Heavy Metal Detection and Removal by Composite Carbon Quantum Dots/Ionomer Membranes.

The combination of ion exchange membranes with carbon quantum dots (CQDs) is a promising field that could lead to significant advances in water treatment. Composite membranes formed by sulfonated poly(ether ether ketone) (SPEEK) with embedded CQDs were used for the detection and removal of heavy metal ions, such as lead and cadmium, from water. SPEEK is responsible for the capture of heavy metals based on the cation exchange mechanism, while CQDs detect their contamination by exhibiting changes in fluorescence. Water-insoluble "red" carbon quantum dots (rCQDs) were synthesized from p-phenylenediamine so that their photoluminescence was shifted from that of the polymer matrix. CQDs and the composites were characterized by several techniques: FTIR, Raman, UV/VIS, photoluminescence, XPS spectroscopies, and AFM microscopy. The heavy metal ion concentration was analyzed by inductively coupled plasma-optical emission spectroscopy (ICP-OES). The concentration ranges were 10.8-0.1 mM for Pb2+ and 10.0-0.27 mM for Cd2+. SPEEK/rCQDs showed a more pronounced turn-off effect for lead. The composite achieved 100% removal efficiency for lead and cadmium when the concentration was below a half of the ion exchange capacity of SPEEK. The regeneration of membranes in 1 M NaCl was also studied. A second order law was effective to describe the kinetics of the process.

A novel and efficient concentration of pomegranate juice with enhanced antioxidant activity.

In the present study we investigated the performance of a panel of 13 solid sorbents comprising layered double hydroxides, zirconium phosphate-based materials, and phyllosilicates as heterogeneous supports for the concentration of pomegranate (Punica granatum L.) juice. Mg-containing clays exhibited an almost complete bleaching capacityof pomegranate juice and more interestingly provided blends with an increased antioxidant capacity (around 1.5-fold) respect to the parent juice when assayed for the Trolox equivalent antioxidant capacity (TEAC) coupled to ABTS decolorization test. Such an activity remained practically unaltered after 4 days during which the pomegranate concentrated preparations remained supported on clays. The approach investigated herein and used for the concentration of pomegranate juice and the discovery of the preservation for long periods of the antioxidant activities of pomegranate extracts when supported on solid sorbents have been reported herein for the first time in the literature to the best of our knowledge.

An easy way for the hydrolysis, pre-concentration, and chemical stabilization of crocetin from saffron powder.

To date there are no methods in the literature leading to crocetin selective concentration from saffron powder aqueous solutions. To this aim, we decided to test the performance of its heterogeneous extraction by means of a panel of 21 synthetic clays, 4 of which demonstrated to selectively retain crocetin in the solid phase after hydrolysis of its digentiobyosil ester (crocin) (and its isomers) and to its chemical stabilization (e.g., oxidation) over time. The best adsorption yield was obtained with zinc hydroxy chloride (66.18 ± 0.06 µg/g dry powder). This phenomenon was assessed by HPLC-DAD analyses after desorption of crocetin from the respective support and assessing its degradation along a period of 30 days. The method we established could represent a good mean to provide pure crocetin from saffron powder, preserving in the meantime its chemical properties for a concrete future exploitation for food pharmaceutical, and cosmetic purposes.

An improved method for the isolation of amarogentin, the bitter principle of yellow gentian roots.

Amarogentin is well known to be among the most bitter naturally occurring compound. Either as an individual one or extracts, amarogentin is used as a food additive and as a dietary supplement. The aim of the present investigation is to set-up a convenient process to selectively isolate amarogentin from the ethanolic roots extract of Gentiana lutea. The process consisted in the treatment of an aqueous suspension of such an extract with a panel of 21 solid inorganic / organic sorbents followed by filtration, desorption, and high performance liquid chromatography (HPLC) analyses. Among the solid materials tested, those containing Mg+2 in the frame of a lamellar structure provided very good adsorption yields in the range 86.4% - 99.9% (p < 0.05 at Student's t-test). The method we set up could be in principle useful to obtain a pure nature-derived food additive to provide bitter taste to foods and beverages.

