An electrochemically controlled supramolecular zip tie based on host-guest chemistry of CB[8].

Three molecular threads incorporating two viologen units attached by an oligo-ethylene glycol chain of variable length and an electron rich naphthalene moiety were prepared. The internal viologen unit is connected to the naphthalene by a rigid linker that prevents the simultaneous complexation of these systems. The axle with the shortest chain (14+) in the presence of CB[8] placed the chain inside the macrocycle in aqueous media. In contrast, the longer chains in 24+ and 34+ allow locating the terminal viologen and the electron rich unit inside the cavity. Upon reduction of the bipyridinium salts, the system behaves like a zip tie relaxing the chain as a consequence of the insertion of both radical cation moieties within the CB[8] and making these switches as potential components for molecular machinery.

Sustainable Low-Cost Phosphorus Recovery Using Nanostructured Materials with Reusability Potential.

A new low-cost material with a polymeric base formed from sodium silicate was developed. The material presents a nanostructured, highly rich iron surface with a large phosphorus retention capacity and potential reuse as a crop fertilizer. In the present study, we demonstrate that iron is the element that acts as an adsorbent for phosphate, while the polymeric base functions exclusively as a support for iron. The iron is uniformly adsorbed on the surface of the material, forming nanostructures, which ensure that iron works similarly to nanoparticles in solution but avoid other problems, such as particle agglomeration or the difficulty of separating them after the removal process. Materials were characterised by SEM, EDS, N2 sorption, and image processing, and the effect of pH, ionic strength, and temperature was studied. Sorption kinetics were analysed using Boyd's diffusion model, and adsorption equilibria were studied using several adsorption models. A maximum iron adsorption on the polymeric base of 23.9 ± 0.3 mg Fe∙g-1 was found, while maximum phosphorus adsorption was 366 ± 21 mg P∙g-1 Fe. Thus, phosphorus is recovered from the aqueous medium with an inexpensive material that has the potential to be used directly as a fertilizer.

Towards the Development of Sustainable Hybrid Materials to Achieve High Cr(VI) Removals in a One-Pot Process.

Rising manufacturing costs resulting from the current global situation make it necessary to economize at all stages of production, including waste management. Cost-effective materials that reduce the release of pollutants into the environment are becoming mandatory. In this work, a sodium silicate polymeric material, functionalized with iron, was synthesized. The material contains iron-rich nanostructures on the surface, which are responsible for the decontamination process. The inorganic material was further treated with a reducing eucalyptus extract to improve its decontamination performance. Both the inorganic and hybrid materials were used for decontamination of Cr(VI), a widely emitted chemical waste product. The hybrid material provided the best results (1.7 g Cr(VI)·g-1 Fe) in a one-pot process combining reduction and adsorption. The Langmuir-Freundlich model and a statistical thermodynamics adsorption model, together with removal rates, were used to study the processes. High adsorption energies were found, especially in the adsorption of Fe(II) on the polymeric base (33.2 kJ∙mol-1). All materials were characterized using SEM, EDS and N2 sorption, TGA, and IR analyses. In conclusion, the hybrid material synthesized in this study is cheap and easy to produce through environmentally friendly synthesis, and it is a promising adsorbent for the prevention of pollution issues in effluent discharges.

Antioxidant Capacity Assessment of Plant Extracts for Green Synthesis of Nanoparticles.

In this work, water extracts from different bio-based products of plant origin were studied to evaluate their antioxidant capacity and their potential to form metal nanoparticles from aqueous solutions. Two traditional tests, the Folin-Ciocalteu assay and the DPPH radical scavenging capacity method were compared with a more recent one, SNPAC, based on the formation of silver nanoparticles. The silver nanoparticle antioxidant capacity method (SNPAC) was optimized for its application in the characterization of the extracts selected in this work; kinetic studies and extract concentration were also evaluated. The extracts were obtained from leaves of oak, eucalyptus, green tea, white and common thyme, white cedar, mint, rosemary, bay, lemon, and the seaweed Sargassum muticum. The results demonstrate that any of these three methods can be used as a quick test to identify an extract to be employed for nanoparticle formation. Additionally, we studied the synthesis of Cu, Fe, Pb, Ni, and Ag nanoparticles using eucalyptus extracts demonstrating the efficiency of this plant extract to form metallic nanoparticles from aqueous metal salt solutions. Metal nanoparticles were characterized by transmission electron microscopy and dynamic light scattering techniques.

Thinking outside the "Blue Box": from molecular to supramolecular pH-responsiveness.

