Cholesterol modulates amiodarone-membrane interactions in model and native membranes

The effects of cholesterol, a lipid mostly found in the sarcolemmal membranes, on the interaction of amiodarone with synthetic models of dimyristoylphosphatidylcholine (DMPC) and with native models of mitochondria and brain microsomes was studied. Alterations on the structural order of lipids were assessed by fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) probing the bilayer core, and of the propionic acid derivative 3-(p-(6-phenyl)-1,3,5-hexatrienyl)phenylpropionic acid (DPH-PA) probing the outer regions of the bilayer. As detected by the probes and according to classic observations, cholesterol progressively increased the molecular order in the fluid phase of DMPC. Additionally, it modulated the type and extension of amiodarone effects. For low cholesterol concentrations (≤10–15 mol%), amiodarone (50 μM) ordered DMPC bilayers and the effects were almost identical to those observed in pure DMPC. For higher cholesterol concentrations, amiodarone ordering effects decreased slightly and faded for cholesterol concentrations as high as 25 and 30 mol%, when detected by DPH-PA and DPH, respectively. Above these high cholesterol concentrations, a crossover from ordering to disordering effects of amiodarone was apparent, either in the upper region of the bilayer or the hydrophobic core. The effects of amiodarone in native membranes of mitochondria and brain microsomes, in which "native" cholesterol accounts for about 0 and 25 mol%, respectively, correlated reasonably with the results in models of synthetic lipids. There is a close relationship between cholesterol concentration and amiodarone effects, in either synthetic models or native model membranes. Therefore, it may be predicted that the lipid physicochemical properties regulated by cholesterol concentration will also modulate the effects of amiodarone in sarcolemma.     

Comparison of the effectiveness of epoxy cure accelerators using a fluorescent molecular probe

A simple optical method for quantitative comparison of the effectiveness of epoxy cure accelerators, used for speeding up the crosslinking process of epoxy resins with cyclic anhydrides, is described. Fluorescent molecular probes and a miniature fiber optic spectrometer have been applied for measurement of the cure kinetics of a model epoxy resin/anhydride composition in the presence of various cure accelerators. A quantitative index of accelerator performance has been determined for several of the most common accelerators.     

Substituent effects on the photophysical properties of amino-aurone-derivatives

ABSTRACT

Aurones are potential candidates to be employed as fluorescent probes or as pharmacophores for biological applications. This work describes a density functional theory (DFT) and time-dependent -DFT study at the PBE0/6-31?+?G(d) level of theory to analyse the structural, electronic and photophysical properties of a series of new proposed 4′-amine-aurone derivatives in its E and Z isomeric conformations. The maximum absorption wavelength of the proposed aurones appears in the range 390???514?nm, while the most allowed emission pathways were computed in the range 493–530?nm. The bathochromic shift of these compounds with respect to the non-substituted aurone is modulated by the acceptor strength of the added 4-substituents, in addition to the ability of the substituents to localise the frontier molecular orbitals over the acceptor benzofuranone moiety without losing the tricyclic planarity, which favours the push–pull nature of these molecules. The influence of the 4-substituent is also evidenced in the Stokes shifts for the whole series; as the electron-withdrawing character of the 4-substituents enhances, higher is the polarisation of the structure resulting in higher Stokes shifts. As a result, -CF₃ and -NO₂ substituents were responsible of larger Stokes shifts, then compounds containing these substituents are proposed as potential fluorescence probes for useful applications in biological systems.     

Sustainable alternative in environmental monitoring using carbon nanoparticles as optical probes

Environmental monitoring is getting more important nowadays due to the greater stress faced by the natural environment in the era of urbanisation and industrialisation. To accomplish the task, rapid and reliable analytical probes are essentially needed to perform the monitoring at real time basis with high sensitivity and accuracy. In view of this, analytical probes developed using carbon nanoparticles are one of the latest alternatives that are proven with capability to detect various analytes of the environment. Carbon nanoparticles portray good fluorescence property that enables the integration onto optical sensing transducers. Further engineering via surface functionalization can be performed in the interest to improve the selectivity and sensitivity of the probes. There are several advantages of using carbon nanoparticles and the most significant benefit is the sustainability prospect as compared to other groups of fluorophores. Carbon nanoparticles can be synthesised with greener approach via simple pyrolysis or hydrolysis processes that involve minimum use of toxic or harmful starting precursors, besides able to tap on using renewable resources such as carbon rich agricultural wastes. The synthesis is often performed under mild condition and produces less or no side chemical products. Carbon nanoparticles by nature show low toxicity effect to the environment. This review focuses specifically of the sustainable significances, advantages and achievements in adopting carbon nanoparticles as an alternative for environmental monitoring.     

Potent Anticancer Efficacy of First-In-Class CuII and AuIII Metaled Phosphorus Dendrons with Distinct Cell Death Pathways

First-in-class Cu^II and Au^III metaled phosphorus dendrons were synthesized and showed significant antiproliferative activity against several aggressive breast cancer cell lines. The data suggest that the cytotoxicity increases with reducing length of the alkyl chains, whereas the replacement of Cu^II with Au^III considerably increases the antiproliferative activity of metaled phosphorus dendrons. Very interestingly, we found that the cell death pathway is related to the nature of the metal complexed by the plain dendrons. Cu^II metaled dendrons showed a potent caspase-independent cell death pathway, whereas Au^III metaled dendrons displayed a caspase-dependent apoptotic pathway. The complexation of plain dendrons with Au^III increased the cellular lethality versus dendrons with Cu^II and promoted the translocation of Bax into the mitochondria and the release of Cytochrome C (Cyto C).     

Kinetic modeling of liquid-phase esterification of acetic acid with n-butanol using heterogeneous poly(o-methylene p-toluene sulfonic acid) as catalyst

Liquid-phase esterification of acetic acid with n-butanol to n-butyl acetate is studied in the presence of a polymeric catalyst, that is, poly(o-methylene p-toluene sulfonic acid). The performance of the proposed catalyst is compared with the other commercially available homogeneous and heterogeneous catalysts in terms of its activity. Experiments are conducted in an isothermal stirred batch reactor to study the effects of speed of agitation, temperature, and catalyst loading on the rate of reaction. A concentration-based pseudo-homogeneous (PH) kinetic model and activity-based kinetic models such as PH, Eley-Rideal (ER), and Langmuir-Hinselwood-Hougen-Watson (LHHW) models are developed. All the models considered in this study resulted in similar percentage deviation close to 4%. Further, kinetic models are validated through additional experiments, and it is observed that the simple concentration-based PH model is able to predict experimental data with least deviation compared to activity-based PH, ER, and LHHW models. The developed kinetic models are also tested using the Fisher-Snedecor test (F-test) and are found to be acceptable. By incorporating both modeling data and validation data, the overall absolute average deviations of different models are found to be concentration-based PH model 4.354%, activity-based PH model 5.006%, ER I model 5.189%, ER II model 5.403%, ER III model 5.437%, and LHHW model 6.104%, illustrating the superiority of the simple concentration-based PH model.