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1.
Molecules ; 29(2)2024 Jan 06.
Article in English | MEDLINE | ID: mdl-38257213

ABSTRACT

Enhanced oil recovery (EOR) processes are technologies used in the oil and gas industry to maximize the extraction of residual oil from reservoirs after primary and secondary recovery methods have been carried out. The injection into the reservoir of surface-active substances capable of reducing the surface tension between oil and the rock surface should favor its extraction with significant economic repercussions. However, the most commonly used surfactants in EOR are derived from petroleum, and their use can have negative environmental impacts, such as toxicity and persistence in the environment. Biosurfactants on the other hand, are derived from renewable resources and are biodegradable, making them potentially more sustainable and environmentally friendly. The present review intends to offer an updated overview of the most significant results available in scientific literature on the potential application of biosurfactants in the context of EOR processes. Aspects such as production strategies, techniques for characterizing the mechanisms of action and the pros and cons of the application of biosurfactants as a principal method for EOR will be illustrated and discussed in detail. Optimized concepts such as the HLD in biosurfactant choice and design for EOR are also discussed. The scientific findings that are illustrated and reviewed in this paper show why general emphasis needs to be placed on the development and adoption of biosurfactants in EOR as a substantial contribution to a more sustainable and environmentally friendly oil and gas industry.


Subject(s)
Anthracenes , Petroleum , Industry , Surface Tension
2.
Heliyon ; 10(1): e23192, 2024 Jan 15.
Article in English | MEDLINE | ID: mdl-38205314

ABSTRACT

Improving the mechanical properties of bitumen is an important goal for road pavements design. For this reason, new compounds are now being sought for testing as bitumen modifiers. In this work, the authors studied the effect that two different chars have on two 50/70 bitumens with different chemical and physical characteristics. A complete morphological, surface and bulk characterization of the two additives was carried out. In addition, rheology, Nuclear Magnetic Resonance (NMR) relaxometry and atomic force microscopy were used to analyze the effect that the two additives exert on the properties of the bitumens. According to the results, the char sample with high porosity could be used as a modifier of mechanical properties, while no rejuvenation effects were observed for either of the two additives tested. In addition, the two additives do not give rise to segregation phenomena.

3.
Chemphyschem ; 24(24): e202300217, 2023 Dec 14.
Article in English | MEDLINE | ID: mdl-37691003

ABSTRACT

In this investigation the dynamics of two types of bitumens with different penetration grade were tested by using dynamic shear rheometry (DSR) and Nuclear Magnetic Resonance (NMR) at unaged conditions, and upon both short- and long-term artificial aging. The gel-sol transition temperature T g e l → s o l * ${{T}_{gel\to sol}^{^{\ast}}}$ was found to increase with increasing the time of aging treatment. Arrhenius parameters of the viscosity were found, unexpectedly, to be correlated with those of simple liquids, suggesting that the two kinds of systems, although chemically and physically quite different, share the same basic process at the molecular level. The molecular dynamics has been then investigated by NMR Pulsed Field Gradient Stimulated-Echo (PFGSE) and relaxometry (Carr-Purcell-Meiboom-Gill, CPMG, spin-echo pulse sequence) to capture the effect of aging upon dynamics variables such as self-diffusion coefficients D and transverse relaxation times T2 . The translational diffusion at T> T g e l → s o l * ${{T}_{gel\to sol}^{^{\ast}}}$ of the light molecular components of both types of bitumens was characterized by broad distributions of D which were found independent of the experimental time scale up to 0.2 s. Similarly, T2 data could be described as a continuous unimodal distributions of relaxation times determined both at T< T g e l → s o l * ${{T}_{gel\to sol}^{^{\ast}}}$ and T> T g e l → s o l * ${{T}_{gel\to sol}^{^{\ast}}}$ .

