Azocalix[4]arene-Rhodamine Supramolecular Hypoxia-Sensitive Systems: A Search for the Best Calixarene Hosts and Rhodamine Guests

A potential hypoxia-sensitive system host-guest complex of three calixarenes (including two with four anionic carboxyl and sulphonate azo fragments on the upper rim and a newly synthesized bis-azo adduct of calixarene in the cone configuration with azo fragments on the lower rim with the most widespread cationic and zwitterionic rhodamine dyes (123, 6G and B)) was studied using UV-VIS spectrometry and fluorescence as well as 1D and 2D NMR techniques. It was found that all three calixarenes form a complex with rhodamine dyes with a 1:1 composition. The association constants of calixarene-dye complexes with sulfonate calixarenes, especially in the case of tetra-anionic calixarene, turned out to be higher compared with carboxyl calixarene due to the more intense electrostatic interactions. For the first time using an HRESI MS technique, it was shown that the treatment of rhodamine 6G and 123 with sodium dithionite (SDT) produces a non-fluorescent leuco form of the dye, and only rhodamine B can be used with SDT without the occurrence of a side reduction. Moreover, it was identified that in addition to the reduction in the azo groups, SDT causes partial cleavage of the aryl ether bonds. The found features of SDT should be taken into account when SDT is used as an azoreductase mimic.

DELIVERY OF STIMULI-SENSITIVE NANOPARTICLES FOR VISUALIZATION OF REACTIVE OXYGEN SPECIES IN LIVER DISEASES

We developed lipid nanoparticles for effective visualization of reactive oxygen species (ROS) in damaged hepatocytes. These nanoparticles contain ROS - sensor: 1) HyPer – plasmid DNA encoded the same protein that is sensitive to the hydrogen peroxide or 2) hydrocyanine (leuco-form of cyanine) 5). The physicochemical characterization of the obtained particles was carried out, as well as their efficacy in vitro and in vivo was evaluated.

Chromatic Sensor to Determine Oxygen Presence for Applications in Intelligent Packaging

A chromatic sensor has been designed for the detection of oxygen in package headspace. The sensor is based on the redox change of methylene blue (MB) to its leuco form. Its formulation includes the pigment, glycerol, as a sacrificial electron donor, TiO2, as a photocatalyst and ethylene-vinyl alcohol copolymer (EVOH), as a structural polymer matrix. The final sensor design that allows its manufacture by conventional printing and laminating technologies consists of the sensing polymer matrix (MB-EVOH) sandwiched in a suitable transparent multilayer structure. The outer layers protect the sensor from the external atmosphere and allow visualization of the colour. The inner layer is sufficiently opaque to facilitate sensor reading from the outside, is thick enough to avoid direct contact with food (functional barrier), and is oxygen-permeable to expose the sensing material to the internal package atmosphere. In the absence of oxygen, the sensor becomes white by irradiation with halogen lamps in less than 60 s. All components are substances permitted for food contact except the pigment, but specific migration analysis showed no trace of migration thanks to the functional barrier included in the design.

Clean Process: Reducing indigo by using environmentally friendly 3-hydroxybutanone on dyed cotton modified with Denitex BC 200%

Industrial processes in everyday life need to take into consideration environmental safety. This is the major goal of today's scientific research. Textile research is no exception. This paper illustrates a green process in which indigo is converted into its water-soluble leuco form by using a reducing agent that is ecologically friendly: 3-hydroxybutanone (C4H8O2). The effect of alkalinity and reducing temperature on the reducing power of C4H8O2 has been evaluated in the absence and presence of indigo. The dyeing quality of the modified cotton resultant of the exhaust process is studied. Cotton modification is carried out by using Denitex BC 200% in order to improve the quality of the exhaustion dyeing process. Modified cotton fibres are characterized through a morphology analysis (by using a SEM), Fourier transform infrared spectroscopy and X-ray diffraction analysis. The performances of the indigo dyeing process are evaluated by measuring the redox potentials generated in the medium with and without indigo, dyeing bath exhaustion (E(%)), and colour yield (K/S) of the coloured cotton at 660 nm, brightness index (B(%)) and dyeing fastness of both the untreated and modified cotton fabrics.

An NAD(P)H-Nicotine Blue Oxidoreductase Is Part of the Nicotine Regulon and May Protect Arthrobacter nicotinovorans from Oxidative Stress during Nicotine Catabolism

ABSTRACT An NAD(P)H-nicotine blue (quinone) oxidoreductase was discovered as a member of the nicotine catabolic pathway of Arthrobacter nicotinovorans. Transcriptional analysis and electromobility shift assays showed that the enzyme gene was expressed in a nicotine-dependent manner under the control of the transcriptional activator PmfR and thus was part of the nicotine regulon of A. nicotinovorans. The flavin mononucleotide-containing enzyme uses NADH and, with lower efficiency, NADPH to reduce, by a two-electron transfer, nicotine blue to the nicotine blue leuco form (hydroquinone). Besides nicotine blue, several other quinones were reduced by the enzyme. The NAD(P)H-nicotine blue oxidoreductase may prevent intracellular one-electron reductions of nicotine blue which may lead to semiquinone radicals and potentially toxic reactive oxygen species.

Liquid Chromatographic Determination of Methylene Blue and Its Metabolites in Milk

A method is described for the liquid chromatographic (LC) determination of trace levels of methylene blue (MB) and its metabolites in milk. The cleanup involves protein precipitation with acetonitrile, extraction into chloroform of MB and its metabolites (azure A [AZA], azure B [AZB], and azure C [AZC]), extraction by chloroform of thionin at pH 10, and solid-phase extraction on a disposable carboxylic acid column. LC separation and quantitation are performed with an isocratic acetonitrile-acetate buffer mobile phase on a cyano column. Average recoveries (5-20 ppb levels) of MB, AZA, AZB, and thionin from fortified milk were 83.2,60.0, 84.4, and 22.5%, respectively. Some incurred MB metabolites in milk are bound organically to a fraction of the milk substrate, whereas others are free demethylated forms of MB. Analysis of milk collected 8 h after administration of MB contained the following average levels (n = 6) of free MB and metabolites: MB, 31.0 ppb; AZA, 21.3 ppb; and AZB, 54.1 ppb. Depletion of free MB and metabolites AZA and AZB from milk after administration of MB to lactating cows occurred in less than 40 h. Metabolites of MB that formed complexes with organic compounds were hydrolyzed in part to the free forms. The leuco form of MB cou

Determination of Malachite Green and Its Leuco Form in Water

Liquid chromatographic (LC) analysis can detect malachite green residues in water at less than 10µg/L. Water samples were concentrated on disposable diol columns, eluted with 0.05M p-toluenesulfonic acid in methanol, and determined by reversed- phase LC. When combined with a lead oxide postcolumn reactor, the LC method can simultaneously determine both leuco and chromatic forms of malachite green. Recoveries averaged 95.4% for the chromatic form and 57.3% for the leuco form of malachite green oxalate and leuco malachite green in spiked pond water samples. Recoveries of the carbinol form of malachite green (an equilibrium product of the dye in water) from spiked tap water samples averaged 98.6%. Recoveries of leuco malachite green were low and pH-dependent.