0000000000463543
AUTHOR
Luciana Sciascia
Effect of a zwitterionic surfactant on the dynamics of a pH oscillator
Effetto del polimero polipropilenglicole sulla dinamica della reazione di Belousov-Zabotinsky
Emulsion polymerizationcoupled to the Belousov-Zhabotinsky oscillating reaction
Amphiphilic derivatives of a polyaspartamide: their aggregation and solubilization ability
Abstract The self-aggregation and solubilization capability of a series of amphiphilic copolymers obtained by derivatisation of polymeric chain of α,β-poly(N-2-hydroxyethyl)- dl -aspartamide (PHEA) with polyethylene glycols (PEG, being different molecular weight 2000 or 5000 Da, PEG2000 and PEG5000, respectively) and/or hexadecylamine alkyl chain (C16), namely PHEA–PEG2000, PHEA–PEG5000, PHEA–C16, PHEA–PEG2000–C16 and PHEA–PEG5000–C16, have been evidenced by performing systematic tensiometric and spectrophotometric studies. All measurements have been performed at 25.0 °C over a wide copolymer concentration range. The tensiometric results have shown that, for all copolymers studied, the surf…
Ab-initio investigation of the thermodynamic stability of the magnesio-wüstite solid solution under Earth’s lower mantle conditions
Kinetic evidence for the incorporation of the [(pentamethylcyclopentadienyl) (2,2′-bipyridyl)(aquo)rhodium(III)] complex into DPPC vesicles
Abstract The binding of the [(pentamethylcyclopentadienyl) (2,2′-bipyridyl)(aquo)rhodium(III)] complex [Cp*RhIII(bpy)H2O]2+, to l -α-dipalmitoylphosphatidyl choline (DPPC) vesicles has been estimated by studying the kinetics of the electron transfer reaction between the rhodium(III) complex and formiate ions. Kinetic measurements carried out under anaerobic conditions in absence and presence of DPPC show that the total reaction is composed of two steps. The rate of the first reaction increases with the phospholipid concentration, while that of the second process is independent of the concentration of DPPC. This is consistent with a reaction, where the two reacting species are partitioned be…
Regression diagnostics applied in kinetic data processing: Outlier recognition and robust weighting procedures
An efficient protocol, based on advanced statistical diagnostics and robust fitting techniques applied to the least-squares processing of kinetic data of chemical reactions, is presented and discussed. The procedure, which is aimed at obtaining highly accurate estimation of the fitting parameters, consists of the identification of the outliers that remarkably impair the fitting by means of the so-called “leverage analysis” and some related diagnostics. This approach allows the elimination of the actually aberrant observations from the data set and/or their robust weighting to inhibit the negative effects induced on the data fitting, with consequent reduction of the bias introduced into the …
Bader’s topological analysis of the electron density in the pressure-induced phase transitions/amorphization in α-quartz from the catastrophe theory viewpoint
In this work, the Bader's topological analysis of the electron density, coupled with Thom's catastrophe theory, was used to characterize the pressure-induced transformations in α-quartz. In particular, ab initio calculations of the α-quartz structures in the range 0-105 Gpa have been performed at the HF/DFT exchange-correlation terms level, using Hamiltonians based on a WC1LYP hybrid scheme. The electron densities calculated throughout the ab initio wave functions have been analysed by means of the Bader's theory, seeking for some catastrophic mechanism in the sense of Thom's theory. The analysis mainly showed that there is a typical fold catastrophe feature involving an O-O interaction at …
Fe-periclase reactivity at Earth's lower mantle conditions: Ab-initio geochemical modelling
Intrinsic and extrinsic stability of the (Mg, Fe) O solid mixture in the Fe-Mg-Si-O system at high P, T conditions relevant to the Earth's mantle is investigated by the combination of quantum mechanical calculations (Hartree-26 Fock/DFT hybrid scheme), cluster expansion techniques and statistical thermodynamics. Iron in the (Mg, Fe) O binary mixture is assumed to be either in the low spin (LS) or in the high spin (HS) state. Un-mixing at solid state is observed only for the LS condition in the 23-42 GPa pressure range, whereas HS does not give rise to un-mixing. LS (Mg, Fe) O un-mixings are shown to be able to incorporate iron by subsolidus reactions with a reservoir of a virtual bridgmanit…