4.
Molecules ; 27(23)2022 Nov 22.
Article in English | MEDLINE | ID: mdl-36500207

ABSTRACT

Refuse-Derived Fuels (RDFs) are segregated forms of wastes obtained by a combined mechanical-biological processing of municipal solid wastes (MSWs). The narrower characteristics, e.g., high calorific value (18-24 MJ/kg), low moisture content (3-6%) and high volatile (77-84%) and carbon (47-56%) contents, make RDFs more suitable than MSWs for thermochemical valorization purposes. As a matter of fact, EU regulations encourage the use of RDF as a source of energy in the frameworks of sustainability and the circular economy. Pyrolysis and gasification are promising thermochemical processes for RDF treatment, since, compared to incineration, they ensure an increase in energy recovery efficiency, a reduction of pollutant emissions and the production of value-added products as chemical platforms or fuels. Despite the growing interest towards RDFs as feedstock, the literature on the thermochemical treatment of RDFs under pyrolysis and gasification conditions still appears to be limited. In this work, results on pyrolysis and gasification tests on a real RDF are reported and coupled with a detailed characterization of the gaseous, condensable and solid products. Pyrolysis tests have been performed in a tubular reactor up to three different final temperatures (550, 650 and 750 °C) while an air gasification test at 850 °C has been performed in a fluidized bed reactor using sand as the bed material. The results of the two thermochemical processes are analyzed in terms of yield, characteristics and quality of the products to highlight how the two thermochemical conversion processes can be used to accomplish waste-to-materials and waste-to-energy targets. The RDF gasification process leads to the production of a syngas with a H2/CO ratio of 0.51 and a tar concentration of 3.15 g/m3.


Subject(s)
Garbage , Refuse Disposal , Refuse Disposal/methods , Pyrolysis , Incineration , Solid Waste
5.
Molecules ; 27(13)2022 Jun 29.
Article in English | MEDLINE | ID: mdl-35807425

ABSTRACT

A gold nanoparticles transparent electrode was realized by chemical reduction. This work aims to compare the transparent gold nanoparticles electrode with a more commonly utilized gold-film-coated electrode in order to investigate its potential use as counter-electrode (CE) in dye-sensitized solar cells (DSSCs). A series of DSSC devices, utilizing I-/I3- and Co(III)/(II) polypyridine redox mediators [Co(dtb)3]3+/2+; dtb = 4,4'ditert-butyl-2,2'-bipyridine)], were evaluated. The investigation focused firstly on the structural characterization of the deposited gold layers and then on the electrochemical study. The novelty of the work is the realization of a gold nanoparticles CE that reached 80% of average visible transmittance. We finally examined the performance of the transparent gold nanoparticles CE in DSSC devices. A maximum power conversion efficiency (PCE) of 4.56% was obtained with a commercial I-/I3--based electrolyte, while a maximum 3.1% of PCE was obtained with the homemade Co-based electrolyte.

6.
Molecules ; 27(10)2022 May 20.
Article in English | MEDLINE | ID: mdl-35630760

ABSTRACT

This paper considers the effect of aging processes on viscoelastic characteristics of vacuum residue oxidation products modified with crumb rubber. Viscoelastic properties were compared to original bitumen raw material-vacuum residue and vacuum residue oxidation products during short-term and long-term aging. The complex shear modulus of the vacuum residue and its oxidation products decreased with an increase in temperature. Short-term aging resulted in increased shear modulus for all samples.The vacuum residue oxidation product modified with crumb rubber had the maximum values of the rutting parameter and fatigue parameter. There was an expansion of the temperature range of plasticity: for the vacuum residue oxidation product with crumb rubber, its value was 67.2 °C. The curves of the black diagram of the modified vacuum residue oxidation product are shifted towards smaller phase angles with the increase in the shear modulus, which indicates the increase in the stiffness and elasticity of the rubber bitumen binders. The vacuum residue oxidation product modified with crumb rubber corresponded to the rubber bitumen binder of the grade RBB 60/90, according to its physical and mechanical indicators.


Subject(s)
Rubber , Oxidation-Reduction , Rubber/chemistry , Temperature , Vacuum
7.
J Colloid Interface Sci ; 614: 277-287, 2022 May 15.
Article in English | MEDLINE | ID: mdl-35101675

ABSTRACT

HYPOTHESIS: Inorganic small particles stemming from mineral extraction (i.e. mining waste) could be used as additive for road paving applications to improve bitumen mechanical properties. Such an approach is expected to increase bitumen life-cycle cutting costs connected to their preparation and to reduce environmental issues. Experiment: Bitumens containing various amounts (up to 10% w/w) of filler made of mining tailings fine powder were characterized by means of oscillatory rheometry focusing on the effect of the filler content, temperature and filler milling time. FINDINGS: (i) Superior resistance to stress, rutting, and fatigue were shown by the filler-containing mixtures. In addition, higher durability was observed for the filler concentration of 10% w/w. These effects were interpreted on the grounds of the physico-chemical interactions between the bitumen and the inorganic filler suggesting important utilizations. (ii) The present research points towards a circular economy path. Particularly, this study demonstrates how an abundant and potentially harmful waste can be converted into a high value-added component for road paving. Furthermore, increased durability of bitumen is beneficial in both economic and environmental terms.


