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Piero Baglioni

Publications and source records attributed to Piero Baglioni.

30 records · Page 2Linked to original sources

Nanostructured fluids based on propylene carbonate/water mixtures.

The microstructure of aggregates formed by sodium dodecyl sulfate (SDS) and 1-pentanol in mixtures of water and a polar aprotic solvent (propylene carbonate, PC) was investigated by means of pulsed gradient spin-echo NMR, dynamic light scattering, viscosity, and conductivity measurements. PC partitions itself between micelles and aqueous bulk. The fraction of micellized propylene carbonate remains constant along PC-dilution, and the phase separation takes place when the composition of continuous phase attains the PC/water miscibility gap. The micellized PC is present mainly in the micelle's palisade and strongly increases the total interfacial area, thus acting as a cosurfactant. At high PC content, the system is composed by very small aggregates (around 10 A in radius) made by few SDS molecules (10-6) and PC and pentanol. The resulting system can be described as a nanostructured fluid with a huge interfacial area and a small dispersed phase.

Journal Article↗

Anion effects on calixarene monolayers: a Hofmeister series study.

Due to their amphiphilic structure, calixarenes adsorb at the air/water interface and form stable Langmuir films. We have explored the effect of salts on calix[6]- and calix[8]arene spreading isotherms at the air/water interface. A wide range of different potassium salts was used in the subphase: KCl, KI, KBr, KSCN, KNO(3), CH(3)COOK, K(2)SO(4), and K(3)PO(4). The differences in Langmuir isotherms are due to the presence of different anions in the subphase, to the different conformations of the ligands at the interface, and to the different complexing affinities of calix[6]- and calix[8]arene for potassium ions. The two systems show a significant specific ion effect that can be discussed in terms of Hofmeister series. Characteristic monolayer parameters, e.g., limiting area (A(lim)), collapse pressure (pi(coll)), modulus of compressibility (C(s)(-1)), and surface potential (DeltaV), are discussed in terms of some physicochemical parameters that reflect dispersion forces: in particular, anion polarizabilities, lyotropic number (N), molar surface tension increment (sigma), and partial molar volume (nu(s)).

Journal Article↗

The influence of superplasticizers on the first steps of tricalcium silicate hydration studied by NMR techniques.

The influence of superplasticizer sulfonated naphthalene formaldehyde (SNF) on the hydration process of tricalcium silicate (C3S) paste was investigated by (1)H nuclear magnetic resonance spin-spin and spin lattice relaxation times. The addition of SNF superplasticizer to C3S paste clearly affects the morphology and growth rates of the hydration products, mainly by increasing the dormant period length, which lasts for several hours more than in conventional C3S hydrated paste, while reducing the acceleration period length. The relaxation data indicated that a pronounced delay occurs in the C3S hardening when sulfonated polymers are added to the makeup water. For all the analyzed samples, prepared with a water-to-C3S ratio of 0.4, the decay of the echo magnetization has been fitted by adopting both a monoexponential and a biexponential relaxation model in order to evaluate the contributions from water in different regimes of hydration.

Calcium Compounds↗

Specific ion effects on the growth rates of Staphylococcus aureus and Pseudomonas aeruginosa.

Motivated by recent advances in the physical and chemical basis of the Hofmeister effect, we measured the rate cell growth of S. aureus--a halophilic pathogenic bacterium--and of P. aeruginosa, an opportunistic pathogen, in the presence of different aqueous salt solutions at different concentrations (0.2, 0.6 and 0.9 M). Microorganism growth rates depend strongly on the kind of anion in the growth medium. In the case of S. aureus, chloride provides a favorable growth medium, while both kosmotropes (water structure makers) and chaotropes (water structure breakers) reduce the microorganism growth. In the case of P. aeruginosa, all ions affect adversely the bacterial survival. In both cases, the trends parallel the specific ion, or Hofmeister, sequences observed in a wide range of physico-chemical systems. The correspondence with specific ion effect obtained in other studies, on the activities of a DNA restriction enzyme, of horseradish peroxidase, and of Lipase A (Aspergillus niger) is particularly striking. This work provides compelling evidence for Hofmeister effects, physical chemistry in action, in these organisms.

Adsorption↗

Quasielastic and inelastic neutron scattering on hydrated calcium silicate pastes.