Pre-concentration of active principles from different varieties of Camellia sinensis extracts by solid sorbents.

In this article we studied the phytochemical composition of leaves extracts of different varieties of Camellia sinensis(L.) Kuntze after treatment with 16 selected solid sorbents (namely hydrotalcites, magnesium oxide and hydroxide, zirconium phosphates, and phyllosilicates). The pre-concentration and selective adsorption of the main active principles of this food and medicinal plant [e.g. gallic acid, (-)-epicatechin, (-)-epicatechin gallate, and caffeine] were investigated. The quantities of phytochemicals adsorbed by solids were measured by HPLC analysis, coupled to photodiode array detection and calculated as the difference between the quantities in the parent untreated extracts and those recorded in the filtrates. Caffeine was selectively adsorbed by bentonite to a large extent, while for the remaining phytochemicals different patterns were recorded depending on the type of leaves extract. A comparison with pure chemicals revealed a strong effect of the phytocomplex composition on the adsorption yields. The methodology outlined herein may be useful to obtain tea extracts enriched in selective active principles also for industrial scopes.

3D additive manufactured composite scaffolds with antibiotic-loaded lamellar fillers for bone infection prevention and tissue regeneration.

Bone infections following open bone fracture or implant surgery remain a challenge in the orthopedics field. In order to avoid high doses of systemic drug administration, optimized local antibiotic release from scaffolds is required. 3D additive manufactured (AM) scaffolds made with biodegradable polymers are ideal to support bone healing in non-union scenarios and can be given antimicrobial properties by the incorporation of antibiotics. In this study, ciprofloxacin and gentamicin intercalated in the interlamellar spaces of magnesium aluminum layered double hydroxides (MgAl) and α-zirconium phosphates (ZrP), respectively, are dispersed within a thermoplastic polymer by melt compounding and subsequently processed via high temperature melt extrusion AM (~190 °C) into 3D scaffolds. The inorganic fillers enable a sustained antibiotics release through the polymer matrix, controlled by antibiotics counterions exchange or pH conditions. Importantly, both antibiotics retain their functionality after the manufacturing process at high temperatures, as verified by their activity against both Gram + and Gram - bacterial strains. Moreover, scaffolds loaded with filler-antibiotic do not impair human mesenchymal stromal cells osteogenic differentiation, allowing matrix mineralization and the expression of relevant osteogenic markers. Overall, these results suggest the possibility of fabricating dual functionality 3D scaffolds via high temperature melt extrusion for bone regeneration and infection prevention.

Solid phase adsorption of anthraquinones from plant extracts by lamellar solids.

Solid phase extraction is nowadays a well validated and powerful technique applicable to complex matrices like plant extracts and phytocomplexes. This process provides concentration and/or purification of selected secondary metabolites from these matrices for subsequent analysis and isolation. In this research article sixteen lamellar solids, comprising layered structures (hydrotalcites, zirconium phosphates, magnesium hydroxide), magnesium oxide, and the phyllosilicates talc and bentonite were investigated for their capacity and performance to selectively adsorb five naturally occurring and widespread anthraquinones (aloe, aloe-emodin, rhein, chrysophanol, and physcion) contained in three ethanolic extracts of well known plants with purgative effects (frangula, senna, and rhubarb). Ethanolic solutions of extracts from these species were vigorously magnetically stirred with fixed quantities of each solid support at room temperature for 1 h. Subsequent HPLC analysis, coupled to photodiode array detection, revealed that, among the solids tested, the hydrotalcite zinc aluminum oleate and magnesium aluminum azelate and magnesium oxide were largely the most effective to this concern allowing to recover anthraquinones (all or some) in good to excellent percentages. Another interesting result was the selective and total removal of rhein by some sorbents from senna and rhubarb extracts. Sorbents were also recyclable and could be re-used to accomplish additional steps without appreciable loss of adsorption capacity. The application of the title solid inorganic and mixed inorganic/organic supports for the selective adsorption and concentration in the solid phase of anthraquinones from commonly used laxative plant species is reported herein for the first time.

Solid phase adsorption of emodin on hydrotalcites and inorganic oxides: A preliminary study.

