Synthesis and Spectroscopic Characterization of Fluorophore‐Labeled Oligospiroketal Rods

Fluorescence probes consisting of well‐established fluorophores in combination with rigid molecular rods based on spirane‐type structures were investigated with respect to their fluorescence properties under different solvent conditions. The attachment of the dyes was accomplished by 1,3‐dipolar cycloaddition between alkynes and azides (‘click’ reaction) and is a prime example for a novel class of sensor constructs. Especially, the attachment of two (different) fluorophores on opposite sides of the molecular rods paves the way to new sensor systems with less bulky (compared to the conventional DNA‐ or protein‐based concepts), nevertheless rigid spacer constructs, e.g., for FRET‐based sensing applications. A detailed photophysical characterization was performed in MeOH (and in basic H₂O/MeOH mixtures) for i) rod constructs containing carboxyfluorescein, ii) rod constructs containing carboxyrhodamine, iii) rod constructs containing both carboxyfluorescein and carboxyrhodamine, and iv) rod constructs containing both pyrene and perylene parts. For each dye (pair), two rod lengths with different numbers of spirane units were synthesized and investigated. The rod constructs were characterized in ensemble as well as single‐molecule fluorescence experiments with respect to i) specific rod? dye and ii) dye? dye interactions. In addition to MeOH and MeOH/NaOH, the rod constructs were also investigated in micellar systems, which were chosen as a simplified model for membranes.     

Zinc Oxide Nanoparticles and Zinc Sulfate Impact Physiological Parameters and Boosts Lipid Peroxidation in Soil Grown Coriander Plants (Coriandrum sativum)

The objective of this study was to determine the oxidative stress and the physiological and antioxidant responses of coriander plants (Coriandrum sativum) grown for 58 days in soil with zinc oxide nanoparticles (ZnO NPs) and zinc sulfate (ZnSO₄) at concentrations of 0, 100, 200, 300, and 400 mg of Zn/kg of soil. The results revealed that all Zn compounds increased the total chlorophyll content (CHLt) by at least 45%, compared to the control group; however, with 400 mg/kg of ZnSO₄, chlorophyll accumulation decreased by 34.6%. Zn determination by induction-plasma-coupled atomic emission spectrometry (ICP–AES) showed that Zn absorption in roots and shoots occurred in plants exposed to ZnSO₄ at all concentrations, which resulted in high levels of hydrogen peroxide (H₂O₂) and malondialdehyde (MDA). Only at 400 mg/kg of ZnSO₄, a 78.6% decrease in the MDA levels was observed. According to the results, the ZnSO₄ treatments were more effective than the ZnO NPs to increase the antioxidant activity of catalase (CAT), ascorbate peroxidase (APX), and peroxidases (POD). The results corroborate that phytotoxicity was higher in plants subjected to ZnSO₄ compared to treatments with ZnO NPs, which suggests that the toxicity was due to Zn accumulation in the tissues by absorbing dissolved Zn⁺⁺ ions.     

The hydration of sodium dehydrocholate micelles

The hydration of micellised sodium dehydrocholate molecules was determined by viscosity measurements. It was found that there are 39 water molecules for each micellised surfactant molecule. About ten water molecules may be attributed to the hydration of the sodium carboxylate group. By assignation of two water molecules to each of the three carbonyl groups, the total hydration of a micellised sodium dehydrocholate molecule was estimated as about 16 water molecules. The remaining 23 water molecules per micellised sodium dehydrocholate molecule may be attributed to water trapped in the structure of micelles.     

Gleason parts in uniform Fréchet algebras

We prove that Gleason parts in uniform distinguished Fréchet algebras are open and closed in the weak topology.     

Characterization of the behaviour of flavour microcapsules in cotton fabrics

Nanotechnology processes have recently been introduced into the textile field. One of these processes involves encapsulated nanoparticles or nanoproducts, known as microcapsules. They are available with a wide range of products which confer different properties related to the nature of the encapsulated product. The composition of the wall material determines the release of the product into the fabric and is the object of study in the present work. The behaviour of microencapsulated peppermint was analyzed on cotton fabrics.Different application methods have been tested, impregnation versus bath exhaustion. As impregnation turned out to be the most efficient, some recipes were assayed and the effect of microcapsules on maintenance conditions was evaluated in order to determine the most suitable method with the longest lasting effect on fabrics.The effect of microcapsules is usually measured by the presence of a property such as odour measurements when flavours are encapsulated. The aim of this work is to explain the behaviour of the cotton fabrics with microcapsules bound to their fibers, to determine the relationship between their macroscopic properties and microscopic characteristics. A procedure based in FTIR spectroscopy is also proposed to quantify the presence of microcapsules in the fabrics.IR spectra of the textiles were obtained to determine the presence of microcapsules, which was corroborated by SEM techniques.     

