Metal ions modulate thermal aggregation of betalactoglobulin: a join chemical and physical characterization

Abstract Molecular basis of the role played by Cu 2 + and Zn 2 + ions during the thermal aggregation processes of beta-lactoglobulin (BLG) was studied by using a joint application of different techniques. In particular, Raman spectroscopy was very useful in identifying the different effects caused by the two metals at molecular level (i.e. changes in His protonation state, disulfides bridge conformation, and micro-environment of aromatic residues), evidencing the primary importance of the protein charge distribution during the aggregation process. Both metal ions are able to act on this factor and favor the protein aggregation, but Zn 2 + is able to alter the natural conformational state of…

Thermal aggregation of proteins in presence of metal ions.

The study of the aggregation processes in presence of metal ions is an essential step for understanding the key role of metals in protein-protein and protein-solvent interactions. Indeed, the presence of metal ions can radically change the main features of the standard denaturation/aggregation processes and such effects result to be strongly dependent on the kind of metal and on its concentration. Metal ions have an active role in thermal aggregation and cold set gelation processes. These processes are intrinsically different, but both are based on the proteins ability to form aggregates.

Data concerning the proteolytic resistance and oxidative stress in LAN5 cells after treatment with BSA hydrogels

AbstractProteolytic resistance is a relevant aspect to be tested in the formulation of new nanoscale biomaterials. The action of proteolytic enzymes is a very fast process occurring in the range of few minutes. Here, we report data concerning the proteolytic resistance of a heat-set BSA hydrogel obtained after 20-hour incubation at 60°C prepared at the pH value of 3.9, pH at which the hydrogel presents the highest elastic character with respect to gel formed at pH 5.9 and 7.4 “Heat-and pH-induced BSA conformational changes, hydrogel formation and application as 3D cell scaffold” (G. Navarra, C. Peres, M. Contardi, P. Picone, P.L. San Biagio, M. Di Carlo, D. Giacomazza, V. Militello, 2016) […

OH-related infrared bands in oxide glasses

Nucleation mechanism of Lysozyme at physiological pH

pH effect on thermal aggregation of concanavalin A

Spectroscopic and microscopic characterization of BSA hydrogels: towards new biomaterials

Lysozyme Aggregation Driven by Unfolding: the Role of Metal Ions

Absorption edge in silica glass

Measurements of optical absorption in the v-UV range in a variety of silica glass are used to determine the width of the absorption edge (Urbach energy). Measured values range from 60 meV up to 180 meV. So high a variability over silica types is tentatively ascribed to the different disorder degree, which characterizes different materials.

Thermal evolution of the OH-related infrared absorption lineshape in synthetic wet silica

Thermal aggregation of glycated bovine serum albumin

International audience; Aggregation and glycation processes in proteins have a particular interest in medicine fields and in food technology. Serum albumins are model proteins which are able to self-assembly in aggregates and also sensitive to a non-enzymatic glycation in cases of diabetes. In this work, we firstly reported a study on the glycation and oxidation effects on the structure of bovine serum albumin (BSA). The experimental approach is based on the study of conformational changes of BSA at secondary and tertiary structures by FTIR absorption and fluorescence spectroscopy, respectively. Secondly, we analysed the thermal aggregation process on BSA glycated with different glucose con…

Role of copper and zinc ions on the heat- induced aggregation

Pre-aggregates characterization and viscoelastic studies of BSA cold gels induced by metal ions

Temperature effects on the IR absorption bands of hydroxyl and deuteroxyl groups in silica glass

Abstract In this report we will show the changes of the band shape of the hydroxyl group (SiOH) infrared (IR) absorption band (∼3670 cm −1 ) in silica glass induced by lowering temperature in the range from 290 to 20 K. This band is considered as the overlap of several spectral components associated to the vibrational activity of hydroxyl groups in different bond configurations. By a suitable analysis of the experimental band profile in terms of different sub-bands, we studied the thermal evolution of each component and we reconsidered their assignations. For comparison we examined the SiOD absorption band (∼2710 cm −1 ) as a function of temperature as well. Our data can be interpreted as a…

Vacuum-ultraviolet absorption of amorphous SiO2: intrinsic disorder and role of silanol groups

