1,720,971 research outputs found

    Effect of electrolytes on proteins physisorption on ordered mesoporous silica materials

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    This short review highlights the effect of electrolytes on the performance of proteins-mesoporous silica conjugates which can open interesting perspectives in biotechnological fields, particularly nanomedicine and biocatalysis. Indeed therapeutic proteins and peptides represent a challenging innovation for several kinds of diseases, but since their self-life in biological fluids is very short, they need a stealth protective carrier. Similarly, enzymes need a solid support to improve thermal stability and to allow for recycling. Ordered mesoporous silica materials represent a valid choice as widely demonstrated. Both proteins and silica mesoporous materials possess charged surfaces, and here, the crucial role of pH, buffer, ionic strength and electrolyte type is posed in relation with loading/release of proteins onto/from the silica support through the analysis of adsorption and release processes. A delicate interplay of electrostatic and van der Waals interactions arises from considering electrolytes' effects on the two different charged surfaces. Clear outcomes concern the effect of pH and ionic strength. Protein loading onto the silica matrix is favored by an adsorbing solution having a pH close to the protein p. I, and by a high ionic strength that reduces the Debye length. Release is instead favored by an adsorbing solution characterized by an intermediate ionic strength, close to the physiological values. Significant specific ions effects are shown to affect both proteins and silica matrices, as well as protein adsorption onto silica matrices. Further work is needed to quantify specific ion effects on the preservation of the biological activity, and on the release performanc

    Adsorption and release of ampicillin antibiotic from ordered mesoporous silica

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    In this work the adsorption and the release of ampicillin - a β-lactam penicillin-like antibiotic - from MCM-41, SBA-15, and (amino functionalized) SBA-15-NH2 ordered mesoporous silica (OMS) materials were investigated. The silica matrices differ for their pore size (SBA-15 vs. MCM-41) mainly, and also for surface charge (SBA-15 and MCM-41, vs. SBA-15-NH2). OMS samples were characterized through small-angle X-rays scattering (SAXS), transmission electron microscopy (TEM), N2 adsorption–desorption isotherms, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and potentiometric titrations. The quantification of immobilized and released ampicillin was monitored by mean of UV–Vis spectroscopy. Experimental adsorption isotherms evidenced that ampicillin's loading is not related to the pore size (dBJH) of the adsorbent. Indeed the maximal loadings were 237 mg/g for SBA-15 (dBJH = 6.5 nm), 278 mg/g for MCM-41 (dBJH = 2.2 nm), and 333 mg/g for SBA-15-NH2 (dBJH = 5.6 nm). Loading seems, instead, to be related to the surface charge density (σ) of the sorbent surface. Indeed, at pH 7.4 ampicillin drug is negatively charged and likely prefers to interact with SBA-15-NH2 (σSBA-15-NH2 = +0.223 C m−2) rather than the slightly negatively charged silicas (σSBA-15 = −0.044 C m−2 and σMCM-41 = −0.033 C m−2). Similarly, ampicillin release is affected by interfacial interactions. Indeed, we found a burst release from pure silica samples (SBA-15 and MCM-41), whereas a sustained one from SBA-15-NH2 sample. We explain this behavior as a result of an attractive interaction between the protonated amino group of SBA-15-NH2 and the negatively charged carboxylate group of ampicillin. In summary, in order to obtain a sustained drug release, the chemical nature of the matrix's surface plays a role which is more important than its textural features. SBA-15-NH2 matrix is hence a suitable candidate for local sustained release of antibiotic drugs

