Electroless deposition of metallic silver from a choline chloride-based ionic liquid: a study using acoustic impedance spectroscopy, SEM and atomic force microscopy

In this paper, we describe the first example of a sustained galvanic coating deposited on a surface from a non-aqueous liquid. We present the surface characterization of electroless silver deposits on copper substrates from a solution of Ag(+) ions in an ionic liquid based on a choline chloride (ChCl) eutectic. Through a study of these deposits and the mechanism of formation using acoustic impedance spectroscopy (QCM), probe microscopy (AFM) and electron microscopy (SEM/EDX), we demonstrate that sustained growth of the silver deposit is facilitated by the porous nature of the silver. This is in contrast to the dip-coating reaction of silver ions in aqueous media, where the reaction stops when surface coverage is reached. Electroless silver deposits of up to several microns have been obtained by dip coating in ionic liquids without the use of catalysts of strong inorganic acids.     

A novel structural class of photoswitchable oligonucleotide

Directed Michaelis-Arbuzov reactions of support-bound internucleotide O-benzyl- or O-methyl-phosphite triesters with meta-phenylazobenzylamine or alkane-/glycol-linked α,ω-diamines were effected in the presence of iodine. The corresponding tritylated phosphoramidate-linked 11-mers were fully deprotected and released from the support under standard conditions and the fast- and slow-diastereoisomers of both the E- and the Z-meta-phenylazobenzyl-appended oligomers were readily resolved by RP-HPLC. The primary amine-functionalised oligonucleotides were either purified, detritylated and then finally treated with N-hydroxysuccinimidyl carboxylic acid ester derivatives of photoswitchable moieties (Route A) or first derivatised and then subsequently purified and detritylated (Route B). This latter route enabled resolution of fast- and slow-isomers of the trityl-on oligomers bearing novel photoswitchable azopyridine or 9-alkoxyanthracene moieties using RP-HPLC, following which the pure diastereoisomers were detritylated and characterised by MALDI-MS.     

Colonic drug delivery using amylose films: the role of aqueous ethylcellulose dispersions in controlling drug release

Amylose, a plant polysaccharide from starch, can be combined with ethylcellulose to produce a film coating capable of effecting colon specific drug release from a dosage form through bacterial fermentation of the amylose component. Ethylcellulose is present in the system as a structuring agent in the form of the aqueous dispersion Surelease^® grade EA-7100. There are, however, two other grades of Surelease^® (E-7-7050 and E-7-19010), which vary slightly in terms of their composition. The aim of the study was to establish whether these grades differ in their drug release profiles, when used as a film coat, either as one-component coatings, or in combination with amylose. The dissolution profiles of Surelease^® coated pellets were investigated and it was found that there was no difference between the grades when used as coating materials on their own. However, when used in combination with amylose, it was found that grade EA-7100 showed retardation of drug release in simulated upper gastro-intestinal (GI) conditions, whereas grades E-7-7050 and E-7-19010 did not limit the release to the same extent. E-7-19010 showed very poor controlled release properties when combined with amylose. These differences could not be attributed to the minimum film forming temperature (MFT) of the coating formulation, which was found to be independent of the grade of Surelease^®. It was also confirmed that the film coated pellets prepared from amylose and EA-7100 showed good release in human faecal slurry, i.e. simulated colonic conditions. It was concluded that the grades of Surelease^®, when combined with amylose, are not interchangeable.     

Deep Learning and Entropy-Based Texture Features for Color Image Classification

In the domain of computer vision, entropy—defined as a measure of irregularity—has been proposed as an effective method for analyzing the texture of images. Several studies have shown that, with specific parameter tuning, entropy-based approaches achieve high accuracy in terms of classification results for texture images, when associated with machine learning classifiers. However, few entropy measures have been extended to studying color images. Moreover, the literature is missing comparative analyses of entropy-based and modern deep learning-based classification methods for RGB color images. In order to address this matter, we first propose a new entropy-based measure for RGB images based on a multivariate approach. This multivariate approach is a bi-dimensional extension of the methods that have been successfully applied to multivariate signals (unidimensional data). Then, we compare the classification results of this new approach with those obtained from several deep learning methods. The entropy-based method for RGB image classification that we propose leads to promising results. In future studies, the measure could be extended to study other color spaces as well.     

Chaotic behaviour of the map x ↦ ω(x, f)

Let K(2^?) be the class of compact subsets of the Cantor space 2^?, furnished with the Hausdorff metric. Let f ∈ C(2^?). We study the map ω _f : 2 ^? → K(2^?) defined as ω _f (x) = ω(x, f), the ω-limit set of x under f. Unlike the case of n-dimensional manifolds, n ≥ 1, we show that ω _f is continuous for the generic self-map f of the Cantor space, even though the set of functions for which ω _f is everywhere discontinuous on a subsystem is dense in C(2^?). The relationships between the continuity of ω _f and some forms of chaos are investigated.     

Trimethylsilylation of framework Brønsted acid sites in microporous zeolites and silico-aluminophosphates

Framework-bound alkoxy groups are well-studied intermediates in zeolite chemistry, but their low stability complicates their spectroscopic study in high-temperature reactions such as alkylation or dealkylation. Taking advantage of the much higher bond strength of Si-O versus C-O, we synthesized trimethylsilylated zeolites by reacting them with phenyltrimethylsilane in a catalytic flow reactor at 648 K. In favorable cases, the reaction accurately titrated the acid sites, and 29Si and 13C MAS NMR spectra of the derivatized catalysts measured at room temperature confirmed the proposed reaction.     

Asymmetric cyanohydrin synthesis using an aluminium(salan) complex

The asymmetric addition of trimethylsilyl cyanide to aldehydes catalysed by chiral metal(salan) complexes has been investigated. Salan complexes of titanium and vanadium displayed only low catalytic activity, but a bimetallic aluminium(salan) complex gave high levels of catalytic activity and reasonable asymmetric induction when used with triphenylphosphine oxide as a cocatalyst. Mechanistic studies showed that the reactions were first order in catalyst and aldehyde concentrations, but zero order in trimethylsilyl cyanide and triphenylphosphine oxide concentrations. A Hammett analysis indicated that there was no significant change in the electron density at the aldehyde benzylic position during the rate determining step of the catalytic cycle. On the basis of the kinetic data, a catalytic cycle is proposed which accounts for the differences observed between [Al(salen)]₂O and [Al(salan)]₂O based catalysts.     

Fast determination of paracetamol and its hydrolytic degradation product p-aminophenol by capillary and microchip electrophoresis with contactless conductivity detection

Paracetamol (PAC) is one of the most extensively used analgesics and antipyretic drugs to treat mild and moderate pain. P-aminophenol (PAP), the main hydrolytic degradation product of PAC, can be found in environmental water. Recently, CE has been developed for the detection of a wide variety of chemical substances. The purpose of this study is to develop a simple and fast method for the detection and separation of PAC and its main hydrolysis product PAP using CE and microchip electrophoresis with capacitively coupled contactless conductivity detection. The determination of these compounds using microchip electrophoresis with capacitively coupled contactless conductivity detection is being reported for the first time. The separation was run for all analytes using a BGE (20 mM β-alanine, pH 11) containing 14% (v/v) methanol. The RSDs obtained for migration time were less than 4%, and RSDs obtained for peak area were less than 7%. The detection limits (S/N = 3) that were achieved ranged from 0.3 to 0.6 mg/L without sample preconcentration. The presented method showed rapid analysis time (less than 1 min), high efficiency and precision, low cost, and a significant decrease in the consumption of reagents. The microchip system has proved to be an excellent analytical technique for fast and reliable environmental applications.