Subject(s)
Hydrocarbons , Hydrocarbons/chemistry , Temperature
8.
ACS Sustain Chem Eng ; 10(5): 1888-1898, 2022 Feb 07.
Article in English | MEDLINE | ID: mdl-35154910

ABSTRACT

The fabrication of enzyme-based biosensors has received much attention for their selectivity and sensitivity. In particular, laccase-based biosensors have attracted a lot of interest for their capacity to detect highly toxic molecules in the environment, becoming essential tools in the fields of white biotechnology and green chemistry. The manufacturing of a new, metal-free, laccase-based biosensor with unprecedented reuse and storage capabilities has been achieved in this work through the application of the electrospray deposition (ESD) methodology as the enzyme immobilization technique. Electrospray ionization (ESI) has been used for ambient soft-landing of laccase enzymes on a carbon substrate, employing sustainable chemistry. This study shows how the ESD technique can be successfully exploited for the fabrication of a new promising environment-friendly electrochemical amperometric laccase-based biosensor, with storage capability up to two months without any particular care and reuse performance up to 63 measurements on the same electrode just prepared and 20 measurements on the one-year-old electrode subjected to redeposition. The laccase-based biosensor has been tested for catechol detection in the linear range 2-100 µM, with a limit of detection of 1.7 µM, without interference from chrome, cadmium, arsenic, and zinc and without any memory effects.

9.
Talanta ; 224: 121854, 2021 Mar 01.
Article in English | MEDLINE | ID: mdl-33379070

ABSTRACT

Herein we describe the design and synthesis of novel artificial peptides mimicking the plastoquinone binding niche of the D1 protein from the green photosynthetic alga Chlamydomonas reinhardtii, also able to bind herbicides. In particular, molecular dynamics (MD) simulations were performed to model in silico the behaviour of three peptides, D1Pep70-H, D1Pep70-S264K and D1Pep70-S268C, as genetic variants with different affinity towards the photosynthetic herbicide atrazine. Then the photosynthetic peptides were functionalised with quantum dots for the development of a hybrid optosensor for the detection of atrazine, one of the most employed herbicides for weed control in agriculture as well as considered as a putative endocrine disruptor case study. The excellent agreement between computational and experimental results self consistently shows resistance or super-sensitivity toward the atrazine target, with detection limits in the µg/L concentration range, meeting the requirements of E.U. legislation.


Subject(s)
Chlamydomonas reinhardtii , Endocrine Disruptors , Herbicides , Quantum Dots , Herbicides/analysis , Peptides , Photosystem II Protein Complex
10.
Molecules ; 25(23)2020 Nov 29.
Article in English | MEDLINE | ID: mdl-33260426

ABSTRACT

Scattering techniques represent non-invasive experimental approaches and powerful tools for the investigation of structure and conformation of biomaterial systems in a wide range of distances, ranging from the nanometric to micrometric scale. More specifically, small-angle X-rays and neutron scattering and light scattering techniques represent well-established experimental techniques for the investigation of the structural properties of biomaterials and, through the use of suitable models, they allow to study and mimic various biological systems under physiologically relevant conditions. They provide the ensemble averaged (and then statistically relevant) information under in situ and operando conditions, and represent useful tools complementary to the various traditional imaging techniques that, on the contrary, reveal more local structural information. Together with the classical structure characterization approaches, we introduce the basic concepts that make it possible to examine inter-particles interactions, and to study the growth processes and conformational changes in nanostructures, which have become increasingly relevant for an accurate understanding and prediction of various mechanisms in the fields of biotechnology and nanotechnology. The upgrade of the various scattering techniques, such as the contrast variation or time resolved experiments, offers unique opportunities to study the nano- and mesoscopic structure and their evolution with time in a way not accessible by other techniques. For this reason, highly performant instruments are installed at most of the facility research centers worldwide. These new insights allow to largely ameliorate the control of (chemico-physical and biologic) processes of complex (bio-)materials at the molecular length scales, and open a full potential for the development and engineering of a variety of nano-scale biomaterials for advanced applications.