Clay/Non-Ionic Surfactant Hybrid Nanocomposites
This chapter gives an overview of the structural and chemical physical properties of nanocomposites formed by clay minerals and surfactants, which represent a class of materials with promising features for applications in different industrial, biomedical, and environmental applications. Due to their non-toxicity and biocompatibility, a great deal of attention is nowadays devoted to the study of non-ionic surfactants. Among them, block copolymers represent a combination of the properties of common amphiphilic molecules and long polymer chains. These macromolecules can form a great variety of supra-molecular structures generated from self-organization phenomena in aqueous media. Nanostructure…
Modelling of thermo-chemical properties over the sub-solidus MgO–FeO binary, as a function of iron spin configuration, composition and temperature
Thermo-chemical properties and T–X phase relations diagram of the (Mg,Fe)O solid solution are modelled using mixing Helmholtz energy, ΔF(T,x)mixing, calculated by quantum mechanical and semi-empirical techniques. The sub-solidus MgO–FeO binary has been explored as a function of composition, with iron either in high-spin (HS) or low-spin (LS) configuration. Only the HS model provides physically sound results at room pressure, yielding a correct trend of cell edge versus composition, whereas LS’s issues are at variance with observations. Mixing Helmholtz energy has been parametrized by the following relationship: ΔF(T,x)mixing = x × y × [U0(T) + U1(T) × (x – y) + U2(T) × (x − y)2]−T × S(x,y)c…
A Bader’s topological approach for the investigation of the high pressure stability field of the Mg-perovskite phase
Dynamic evolution of the oscillatory Belousov-Zhabotinsky reaction upon addition of a non-ionic polymer
Abstract The dynamic evolution of the oscillatory Belousov–Zhabotinsky reaction upon addition of increasing amount of the non-ionic polymer polypropylene glycol with molecular weight 425 g mol−1 (PPG-425) was investigated in a stirred-batch reactor by monitoring the Ce(IV) absorbance changes. The oscillatory parameters are significantly altered by the presence of the polymer. The findings obtained in the present work revealed that the PPG-425 is not only more effective, than other polymer previously [R. Lombardo, C. Sbriziolo, M.L. Turco Liveri, K. Pelle, M. Wittmann, Z. Noszticzius, in: J.A. Pojman, Q. Tran-Cong-Miyata (Eds.), Nonlinear Dynamics in Polymeric Systems, American Chemical Soci…
Source of the CO in the oscillating BZ reaction systems
Bader's topologycal analysis of the electron density and the laplacian in TOT Phyllosilicates: the case of pyrophyllite and talc
Iteratively reweighted least squares in crystal structure refinements
The use of robust techniques in crystal structure multipole refinements of small molecules as an alternative to the commonly adopted weighted least squares is presented and discussed. As is well known, the main disadvantage of least-squares fitting is its sensitivity to outliers. The elimination from the data set of the most aberrant reflections (due to both experimental errors and incompleteness of the model) is an effective practice that could yield satisfactory results, but it is often complicated in the presence of a great number of bad data points, whose one-by-one elimination could become unattainable. This problem can be circumvented by means of a robust least-squares regression that…
Clay-biosurfactant materials as functional drug delivery systems: Slowing down effect in the in vitro release of cinnamic acid
Abstract The main objectives of the present paper were the preparation and characterization of new surfactant-modified clays and the evaluation of their potential applicability as drug delivery systems for the oral administration of the cinnamic acid (CA) drug. The organoclays (OC) were prepared by loading different amounts of the biocompatible nonionic polyoxyethylene sorbitan monolaurate surfactant (Tween20) onto K10 montmorillonite (Mt) clay and characterized through the construction of the adsorption isotherms by means of the spectrophotometric method. The performance of the prepared material was verified by gathering the adsorption isotherms of the cinnamic acid onto the Mt/Tween20 org…
Emulsion Polymerization Coupled To Belousov-Zhabotinsky Oscillating Reaction: New Route To Produce Smart Materials
