The separation and determination of the ten water-soluble vitamins by using capillary electrophoresis in the micellar electrokinetic chromatography in a single run are proposed. The method uses low toxicity and cost solvent (ethanol) as modifier of background electrolyte (BGE) attending to the Green Chemistry principles. The electrophoretic method uses 10.0 % (v/v) ethanol, 2.0 % (w/v) SDS, 0.02 mol L⁻¹borate at pH 8.70 as BGE. The standard and real sample solutions were injected in the eletrophoretic system by hydrodynamic injection under pressure of 0.80 psi for 8 s, and the separation was carried out in a fused silica capillary under a potential of 28 kV at 25 °C; the analytical signals were monitored at 214 nm. The analytical method is precise (r.s.d. < 6 %), accurate (better than 9 %), selective, sensitive, robust, simple, and presents high analytical frequency as ten water-soluble vitamins were separated in only 18 min, with migration times of 5.75 ± 0.02, 6.81 ± 0.02, 8.13 ± 0.04, 8.80 ± 0.07, 8.98 ± 0.06, 11.10 ± 0.08, 11.34 ± 0.05, 13.85 ± 0.15, 14.82 ± 0.04, and 17.85 ± 0.30 min. Detection and quantification limits of 0.34, 0.32, 0.27, 0.20, 2.50, 4.98, 4.92, 0.30, 0.86 and 0.28 mg L⁻¹and 1.02, 0.97, 0.83, 0.62, 7.56, 15.09, 14.91, 0.90, 2.59 and 0.83 mg L⁻¹, for vitamins PP (nicotinamide), B₁₂(cyanocobalamin), B₂(riboflavin), B₆(pyridoxine), B₈(biotin), C (ascorbic acid), B₅(pantothenic acid), B₃(nicotinic acid), B₁(thiamine), and B₉(folic acid), respectively. Excellent recoveries (intra and inter-day) were obtained and, when the method was applied to food supplement analyses the results were in agreement with the conventional HPLC methods.

Motivated by the increasing need for new solutions with less environmental impact, in this work we have investigated the benefits of depositing a wheat gluten (WG) coating on paperboard substrates intended for food packaging applications. To overcome the inherent moisture sensitivity of this protein, WG was combined with a silica network obtained by sol-gel chemistry. WG/silica hybrid coatings were characterized in terms of structural, thermal, morphological, surface, and water vapor barrier properties. Spectrometric analysis demonstrated that the organic and inorganic phases interacted primarily through hydrogen bonding. This was also supported by thermal experiments, which revealed a higher Tg measured for the hybrid materials with the higher silica content (114 ± 1 °C and 128 ± 2 °C, respectively) compared to the pure WG material (Tg = 89 ± 1 °C). Scanning electron microscopy showed that the surfaces of the coatings were very smooth, though the presence of pinholes, cracks, fractures, and voids was detected, especially for the silica-rich formulations. Upon deposition of the coatings, the wettability of the bare paperboard increased, as demonstrated by the lower water contact angle values. In addition, hybrid coatings exhibited a higher wettability over the pristine WG coating, which was due to a more intense spreading phenomenon. The deposition of the coatings led to a ∼ 4-fold reduction in water vapor transmission rate (WVTR ∼ 90 g m⁻² 24 h⁻¹ at 23 °C and 65% relative humidity) of the specific cellulosic substrate tested in this work (WVTR ∼ 350 g m⁻² 24⁻¹).

The identification of CN– in water, seeds, and biological systems has, because of its high toxicity, attracted the increasing attention of many chemical industry researchers. In the work, a novel highly selective and reversible sensor, MMY, was shown to recognize CN– effectively. The color and fluorescent changes verified the interaction of MMY with CN–, and the fluorescence lifetime of MMY was also changed upon addition of CN–. A mode of interaction of MMY with CN– based on the results of various experiments was speculated. The LOD of MMY toward CN– was 9.4 × 10–¹⁰ M, lower than the concentration of CN– deemed acceptable by the WHO (World Health Organization) and the U.S. EPA (United States Environmental Protection Agency). MMY showed good reversibility and reusability for detecting CN–. In addition, test slips and silica plates were both earned by ourselves, which were able to recognize CN– qualitatively. Additionally, MMY could recognize CN– in tap water quantitatively with the use of a smartphone APP. Interestingly, MMY was also used to detect CN– in seeds. It was valid to image CN– in Caenorhabditis elegans and mice with a vivid “turn-on” fluorescence. MMY thus can circulate in the bloodstream.