Subject(s)
Biocompatible Materials/chemistry , Dynamic Light Scattering/methods , Neutron Diffraction/methods , Scattering, Small Angle , X-Ray Diffraction/methods , Biocompatible Materials/metabolism , Dynamic Light Scattering/instrumentation , Neutron Diffraction/instrumentation , Structure-Activity Relationship , X-Ray Diffraction/instrumentation
11.
Adv Colloid Interface Sci ; 285: 102283, 2020 Nov.
Article in English | MEDLINE | ID: mdl-33099178

ABSTRACT

Asphalt concretes are biphasic systems, with a predominant phase (c.a. 93-96% w/w) made by the macro-meter sized inorganic aggregates hold together by small amounts of a viscoelastic binding bitumen (c.a. 5%). Even if the bitumen is in minor amount, it plays an important role dictating all the desired properties: rheological performances, resistance to aging etc. What happens if nanoparticles are used as additive in such materials? They usually confer enhanced resistance under mechanical stress and give sometimes interesting added-values properties so, despite the high costs of their production, nanoparticles are interesting materials which are being monitored for large scales applications. This work introduces the reader to the properties of nanoparticles in an easy to review their use in bitumen and asphalt preparation. Silica, ceramic, clay, other oxides and inorganic nanoparticles are presented and critically discussed in the framework of their use in bitumen and asphalt preparation for various scopes. Organic and functionalized nanoparticles are likewise discussed. Perspectives and cost analysis are also given for a more complete view of the problematic, hoping this could help researchers in their piloted design of material for road pavements with ever-increasing performances.

12.
Int J Biol Macromol ; 163: 817-823, 2020 Nov 15.
Article in English | MEDLINE | ID: mdl-32653377

ABSTRACT

Biomimetic design represents an emerging field for improving knowledge of natural molecules, as well as to project novel artificial tools with specific functions for biosensing. Effective strategies have been exploited to design artificial bioreceptors, taking inspiration from complex supramolecular assemblies. Among them, size-minimization strategy sounds promising to provide bioreceptors with tuned sensitivity, stability, and selectivity, through the ad hoc manipulation of chemical species at the molecular scale. Herein, a novel biomimetic peptide enabling herbicide binding was designed bioinspired to the D1 protein of the Photosystem II of the green alga Chlamydomonas reinhardtii. The D1 protein portion corresponding to the QB plastoquinone binding niche is capable of interacting with photosynthetic herbicides. A 50-mer peptide in the region of D1 protein from the residue 211 to 280 was designed in silico, and molecular dynamic simulations were performed alone and in complex with atrazine. An equilibrated structure was obtained with a stable pocked for atrazine binding by three H-bonds with SER222, ASN247, and HIS272 residues. Computational data were confirmed by fluorescence spectroscopy and circular dichroism on the peptide obtained by automated synthesis. Atrazine binding at nanomolar concentrations was followed by fluorescence spectroscopy, highlighting peptide suitability for optical sensing of herbicides at safety limits.


Subject(s)
Atrazine/pharmacology , Chlamydomonas reinhardtii/drug effects , Chlamydomonas reinhardtii/physiology , Photosynthesis , Photosystem II Protein Complex/metabolism , Amino Acid Sequence , Biomimetics/methods , Molecular Dynamics Simulation , Peptides/chemistry , Photosynthesis/drug effects , Photosystem II Protein Complex/chemistry , Protein Conformation , Spectrometry, Fluorescence , Thermodynamics
13.
Nanomaterials (Basel) ; 10(6)2020 Jun 19.
Article in English | MEDLINE | ID: mdl-32575602