Pressure stability field of Mg-perovskite under deep mantle conditions: A topological approach based on Bader's analysis coupled with catastrophe theory
Abstract The pressure stability field of the Mg-perovskite phase was investigated by characterizing the evolution of the electron arrangement in the crystal. Ab initio calculations of the perovskite structures in the range 0–185 GPa were performed at the HF/DFT (Hartree-Fock/Density Functional Theory) exchange–correlation terms level. The electron densities, calculated throughout the ab-initio wave functions, were analysed by means of the Bader's theory, coupled with Thom's catastrophe theory. To the best of our knowledge the approach is used for the first time. The topological results show the occurrence of two topological anomalies at P~20 GPa and P~110 GPa which delineate the pressure ra…
The Source of the Carbon Monoxide in the Classical Belousov-Zhabotinsky Reaction
CO and CO2 evolution was measured in a cerium and in a ferroin-catalyzed Belousov−Zhabotinsky (BZ) reaction. These gases were stripped from the reaction mixture by a N2 carrier gas, mixed with H2, converted to methane on a Ni catalyst, and then measured by a flame ionization detector (FID). CO could be detected separately by absorbing CO2 on a soda lime column. In separate experiments it was proven that CO is produced in a reaction of BrO2• radicals with bromomalonic acid (BrMA). To this end BrO2• radicals were generated in two different ways: (i) in the reaction HBrO2 + HBrO3 ↔ 2 BrO2• + H2O and (ii) by reducing HBrO3 to BrO2• by Fe2+. It was found that •OH radicals produced by Fenton's r…
Perturbation of the BZ system with non ionic polymers: effect of components concentration
ADSORPTION OF WATER MOLECULES ONTO 1:1 DIOCTAHEDRAL CLAY MINERALS: A BADER'S TOPOLOGICAL ANALYSIS OF THE AB-INITIO ELECTRON DENSITIES
Peculiar mechanism of solubilization of a sparingly water soluble drug into polymeric micelles. Kinetic and equilibrium studies.
Complementary kinetic and equilibrium studies on the solubilization process of the sparingly water soluble tamoxifen (TAM) drug in polymeric aqueous solutions have been performed by using the spectrophotometric method. In particular, the amphiphilic copolymers obtained by derivatization of polymeric chain of poly(N-2-hydroxyethyl)-dl-aspartamide, PHEA, with poly(ethylene glycol)s, PEG (2000 or 5000 Da), and/or hexadecylamine chain, C16, namely PHEA-PEG2000-C16, PHEA-PEG5000-C16, PHEA-C16, have been employed. Preliminary to the kinetic and equilibrium data quantitative treatment, the molar absorption coefficient of TAM in polymeric micelle aqueous solution has been determined. By these studi…
Spectrophotometric evidence for the solubilization site of betalain pigments in membrane biomimetic systems.
The solubilization site of two betalain pigments, namely, betanin and indicaxantin, into l-alpha-dipalmitoyl-phosphatidylcholine (DPPC) and dimyristoylphosphatidylcholine (DMPC) vesicles was investigated by a spectrophotometric study. Pigment absorbance was monitored by varying phospholipid concentration, at a constant temperature that was varied in a range including the main phase transition temperature (Tm) of the relevant phospholipid bilayer. Maximum betanin absorption increased with the increase of DPPC concentration within the entire temperature range, reaching a plateau. The binding constant (Kb) of the pigment, calculated according to a pseudo-two-phase model, varied with the temper…
Partition of Indicaxanthin in Membrane Biomimetic Systems. A Kinetic and Modeling Approach
The solubilization site of indicaxanthin (Ind) in lipid bilayers was investigated by the kinetics of Ind oxidation by peroxyl radicals in water and in aqueous/L-alpha-dipalmitoyl-phosphatidylcholine (DPPC) vesicles, pH 7.4, and 37.0 and 48.0 degrees C, that is, in a gel-like and a crystal liquidlike bilayer state, respectively. The time-dependent Ind absorbance decay, matched with a successful simulation of the reaction kinetic mechanism by Gepasi software, supported a multistep pathway. Computer-assisted analysis allowed calculation of the rate constants associated with the reactions involved, the values of which decreased with increasing DPPC concentration. The binding constant calculated…
ELECTRONIC, MAGNETIC AND STRUCTURAL PROPERTIES OF NIO AND FEO THIN FILMS EPITAXIALLY GROWN ON SURFACES OF CU(001) : AN AB-INITIO DENSITY FUNCTIONAL STUDY
Montmorillonite nanodevices for the colon metronidazole delivery.