We present a study on the vacuum-ultraviolet VUV absorption properties of amorphous SiO2 a-SiO2 with high concentrations of silanol groups Si-OH . We found that the absorption spectra are made up of a couple of exponential profiles. The first, in the range from 7.5 to 8.1 eV, was attributed to Si-OH group absorption, while the second, in the range from 8.1 to 8.25 eV, was ascribed to the intrinsic absorption. The VUV absorption cross section of Si-OH groups in a-SiO2 was determined as well. The intrinsic absorption was found to be affected by the Si-OH concentration: high silanol group contents allow lower values of the Urbach energy. This result is interpreted in terms of a reduction in th…

Deciphering metal-induced oxidative damages on glycated albumin structure and function

Background: Metal ions such as copper or zinc are involved in the development of neurodegenerative pathologies and metabolic diseases such as diabetes mellitus. Albumin structure and functions are impaired following metal-and glucose-mediated oxidative alterations. The aim of this study was to elucidate effects of Cu(II) and Zn(II) ions on glucose-induced modifications in albumin by focusing on glycation, aggregation, oxidation and functional aspects. Methods: Aggregation and conformational changes in albumin were monitored by spectroscopy, fluorescence and microscopy techniques. Biochemical assays such as carbonyl, thiol groups, albumin-bound Cu, fructosamine and amine group measurements w…

Irradiation effects on the absorption edge of silica glass

Abstract Vacuum ultraviolet absorption experiments were carried out on a variety of specimens of amorphous silica β-irradiated at different doses from ∼103 to 5 × 106 kGy. Changes in the width of the absorption (Urbach) edge were investigated. These changes strongly depend on the kind of silica considered: in particular the Urbach energy of silica of industrial manufacture increases in the irradiated samples, whereas in sol–gel silica it is poorly influenced by the irradiation. The fictive temperature of the different materials before and after irradiation was also monitored. The changes of the Urbach energy and of the fictive temperature are tentatively discussed considering the disorder d…

Heat- and pH-induced BSA conformational changes, hydrogel formation and application as 3D cell scaffold

Aggregation and gelation of globular proteins can be an advantage to generate new forms of nanoscale biomaterials based on the fibrillar architecture. Here, we report results obtained by exploiting the proteins' natural tendency to self-organize in 3D network, for the production of new material based on BSA for medical application. In particular, at five different pH values the conformational and structural changes of the BSA during all the steps of the thermal aggregation and gelation have been analyzed by FTIR spectroscopy. The macroscopic mechanical properties of these hydrogels have been obtained by rheological measurements. The microscopic structure of the gels have been studied by AFM…

Influence of exogenous and endogenous ions on the properties of BSA

OH-related infrared absorption bands in oxide glasses

Oxidative changes in Sicilian extra virgin olive oil under heating treatment detected by FTIR spectroscopy, viscosimetry and time-resolved luminescence

A two-component model for the 2260cm−1 infrared absorption band in electron irradiated amorphous SiO2

Abstract We report an experimental study by infrared absorption (IR) measurements focused on the effects of electron irradiation in the dose range from 1.2 × 10 3  kGy to 5 × 10 6  kGy on the intrinsic band peaked at 2260 cm − 1 in amorphous silicon dioxide (a-SiO 2 ) materials. This IR band is particularly relevant as it is assigned to an overtone of the strong asymmetric stretching vibration of Si–O–Si bridges and consequently it is intimately related to the Si–O–Si bond angle distribution. In a recent work we have shown that structural modifications induced by irradiation take place through the nucleation of confined high-defective and densified regions statistically dispersed into the w…

Forze di attrito e determinazione del coefficiente di attrito statico

Thermal oxidative process in extra-virgin olive oils studied by FTIR, rheology and time-resolved luminescence

Abstract With the aim to characterise the antioxidant properties of different extra-virgin olive oils and to understand in more detail the mechanisms of oil degradation, we have made an experimental study on thermal induced oxidative processes of extra-virgin olive oils by using different techniques: Fourier Transform Infrared (FTIR) spectroscopy, rheology and time-resolved luminescence. The oxidation process was followed at three different heating temperatures (30, 60 and 90 °C) as a function of time up to 35 days. Thermal treatment induced changes in the FTIR spectra in the wavenumbers region 3100–3600 cm −1 : in particular, the absorption profiles show an initial formation of hydroperoxi…

Inhomogeneity Effects On Point Defects Studied By Photoluminescence Time Decay In SiO2.

