Ultrafiltration of Polymer-Metal Complexes for Metal Ion Removal from Wastewaters

Summary: A case-study using macromolecular metal complexes is described. The results of a process named Polymer Assisted Ultrafiltration (PAUF) for ion removal from various types of waters is reported. The water soluble polymers such as polyetilenimine (PEI), polyacrylic acid (PAA), polyacrylic acid sodium salt (PAASS) and poly(dimethylamine–co–epichlorohydrin–co–ethylenediamine) (PDEHED) as chelating agents, the Cu²⁺ as model ion and five ultrafiltration membranes have been used. The complexing agents were previously tested to establish the binding capacity and the best operating conditions for the process. Among the tested polymers the PEI appeared the most interesting one because its binding mechanism does not involve a counter ion release. It was tested in the simulation of wastewaters treatment containing the Cu²⁺ ion chelated with citric acid; this is a problem of interest in the recycling of water from soil washing operations. The polyethylenimine quantitatively bound the copper-citrate chelate at pH 5.5 and the three component complex was separated by UF membranes producing a permeate with very low metal concentration. The polymer regeneration was carried out with good results by operating with the diafiltration method. The copper ion present in the diafiltration permeate in a form chelated with citric acid was recovered by oxidising the citrate in a membrane photoreactor. The positive results of the described case-study show that Macromolecule-Metal Complexes play a key role for running effectively and selectively the PAUF process for removing metal ions from various type of waters.     

Performance and characteristics of a trace gas analyzer for the determination of volatile organic compounds in air

An instrument has been developed and tested for the continuous measurement of volatile organic compounds (VOC) in air. The system consists of a gas chromatograph equipped with a dedicated sampling device that allows the sample to be transferred to a cooled microtrap via sampling loops (10, 100, 250 ml) or via a direct pump transfer to the trap. The microtrap is placed in the chromatographic oven just below a modified split-splitless injector, allowing direct liquid injection for calibration of the system; the injector is in communication with the sampling valve equipped with the loop and the sampling pump. The system allows 24-hour sampling and analysis of a large number of VOC (up to 25 individual hydrocarbons ranging from C2 C9) and also polar volatile organic compounds PVOC. Thanks to the particular trap geometry, a minimum consumption of liquid nitrogen (between 150 300 ml) is needed for each analytical run and no water managing system is normally required for humid air samples.     

Substituent Effect on the Competition between Hetero‐Diels‐Alder and Cheletropic Additions of Sulfur Dioxide to 1‐Substituted Buta‐1,3‐dienes

The reactivity of sulfur dioxide toward variously substituted butadienes was explored in an effort to define the factors affecting the competition between the hetero‐Diels‐Alder and cheletropic additions. At low temperature (<−70°), 1‐alkyl‐substituted 1,3‐dienes 1 that can adopt s‐cis‐conformations add to SO₂ in the hetero‐Diels‐Alder mode in the presence of CF₃COOH as promoter. In the case of (E)‐1‐ethylidene‐2‐methylidenecyclohexane ((E)‐ 4a ), the [4+2] cycloaddition of SO₂ is fast at −90° without acid catalyst. (E)‐1‐(Acyloxy)buta‐1,3‐dienes (E)‐ 1c , (E)‐ 1y , and (E)‐ 1z with AcO, BzO, and naphthalene‐2‐(carbonyloxy) substituents, respectively also undergo the hetero‐Diels‐Alder addition with SO₂+CF₃COOH at low temperatures, giving a 1 : 10 mixture of the corresponding cis‐ and trans‐6‐(acyloxy)sultines c‐ 2c,y,z and t‐ 2c,y,z , respectively). Above −50°, the sultines undergo complete cycloreversion to the corresponding dienes and SO₂, which that add in the cheletropic mode at higher temperature to give the corresponding 2‐substituted sulfolenes (=2,5‐dihydrothiophene 1,1‐dioxides) 3 . The hetero‐Diels‐Alder additions of SO₂ follow the Alder endo rule, giving first the 6‐substituted cis‐sultines that equilibrate then with the more stable trans‐isomers. This statement is based on the assumption that the S=O group in the sultine prefers a pseudo‐axial rather than a pseudo‐equatorial position, as predicted by quantum calculations. The most striking observation is that electron‐rich dienes such as 1‐cyclopropyl‐, 1‐phenyl‐, 1‐(4‐methoxyphenyl)‐, 1‐(trimethylsilyl)‐, 1‐phenoxy‐, 1‐(4‐chlorophenoxy)‐, 1‐(4‐methoxyphenoxy)‐, 1‐(4‐nitrophenoxy)‐, 1‐(naphthalen‐2‐yloxy)‐, 1‐(methylthio)‐, 1‐(phenylthio)‐, 1‐[(4‐chlorophenyl)thio]‐, 1‐[(4‐methoxyphenyl)thio]‐, 1‐[(4‐nitrophenyl)thio]‐, and 1‐(phenylseleno)buta‐1,3‐diene, as well as 1‐(methoxymethylidene)‐2‐methylidenecyclohexane ( 4f ) do not equilibrate with the corresponding sultines between −100 and −10°, in the presence of a large excess of SO₂, with or without acidic promoter. The hetero‐Diels‐Alder additions of SO₂ to 1‐substituted (E)‐buta‐1,3‐dienes are highly regioselective, giving exclusively the corresponding 6‐substituted sultines. The 1‐substituted (Z)‐buta‐1,3‐dienes do not undergo the hetero‐Diels‐Alder additions with sulfur dioxide.     