The adsorption profiles of the antibiotic metronidazole (MNE) into the K10-montmorillonite (MMT-K10) clay and the subsequent release have been investigated as a function of pH and MNE/MMT-K10 ratio, in order to evaluate the potential of the MNE/MMT-K10 hybrids as controlled drug delivery system. The adsorption mechanism has been first elucidated by performing complementary equilibrium and kinetic studies and through the X-ray diffractometry (XRD) characterization of the obtained composite materials. The gathered results allowed us to propose a mechanism consisting of a multi-step pathway involving the neutral and the cationic form of the drug, which interact with different sites of the clay…
Ordering kinetics in synthetic Mg(Al,Fe3+)2O4 spinels: Quantitative elucidation of the whole Al-Mg-Fe partitioning, rate constants, activation energies
A novel procedure, based on the application of the kinetics simulator Gepasi, has been successfully applied for modeling the cation ordering process in two synthetic Mg(Al2-yFe3+y)O4 spinels (y~ 0.39 and 0.54, samples F39 and F54, respectively). The kinetic profiles suggested a two-stage mechanism, with rapid inter-site exchange of Fe3+ with Mg followed by slow exchange of Al with Mg. The trial to apply the classical approaches, based on the explicit solutions of the differential equations corresponding to single-cation (Sha-Chappel model) or two-cation (Müller model) exchange reactions, proved not feasible in the whole time range, thus implying a lack of information about the exchange proc…
Synthesis and characterization of taylor-made organo-clays for biotechnological applications
Bader's topologycal analysis of teh electron density and the laplacian in kaolinite and dikite.
Regression diagnostics applied in kinetic data processing: outlier recognition and robust weighting procedures
An efficient protocol, based on advanced statistical diagnostics and robust fitting techniques applied to the least-squares processing of kinetic data of chemical reactions, is here presented and discussed. The procedure, which is aimed at obtaining highly accurate estimation of the fitting parameters, consists in the identification of the outliers that remarkably impair the fitting by means of the so called 'leverage analysis' and some related diagnostics, allowing the elimination of the actually aberrant observations from the data set and/or their robust weighting to inhibit the negative effects induced on the data fitting and to reduce the bias introduced into the parameter estimates. It…
New tailor-made bio-organoclays for the remediation of olive mill waste water
A systematic study aimed at obtaining new organoclays for the treatment of Olive Mill Waste water (OMW) has been performed. Several organoclays have been prepared by loading different amounts of the biocompatible surfactant Tween20 onto the K10 montmorillonite (MMT). Complementary kinetic and equilibrium studies on the adsorption of the Tween20 onto the MMT have been carried out and the characterization of the new tailor-made bio-materials has been performed by means of the XRD and FT-IR measurements. Finally the prepared bio-organoclays have been successfully applied for the OMW remediation and they proved to be highly effective in decreasing the organic content (OC) to an extent that depe…
Modified Montmorillonite as Drug Delivery Agent for Enhancing Antibiotic Therapy
The appealing properties of surfactant-intercalated Montmorillonites (Organo-montmorillonite, OMt) were successfully investigated to propose an effective drug delivery system for metronidazole (MNE) antibiotic therapy. This represents a serious pharmaceutical concern due to the adverse drug reactions and the low targeting ability of MNE. The non-ionic surfactant Tween 20 was used to functionalize montmorillonite, thus accomplishing the two-fold objective of enhancing the stability of clay dispersion and better controlling drug uptake and release. The adsorption process was performed under different experimental conditions and investigated by constructing the adsorption isotherms through hig…
Preparation and characterization of bio-organoclays using nonionic surfactant
The present study was aimed at the preparation and characterization of tailor made hybrid materials, whose peculiar hosting capability could be exploited in biotechnological applications. With this purpose, the modification of K10 montmorillonite by intercalation of Tween 20 surfactant, was accomplished. The influence of two internal parameters, namely pH and surfactant/clay ratio, on the surfactant uptake ability by clay was investigated. The adsorption mechanism was elucidated on the basis of complementary kinetic and equilibrium studies and, then, corroborated by the useful information provided by the FT-IR, TGA and XRD characterization. The gathered results allow to draw the conclusion …
Characterization of the pressure induced Ringwoodite toMg-perovskite and Mg-wüstite phase transition by Catastrophe Theory
Spatio-temporal perturbation of the dynamics of the ferroin catalyzed Belousov-Zhabotinsky reaction in a batch reactor caused by sodium dodecyl sulfate micelles.
