Certification of nitrate in spinach powder reference material SPIN-1 by high-precision isotope dilution GC–MS

A high-precision exact-matching quadruple isotope dilution method (ID⁴MS) was employed for the quantitation of nitrate in an air-dried spinach powder Certified Reference Material (CRM). The analyte was extracted in hot water following addition of ¹⁵NO\({}_{3}^{-}\) internal standard. The blend was then treated with sulfamic acid to remove nitrite and with triethyloxonium tetrafluoroborate to promote aqueous conversion of nitrate into volatile EtONO₂. The derivative was analyzed by headspace GC–MS with 3-min elution time. The method performance was validated with a series of tests which demonstrated adequate selectivity and ruggedness. This method supported the development of novel SPIN-1 CRM giving a modest contribution to its uncertainty (u_char = 0.85%). With respect to previous attempts, the SPIN-1 was proven stable, homogeneous (u_hom = 0.44%), and suitable for spinach monitoring under EU regulations. On dried basis, the nitrate content of SPIN-1 was found to be 22.53 ± 0.43 mg/g (U_c = 1.9%, k = 2). The material was also used in an inter-laboratory study where four laboratories employed a total of ten measurement methods.

SPIN-1 Certified Reference Material for nitrate in spinach powder

     

Highly Efficient Copper(II) Ion Sorbents Obtained by Calcium Carbonate Mineralization on Functionalized Cross‐Linked Copolymers

A new type of Cu^II ion sorbents is presented. These are obtained by CaCO₃ mineralization from supersaturated solutions on gel‐like cross‐linked polymeric beads as insoluble templates. A divinylbenzene–ethylacrylate–acrylonitrile cross‐linked copolymer functionalized with weakly acidic, basic, or amphoteric functional groups has been used, as well as different initial inorganic concentrations and addition procedures for CaCO₃ crystal growth. The morphology of the new composites was investigated by SEM and compared to that of the unmodified beads, and the polymorph content was established by X‐ray diffraction. The beads, before and after CaCO₃ mineralization, were tested as sorbents for Cu^II ions. The newly formed patterns on the bead surface after Cu^II sorption were observed by SEM, and the elemental distribution on the composites and the chemical structure of crystals after interaction with Cu^II were investigated by EDAX elemental mapping and by FTIR‐ATR spectroscopy, respectively. The sorption capacity increased significantly after CaCO₃ crystals growth on the weak anionic bead surface (up to 1041.5 mg Cu^II/g sample) compared to that of unmodified beads (491.5 mg Cu^II/g sample).     

Boundary behaviour of the mappings satisfying generalized inverse modular inequalities

We study the geometric properties of the mappings for which generalized inverse modular inequalities hold. We generalize in this way known theorems from the theory of analytic mappings and the theory of quasiregular mappings, like the theorems of Fatou, M. and F. Riesz, Beurling and Lindelöf and their extensions given for quasiregular mappings by Martio, Rickman and Vuorinen.     

Thermostable Trioxane-Dioxolane Copolymers Obtained with Boron Trifluoride: Acrylonitrile Complex as Initiator

Trioxane was copolymerized with small amounts of dioxolane in benzene in the presence of a boron trifluoride:a crylonitrile complex as initiator. The kinetics of reactions was expressed in terms of topoenergetic principles. The copolymerizations had no induction periods and the maximum reaction rate was found proportional to the square of both the initiator and monomers concentrations. A zwitterionic mechanism is suggested for initiation. The activation energy for the system with 5% dioxolane was determined as 18.3 kcal/mol. The melting behavior of the copolymers is briefly discussed as a function of the dioxolane initial content, and is indicative of the amorphous-crystalline coupling phenomenon. The copolymers with ～ 5% dioxolane are thermostable in air up to 250%deg; and are recommended for practical purposes.     

