Iron-based sulfur and nitrogen dual doped porous carbon as durable electrocatalysts for oxygen reduction reaction

The widespread use of fuel cell technology is hampered by the use of expensive and scarce platinum metal in electrodes which is required to facilitate the sluggish oxygen reduction reaction (ORR). In this work, a viable synthetic approach was developed to prepare iron-based sulfur and nitrogen dual doped porous carbon (Fe@SNDC) for use in ORR. Benzimidazole, a commercially available monomer, was used as a precursor for N doped carbon and calcined with potassium thiocyanate at different temperatures to tune the pore size, nitrogen content and different types of nitrogen functionality such as pyridinic, pyrrolic and graphitic. The Fe@SNDC–950 with high surface area, optimum N content of about 5 at% and high amount of pyridinic and graphitic N displayed an onset potential and half-wave potential of 0.98 and 0.83 V vs RHE, respectively, in 0.1 M KOH solution. The catalyst also exhibits similar oxygen reduction reaction performance compared to Pt/C (20 wt%) in acidic media. Furthermore, when compared to commercially available Pt/C (20 wt%), Fe@SNDC–950 showed enhanced durability over 6 h and poison tolerance in case of methanol crossover with the concentration up to 3.0 M in oxygen saturated alkaline electrolyte. Our study demonstrates that the presence of N and S along with Fe-N moieties synergistically served as ORR active sites while the high surface area with accessible pores allowed for efficient mass transfer and interaction of oxygen molecules to the active sites contributing to the ORR activity of the catalyst.     

Vertex-Edge Degree Based Indices of Honey Comb Derived Network

Chemical graph theory is a branch of mathematics which combines graph theory and chemistry. Chemical reaction network theory is a territory of applied mathematics that endeavors to display the conduct of genuine compound frameworks. It pulled the research community due to its applications in theoretical and organic chemistry since 1960. Additionally, it also increases the interest the mathematicians due to the interesting mathematical structures and problems are involved. The structure of an interconnection network can be represented by a graph. In the network, vertices represent the processor nodes and edges represent the links between the processor nodes. Graph invariants play a vital feature in graph theory and distinguish the structural properties of graphs and networks. In this paper, we determined the newly introduced topological indices namely, first -degree Zagreb index, first -degree Zagreb index, second -degree Zagreb index, -degree Randic index, -degree atom-bond connectivity index, -degree geometric-arithmetic index, -degree harmonic index and -degree sum-connectivity index for honey comb derived network. In the analysis of the quantitative structure property relationships (QSPRs) and the quantitative structureactivity relationships (QSARs), graph invariants are important tools to approximate and predicate the properties of the biological and chemical compounds. Also, we give the numerical and graphical representation of our outcomes.     

Dual pH‐ and thermal‐responsive nanocomposite hydrogels for controllable delivery of hydrophobic drug baicalein

Hydrogels have been widely used as mild biomaterials due to their bio‐affinity, high drug loading capability and controllable release profiles. However, hydrogel‐based carriers are greatly limited for the delivery of hydrophobic payloads due to the lack of hydrophobic binding sites. Herein, nano‐liposome micelles were embedded in semi‐interpenetrating poly[(N‐isopropylacrylamide)‐co‐chitosan] (PNIPAAm‐co‐CS) and poly[(N‐isopropylacrylamide)‐co‐(sodium alginate)] (PNIPAAm‐co‐SA) hydrogels which were responsive to both temperature and pH, thereby establishing tunable nanocomposite hydrogel delivery systems. Nano‐micelles formed via the self‐assembly of phospholipid could serve as the link between hydrophobic drug and hydrophilic hydrogel due to their special amphiphilic structure. The results of transmission and scanning electron microscopies and infrared spectroscopy showed that the porous hydrogels were successfully fabricated and the liposomes encapsulated with baicalein could be well contained in the network. In addition, the experimental results of response release in vitro revealed that the smart hydrogels showed different degree of sensitiveness under different pH and temperature stimuli. The results of the study demonstrate that combining PNIPAAm‐co‐SA and PNIPAAm‐co‐CS hydrogels with liposomes encapsulated with hydrophobic drugs is a feasible method for hydrophobic drug delivery and have potential application prospects in the medical field. © 2018 Society of Chemical Industry     

Elliptical distribution-based weight-determining method for ordered weighted averaging operators

The ordered weighted averaging (OWA) operators play a crucial role in aggregating multiple criteria evaluations into an overall assessment supporting the decision makers’ choice. One key point steps is to determine the associated weights. In this paper, we first briefly review some main methods for determining the weights by using distribution functions. Then we propose a new approach for determining OWA weights by using the regular increasing monotone quantifier. Motivated by the idea of normal distribution-based method to determine the OWA weights, we develop a method based on elliptical distributions for determining the OWA weights, and some of its desirable properties have been investigated.     