The effects of the anionic surfactant sodium dodecyl sulfate (SDS) on the spatio-temporal and temporal dynamics of the ferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction have been studied over a wide surfactant concentration range. For the first time, investigations were performed also for unstirred systems. The presence of SDS in the reaction mixture influences the oscillatory parameters to an extent that significantly depends on the surfactant concentration. The trend of the wave speed v upon the increasing amount of SDS was found to have a maximum at [SDS] = 0.075 mol dm (-3) ( v = 0.071 mm s (-1)), after which the speed decreased to 0.043 mm s (-1) at [SDS] = 0.5 mol dm (-3), which is…
Olive mill wastewaters decontamination based on organo-nano-clay composites
Abstract Green composites for environmental applications were successfully prepared by intercalation of the biosurfactant Quillaja saponin onto montmorillonite mineral clay on varying pH and surfactant/clay ratio. Equilibrium adsorption isotherms were constructed and the system was characterized by performing TGA and XRD analyses. The efficiency of the surfactant-modified clay in the removal of the organic content present in olive mill wastewaters (OMW) was evaluated by means of spectrophotometric measurements. The interest for this cogent issue comes from the consideration that, despite their high pollutant content, OMW can be considered as a potential resource of several organic compounds…
The pressure-induced ringwoodite to Mg-perovskite and periclase post-spinel phase transition: a Bader’s topological analysis of the ab initio electron densities
In order to characterize the pressure-induced decomposition of ringwoodite (c-Mg2SiO4), the topological analysis of the electron density q(r), based upon the theory of atoms in molecules (AIM) developed by Bader in the framework of the catastrophe theory, has been performed. Calculations have been carried out by means of the ab initio CRYSTAL09 code at the HF/DFT level, using Hamiltonians based on the Becke- LYP scheme containing hybrid Hartree– Fock/density functional exchange–correlation terms. The equation of state at 0 K has been constructed for the three phases involved in the post-spinel phase transition (ringwoodite -> Mg-perovskite + periclase) occurring at the transition zone–lower…
The formation of silica high temperature polymorphs from quartz: Influence of grain size and mineralising agents
Abstract The formation of high-temperature silica polymorphs in presence of Na and K has been studied at various temperatures and soaking times, starting from quartzes of different grain size, ex situ as well as in situ. The results show that cristobalite and tridymite formation is strongly influenced by the nature and the amount of mineraliser added. In particular, K seems to discriminate more between the two structures, as it produces the largest observed amount of cristobalite. The disappearance of quartz can be controlled by the proper combination of mineraliser/temperature/time, which in turn control the amount and the type of polymorph formed, together with the amount of amorphous mat…
Effect of the Biopolymer Charge and the Nanoclay Morphology on Nanocomposite Materials
This work represents a contribution to the design, preparation, and characterization of nanocomposite materials based on biocompatible components. The effects of composition, filler geometry, and polymer charge were highlighted, and their role on the final properties of the nanocomposites was revealed. We combined some biopolymers (methylcellulose, alginate, chitosan) with two nanoclays (kaolinite sheets and halloysite nanotubes) to prepare nanocomposites by means of the casting method from water. The thermal stability, the surface wettability, and the mechanical properties of the obtained films were studied. SEM micrographs highlighted the surface morphology of the biocomposite materials. …
Kinetic and equilibrium studies for the adsorption of acid nucleic bases onto K10 montmorillonite
Abstract The kinetic of the adsorption of two nucleic acid bases, namely adenine (A) and cytosine (C), on K10 montmorillonite (MMT) clay has been investigated over a wide range of nitrogenous bases concentrations, by using the spectrophotometric method. The measurements have been performed at T = 25.0 °C and pH = 4.0 where adenine and cytosine exist both in their protonated and neutral forms. Preliminary to the kinetic data treatment, the adsorption isotherms have been gathered and, then, analyzed by using the Freundlich and the Dubinin–Radushkevich model. The obtained results allow to draw the conclusion that physisorption of adenine and cytosine on MMT occurs and the process is mainly gov…