Development and Characterization of Curcumin-Silver Nanoparticles as a Promising Formulation to Test on Human Pterygium-Derived Keratinocytes

Pterygium is a progressive disease of the human eye arising from sub-conjunctival tissue and extending onto the cornea. Due to its invasive growth, pterygium can reach the pupil compromising visual function. Currently available medical treatments have limited success in suppressing efficiently the disease. Previous studies have demonstrated that curcumin, polyphenol isolated from the rhizome of Curcuma longa, induces apoptosis of human pterygium fibroblasts in a dose- and time-dependent manner showing promising activity in the treatment of this ophthalmic disease. However, this molecule is not very soluble in water in either neutral or acidic pH and is only slightly more soluble in alkaline conditions, while its dissolving in organic solvents drastically reduces its potential use for biomedical applications. A nanoformulation of curcumin stabilized silver nanoparticles (Cur-AgNPs) seems an effective strategy to increase the bioavailability of curcumin without inducing toxic effects. In fact, silver nitrates have been used safely for the treatment of many ophthalmic conditions and diseases for a long time and the concentration of AgNPs in this formulation is quite low. The synthesis of this new compound was achieved through a modified Bettini’s method adapted to improve the quality of the product intended for human use. Indeed, the pH of the reaction was changed to 9, the temperature of the reaction was increased from 90 °C to 100 °C and after the synthesis the Cur-AgNPs were dispersed in Borax buffer using a dialysis step to improve the biocompatibility of the formulation. This new compound will be able to deliver both components (curcumin and silver) at the same time to the affected tissue, representing an alternative and a more sophisticated strategy for the treatment of human pterygium. Further in vitro and in vivo assays will be required to validate this formulation.     

Transition mechanisms in laminar separation bubbles with and without incoming wakes and synthetic jet effects

Laminar separation and transition processes of the boundary layer developing under a strong adverse pressure gradient, typical of Ultra-High-Lift turbine profiles, have been experimentally investigated for a low Reynolds number case. The boundary layer development has been surveyed for different conditions: with steady inflow, with incoming wakes and with the synchronized forcing effects due to both incoming wakes and synthetic jet (zero net mass flow rate jet). In this latter case, the jet Strouhal number has been set equal to half the wake-reduced frequency to synchronize the unsteady forcing effects on the boundary layer. Measurements have been taken by means of a single-sensor hot-wire anemometer. For the steady inflow case, particle image velocimetry has been employed to visualize the large-scale vortical structures shed as a consequence of the Kelvin?CHelmholtz instability mechanism. For the unsteady inflow cases, a phase-locked ensemble averaging technique, synchronized with the wake and the synthetic jet frequencies, has been adopted to reconstruct the boundary layer space-time evolution. Results have been represented as color plots, for several time instants of the forcing effect period, in order to provide an overall view of the time-dependent transition and separation processes in terms of ensemble-averaged velocity and unresolved unsteadiness distributions. The phase-locked distributions of the unresolved unsteadiness allowed the identification of the instability mechanisms driving transition as well as the Kelvin?CHelmholtz structures that grow within the separated shear layer during the incoming wake interval and the synthetic jet operating period. Incoming wakes and synthetic jet effects in reducing and/or suppressing flow separation are investigated in depth.     

Functionalized Biomimetic Magnetic Nanoparticles as Effective Nanocarriers for Targeted Chemotherapy

Novel MamC‐mediated biomimetic magnetic nanoparticles (BMNPs) are proposed as valuable carriers for targeted chemotherapy because of the size (36 ± 12 nm) and of surface properties conferred by MamC coating. They are super‐paramagnetic at room and body temperatures, have a large magnetic moment per particle, mediate hyperthermia, are cytocompatible, and, having a negative surface charge at physiological pH, can be efficiently coupled with DOXOrubicin (DOXO) and a monoclonal antibody (mAb) directed against the human Met/hepatocyte growth factor receptor (overexpressed in many cancers) displaying coupling stability, while releasing DOXO at acidic pH. This release can be enhanced by hyperthermia. The DOXO‐mAb‐BMNPs selectively recognize Met, bind efficiently to Met⁺ tumor cells, and discharge DOXO within their nuclei more efficiently than DOXO‐BMNPs, exerting cytotoxicity. These data represent proof of concept for future in vivo experiments in which the controlled dual targeting (mAb‐mediated and magnetic) approach and combined (chemotherapy and hyperthermia) therapy will be studied.     

Non-linear behavior of heavy stays

The behavior of cable structures, widely employed in several engineering fields, is highly non-linear. A common procedure to treat the cables is to substitute them with straight rods assuring an equivalent stiffness. But classical methods allow to determine satisfactorily the equivalent stiffness only when the cable is sensibly stretched, the cable sag is small and the cable is horizontal, since they generally disregard the effects of the self-weight component along the chord. To study non-linear behavior of inclined cables, we extend here a rational criterion stemming from the virtual work principle, formerly proposed for horizontal cables.     

Optimal design of steel frames accounting for buckling

A formulation of a special design problem devoted to elastic perfectly plastic steel frame structures subjected to different combinations of static and dynamic loads is presented. In particular, a minimum volume design problem formulation is presented and the structure is designed to be able to elastically behave for the assigned fixed loads, to elastically shakedown in presence of serviceability load conditions and to prevent the instantaneous collapse for suitably chosen combinations of fixed and ultimate seismic loadings as well as of fixed and wind actions. The actions that the structure must suffer are evaluated by making reference to the actual Italian seismic code. The dynamic response of the structure is performed by utilizing a modal technique. In order to prevent other undesired collapse modes further constraints are introduced in the relevant optimization problem taking into account the risk of element buckling. Different applications devoted to flexural frames conclude the paper. The sensitivity of the structural response has been investigated on the grounds of the determination and interpretation of the Bree diagrams of the obtained optimal structures.     

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