Aggregation processes in beta-lactoglobulin studied by FTIR spectroscopy

Thermal aggregation of glycated Bovine Serum Albumin

Chemical and physical characterization of thermal aggregation of model proteins modulated by zinc(II) and copper(II) ions

BACKGROUND: Metal ions are implicated in protein aggregation processes of several neurodegenerative pathologies, where the protein deposition occurs, and in the biotechnology field like the food technology where many processes in food manufacturing are based on thermal treatments. OBJECTIVE: The influence of Cu2+ or Zn2+ ions on the thermal aggregation process of Bovine beta-lactoglobulin (BLG) and Bovine Serum Albumin (BSA), two protein models, was studied with the aim of delineating the role of these ions in the protein aggregation kinetics and to clarify the related molecular mechanisms. METHODS: The protein structure changes were monitored by Raman spectroscopy, whereas the aggregate gr…

The role of metal ions in the thermal aggregation of Bovine Serum Albumin

Metallic Ions Effects on the Heat-aggregation Process of b-Lactoglobulin

Review: "Thermal aggregation of proteins in the presence of metal ions"

Thermal aggregation of beta-lactoglobulin in presence of metal ions.

In this work, we report a study of the effects of zinc and copper ions on the heat-induced aggregation of beta-lactoglobulin (BLG). Kinetics investigations on aggregates growth by light scattering measurements and on secondary structure changes by FTIR absorption measurements show the different role played by the two metals during the whole process. In particular, the presence of zinc in solution promotes the formation of aggregates of BLG at a lower temperature than copper. Then, at fixed temperature, formation of a large amount of aggregates, of large dimension, is observed for Zn-BLG in shorter time; on the contrary, the presence of copper in solution does not affect the aggregation proc…

OH-related Infrared Absorption Bands in Oxide Glasses

We report the infrared activity, in the spectral region of the OH stretching modes, of different composite silicate glasses whose chemical composition is established by X-ray fluorescence measurements. The analysis of the absorption line profiles is made in terms of different spectral contributions, Gaussian in shape. The comparison with analogous spectra obtained in vitreous silica samples with impurity concentrations < 100 part per million moles is evidence of the effects of the different oxides on the vibrational properties of the OH groups. In particular, for oxide glasses a red shift of the composite band at about 3670 cm(-1), assigned to the OH stretching modes of free Si-OH groups an…

Simultaneous Determination of Caffeine and Chlorogenic Acids in Green Coffee by UV/Vis Spectroscopy

A simple method for the simultaneous determination of caffeine and chlorogenic acids content in green coffee was reported. The method was based on the use of UV/Vis absorption. It is relevant that the quantification of both caffeine and chlorogenic acids was performed without their preliminary chemical separation despite their spectral overlap in the range 250–350 nm. Green coffee was extracted with 70% ethanol aqueous solution; then the solution was analyzed by spectroscopy. Quantitative determination was obtained analytically through deconvolution of the absorption spectrum and by applying the Lambert-Beer law. The bands used for the deconvolution were the absorption bands of both caffein…

Two distinct phases characterize thermal aggregation of b-Lactoglobulin at neutral pH

Irradiation effects on the OH-related infrared absorption band in synthetic wet silica.

The effects of b-irradiation on the OH-related infrared (IR) absorption band in synthetic wet silica samples have been investigated by Fourier transform infrared spectroscopy. Depending on the accumulated doses, b-irradiation affects different zones of the IR composite band at about 3670 cm 1 , assigned to the OH stretching modes of silanol groups. These modifications are independent of the original OH content. The results are discussed considering possible radiation-induced changes of the silanol bonding configuration and of the glass network. These are monitored by revealing the IR band a 2260 cm 1 , which is related to the distribution of Si–O–Si bond angle. We have identified the existence of…

Aggregation of albumin: influence of the protein glycation

Free radicals are a normal component of cellular oxygen metabolism in mammals. However, free radical-associated damage is an important factor in many pathological processes. Aggregation, glycation and oxidative damage cause protein modifications, frequently observed in numerous diseases. Albumin represents the most abundant circulating protein. Many epidemiological studies have established an inverse relationship between the level of serum albumin and the risk of death. Albumin is involved in several biological functions, including the regulation of oncotic pressure, and the binding and transport of many molecules. In addition, albumin displays potent antioxidant and free radical scavenging…

Temperature dependence of the absorption properties of silanol groups in amorphous SiO2: Are silanol groups organized in clusters?