ABSTRACT

The asphalt industry's incentive to reduce greenhouse gas emissions has increased since the 1990s due to growing concerns on environmental issues such as global warming and carbon footprint. This has stimulated the introduction of Warm Mix Asphalt (WMA) and its technologies which serve the purpose of reducing greenhouse gas emissions by reducing the mixing and compaction temperatures of asphalt mix. WMA gained popularity due to the environmental benefit it offers without compromising the properties, performance and quality of the asphalt mix. WMA is produced at significantly lower temperatures (slightly above 100 °C) and thus results in less energy consumption, fewer emissions, reduced ageing, lower mixing and compaction temperatures, cool weather paving and better workability of the mix. The latter of these benefits is attributed to the incorporation of additives into WMA. These additives can also confer even better performance of WMA in comparison to conventional Hot Mix Asphalt (HMA) methods. Even though there are recommended dosages of several WMA additives, there is no general standardized mixture design procedure and this makes it challenging to characterize the mechanism(s) of action of these additives in the warm mix. The effects of the addition of additives into WMA are known to a reasonable extent but not so much is known about the underlying interactions and phenomena which bring about the mechanism(s) by which these additives confer beneficial features into the warm mix. Additives in a certain way are being used to bridge the gap and minimize or even nullify the effect of the mixing temperature deficit involved in WMA processes while improving the general properties of the mix. This review presents WMA technologies such as wax, chemical additives and foaming processes and the mechanisms by which they function to confer desired characteristics and improve the durability of the mix. Hybrid techniques are also briefly mentioned in this paper in addition to a detailed description of the specific modes of action of popular WMA technologies such as Sasobit, Evotherm and Advera. This paper highlights the environmental and technical advantages of WMA over the conventional HMA methods and also comprehensively analyzes the mechanism(s) of action of additives in conferring desirable characteristics on WMA, which ultimately improves its durability.

14.
Biosens Bioelectron ; 163: 112299, 2020 Sep 01.
Article in English | MEDLINE | ID: mdl-32568697

ABSTRACT

Enzymes immobilisation represents a critical issue in the design of biosensors to achieve standardization as well as suitable analytical performances in terms of sensitivity, selectivity, and stability. In this work electrospray deposition (ESD) has been exploited as a novel technique for the immobilisation of laccase enzyme on carbon black modified screen-printed electrodes. The aim is to fabricate an amperometric biosensor for phenolic compound detection. The electrodes produced by ESD have been analysed by scanning electron microscopy and characterised electrochemically to prove that this immobilisation technique is suited to manufacture high performance biosensors. The results show that the laccase enzyme maintains its activity after undergoing the electrospray ionisation process and deposition and the fabricated biosensor has improved performances in terms of storage (up to 3 months at room temperature) and working (up to 25 measurements on the same electrode) stability. The laccase-based biosensor has been tested for phenolic compound detection, with catechol as target analyte, in the linear range 2.5-50 µM, with 2.0 µM limit of detection, without interference from lead, cadmium, atrazine, and paraoxon, and without matrix effect in drinking, surface, and wastewater.


Subject(s)
Biosensing Techniques , Laccase , Carbon , Electrodes , Enzymes, Immobilized , Soot
15.
Materials (Basel) ; 13(5)2020 Feb 26.
Article in English | MEDLINE | ID: mdl-32110877

ABSTRACT

In this paper, we survey recent advances in the self-assembly processes of novel functional platforms for nanomaterials and biomaterials applications. We provide an organized overview, by analyzing the main factors that influence the formation of organic nanostructured systems, while putting into evidence the main challenges, limitations and emerging approaches in the various fields of nanotechology and biotechnology. We outline how the building blocks properties, the mutual and cooperative interactions, as well as the initial spatial configuration (and environment conditions) play a fundamental role in the construction of efficient nanostructured materials with desired functional properties. The insertion of functional endgroups (such as polymers, peptides or DNA) within the nanostructured units has enormously increased the complexity of morphologies and functions that can be designed in the fabrication of bio-inspired materials capable of mimicking biological activity. However, unwanted or uncontrollable effects originating from unexpected thermodynamic perturbations or complex cooperative interactions interfere at the molecular level with the designed assembly process. Correction and harmonization of unwanted processes is one of the major challenges of the next decades and requires a deeper knowledge and understanding of the key factors that drive the formation of nanomaterials. Self-assembly of nanomaterials still remains a central topic of current research located at the interface between material science and engineering, biotechnology and nanomedicine, and it will continue to stimulate the renewed interest of biologist, physicists and materials engineers by combining the principles of molecular self-assembly with the concept of supramolecular chemistry.

