Versatile Metalloporphyrin-Based Electrochemical Sensing Applications: From Small Gasotransmitters to Macromolecules

At the beginning of his youthful sixth decade, this work is dedicated to Prof. Dr. Fabio Doctorovich. He is distinctive in organometallic chemistry. During his successful career, he has been studying the reactivity and application of metalloporphyrins. Metalloporphyrins are organometallic complexes that exhibit, through synthetic modifications, the ability to tune their optical and electrochemical properties and their selectivity towards a particular molecule or ion. For this reason, they are systems extremely useful as electrochemical sensors to detect and quantify a wide variety of analytes with high selectivity, even in real samples such as food, water, biological fluids, or pharmaceutical compounds. This review presents an up-to-date list of reports in which metalloporphyrins are used as electrochemical sensors. In addition to compiling a comprehensive and up-to-date list of reported sensors that utilize metalloporphyrins, this work aims to provide an overview of currently available tools and techniques for the detection of various chemical species through similar approaches, which are constantly being developed.     

Morita Equivalence for Many-Sorted Enriched Theories

Morita equivalence detects the situation in which two different theories admit the same class of models for the given theories. We generalise the result of Adámek, Sobral and Sousa concerning Morita equivalence of many-sorted algebraic theories. This generalisation is two-fold. We work in an enriched setting, so the result is parametric in the choice of enrichment. Secondly, the result works for a reasonably general notion of a theory: the class of limits in the theory can be varied. As an example of an application of our result, we show enriched and many-sorted Morita equivalence results, and we recover the known results in the ordinary case.     

Ethanol oxidation at metal–zeolite-modified electrodes in alkaline medium. Part-1: gold–zeolite-modified graphite electrode

Gold–zeolite-modified graphite (AuZG) electrode shows higher catalytic activity for ethanol oxidation in alkaline medium compared with massive gold or gold-modified graphite (Au/G) electrodes. The activity of this electrode depends on the amount of zeolite loaded on the graphite surface and on the soaking time in Au³⁺ solution. The effects of both scan rate and ethanol concentration on the anodic peak height are indicatives of a diffusion-controlled process. Current decay measurements indicate that the activity of studied electrodes towards poisoning tolerance decreases in the following order: AuZG > Au/G > Au. This paper is dedicated to Prof. Dr. T. Iwasita for her 65th birthday.     

New proaporphines from the bark of Phoebe scortechinii

The phytochemical study of the bark of Malaysian Phoebe scortechinii (Lauraceae) has resulted in the isolation and identification of two new proaporphine alkaloids; (+)-scortechiniine A (1) and (+)-scortechiniine B (2) together with two known proaporphines; (-)-hexahydromecambrine A (3), (-)-norhexahydromecambrine A (4), and one aporphine; norboldine (5). Structural elucidations of these alkaloids were performed using spectroscopic methods especially 1D and 2D (1)H and (13)C NMR.     

Magnetic nanoparticles entrapped in siliceous mesocellular foam: a new catalyst support

γ-Fe(2)O(3) nanoparticles were formed inside the cage-like pores of mesocellular foam (MCF). These magnetic nanoparticles showed a uniform size distribution that could be easily controlled by the MCF pore size, as well as by the hydrocarbon chain length used for MCF surface modification. Throughout the entrapment process, the pore structure and surface area of the MCF remained intact. The resulting magnetic MCF facilitated the immobilization of biocatalysts, homogeneous catalysts, and nanoclusters. Moreover, the MCF allowed for facile catalyst recovery by using a simple magnet. The supported catalysts exhibited excellent catalytic efficiencies that were comparable to their homogeneous counterparts.     

Catalytic activity and stability of laccase entrapped in sol–gel silica with additives

This study investigated the effects of different additives and precursors on the catalytic activity of laccase entrapped in sol–gel silica. It was found that the laccase catalytic activity and stability of sol–gel laccase could be enhanced if the entrapment was performed in the presence of additives such as PVA, PEG and APTS. The use of TEOS as a precursor showed slightly higher laccase catalytic activity compared to TMOS. The PVA as an additive showed a better catalytic activity enhancement compared to the PEG and APTMS with the optimum PVA concentration of 0.03 mg/mL. The optimal temperatures of sol–gel laccase without and with additives were found to be at 40 and 27°C, respectively. After 70 days of storage at 27°C, the catalytic activity of the immobilized sol–gel laccase with additives maintained its catalytic activity compared to only 30% of its original catalytic activity for the sol–gel laccase without additives.     