We present herein the development of a new polycationic cyclophane: the "red box", second in a series of hydrazone-based analogues of the well-known organic receptor cyclobis(paraquat-p-phenylene)cyclophane ("blue box"). The macrocycle has been prepared in an excellent yield in aqueous media, and shows both a remarkable pH-responsiveness and unusual hydrolytic stability of the two hydrazone C[double bond, length as m-dash]N bonds, associated with charge delocalization of the amine lone pair. Whilst in aqueous media the "red box" is able to complex a variety of aromatic substrates, both in its acidic and basic form, in organic media the cyclophane is only able to capture those in the acidic form, resulting in supramolecular pH-responsiveness.

Experimental evidences for a new model in the description of the adsorption-coupled reduction of Cr(VI) by protonated banana skin.

This work reports experimental evidences, not previously considered, to evaluate the Cr(VI) removal by protonated banana skin biomass. Variations in the number of hydroxyl groups, quantified by potentiometric titrations, and CO2 evolution during experiments, were attributed mainly to the oxidation of hydroxylic entities present in the studied material. The results indicate that these groups together with the carboxylic moieties are the main functionalities involved on the adsorption-coupled reduction process. The column experiment carried out provides a new approach to obtain the maximum reduction capacity of the material (3.72 mmol g(-1)). Moreover, we hereby propose a model that reports the first evidence for the instant bound of Cr(III) species to the material used, formed after the reduction of Cr(VI) present in solution. The removal process was quantified carrying out experiments under various pHs, biomass doses and Cr(VI) concentrations, and the mechanism underlying chromium removal was identified.

A physicochemical study of Al(+3) interactions with edible seaweed biomass in acidic waters.

UNLABELLED: In this article, a study of the Al(+3) interactions in acidic waters with biomass of different edible seaweeds: brown (Fucus vesiculosus, Saccorhiza polyschides), red (Mastocarpus stellatus, Gelidium sesquipedale, Chondrus crispus), and green (Ulva rigida, Codium tomentosum), has been performed. The influence of both, the initial concentration of metal and the solution pH, on the Al-uptake capacity of the biomass has been analyzed. From preliminary tests, species Fucus vesiculosus and Gelidium sesquipedale have been selected for a more exhaustive analysis. Sorption kinetic studies demonstrated that 60 min are enough to reach equilibrium. The intraparticle diffusion model has been used to describe kinetic data. Equilibrium studies have been carried out at pH values of 1, 2.5, and 4. Langmuir isotherms showed that the best uptake values, obtained at pH 4, were 33 mg/g for F. vesiculosus and 9.2 mg/g for G. sesquipedale. These edible seaweeds have been found particularly effective in binding aluminum metal ions for most of the conditions tested. Physicochemical data reported at these low pH values could be of interest, not only in modeling aluminum-containing antacids-food pharmacokinetic processes produced in the stomach (pH values 1 to 3) but in remediation studies in acidic waters. PRACTICAL APPLICATION: Aluminum is thought to be linked to neurological disruptions such as Alzheimer's disease. In this article, the adsorption ability of different types of edible seaweeds toward aluminum has been studied. The choice of low pH values is due to the fact that stomach region is acidic with a pH value between 1 and 3 as a consequence of hydrochloric secretion; so physicochemical data reported in this study could be of interest in modeling drug-food interactions, in particular those referring to aluminum-containing antacids-food pharmacokinetic processes produced in the gastrointestinal tract.

Adsorptive behaviour of mercury on algal biomass: competition with divalent cations and organic compounds.

Biosorption processes constitute an effective technique for mercury elimination. Sorption properties of native and acid-treated Sargassum muticum have been studied. Effect of pH, initial mercury concentration and contact time studies provided fundamental information about the sorption process. This information was used as the reference values to analyse mercury sorption under competition conditions. Saline effect has shown little influence in sorption, when only electrostatic modifications took place upon salt addition. On the contrary, if mercury speciation dramatically changed owing to the addition of an electrolyte, such as in the case of chloride salt, very large modifications in mercury sorption were observed. Competition with other divalent cations or organic compounds has shown little or none effect on mercury, indicating that a different mechanism is taking place during the removal of these pollutants. Finally, continuous flow experiments have clearly shown that a reduction process is also taking place during mercury removal. This fact is not obvious to elucidate under batch sorption experiments. Scanning Electron Microscopy analysis of the surface of the materials show deposits of mercury(I) and metallic mercury which is indicative of the reduction process proposed.