Vacuum-ultraviolet absorption of amorphousSiO2: Intrinsic contribution and role of silanol groups

We present a study on the vacuum-ultraviolet (VUV) absorption properties of amorphous ${\text{SiO}}_{2}$ $(a{\text{-SiO}}_{2})$ with high concentrations of silanol groups (Si-OH). We found that the absorption spectra are made up of a couple of exponential profiles. The first, in the range from $\ensuremath{\sim}7.5$ to $\ensuremath{\sim}8.1\text{ }\text{eV}$, was attributed to Si-OH group absorption, while the second, in the range from $\ensuremath{\sim}8.1$ to $\ensuremath{\sim}8.25\text{ }\text{eV}$, was ascribed to the intrinsic absorption. The VUV absorption cross section of Si-OH groups in $a{\text{-SiO}}_{2}$ was determined as well. The intrinsic absorption was found to be affected by…

Caratterizzazione chimico-fisica della denaturazione termica della b-Lattoglobulina, modulata da ioni metallici

Influence of metal ions on thermal aggregation of bovine serum albumin: aggregation kinetics and structural changes

Metal ions are implicated in protein aggregation processes of several neurodegenerative pathologies. In this work the effects of Cu(II) and Zn(II) ions on heat-induced structural modifications of bovine serum albumin (BSA) were studied, with the aim of delineating the role of these ions in the early stages of proteins aggregation kinetics. A joint application of different techniques was used. The aggregate growth was followed by dynamic light scattering measurements, whereas the conformational changes occurring in the protein structure were monitored by Raman and IR spectroscopy. Both in absence and in presence of metal ions, heating treatment gave rise to b-structures to the detriment of a…

Protein aggregation induced by metallic ions: a FTIR study

Temperature dependence of the absorption properties of silanol groups in amorphous : Are silanol groups organized in clusters?

Abstract We present a study on the vacuum-ultraviolet (VUV) and infrared (IR) absorption of silanol groups in amorphous silicon dioxide ( a - SiO 2 ) in the range of temperature from 4 to 300 K. The observed temperature induced modifications of IR and VUV absorption spectra are interpreted as due to a process of conversion of free into H-bonded silanol groups. The changes of the amplitude of the VUV absorption spectra are shown to be linearly correlated to the changes of the IR absorption of free Si–OH groups. This point together with the evidence that the shape of the Si–OH VUV absorption does not depend on temperature demonstrates that the different silanol group sub-species have differen…

Infrared activity of hydroxyl groups embedded in silica glasses.

Thermal aggregation and ion-induced cold-gelation of bovine serum albumin

Protein cold-gelation has recently received particular attention for its relevance in bio and food technology. In this work, we report a study on bovine serum albumin cold-gelation induced by copper or zinc ions. Metal-induced cold-gelation of proteins requires two steps: during the first one, the heat treatment causes protein partial unfolding and aggregation; then, after cooling the solution to room temperature, gels are formed upon the addition of metal ions. The thermally induced behaviour has been mainly investigated through different techniques: Fourier transform infrared (FTIR) spectroscopy, circular dichroism, dynamic light scattering (DLS) and rheology. Data have shown that the agg…

Characterization of the nucleation process of lysozyme at physiological pH: Primary but not sole process

We report on a kinetic study of the heat-induced aggregation process of lysozyme at physiological pH. The time evolution of the aggregation extent and the conformational changes of the protein were followed by dynamic light scattering (DLS) and FTIR spectroscopy, respectively, whereas the morphology of the aggregates was observed by Atomic Force Microscopy (AFM). The conformational changes of the secondary and tertiary structures were simultaneous and distinct in time with respect to the formation of aggregates. Oligomer formation occurred through at least two different aggregation processes: a nucleation process and a homogeneous non-nucleative diffusion-controlled process. FTIR measuremen…