Titanium dioxide nanoparticles seem to have a low toxicity to terrestrial organisms, though few studies are published in this area. TiO₂ used in sunscreens are nanocomposites where TiO₂ has been coated with magnesium, silica or alumina, as well as amphiphilic organics like polydimethyl siloxane (PDMS), and these coatings are modified by ageing. We assessed the ecotoxicity and propensity for bioaccumulation of an aged TiO₂ nanocomposite used in sunscreen cosmetics, and its potential effect on the frequency of apoptosis in different earthworm tissues. The earthworm Lumbricus terrestris was exposed to the TiO₂ nanocomposite for 7days in water or 2–8weeks in soil with the nanocomposite mixed either into food or soil at concentrations ranging from 0 to 100mgkg⁻¹. Apoptosis was then measured by immunohistochemistry and Ti localized by XRF microscopy. Results showed no mortality, but an enhanced apoptotic frequency which was higher in the cuticule, intestinal epithelium and chloragogenous tissue than in the longitudinal and circular musculature. TiO₂ nanoparticles did not seem to cross the intestinal epithelium/chloragogenous matrix barrier to enter the coelomic liquid, or the cuticule barrier to reach the muscular layers. No bioaccumulation of TiO₂ nanocomposites could thus be observed.

A composite of MCM-41 silica with rice husk was modified with dithizone with the aid of microwave radiation. The modified composite was characterized by different techniques and utilized for preconcentration of Cu²⁺, Zn²⁺ and Pb²⁺ prior to determination by flame atomic absorption spectrometry (FAAS). The adsorption process is optimized to attain the maximum efficiency. The procedure presented satisfying uptake characteristics with maximum adsorption capacity of 142.7, 102.9 and 228.8 mg g⁻¹ towards Cu²⁺, Zn²⁺ and Pb²⁺, respectively. The calibration graphs were linear up to 400 μg L⁻¹ for Cu²⁺ and Zn²⁺ and up to 800 μg L⁻¹ for Pb²⁺ with preconcentration factor of 240. The limits of detection were 0.28, 0.21 and 0.48 μg L⁻¹ for Cu²⁺, Zn²⁺ and Pb²⁺, respectively. The optimized procedure was utilized for the preconcentration of Cu²⁺, Zn²⁺ and Pb²⁺ in water and food samples prior to determination by FAAS with accepted precision and accuracy.

Riverine transport of dissolved inorganic carbon (DIC) from land to the ocean is an important carbon flux that influences the carbon budget at the watershed scale. However, the dynamics of DIC in an entire river network has remained unknown, especially in mountainous Japanese watersheds. We examined the effects of watershed land use and geology on the transports of inorganic carbon as well as weathered silica (Si) and calcium (Ca) in the Iwaki River system where agricultural and residential areas have developed in the middle and lower parts of the watershed. The concentration and stable carbon isotope ratios (δ¹³C) of DIC showed the longitudinal increase of ¹³C-depleted inorganic carbon along the river. As a result, most streams and rivers were supersaturated in dissolved CO₂ that will eventually be emitted to the atmosphere. The possible origin of ¹³C-depleted carbon is CO₂ derived from the decomposition of organic matter in agricultural and urban landscapes, as well as from in-stream respiration. In addition, agricultural and urban areas, respectively, exported the large amount of dissolved Si and Ca to the rivers, suggesting that CO₂ increased by respiration accelerates the chemical weathering of silicate and carbonate materials in soils, river sediments, and/or urban infrastructure. Furthermore, riverine bicarbonate flux is likely to enter shell carbonates of Corbicula japonica, an aragonitic bivalve, in the downstream brackish lake (Lake Jusan). These results revealed that the flux of DIC from the human-dominated watersheds is a key to understanding the carbon dynamics and food-web structure along the land-to-river-to-ocean continuum.