    Specific ion effects on the electrochemical properties of cytochrome c

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    The range of salts used as supporting electrolytes in electrochemical studies of redox proteins and enzymes varies widely, with the choice of an electrolyte relying on the assumption that the electrolyte used does not affect the electrochemical properties of the proteins and enzymes under investigation. Examination of the electrochemical properties of the redox protein cytochrome c (cyt c) at a 4,4′-bipyridyl modified gold electrode demonstrates that both the redox potential (E o′) and the faradaic current are influenced by the nature of the electrolyte used, in a manner explained primarily by Hofmeister effects. The faradaic peak currents display an atypical trend on switching from kosmotropic to chaotropic anions, with a maximum current observed in the presence of Cl -. For a series of cations, the peak current increased in the sequence: Li + (0.34 μA) Br - (0.35 μA) > ClO 4 - (0.35 μA) > SCN - (0.31 μA) > F - (0.30 μA). E o′ decreased by a total of 24 mV across the series F - > Cl - > Br - > ClO 4 - > SCN - whereas no specific ion effect on E o′ was observed for cations. Factorisation of E o′ into its enthalpic and entropic components showed that while no specific trends were observed, large changes in ΔH o′ and ΔS o′ occurred with individual ions. The effect of anions on the faradaic peak current can be qualitatively explained by considering Collins' empirical rule of 'matching water affinities'. The effect of cations cannot be explained by this rule. However, both anion and cation effects can be understood by taking into account the cooperative action of electrostatic and ion dispersion forces. The results demonstrate that the choice of a supporting electrolyte in electrochemical investigations of redox proteins is important and emphasize that care needs to be taken in the determination and comparison of E o′, ΔH o′ and ΔS o′ in different solutions

    Gold nanoparticles: A powerful tool to visualize proteins on ordered mesoporous silica and for the realization of theranostic nanobioconjugates

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    Ordered mesoporous silica (OMS) is a very interesting nanostructured material for the design and engineering of new target and controlled drug-delivery systems. Particularly relevant is the interaction between OMS and proteins. Large pores (6–9 nm) micrometric particles can be used for the realization of a drug depot system where therapeutic proteins are adsorbed either inside the mesopores or on the external surface. Small pores (1–2 nm) mesoporous silica nanoparticles (MSNs), can be injected in the blood stream. In the latter case, therapeutic proteins are mainly adsorbed on the MSNs’ external surface. Whenever a protein-OMS conjugate is prepared, a diagnostic method to locate the protein either on the internal or the external silica surface is of utmost importance. To visualize the fine localization of proteins adsorbed in mesoporous silica micro- and nanoparticles, we have employed specific transmission electron microscopy (TEM) analytical strategies based on the use of gold nanoparticles (GNPs) conjugates. GNPs are gaining in popularity, representing a fundamental tool to design future applications of MSNs in nanomedicine by realizing theranostic nanobioconjugates. It may be pointed out that we are at the very beginning of a new age of the nanomaterial science: the “mesoporous golden age”

    Lysozyme Adsorption and Release from Ordered Mesoporous Materials

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    Ordered mesoporous materials (OMMs) are interesting matrixes for nanomedicine applications such as innovative drug delivery systems. Here, we compare the behavior of the widely studied SBA-15 mesoporous silica with that of the less investigated MSE (a periodic mesoporous organosilica whose silicon atoms are alternatively connected by means of -Si-O-Si- and -Si-CH(2)-CH(2)-Si- groups) toward the adsorption (pH 7.0 and 9.6) and in vitro release (pH 7.4; T = 37 degrees C) of an antimicrobial protein (hen egg white lysozyme). Both OMMs have a hexagonal ordered mesoporous structure and texture, as confirmed by SAXS, TEM, and N(2) adsorption isotherms, but differ for the chemical composition and surface charge density, as determined by ATR-FTIR spectroscopy and potentiometric titrations, respectively. Rather than the structural and textural features, the different chemical composition of SBA-15 and MSE seems to be responsible for the different lysozyme loading and release and for the different stability toward the lixiviating action of the physiological medium (pH 7.4; T = 37 degrees C)

    Going Beyond Counting First Authors in Author Co-citation Analysis

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    The present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed

    Ion Specific Surface Charge Density of SBA-15 Mesoporous Silica

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    Potentiometric titrations were used to estimate the surface charge density of SBA-15 mesoporous silica in different salt solutions. It was found that surface charge depends both on cation type, following a Hofmeister series (Cs+ < Guanidinium+ < K+ < Na+ < Li+), and on salt concentration (in the range 0.05-1 M). The surface charge series is reproduced by theoretical calculations performed using a modified Poisson-Boltzmann equation that includes ionic dispersion forces with ab initio ion polarizabilities and hydrated ions. The hydration model assigns an explicit hydration shell to kosmotropic (strong hydrated) ions only. The Hofmeister series appears to be due to the combination of ion surface dispersion interactions and ion hydration

    Variations on the Author

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    “Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship

    Appropriate Similarity Measures for Author Cocitation Analysis

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    We provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
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