16.
J Nanosci Nanotechnol ; 20(7): 4574-4579, 2020 07 01.
Article in English | MEDLINE | ID: mdl-31968520

ABSTRACT

Bitumens are composite systems extensively used in road pavements. Due to their complex nature, a rational understanding of the relationships between composition, structure and performances of these materials is still far from being achieved, so research attempting to shed more light in this field is required. Here, we exploit Wide Angle X-ray Scattering (WAXS) as a technique of choice to shed light on the bitumen structure at different length scales. Diagnostic fingerprints, characterizing the WAXS profile, are correlated to specific Bragg distances which can be reasonably attributed to the molecular and supramolecular aggregation taking place at various levels of complexity leading to the formation of hierarchical structures. Due to the inherent instability of these materials some indications are given to obtain reliable structural data.

17.
Phys Chem Chem Phys ; 21(22): 11983-11991, 2019 Jun 05.
Article in English | MEDLINE | ID: mdl-31134980

ABSTRACT

The self-assembly process in a water solution of an amphiphilic polydimethylsiloxane-b-polyethyleneoxide (PDMS-PEO) diblock copolymer was investigated by means of small-angle X-ray scattering (SAXS) experiments in the concentration region below (and near) the critical micellar concentration (c.m.c. = 0.007 g cm-3). In the highly diluted region, at the copolymer concentration of c = 0.002 g cm-3, the early stage of the self-assembly process was characterized by the formation of small (primary) micellar units (with a radius of R = 2.7 nm) with core-shell morphology, which coexisted with larger supramolecular aggregates of entangled micelles (with an average radius of R = 9.5 nm). The increase in the copolymer concentration (to c = 0.005 and c = 0.01 g cm-3) caused increase in the sizes of both the small micelles and supra-micellar aggregates. Interestingly, at the concentration of c = 0.005 g cm-3, both the size and micelle aggregation number (Nagg) were found to increase on increasing the temperature in the range of 10 ≤ T ≤ 55 °C. This phenomenon was characterised by the dehydration process of the ethylene oxide (EO) segments, as evidenced by the calculation of excess water in the hydrophilic shell of the micelles. The more compact (less hydrated) structure of the hydrophilic PEO chains, which strongly influenced the spontaneous curvature of the amphiphile hydrophilic region, turned out to be the driving factor that favoured the increase in the micelle aggregation number with the increase in temperature. The obtained results evidence that the self-assembly process of PDMS-PEO copolymer amphiphiles is a gradual process that is already present at the very low concentration region (far below the macroscopically determined c.m.c.); moreover, it is characterised by a multi-stage organization process, where the primary building blocks self-assemble into more complex secondary structures that encompass multiple length scales.

18.
Colloids Surf B Biointerfaces ; 170: 609-616, 2018 Oct 01.
Article in English | MEDLINE | ID: mdl-29975909

ABSTRACT

Interactions of charged nanoparticles with model bio-membranes provide important insights about the soft interaction involved and the physico-chemical parameters that influence lipid bilayers stability, thus providing key features of their cytotoxicity effects onto cellular membranes. With this aim, the self-assembly processes between polyamidoamine dendrimers (generation G = 2.0 and G = 4.0) and dipalmitoylphosphatidylcholine (DPPC) lipids were investigated by means of Zeta potential analysis, x-rays, Raman and quasielastic light scattering experiments. Raman scattering data evidenced that dendrimers penetration produce a perturbation of the DPPC vesicles alkyl chains. A linear increase of liposome zeta-potential with increasing PAMAM concentration evidenced that only a fraction of the dendrimers effective charge contributes to the expression of the charge at the surface of the DPPC liposome. The linear region of the zeta-potential extends toward higher PAMAM concentrations as the dendrimer generation decreases from G = 4.0 to G = 2.0. Further increase in PAMAM concentration, outside of the linear region, causes a perturbation of the bilayer characterized by the loss in multilamellar correlation and the increase of DPPC liposome hydrodynamic radius. The findings of our investigation help to rationalize the effect of nanoparticles electrostatic interaction within lipid vesicles as well as to provide important insights about the perturbation of lipid bilayers membrane induced by nanoparticles inclusion.