Solid phase extraction applied to plant matrices is nowadays a well validated technique allowing the concentration and purification of selected secondary metabolites for subsequent analysis. In this short communication we screened the efficiency of 16 selected solid supports including layered structures (hydrotalcites and zirconium phosphate), magnesium oxide and hydroxide, and finally the phyllosilicates talc and bentonite for the selective concentration of the anthraquinone emodin from raw solid extracts of Polygonum cuspidatum Siebold & Zucc. (sin. Reynoutria japonica Houtt.) (Polygonaceae), commonly known as "Japanese knotweed". An ethanolic solution of sample extract from this plant was vigorously mixed with fixed quantities of each solid support. Subsequent HPLC analysis, coupled to photodiode array detection, revealed that, among the solid supports assayed, the hydrotalcite zinc aluminum oleate and magnesium oxide were largely the most effective to this concern. Both were able to extract emodin from the raw extract in percentages of 81.5 % and 92.4 %, respectively. The application of the title supports for the extraction and concentration in the solid phase of anthraquinones from raw plant extracts have been reported herein for the first time.

The Rheology of PEOT/PBT Block Copolymers in the Melt State and in the Thermally-Induced Sol/Gel Transition. Implications on the 3D-Printing Bio-Scaffold Process.

Poly(ethyleneoxideterephthalate)/poly(butyleneterephthalate) (PEOT/PBT) segmented block copolymers are widely used for the manufacturing of 3D-printed bio-scaffolds, due to a combination of several properties, such as cell viability, bio-compatibility, and bio-degradability. Furthermore, they are characterized by a relatively low viscosity at high temperatures, which is desired during the injection stages of the printing process. At the same time, the microphase separated morphology generated by the demixing of hard and soft segments at intermediate temperatures allows for a quick transition from a liquid-like to a solid-like behavior, thus favoring the shaping and the dimensional stability of the scaffold. In this work, for the first time, the rheology of a commercial PEOT/PBT material is studied over a wide range of temperatures encompassing both the melt state and the phase transition regime. Non-isothermal viscoelastic measurements under oscillatory shear flow allow for a quantitative determination of the material processability in the melt state. Additionally, isothermal experiments below the order⁻disorder temperature are used to determine the temperature dependence of the phase transition kinetics. The importance of the rheological characterization when designing the 3D-printing scaffold process is also discussed.

Solid Dispersion of Resveratrol Supported on Magnesium DiHydroxide (Resv@MDH) Microparticles Improves Oral Bioavailability.

Resveratrol, because of its low solubility in water and its high membrane permeability, is collocated in the second class of the biopharmaceutical classification system, with limited bioavailability due to its dissolution rate. Solid dispersion of resveratrol supported on Magnesium DiHydroxide (Resv@MDH) was evaluated to improve solubility and increase bioavailability of resveratrol. Fluorimetric microscopy analysis displays three types of microparticles with similar size: Type 1 that emitted preferably fluorescence at 445 nm with bandwidth of 50 nm, type 2 that emitted preferably fluorescence at 605 nm with bandwidth of 70 nm and type 3 that is non-fluorescent. Micronized pure resveratrol displays only microparticles type 1 whereas type 3 are associated to pure magnesium dihydroxide. Dissolution test in simulated gastric environment resveratrol derived from Resv@MDH in comparison to resveratrol alone displayed better solubility. A 3-fold increase of resveratrol bioavailability was observed after oral administration of 50 mg/kg of resveratrol from Resv@MDH in rabbits. We hypothesize that type 2 microparticles represent magnesium dihydroxide microparticles with a resveratrol shell and that they are responsible for the improved resveratrol solubility and bioavailability of Resv@MDH.

Accessing stable zirconium carboxy-aminophosphonate nanosheets as support for highly active Pd nanoparticles.

Thin nanosheets from a layered zirconium phosphate-carboxyphosphonate is reported here. Small Pd nanoparticles have been supported on these nanosheets by an efficient method. The resulting Pd-catalyst was fully characterized and tested in the Suzuki-Miyaura coupling. The catalytic system proved its efficiency as it was reused for several cycles and showed low Pd leaching.