Synthesis of Drim-7,9(11)-diene and Its Hydroxylated Derivatives

This article describes a new efficient synthesis of drim-7,9(11)-diene and its hydroxylated derivates from drim-8-en-7-one. Reduction of this ketone with NaBO₄ in the presence of CeCl₃ · 7H₂O afforded regio- and stereoselectively drim-8-en-7β-ol in a high yield. Its dehydration with H₂SO₄ under mild conditions led to drim-7,9(11)-diene. Noncatalytic oxidation of drim-7,9(11)-diene with OsO₄ and the catalytic oxidation with the pair OsO₄–NMO gave, in a high yield, depending on conditions, driman-7β,8β,9α,11-tetraol or its mixture with drim-7-en-9α,11-diol and drim-9(11)-en-7α,8α-diol. Under optimal conditions the total yield of these diols reached 89%. The separate, noncatalytic oxidation of drim-7-en-9α,11-diol and of drim-9(11)-en-7α,8α-diol with OsO₄ afforded driman-7α,8α,9α,11-tetraol.     

Isoflavonoid-Antibiotic Thin Films Fabricated by MAPLE with Improved Resistance to Microbial Colonization

Staphylococcus aureus (Gram-positive) and Pseudomonas aeruginosa (Gram-negative) bacteria represent major infectious threats in the hospital environment due to their wide distribution, opportunistic behavior, and increasing antibiotic resistance. This study reports on the deposition of polyvinylpyrrolidone/antibiotic/isoflavonoid thin films by the matrix-assisted pulsed laser evaporation (MAPLE) method as anti-adhesion barrier coatings, on biomedical surfaces for improved resistance to microbial colonization. The thin films were characterized by Fourier transform infrared spectroscopy, infrared microscopy, and scanning electron microscopy. In vitro biological assay tests were performed to evaluate the influence of the thin films on the development of biofilms formed by Gram-positive and Gram-negative bacterial strains. In vitro biocompatibility tests were assessed on human endothelial cells examined for up to five days of incubation, via qualitative and quantitative methods. The results of this study revealed that the laser-fabricated coatings are biocompatible and resistant to microbial colonization and biofilm formation, making them successful candidates for biomedical devices and contact surfaces that would otherwise be amenable to contact transmission.     

A Combined Experimental and Computational Study of Chrysanthemin as a Pigment for Dye-Sensitized Solar Cells

The theoretical study of chrysanthemin (cyanidin 3-glucoside) as a pigment for TiO₂-based dye-sensitized solar cells (DSSCs) was performed with the GAUSSSIAN 09 simulation. The electronic spectra of neutral and anionic chrysanthemin molecules were calculated by density functional theory with B3LYP functional and DGDZVP basis set. A better energy level alignment was found for partially deprotonated molecules of chrysanthemin, with the excited photoelectron having enough energy in order to be transferred to the conduction band of TiO₂ semiconductor in DSSCs. In addition, we used the raw aqueous extracts of roselle (Hibiscus sabdariffa) calyces as the source of chrysanthemin and the extracts with various pH values were tested in DSSCs. The extracts and photosensitized semiconductor layers were characterized by UV-Vis spectroscopy, and DSSCs based on raw extracts were characterized by current density-voltage measurements.     

Needle-free electrospinning of nanofibrillated cellulose and graphene nanoplatelets based sustainable poly (butylene succinate) nanofibers

Sustainable materials have slowly overtaken the nanofiber research field while the tailoring of their properties and the upscaling for industrial production are some of the major challenges. We report preparation of nanofibers that are bio-based and biodegradable prepared from poly (butylene succinate) (PBS) with the incorporation of nanofibrillated cellulose (NFC) and graphene nanoplatelets (GN). NFC and GN were combined as hybrid filler, which led to the improved morphological structure for electrospun nanofibers. A needleless approach was used for solution electrospinning fabrication of nanofiber mesh structures to promote application scalability. The polymer crystallization process was examined by differential scanning calorimetry (DSC), the thermal stability was evaluated by thermal gravimetric analysis (TGA), while the extensive investigation of the nanofibers structure was carried out with scanning electron microscopy (SEM) and atomic force microscopy (AFM). NFC and GN loadings were 0.5 and 1.0 wt %; while poly (ethylene glycol) (PEG) was employed as a compatibilizer to enhance fillers’ interaction within the polymer matrix. The interactions in the interface of the fillers and matrix components were studied by FTIR and Raman spectroscopies. The hybrid filler approach proved to be most suitable for consistent and high-quality nanofiber production. The obtained dense mesh-based structures could have foreseeable potential application in biomedical field like scaffolds for the tissue and bone recovery, while other applications could focus on filtration technologies and smart sensors.