Solid-phase extraction is one the most useful and efficient techniques for sample preparation, purification, cleanup, preconcentration, and determination of heavy metals at trace levels. In this paper, functionalized MCM-48 nanoporous silica with 1-(2-pyridylazo)-2-naphthol was applied for trace determination of copper, lead, cadmium, and nickel in water and seafood samples. The experimental conditions such as pH, sample and eluent flow rate, type, concentration and volume of the eluent, breakthrough volume, and effect of coexisting ions were optimized for efficient solid-phase extraction of trace heavy metals in different water and seafood samples. The content of solutions containing the mentioned heavy metals was determined by flame atomic absorption spectrometry (FAAS), and the limits of detection were 0.3, 0.4, 0.6, and 0.9 ng mL⁻¹ for cadmium, copper, nickel, and lead, respectively. Recoveries and precisions were >98.0 and <4 %, respectively. The adsorption capacity of the modified nanoporous silica was 178 mg g⁻¹ for cadmium, 110 mg g⁻¹ for copper, 98 mg g⁻¹ for nickel, and 210 mg g⁻¹ for lead, respectively. The functionalized MCM-48 nanoporous silica with 1-(2-pyridylazo)-2-naphthol was characterized by thermogravimetry analysis (TGA), differential thermal analysis (DTA), transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FT-IR), X-ray diffraction (XRD), elemental analysis (CHN), and N₂ adsorption surface area measurement.

In this study, a new metal-organic framework-monolith composite for in-tube solid phase microextraction phase (IT-SPME) of fluoroquinolones (FQs) was prepared. 4-Vinylbenzoic acid was copolymerized with ethylenedimethacrylate in a fused silica capillary to form porous monolith. After that, zeolitic imidazolate frameworks (ZIF-8) were synthesized in situ within the pores and the surface of the monolith by controlled layer-by-layer self-assembly of Zn2+ and imidazole. The introduction of ZIF-8 enhanced the surface area of monolith composite, and thus, improving the extraction performance of IT-SPME for FQs obviously. Under the optimized conditions, a highly sensitive method for the monitoring of FQs residue in water and honey samples was developed by the on-line combination of IT-SPME with high-performance liquid chromatography with fluorescence detection (HPLC-FLD). The limits of detection (S/N = 3) for the targeted FQs in water and honey samples were as low as 0.14–0.61 ng/L and 0.39–1.1 ng/L, respectively. The relative standard deviations (RSDs) for intra-day and inter-day assay variability were less than 10% in all samples. The established on-line IT-SPME-HPLC-FLD was successfully used to detect ultra-trace FQs in environmental water and honey samples. Recoveries at different spiked concentrations ranged from 80.1% to 119% and 80.2–117% for water and honey samples, respectively, with satisfactory reproducibility. Compared to up-to-date reported methods, the proposed approach exhibits some features such as high sensitivity, convenience, partial automation, low consumptions of sample and solvent.

A versatile and robust solid phase with both magnetic property and a very high adsorption capacity is presented on the basis of modification of iron oxide-silica magnetic particles with a newly synthesized Schiff base (Fe₃O₄/SiO₂/L). The structure of the resulting product was confirmed by Fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD) spectrometry and transmission electron microscopy (TEM). We developed an efficient and cost-effective method for the preconcentration of trace amounts of Pb(II), Cd(II) and Cu(II) in environmental and biological samples using this novel magnetic solid phase. Prepared magnetic solid phase is an ideal support because it has a large surface area, good selectivity and can be easily retrieved from large volumes of aqueous solutions. The possible parameters affecting the enrichment were optimized. Under the optimal conditions, the method detection limit was 0.14, 0.19 and 0.12μgL⁻¹ for Pb(II), Cd(II) and Cu(II) ions, respectively. The established method has been successfully applied to analyze real samples, and satisfactory results were obtained. All these indicated that this magnetic phase had a great potential in environmental and biological fields.