Using the inverse geometry spectrometer QENS at the Intense Pulsed Neutron Source of the Argonne National Laboratory, we collected quasielastic and inelastic neutron scattering spectra of hydrated tricalcium and dicalcium silicate, the main components of ordinary Portland cement. Data were obtained at different curing time, from a few hours to several months. Both the quasielastic and inelastic spectra have been analyzed at the same time according to the relaxing cage model, which is a model developed to describe the dynamics of water at supercooled temperatures. Short-time and long-time dynamics of hydration water in hydrated cement pastes as a function of the curing time have been simultaneously obtained. The results confirm the findings reported in previous experiments showing that it is possible to fit consistently the quasielastic and inelastic spectra giving insights on the effect of the curing time on the short-time vibrational dynamics of hydration water.

Journal Article↗

Spectroscopic and interfacial properties of myoglobin/surfactant complexes.

The complexes of horse myoglobin (Mb) with the anionic surfactant sodium dodecyl sulfate (SDS), and with the cationic surfactants cetyltrimethylammonium chloride (CTAC) and decyltrimethylammonium bromide (DeTAB), have been studied by a combination of surface tension measurements and optical spectroscopy, including heme absorption and aromatic amino acid fluorescence. SDS interacts in a monomeric form with Mb, which suggests the existence of a specific binding site for SDS, and induces the formation of a hexacoordinated Mb heme, possibly involving the distal histidine. Fluorescence spectra display an increase of tryptophan emission. Both effects point to an increased protein flexibility. SDS micelles induce both the appearance of two more heme species, one of which has the features of free heme, and protein unfolding. Mb/CTAC complexes display a very different behavior. CTAC monomers have no effect on the absorption spectra, and only a slight effect on the fluorescence spectra, whereas the formation of CTAC aggregates on the protein strongly affects both absorption and fluorescence. Mb/DeTAB complexes behave in a very similar way as Mb/CTAC complexes. The surface activity of the different Mb/surfactant complexes, as well as the interactions between the surfactants and Mb, are discussed on the basis of their structural properties.

Animals↗

Synthesis and characterization of gels from polyallylamine and carbon dioxide as gellant.

The synthesis and characterization of a novel series of polymer gels are reported. They are formed at ambient temperatures by bubbling CO(2) through solutions of polyallylamine (PAA; a latent gellant) in several organic liquids, including aliphatic alcohols and 1-methyl-2-pyrrolidone. The stabilities of the alcohol gels, as indicated by the (irreversible) degelation temperature, T(g)(dt), were strongly dependent on the number of carbon atoms (C(n)) in the alkyl chains of the alcohol liquids. The mechanism of formation and the microenvironmental properties of PAA-based gels containing a small amount of a pH-sensitive probe, 2,6-naphthalenedicarboxylic acid (2,6-NDCA), have been probed using static and dynamic fluorescence measurements. A measurable pH change and significant alterations to the fluorescence spectra were coincident with gelation of PAA solutions in 1-butanol as CO(2) was bubbled through, and the fluorescence spectra were monitored over several hours until no further changes were detected. Analyses of dynamic fluorescence decay histograms indicate the presence of three decay times due to different microenvironments where the 2,6-NDCA molecules are located.

Journal Article↗

A new lipophilic fluorescent probe for interaction studies of bioactive lipopeptides with membrane models.

The new fluorescent lipophilic moiety 11-[(7-amino-4-methyl-2-oxo-2H-1-benzopyran-3-acetyl)amino]undecanoic acid (AMCA-omegaAud-OH) was introduced by SPPS at the N-terminus of the immunodominant epitope GpMBP(74-85). FRET experiments using the new fluorescent lipopeptide demonstrate that the peptide interacts with much more affinity with the membrane compared to the lipid free analogue.

Animals↗

Photosensitizer accumulation in spontaneous multidrug resistant cells: a comparative study with Rhodamine 123, Rose Bengal acetate and Photofrine.