Subject(s)
Dendrimers/chemistry , Lipid Bilayers/chemistry , Lipids/chemistry , Nanoparticles/chemistry , Particle Size , Surface Properties
19.
Biochim Biophys Acta Gen Subj ; 1861(1 Pt B): 3531-3539, 2017 Jan.
Article in English | MEDLINE | ID: mdl-26971858

ABSTRACT

BACKGROUND: Interactions of ligands with proteins imply changes in the properties of the macromolecules that may deeply modify their biological activities and conformations and allow them to acquire new and, sometimes, unexpected abilities. The flavonoid phloretin has several pharmacological properties that are starting to be elucidated, one of which is the well-known inhibition of glucose transport. METHODS: The interactions of phloretin to human serum albumin have been investigated by fluorescence, UV-visible, FTIR spectroscopy, native electrophoresis, protein ligand docking studies, fluorescence and scanning electron microscopy. RESULTS: Spectroscopic investigations suggest that the flavonoid binds to human serum albumin inducing a decrease in α-helix structures as shown by deconvolution of FTIR Amide I' band. Fluorescence and displacement studies highlight modifications of environment around Trp214 with the primary binding site located in the Sudlow's site I. In the hydrophobic cavity of subdomain IIA, molecular modeling studies suggest that phloretin is in non-planar conformation and hydrogen-bonded with Ser202 and Ser454. These changes make HSA able to withstand protein degradation due to HCLO and fibrillation. GENERAL SIGNIFICANCE: Our work aims to open new perspectives as far as the binding of flavonoids to HSA are concern and shows as the properties of both compounds can be remarkable modified after the complex formation, resulting, for instance, in a protein structure much more resistant to oxidation and fibrillation. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo.


Subject(s)
Flavonoids/metabolism , Oxidative Stress , Protein Aggregates , Serum Albumin/chemistry , Serum Albumin/metabolism , Binding Sites , Humans , Microscopy, Fluorescence , Models, Molecular , Phloretin/chemistry , Protein Binding , Protein Conformation , Proteolysis , Spectrometry, Fluorescence , Spectrophotometry, Ultraviolet , Spectroscopy, Fourier Transform Infrared , Thermodynamics
20.
Biochim Biophys Acta ; 1858(11): 2769-2777, 2016 11.
Article in English | MEDLINE | ID: mdl-27521487

ABSTRACT

In spite of the growing variety of biological applications of dendrimer-based nanocarriers, a major problem of their potential applications in bio-medicine is related to the disruption of lipid bilayers and the cytotoxicity caused by the aggregation processes involved onto cellular membranes. With the aim to study model dendrimer-biomembrane interaction, the self-assembly processes of a mixture of charged polyamidoamine (PAMAM) dendrimers and dipalmitoylphosphatidylcholine (DPPC) lipids were investigated by means of Zeta potential analysis, Raman and x-ray scattering. Zwitterionic DPPC liposomes showed substantially different behaviors during their interaction with negatively charged (generation G=2.5) sodium carboxylate terminated (COO- Na+) dendrimers or positively charged (generation G=3.0) amino terminated (-NH2) dendrimers. More specifically the obtained results evidence the sensitive interactions between dendrimer terminals and lipid molecules at the surface of the liposome, with an enhancement of the liposome surface zeta potential, as well as in the hydrophobic region of the bilayers, where dendrimer penetration produce a perturbation of the hydrophobic alkyl chains of the bilayers. Analysis of the SAXS structure factor with a suitable model for the inter-dendrimers electrostatic potential allows an estimation of an effective charge of 15 ǀeǀ for G=2.5 and 7.6 ǀeǀ for G=3.0 PAMAM dendrimers. Only a fraction (about 1/7) of this charge contributes to the linear increase of liposome zeta-potential with increasing PAMAM/DPPC molar fraction. The findings of our investigation may be applied to rationalize the effect of the nanoparticles electrostatic interaction in solution environments for the design of new drug carriers combining dendrimeric and liposomal technology.


Subject(s)
1,2-Dipalmitoylphosphatidylcholine/chemistry , Dendrimers/chemistry , Drug Carriers , Lipid Bilayers/chemistry , Liposomes/chemistry , Carboxylic Acids/chemistry , Spectrum Analysis, Raman , Static Electricity , Thermodynamics
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