Ultrathin Dual‐Scale Nano‐ and Microporous Membranes for Vascular Transmigration Models

Selective cellular transmigration across the microvascular endothelium regulates innate and adaptive immune responses, stem cell localization, and cancer cell metastasis. Integration of traditional microporous membranes into microfluidic vascular models permits the rapid assay of transmigration events but suffers from poor reproduction of the cell permeable basement membrane. Current microporous membranes in these systems have large nonporous regions between micropores that inhibit cell communication and nutrient exchange on the basolateral surface reducing their physiological relevance. Here, the use of 100 nm thick continuously nanoporous silicon nitride membranes as a base substrate for lithographic fabrication of 3 µm pores is presented, resulting in a highly porous (≈30%), dual‐scale nano‐ and microporous membrane for use in an improved vascular transmigration model. Ultrathin membranes are patterned using a precision laser writer for cost‐effective, rapid micropore design iterations. The optically transparent dual‐scale membranes enable complete observation of leukocyte egress across a variety of pore densities. A maximal density of ≈14 micropores per cell is discovered beyond which cell–substrate interactions are compromised giving rise to endothelial cell losses under flow. Addition of a subluminal extracellular matrix rescues cell adhesion, allowing for the creation of shear‐primed endothelial barrier models on nearly 30% continuously porous substrates.     

具有自动装卸搬运机器人的制造单元建模与分析

针对具有自动装卸搬运机器人的制造单元，着重考虑其双重资源约束的特点，提出了该系统的有限缓冲开排队网的建模方法。根据工件的加工、装卸与搬运等工艺流程，定义该系统的排队网模型的各种状态，基于连续时间马尔可夫链，采用精确解法对该模型进行分析求解，获得系统一系列的稳态性能指标。为了验证排队网建模方法的有效性，建立其对应的仿真模型，分别采用排队网模型的数值计算与仿真模型的仿真统计2种方法求出系统的性能指标进行对比，并基于排队网模型对该制造单元的系统性能进行分析，为该类制造单元的资源配置优化和设施布局优化等问题提供重要的理论支撑。     

Explicit bounds for separation between Oseledets subspaces

We consider a two-sided sequence of bounded operators in a Banach space which are not necessarily injective and satisfy two properties (SVG) and (FI). The singular value gap (SVG) property says that two successive singular values of the cocycle at some index d admit a uniform exponential gap; the fast invertibility (FI) property says that the cocycle is uniformly invertible on the fastest d-dimensional direction. We prove the existence of a uniform equivariant splitting of the Banach space into a fast space of dimension d and a slow space of codimension d. We compute an explicit constant lower bound on the angle between these two spaces using solely the constants defining the properties (SVG) and (FI). We extend the results obtained by Bochi and Gourmelon in the finite-dimensional case for bijective operators and the results obtained by Blumenthal and Morris in the infinite dimensional case for injective norm-continuous cocycles, in the direction that the operators are not required to be globally injective, that no dynamical system is involved and no compactness of the underlying system or smoothness of the cocycle is required. Moreover we give quantitative estimates of the angle between the fast and slow spaces that are new even in the case of finite-dimensional bijective operators in Hilbert spaces.     

Automated delineation of non-small cell lung cancer: A step toward quantitative reasoning in medical decision science

Quantitative reasoning in medical decision science relies on the delineation of pathological objects. For example, evidence-based clinical decisions regarding lung diseases require the segmentation of nodules, tumors, or cancers. Non-small cell lung cancer (NSCLC) tends to be large sized, irregularly shaped, and grows against surrounding structures imposing challenges in the segmentation, even for expert clinicians. An automated delineation tool based on spatial analysis was developed and studied on 25 sets of computed tomography scans of NSCLC. Manual and automated delineations were compared, and the proposed method exhibited robustness in terms of the tumor size (5.32–18.24 mm), shape (spherical or irregular), contouring (lobulated, spiculated, or cavitated), localization (solitary, pleural, mediastinal, endobronchial, or tagging), and laterality (left or right lobe) with accuracy between 80% and 99%. Small discrepancies observed between the manual and automated delineations may arise from the variability in the practitioners' definitions of region of interest or imaging artifacts that reduced the tissue resolution.     

From Oxadiazole to Triazole Analogues: Optimization toward a Dual Orexin Receptor Antagonist with Improved in vivo Efficacy in Dogs

The orexin system is responsible for regulating the sleep-wake cycle. Suvorexant, a dual orexin receptor antagonist (DORA) is approved by the FDA for the treatment of insomnia disorders. Herein, we report the optimization efforts toward a DORA, where our starting point was (5-methoxy-4-methyl-2-[1,2,3]triazol-2-yl-phenyl)-{(S)-2-[5-(2-trifluoromethoxy-phenyl)-[1,2,4]oxadiazol-3-yl]-pyrrolidin-1-yl}methanone ( 6 ), a compound which emerged from our in-house research program. Compound 6 was shown to be a potent, brain-penetrating DORA with in vivo efficacy similar to suvorexant in rats. However, shortcomings from low metabolic stability, high plasma protein binding (PPB), low brain free fraction (f_u brain), and low aqueous solubility, were identified and hence, compound 6 was not an ideal candidate for further development. Our optimization efforts addressing the above-mentioned shortcomings resulted in the identification of (4-chloro-2-[1,2,3]triazol-2-yl-phenyl)-{(S)-2-methyl-2-[5-(2-trifluoromethoxy-phenyl)-4H-[1,2,4]triazol-3-yl]-pyrrolidin-1-yl}l-methanone ( 42 ), a DORA with improved in vivo efficacy compared to 6 .