A dynamic proof of mercury elimination from solution through a combined sorption-reduction process.

Physico-chemical factors affecting mercury elimination from solution using fern as sorbent have been analysed. It was demonstrated that interaction of mercury with this biomass follows two processes, adsorption by the functional groups in the biopolymers of the cell wall and reduction by easily oxidized compounds of the biomass. Batch experiments have been done to analyse the effect of pH, ionic strength of the media or competition with other metals. Ionic strength did not show a significant influence in the process, but mercury speciation with the formation of negatively charge complexes represented an important drawback in metal elimination. Continuous flow conditions were also analysed since many industrial applications will require them. These studies allowed distinguishing the two processes: mercury sorption was observed but also reduction of this metal occurs. Reduction to mercury (I) and metallic mercury has been confirmed by scanning electron microscopy analysis of the column filling after the continuous flow experiments.

Dissolved silver in European estuarine and coastal waters.

Silver is one of the most toxic elements for the marine microbial and invertebrate community. However, little is known about the distribution and behaviour of dissolved silver in marine systems. This paper reports data on dissolved and sediment-associated silver in European estuaries and coastal waters which have been impacted to different extents by past and present anthropogenic inputs. This is the first extended dataset for dissolved silver in European marine waters. Lowest dissolved silver concentrations were observed in the Gullmar Fjord, Sweden (8.9 +/- 2.9 pM; x +/- 1sigma), the Tamar Estuary, UK (9.7 +/- 6.2 pM), the Fal Estuary, UK (20.6 +/- 8.3 pM), and the Adriatic Sea (21.2 +/- 6.8 pM). Enhanced silver concentrations were observed in Atlantic coastal waters receiving untreated sewage effluent from the city of A Coruna, Spain (243 +/- 195 pM), and in the mine-impacted Restronguet Creek, UK (91 +/- 71 pM). Anthropogenic wastewater inputs were a source of dissolved silver in the regions studied, with the exception of the Gullmar Fjord. Remobilisation of dissolved silver from historically contaminated sediments, resulting from acid mine drainage or sewage inputs, provided an additional source of dissolved silver to the estuaries. The ranges in the log particle-water partition coefficient (K(d)) values of 5-6 were similar for the Tamar and Mero estuaries and agreed with reported values for other estuaries. These high K(d) values indicate the particle reactive nature of silver with oxic sediments. In contrast, low K(d) values (1.4-2.7) were observed in the Fal system, which may have been due to enhanced benthic inputs of dissolved silver coupled to limited scavenging of silver on to sediments rich in Fe oxide.

Physicochemical characterisation of the ubiquitous bracken fern as useful biomaterial for preconcentration of heavy metals.

Batch experiments with dry bracken fern have been done to determine cadmium and lead sequestering capacity of this biomaterial. Biomass characterisation was done by infrared spectroscopy and potentiometric analysis. The effect of pH of the metal containing solution, contact time and initial metal concentration has been studied, together with the acid-base properties of the biomaterial. Results obtained have been analysed using mathematical and modelling techniques. Effect of pH on metal sequestration has been correlated with observed acid-base properties of the natural substrate. Kinetic data analysis provided relevant information about metal sequestration rate, showing important differences between lead and cadmium. Maximum uptake was found to be the same for both metals 0.410 mmol/g. This value was also clearly correlated to the number of acidic groups determined for this material which was found to be 0.432 mmol of acidic groups per gram of fern. Results obtained indicate that acidic groups are the functional groups responsible of the sequestration of metal ions and that bracken fern is a promising material for metal preconcentration.

Automation of a flow injection system for the determination of dissolved silver at picomolar concentrations in seawater with inductively coupled plasma mass spectrometry.

An automated flow injection system for the determination of dissolved silver at ultratrace concentrations in seawater, and controlled under LabVIEW, is described. The flow injection system allows online processing of seawater samples before their analysis using a magnetic sector inductively coupled plasma mass spectrometry (MS-ICP-MS) instrument. Samples were analysed with a minimum amount of manipulation, thereby reducing the risk of contamination. In addition, the flow injection approach with incorporation of an anion exchange minicolumn allowed ready removal of analytical interferences caused by the saline matrix. The software allowed full control of all flow injection components (valves and pumps) and removed manual time control and, therefore, operator errors. The optimized system was capable of five sample injections per h, including preconcentration and wash steps. The limit of detection was 0.5 pM for a 240-s sample load time, which allowed the determination of dissolved silver in open ocean waters, where picomolar concentration levels are typically encountered.