On-line double isotope dilution laser ablation inductively coupled plasma mass spectrometry for the quantitative analysis of solid materials

We report on the determination of trace elements in solid samples by the combination of on-line double isotope dilution and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The proposed method requires the sequential analysis of the sample and a certified natural abundance standard by on-line IDMS using the same isotopically-enriched spike solution. In this way, the mass fraction of the analyte in the sample can be directly referred to the certified standard so the previous characterization of the spike solution is not required. To validate the procedure, Sr, Rb and Pb were determined in certified reference materials with different matrices, including silicate glasses (SRM 610, 612 and 614) and powdered samples (PACS-2, SRM 2710a, SRM 1944, SRM 2702 and SRM 2780). The analysis of powdered samples was carried out both by the preparation of pressed pellets and by lithium borate fusion. Experimental results for the analysis of powdered samples were in agreement with the certified values for all materials. Relative standard deviations in the range of 6–21% for pressed pellets and 3–21% for fused solids were obtained from n = 3 independent measurements. Minimal sample preparation, data treatment and consumption of the isotopically-enriched isotopes are the main advantages of the method over previously reported approaches.     

Development and validation of a capillary electrophoresis method for determination of enantiomeric purity and related substances of esomeprazole in raw material and pellets

A capillary electrophoresis method using CDs for quality control of esomeprazole (ESO) in terms of enantiomeric purity and related substances in raw material and pellets was developed. ESO is the S‐enantiomer of omeprazole (OMZ). Several parameters were evaluated, including type and concentration of buffer and CD, concentration of additives and electrolyte pH. Resolution between the enantiomers of OMZ obtained for each parameter tested was calculated and the presence of the main related substance such as OMZ sulfone was carefully monitored. The optimized system consisted of 100 mM Tris‐phosphate buffer pH 2.5 with 20 mM 2‐hydroxypropyl‐β‐CD, 1 mM sodium dithionite, temperature at 15°C, voltage at 28 kV, and UV detection at 301 nm. Once optimized, the electrophoretic system was validated according to ICH guidelines. The limits of detection and quantification for R‐OMZ were 0.6 μg/mL (0.06% w/w of ESO) and 2.0 μg/mL (0.2% w/w of ESO), respectively. A mean concentration of R‐OMZ <0.2% limit established by the United States Pharmacopeia (USP) was found in the raw material and six‐pellet samples of ESO. No other impurities were found in the samples under these conditions. Therefore, the developed method was found to be appropriate not only for enantiomeric quality control of ESO but also for the analysis of ESO and the main related substance in raw material and pharmaceutical formulations as well as for stability indicating studies.     

A thermodynamic study of the aggregation process of oxacillin sodium salt in aqueous solution

The aggregation characteristics of oxacillin in aqueous solutions have been examined by means of conductivity measurements over the temperature range 288.15-313.15 K and by static light scattering measurements at 298.15 K. Two critical concentrations were detected in conductivity and light scattering over the concentration range 0-0.35 mol kg^-1. Light scattering measurements indicate the formation of dimers at the first critical concentration (0.024 mol kg^-1) and the subsequent formation of aggregates with an aggregation number of 8 at the second critical concentration (0.104 molkg^-1). The thermodynamic parameters of aggregation were derived from the critical concentration data using a mass-action model that has been modified for application to systems of low aggregation number. Values for the enthalpy of aggregate formation calculated by this method showed that the aggregation became increasingly exothermic with increasing temperature. The values of the two critical concentrations show that this penicillin, oxacillin, is more hydrophobic than other molecules of similar structure.     

Poly(ethylene oxide)-poly(styrene oxide)-poly(ethylene oxide) copolymers: Micellization, drug solubilization, and gelling features

Two new poly(ethylene oxide)-poly(styrene oxide) triblock copolymers (PEO-PSO-PEO) with optimized block lengths selected on the basis of previous studies were synthesized with the aim of achieving a maximal solubilization ability and a suitable sustained release, while keeping very low material expense and excellent aqueous copolymer solubility. The self-assembling and gelling properties of these copolymers were characterized by means of light scattering, fluorescence spectroscopy, transmission electron microscopy, and rheometry. Both copolymers formed spherical micelles (12-14 nm) at very low concentrations. At larger concentration (>25 wt%), copolymer solutions showed a rich phase behavior, with the appearance of two types of rheologically active (more viscous) fluids and of physical gels depending on solution temperature and concentration. The copolymer behaved notably different despite their relatively similar block lengths. The ability of the polymeric micellar solutions to solubilize the antifungal drug griseofulvin was evaluated and compared to that reported for other structurally-related block copolymers. Drug solubilization values up to 55 mg g⁻¹ were achieved, which are greater than those obtained by previously analyzed poly(ethylene oxide)-poly(styrene oxide), poly(ethylene oxide)-poly(butylene oxide), and poly(ethylene oxide)-poly(propylene oxide) block copolymers. The results indicate that the selected SO/EO ratio and copolymer block lengths were optimal for simultaneously achieving low critical micelle concentrations (cmc) values and large drug encapsulation ability. The amount of drug released from the polymeric micelles was larger at pH 7.4 than at acidic conditions, although still sustained over 1 day.     

In Situ Formation of One‐Dimensional Assemblies of Gold Nanoparticles in Confined Media

The spontaneous in situ formation of one‐dimensional (1D) assemblies of gold nanoparticles (NP) in oleylamine/bis(2‐ethylhexyl) sulfosuccinate sodium salt/water/octane (OAm/AOT/w/o) microemulsions by exploiting both the aurophilic bonding between OAm and gold salt, and the interactions between OAm and AOT surfactant is presented. Control on the structure of the resulting assemblies is achieved by changing in the solvent quality, the [Au]/[AOT] molar ratio and the presence of different cosolutes. A possible mechanism of the formation of the 1D parallel Au NP arrays is proposed.