法对磁刺激内关穴过程中的脑电信 号进行了两两通道间非线性时域关联特性分析, 构建了不同频率刺激前、刺激中、刺激后的脑功能网络, 并基于复杂网络理论对脑功能网络的特征进行了深入研究. 结果表明, 磁刺激频率为3 Hz 时, 大脑功能网络的平均度、平均聚类系数和全局效率与刺激前相比均有显著升高, 平均路径长度显著降低, 并且相应脑功能网络的"小世界"属性有所增强, 信息在大脑各区域间的传递更加高效. 本研究首次开展了磁刺激穴位复杂脑功能网络的构建与分析, 为探索磁刺激穴位对大脑神经调节的作用和机理提供新思路和新方法. 关键词： 复杂网络 磁刺激 脑功能网络 互信息     

Evolution of geometrical structures,stabilities and electronic properties of neutral and anionic Li n Cu λ (n = 1–9, λ = 0, −1) clusters: compare with pure lithium clusters

The structural evolution, stabilities, and electronic properties of copper-doped lithium Li _n Cu^λ (n?=?1–9, λ?=?0, ?1) clusters have been systematically investigated using a density functional method at PW91PW91 level. Extensive searches for ground-state structures were carried out, and the results showed the copper tends to occupy the most highly coordinated position and form the largest probable number of bonds with lithium atoms. By calculating the binding energies per atom, fragmentation energies and the HOMO-LOMO gaps, we found LiCu, Li₇Cu, LiCu^?, Li₂Cu^? and Li₈Cu^? clusters have the stronger relative stability and enhanced chemical stability. The content and pattern of frontier MOs for the most stable doped isomers were analysed to investigate the bond nature of interaction among Li and Cu atoms. The results show some σ-type and π-type bonds are formed among them, and with small admixture of the Cu d characters. To achieve a deep insight into the electron localization and reliable electronic structure information, the natural population analysis and electron localization function were performed and discussed.     

Experimental and molecular modeling investigation of (E)-N-{2-[(2-hydroxybenzylidene)amino]phenyl}benzenesulfonamide

The Schiff base compound (E)-N-{2-[(2-hydroxybenzylidene)amino]phenyl}benzenesulfonamide has been synthesized and characterized by IR, NMR and Uv-vis spectroscopies, and single-crystal X-ray diffraction technique. In addition, quantum chemical calculations employing density functional theory (DFT) method with the 6–311++G(d,p) basis set were performed to study the molecular, spectroscopic and some electronic structure properties of the title compound, and the results were compared with the experimental findings. There exists a good correlation between experimental and theoretical data. Enol-imine/keto-amine tautomerization mechanism was investigated in the gas phase and in solution phase using the polarizable continuum model (PCM) approximation. The energetic and thermodynamic parameters of the enol-imine?→?keto-amine transfer process show that the single proton exchange is thermodynamically unfavored both in the gas phase and in solution phase. However, the reverse reaction seems to be feasible with a low barrier height and is supported by negative values in enthalpy and free energy changes both in the gas phase and in solution phase. The solvent effect is found to be sizable with increasing polarity of the solvents for the reverse reaction. The predicted nonlinear optical properties of the compound are found to be much greater than those of urea.     

Tautomeric populations of the charged species of 1,12‐diamino‐3,6,9‐triazadodecane (SpmTrien) studied with computer simulations and cluster expansions

Correct net charge and protonation pattern in the polyamine backbone is one of the major factors that define the interactions of this class of compounds. 1,12‐diamino‐3,6,9‐triazadodecane (SpmTrien) is a isosteric charge deficient analogue of naturally occurring spermine (Spm) with different biological features. The tautomeric populations of each SpmTrien charge state were estimated with computer simulations, molecular dynamics (MD) and quantum mechanical calculations, and cluster expansions separately. In the computer simulations, tautomeric populations of each charge state were obtained by constrained least‐squares fitting the theoretically calculated (GIAO B3LYP/6‐311 + G**) ¹⁵ N NMR chemical shieldings of SpmTrien tautomers to the experimentally measured chemical shifts. Theoretical chemical shieldings were calculated for water complexes of SpmTrien obtained from MD simulations in explicit water. Both methods gave highly similar realistic results. SpmTrien has many major populations of tautomers at biologically relevant charge states of three (+3) and four (+4) thus enabling a large variety of structures for specific ionic interactions. Copyright © 2013 John Wiley & Sons, Ltd.