Supramolecular Assembly of TPE-Based Glycoclusters with Dicyanomethylene-4H-pyran (DM) Fluorescent Probes Improve Their Properties for Peroxynitrite Sensing and Cell Imaging

Two red-emitting dicyanomethylene-4H-pyran (DM) based fluorescent probes were designed and used for peroxynitrite (ONOO⁻) detection. Nevertheless, the aggregation-caused quenching effect diminished the fluorescence and restricted their further applications. To overcome this problem, tetraphenylethylene (TPE) based glycoclusters were used to self-assemble with these DM probes to obtain supramolecular water-soluble glyco-dots. This self-assembly strategy enhanced the fluorescence intensity, leading to an enhanced selectivity and activity of the resulting glyco-dot comparing to DM probes alone in PBS buffer. The glyco-dots also exhibited better results during fluorescence sensing of intracellular ONOO⁻ than the probes alone, thereby offering scope for the development of other similar supramolecular glyco-systems for chemical biological studies.     

Determination of Allura Red and Tartrazine in Food Samples by Sequential Injection Analysis Combined with Voltammetric Detection at Antimony Film Electrode

An antimony film electrode prepared on‐line and installed as part of a sequential injection system, was used as an electrochemical detector to determine azo dyes in food samples. The influence of several flow variables were evaluated using a central composite design. In optimal conditions, the linear range of the calibration curve varied from 1–5 µM, with a limit of detection limit of 0.3 µM. The relative standard deviation of analytical repeatability was <5.0 %.The method was validated by comparing the results obtained with those provided by HPLC; no significant difference were seen.     

Sulphur content estimation of Venezuelan heavy oil by fast neutron and gamma transmission technique

A compact and modern equipment for implementing the fast neutron and γ-ray transmission technique (FNGT) has been developed in order to estimate the sulphur content of crude oil. FNGT is employed for non- destructive analysis of different kinds of samples. The compact system presented in this work represents an improvement of our previous experimental set-up [1, 2]. It makes use of a ²⁵²Cf source, an EJ-301 liquid scintillator detector (2″ × 2″) with excellent n/γ discrimination capabilities, and modern nuclear electronics based on fast digitizers. The fast neutron and gamma transmission technique was employed to study a system for on-line sulphur concentration measurement in Venezuelan heavy sour oil. The range of sulphur concentrations investigated is between 0.1 and 6.5 wt%. The equipment performances and limitations are compared with those predicted by a Monte Carlo model built in GEANT4 v10.01. The results show the possibility to implement a compact unit for on-line determination of sulphur concentration in crude oil.

     

Measuring centrality and dispersion in directional datasets: the ellipsoidal cone covering approach

Consider a finite collection \(\{\xi _k\}_{k=1}^p\) of vectors in the space \(\mathbb {R}^n\). The \(\xi _k\)’s are not to be seen as position points but as directions. This work addresses the problem of computing the ellipsoidal cone of minimal volume that contains all the \(\xi _k\)’s. The volume of an ellipsoidal cone is defined as the usual n-dimensional volume of a certain truncation of the cone. The central axis of the ellipsoidal cone of minimal volume serves to define the central direction of the datapoints, whereas its volume can be used as measure of dispersion of the datapoints.     

Pseudo–almost‐periodic solutions for delayed differential equations with integrable dichotomies and bi–almost‐periodic Green functions

Using the existence of integrable bi–almost‐periodic Green functions of linear homogeneous differential equations and the contraction fixed point, we are able to prove the existence of almost and pseudo–almost‐periodic mild solutions under quite general hypotheses for the differential equation with constant delay in a Banach space X, where τ>0 is a fixed constant. The results extend the corresponding ones in the case of exponential dichotomy. Some examples illustrate the importance of the concepts.     