Determination of thermophysical properties of high temperature alloy IN713LC by thermal analysis

The presented paper deals with the study of thermophysical properties of cast and complex alloyed nickel based on superalloy Inconel 713LC (IN713LC). In this work, the technique of Differential Thermal Analysis was selected for determination of the phase transformation temperatures and for the study of the effect of varying heating/cooling rate at these temperatures. The samples taken from as-received state of superalloy were analysed at heating and cooling rates of 1, 5, 10, 20 and 50?°C?min^?1 with the help of the experimental system Setaram SETSYS 18_TM. Moreover, the transformation temperatures at zero heating/cooling rate were calculated. The recommended values for IN713LC after correcting to a zero heating rate, are 1,205?°C (T _?á?,solvus), 1,250?°C (solidus) and 1,349?°C (liquidus). Influence of heating/cooling rate on shift of almost all temperatures of phase transformations was established from the DTA curves. Undercooling was observed at the cooling process. The samples before and after DTA analysis were also subjected to the phase analysis by scanning electron microscopy using the microscope JEOL JSM-6490LV equipped with an energy dispersive analyser EDAX (EDS INCA x-act). Documentation of the microstructure was made in the mode of secondary (SEI) and backscattered (BEI) electron imaging. On the basis of DTA analysis and phase analysis it may be stated that development of phase transformations of the alloy IN713LC will probably correspond to the following scheme: melting?????? phase; melting???????+?MC; melting????eutectics ??/?á?; melting???????+?minority phases (e.g. borides); and matrix ???????á?.     

Anti-tumour promoting activity and antioxidant properties of girinimbine isolated from the stem bark of Murraya koenigii S

Girinimbine, a carbazole alkaloid isolated from the stem bark of Murraya koenigii was tested for the in vitro anti-tumour promoting and antioxidant activities. Anti-tumour promoting activity was determined by assaying the capability of this compound to inhibit the expression of early antigen of Epstein-Barr virus (EA-EBV) in Raji cells that was induced by the tumour promoter, phorbol 12-myristate 13-acetate. The concentration of this compound that gave an inhibition rate at fifty percent was 6.0 μg/mL and was not cytotoxic to the cells. Immunoblotting analysis of the expression of EA-EBV showed that girinimbine was able to suppress restricted early antigen (EA-R). However, diffused early antigen (EA-D) was partially suppressed when used at 32.0 μg/mL. Girinimbine exhibited a very strong antioxidant activity as compared to a-tocopherol and was able to inhibit superoxide generation in the 12-O-tetradecanoylphorbol-13-acetate (TPA)-induced differentiated premyelocytic HL-60 cells more than 95%, when treated with the compound at 5.3 and 26.3 μg/mL, respectively. However girinimbine failed to scavenge the stable diphenyl picryl hydrazyl (DPPH)-free radical.     

Repeated dose 28-days oral toxicity study of Carica papaya L. leaf extract in Sprague Dawley rats

Carica papaya L. leaves have been used in ethnomedicine for the treatment of fevers and cancers. Despite its benefits, very few studies on their potential toxicity have been described. The aim of the present study was to characterize the chemical composition of the leaf extract from 'Sekaki' C. papaya cultivar by UPLC-TripleTOF-ESI-MS and to investigate the sub-acute oral toxicity in Sprague Dawley rats at doses of 0.01, 0.14 and 2 g/kg by examining the general behavior, clinical signs, hematological parameters, serum biochemistry and histopathology changes. A total of twelve compounds consisting of one piperidine alkaloid, two organic acids, six malic acid derivatives, and four flavonol glycosides were characterized or tentatively identified in the C. papaya leaf extract. In the sub-acute study, the C. papaya extract did not cause mortality nor were treatment-related changes in body weight, food intake, water level, and hematological parameters observed between treatment and control groups. Some biochemical parameters such as the total protein, HDL-cholesterol, AST, ALT and ALP were elevated in a non-dose dependent manner. Histopathological examination of all organs including liver did not reveal morphological alteration. Other parameters showed non-significant differences between treatment and control groups. The present results suggest that C. papaya leaf extract at a dose up to fourteen times the levels employed in practical use in traditional medicine in Malaysia could be considered safe as a medicinal agent.