The influence both of overexpression of multidrug transporter proteins and of phenotype changes occurring in cells developing spontaneous resistance on the accumulation of photosensitizer molecules was studied on two tumor-derived cell lines (B16, A2780) expressing the MDR-1 phenotype. Rhodamine 123, Rose Bengal acetate (a fluorogenic substrate that is restored to the native active molecule by specific enzyme activity inside cells) and Photofrin were considered. The two resistant variants accumulate Rhodamine 123 to a lesser extent than the respective wild types. Treatment with verapamil markedly enhances Rhodamine 123 accumulation in resistant cells, blocking the drug's extrusion. The amount of Rose Bengal is larger in resistant cells than in wild type cells. Verapamil does not affect drug accumulation, although it significantly impairs the efflux process. The results are explained by the enhancement of both membrane traffic and esterase activity resulting in intracellular Rose Bengal production that counterbalances the increased ability in the outward transport of resistant cells. Photofrin is accumulated to a lower degree in resistant than in wild type cells. Verapamil does not alter the drug accumulation, although the release process is somewhat affected. Different intracellular turnovers of Photofrin take place in the cell variants, and the release of the monomeric fluorescent fractions is greater in resistant than in wild type cells.

Animals↗

Enzymatic Treatments on Tencel in Water and Microemulsion.

Tencel is a relatively new fabric, obtained from wood pulp, that looks like natural cotton. In order to be suitable for commercial purposes, Tencel must be processed to improve its qualities. In this paper we report our studies on the enzymatic defibrillation of Tencel, in which we checked the different behavior of the same set of enzymes dispersed in pure water and in a microemulsion system. Surface properties, such as scanning electron microscopy, contact angle, porosimetry, breaking load, and thickness, were determined, in order to monitor the surface modification of the fabric upon enzymatic defibrillation, and indicate that the process is more efficient and less damaging when carried out in the microemulsion medium. Furthermore, we chemically modified Tencel by attaching fluorinated chains to the fabric surface. Surface properties show that fluorination of Tencel leads to a high degree of water- and oil-repellency in the fabric. Copyright 2001 Academic Press.

Journal Article↗

Water absorbency by wool fibers: Hofmeister effect.

Wool is a complex material, composed of cuticle and epicuticle cells, surrounded by a cell membrane complex. Wool fibers absorb moisture from air, and, once immersed in water, they take up considerable amounts of liquid. The water absorbency parameter can be determined from weight gain, according to a standard method, and used to quantify this phenomenon. In this paper we report a study on the water absorbency (or retention) of untreated wool fibers in the presence of aqueous 1 M salt solutions at 29 degrees C and a relative humidity of either 33% or 56%. The effect of anions was determined by selecting a wide range of different sodium salts, while the effect of cations was checked through some chlorides and nitrates. Our results show a significant specific ion and ion pair "Hofmeister" effects, that change the amount of water absorbed by the fibers. To understand this phenomenon, the water absorbency parameter (A(w)) is compared to different physicochemical parameters such as the lyotropic number, free energy of hydration of ions, molar surface tension increment, polarizability, refractive index increment, and molar refractivity. The data indicate that this Hofmeister phenomenon is controlled by dispersion forces that depend on the polarizability of ionic species, their adsorption frequencies, the solvent, and the substrate. These dispersion forces dominate the behavior in concentrated solutions. They are in accord with new developing theories of solutions and molecular interactions in colloidal systems that account for Hofmeister effects.

Absorption↗

Bioengineering of a cellulosic fabric for insecticide delivery via grafted cyclodextrin.

beta-Cyclodextrin (beta-CD) can be easily grafted onto cellulosic textiles through covalent bonds. In such a way beta-CD empty cavities provide an efficient tool for entrapping different kinds of hydrophobic molecules on the surface of the fabric and releasing them slowly in time. The capability of cyclodextrins to include hydrophobic molecules such as fragrances, antimicrobial agents, and other chemicals can be then exploited to produce new grafted textiles with peculiar and useful performances. In this work we report the inclusion of two different products, the pyrethroid insecticide permethrin (PERM) and the insect repellent N,N-diethyl-m-toluamide (DEET), into beta-CD molecules grafted on cotton fabric. UV-vis spectrophotometry and thermal analysis confirmed the presence of the guest molecules on the fabric surface. Bioassays were carried out on two mosquito species of medical importance, Aedes aegypti and Anopheles stephensi; knock down effect and mortality were measured using standard World Health Organization (WHO) cone tests. Repellency and irritancy (blood feeding inhibition) were also measured using cage tests and a baited tunnel device. PERM-treated fabrics kept the insecticidal/irritant efficacy even for a long time after the treatment, whereas DEET activity lasted more shortly.

Aedes↗