New way to produce smart materials: emulsion polimerization coupled to oscillating reaction
OUTLIER RECOGNITION AND ROBUST WEIGHTING PROCEDURES APPLIED IN CATION ORDERING-DISORDERING KINETIC DATA PROCESSING
DYNAMICS OF THE OSCILLATORY BELOUSOV-ZHABOTINSKY REACTION IN THE PRESENCE OF A NON-IONIC POLYMER
Incorporation of the [(pentamethylcyclopentadienyl) (2,2-bipyridyl)(aquo)rhodium(III)] complex into DPPC vesicles studied by a kinetic method
Simultaneous Removal and Recovery of Metal Ions and Dyes from Wastewater through Montmorillonite Clay Mineral
The main objective of this work was to evaluate the potential of Montmorillonite nanoclay (Mt), readily and inexpensively available, for the simultaneous adsorption (and removal) of two classes of pollutants: metal ions and dyes. The attention was focused on two &ldquo
Kinetic studies on the aerobic reduction of a Rh(III)-complex by formiate ions in the presence of DPPC vesicles
Amphiphilic derivatives of a polyaspartamide: their aggregation and solubilization ability.Tensiometric and spectrophotometric studies
The self-aggregation and solubilization capability of a series of amphiphilic copolymers obtained by derivatisation of polymeric chain of α,β-poly(N-2-hydroxyethyl)-dl-aspartamide (PHEA) with polyethylene glycols (PEG, being different molecular weight 2000 or 5000 Da, PEG2000 and PEG5000, respectively) and/or hexadecylamine alkyl chain (C16), namely PHEA–PEG2000, PHEA–PEG5000, PHEA–C16, PHEA–PEG2000–C16 and PHEA–PEG5000–C16, have been evidenced by performing systematic tensiometric and spectrophotometric studies. All measurements have been performed at 25.0 °C over a wide copolymer concentration range. The tensiometric results have shown that, for all copolymers studied, the surface tension…
Nonlinear response of a batch BZ oscillator to the addition of the anionic surfactant sodium dodecyl sulfate.
The response of the Belousov-Zhabotinsy (BZ) system to the addition of increasing amounts of the anionic surfactant sodium dodecyl sulfate (SDS) was monitored at 25.0 degrees C in stirred batch conditions. The presence of SDS in the reaction mixture influences the oscillatory parameters, i.e., induction period and oscillation period, to an extent that depends on the surfactant concentration. The experimental results have shown that the induction period increases slightly on increasing surfactant concentration and, then, a further increase in the [SDS] leads to an enhancement while the oscillation period increases monotonously on increasing SDS concentration. It has been proposed that the re…
POLY 496-Behavior of the Belousov-Zhabotinsky oscillator in the presence of carboxymethyl-cellulose
Dynamic evolution of the hemin – hydrogen peroxide – sulfite reaction upon addition of a zwitterionic surfactant
Oscillatory dynamics of the Belousov-Zhabotinsky system in the presence of a self-assembling nonionic polymer. Role of the reactants concentration.
In the present study, the role played by the reactants concentration on the nonlinear response of a Belousov–Zhabotinsky (BZ) system to the addition of a self-assembling non-ionic polymer, poly(ethylene glycol) (PEG), has been assessed. The oscillatory parameters are influenced to an extent that significantly depends on the concentration of both the polymer and the Belousov–Zhabotinsky components. The effects obtained were attributed to the reaction among some of the BZ key species and the backbone and the alcoholic functional groups of the polymer, both in its monomeric and aggregated forms. Support to the proposed perturbation mechanism has been provided by performing numerical simulation…
Bader's analysis of the electron density in the Pbca enstatite - Pbcn protoenstatite phase transition
The Bader’s topological analysis of the electron density obtained via ab initio quantum mechanical simulation at Hartree–Fock and DFT level has been performed for experimentally in situ heated structures of enstatite–protoenstatite MgSiO 3 . The measurements have been performed in the temperature range 1200–1400 K. The work was aimed at characterizing both the evolution of the electron arrangement in the crystal and that of the crystal-structure at the enstatite–protoenstatite phase transition in terms of topology of the electron density, with particular care about the Mg–O and the O–O bonds. The observed breaking of some chemical bonds with increasing temperature and/or due to the phase tr…