Ion exchange and intercalation properties of layered double hydroxides towards halide anions.

A layered double hydroxide (LDH) obtained by the urea method, having an empirical formula [Zn(0.61)Al(0.39)(OH)2](CO3)(0.195)·0.50H2O, has been converted into the corresponding chloride form [Zn(0.61)Al(0.39)(OH)2]Cl(0.39)·0.47H2O by making the solid come into contact with a suitable HCl solution. The intercalation of the other halide anions (X(-) = F(-), Br(-), I(-)) via the Cl(-)/X(-) anion exchange has been attained and the respective anion exchange isotherms have been obtained with the batch method. The analysis of the isotherms indicates that the selectivity of LDH towards the halides decreases with the increase of the X(-) ionic radius, the selectivity order being F(-) > Cl(-)≥ Br(-) > I(-). The CO3(2-)/Cl(-) isotherm has also been reported to highlight the extraordinary selectivity of LDH towards carbonate anions. Samples taken from the isotherms at different exchange degrees were analyzed by X-ray diffraction, thermogravimetry and thermodiffractometry to obtain information about the ion exchange mechanism. The Cl(-)/Br(-) and the reverse Br(-)/Cl(-) exchanges occur with the formation of solid solutions, very likely because of the similar ionic radius of the exchanging anions. In contrast, in the Cl(-)/F(-) and Cl(-)/I(-) exchange, the co-existence of the Cl(-) and F(-) (or I(-)) phases in the same sample was detected, indicating the occurrence of a first order phase transition, in which the starting phase is transformed into the final phase, as the process goes on. The variation of the interlayer distances of ZnAl-X intercalation compounds with the hydration degree has been interpreted with a structural model based on the nesting of the guest species into the trigonal pockets of the brucite-like layer surface. Rietveld refinements of the phases with the maximum F(-), Br(-) and I(-) content were also performed and compared with the above model, giving indications of the arrangement and order/disorder of the halide anions in the interlayer region.

Hydrotalcite composites for an effective fluoride buccal administration: a new technological approach.

The aim of this work was to develop new mucoadhesive buccal patches containing an inorganic fluorinated compound, MgAl-F, intended for decay prevention. Firstly MgAl-F was synthesized and characterized, then the patches were prepared starting from a physical blend of mucoadhesive polymers (NaCMC and polycarbophil) in which MgAl-F was dispersed in different amounts in order to obtain the films. The prepared mucoadhesive patches were characterized in terms of swelling capacity, mucoadhesion force and time, surface morphology and in vitro release studies. Moreover, the organoleptic properties and acceptability have been evaluated by in vivo application. The performed studies demonstrated that the proposed formulations are practical, manageable, flexible and adaptable to the biological substrate showing, at the same time, good organoleptic properties. Moreover, the presence of the MgAl-F is able to decrease the strong adhesion of the employed polymers, reducing pain and irritations resulting in a high patient acceptability. Data obtained from release studies revealed that the application of small patch portions is enough able to release, for a prolonged time, an amount of fluoride ions able to reach the efficacious dose. These observations suggest the applicability of such formulations for buccal administration of different active ingredients.

On the intercalation of the iodine-iodide couple on layered double hydroxides with different particle sizes.

Molecular iodine was intercalated from nonaqueous solution into microsized ZnAl-layered double hydroxide (LDH) in the iodide form, generating the I(3)(-)/I(-) redox couple into the interlayer region. Chloroform, ethanol, acetonitrile, or diethyl ether were used as solvents to dissolve the molecular iodine. The intercalation compounds were characterized by thermogravimetric analysis, X-ray powder diffraction, UV-vis spectroscopy, and scanning and transmission electron microscopy. The stability of iodine-solvent adducts and the iodine concentration affected the LDH iodine loading, and samples with I(2)/I(-) molar ratio ranging from 0.14 to 0.82 were prepared. Nanosized, well dispersible LDH, synthesized by the urea method in water-ethylene glycol media, were also prepared and successfully functionalized with the I(3)(-)/I(-) redox couple applying the conditions optimized for the micrometric systems.