A nonconvex formulation for low rank subspace clustering: algorithms and convergence analysis

We consider the problem of subspace clustering with data that is potentially corrupted by both dense noise and sparse gross errors. In particular, we study a recently proposed low rank subspace clustering approach based on a nonconvex modeling formulation. This formulation includes a nonconvex spectral function in the objective function that makes the optimization task challenging, e.g., it is unknown whether the alternating direction method of multipliers (ADMM) framework proposed to solve the nonconvex model formulation is provably convergent. In this paper, we establish that the spectral function is differentiable and give a formula for computing the derivative. Moreover, we show that the derivative of the spectral function is Lipschitz continuous and provide an explicit value for the Lipschitz constant. These facts are then used to provide a lower bound for how the penalty parameter in the ADMM method should be chosen. As long as the penalty parameter is chosen according to this bound, we show that the ADMM algorithm computes iterates that have a limit point satisfying first-order optimality conditions. We also present a second strategy for solving the nonconvex problem that is based on proximal gradient calculations. The convergence and performance of the algorithms is verified through experiments on real data from face and digit clustering and motion segmentation.     

Heuristics for multi-attribute vehicle routing problems: A survey and synthesis

The attributes of vehicle routing problems are additional characteristics or constraints that aim to better take into account the specificities of real applications. The variants thus formed are supported by a well-developed literature, including a large variety of heuristics. This article first reviews the main classes of attributes, providing a survey of heuristics and meta-heuristics for Multi-Attribute Vehicle Routing Problems (MAVRP). It then takes a closer look at the concepts of 64 remarkable meta-heuristics, selected objectively for their outstanding performance on 15 classic MAVRP with different attributes. This cross-analysis leads to the identification of “winning strategies” in designing effective heuristics for MAVRP. This is an important step in the development of general and efficient solution methods for dealing with the large range of vehicle routing variants.     

Transition Metal-Promoted Reactions in Aqueous Media and Biological Settings

During the last decade, there has been a tremendous interest for developing non-natural biocompatible transformations in biologically relevant media. Among the different encountered strategies, the use of transition metal complexes offers unique possibilities due to their high transformative power. However, translating the potential of metal catalysts to biological settings, including living cells or small-animal models such as mice or zebrafish, poses numerous challenges associated to their biocompatibility, and their stability and reactivity in crowded aqueous environments. Herein, we describe the most relevant advances in this direction, with a particular emphasis on the systems’ structure, their mode of action and the mechanistic bases of each transformation. Thus, the key challenges from an organometallic perspective might be more easily identified.     

A New Approach to the Intensity of the Secondary Transition of the Benzene Chromophore with-CH3,-OH,-OCH3, Substituents

Since the beginning of the UV absorption spectroscopy, the intensity of the secondary transition of the benzene chromophore in organic derivatives has been a puzzling challenge. The well known vector model has led to some qualitative evaluation of intensity, but accuracy is very low, and sometimes leads to no less than 50% or 100% error. ^1–8 It is designed for very weak perturbations only, as in methylbenzenes. But, even in that latter case, it is not completely satisfactory. Nevertheless, that model is very easy to use; it allows to determine the sensitive positions around the benzene nucleus: those which could enhance or quench intensity for a given pattern of substitution. On that ground it has been of much help for qualitative evaluations. With SCF methods and CI calculations, evaluation of transition moments for several benzene derivatives has been possible on a firmer ground. In fact, such an approach is useful mainly from a theoretical point of view, when accuracy is not the first aim, for some choosen molecules at the same time, since the involvement of computation is far from being negligible, and since the method is not part of the ones that are of common use in organic chemistry ^9,10 (for a recent example on oscillator strength calculations of π systems see:¹¹). In other words, it is not perfectly valuable on a large scale and routine approach and, from that point of view, UV spectroscopy of benzene derivatives appeared sometimes, from 1965 till now, as being in a cul-de-sac, although it was under thorough examination (for example: 12–30). Until recently ab initio calculations have failed to reach a fit with experiment better than 1 eV for the spectrum of the benzene molecule^31–32)