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1.
Langmuir ; 40(2): 1470-1486, 2024 01 16.
Artigo em Inglês | MEDLINE | ID: mdl-38174846

RESUMO

Peptides are able to self-organize in structural elements including cross-ß structures. Taking advantage of this tendency, in the last decades, peptides have been scrutinized as molecular elements for the development of multivalent supramolecular architectures. In this context, different classes of peptides, also with completely aromatic sequences, were proposed. Our previous studies highlighted that the (FY)3 peptide, which alternates hydrophobic phenylalanine and more hydrophilic tyrosine residues, is able to self-assemble, thanks to the formation of both polar and apolar interfaces. It was observed that the replacement of Phe and Tyr residues with other noncoded aromatic amino acids like 2-naphthylalanine (Nal) and Dopa affects the interactions among peptides with consequences on the supramolecular organization. Herein, we have investigated the self-assembling behavior of two novel (FY)3 analogues with Trp and Dopa residues in place of the Phe and Tyr ones, respectively. Additionally, PEGylation of the N-terminus was analyzed too. The supramolecular organization, morphology, and capability to gel were evaluated using complementary techniques, including fluorescence, Fourier transform infrared spectroscopy, and scanning electron microscopy. Structural periodicities along and perpendicular to the fiber axis were detected by grazing incidence wide-angle X-ray scattering. Finally, molecular dynamics studies provided interesting insights into the atomic structure of the cross-ß that constitutes the basic motif of the assemblies formed by these novel peptide systems.


Assuntos
Triptofano , Tirosina , Tirosina/química , Triptofano/química , Di-Hidroxifenilalanina , Peptídeos/química , Aminoácidos Aromáticos/química
2.
Molecules ; 29(9)2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38731405

RESUMO

Chitin, a ubiquitous biopolymer, holds paramount scientific and economic significance. Historically, it has been primarily isolated from marine crustaceans. However, the surge in demand for chitin and the burgeoning interest in biopolymers have necessitated the exploration of alternative sources. Among these methods, the mulberry silkworm (Bombyx mori) has emerged as a particularly intriguing prospect. To isolate chitin from Bombyx mori, a chemical extraction methodology was employed. This process involved a series of meticulously orchestrated steps, including Folch extraction, demineralization, deproteinization, and decolorization. The resultant chitin was subjected to comprehensive analysis utilizing techniques such as attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), 13C nuclear magnetic resonance (NMR) spectroscopy, and wide-angle X-ray scattering (WAXS). The obtained results allow us to conclude that the Bombyx mori represents an attractive alternative source of α-chitin.


Assuntos
Bombyx , Quitina , Bombyx/química , Animais , Quitina/química , Quitina/isolamento & purificação , Espectroscopia de Infravermelho com Transformada de Fourier , Difração de Raios X , Espectroscopia de Ressonância Magnética , Morus/química
3.
Int J Mol Sci ; 24(3)2023 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-36768265

RESUMO

In the last two decades, fisheries and fish industries by-products have started to be recovered for the extraction of type I collagen because of issues related to the extraction of traditional mammalian tissues. In this work, special attention has been paid to by-products from fish bred in aquaponic plants. The valorization of aquaponic fish wastes as sources of biopolymers would make the derived materials eco-friendlier and attractive in terms of profitability and cost effectiveness. Among fish species, Nile Tilapia is the second-most farmed species in the world and its skin is commonly chosen as a collagen extraction source. However, to the best of our knowledge, no studies have been carried out to investigate, in depth, the age-related differences in fish skin with the final aim of selecting the most advantageous fish size for collagen extraction. In this work, the impact of age on the structural and compositional properties of Tilapia skin was evaluated with the aim of selecting the condition that best lends itself to the extraction of type I collagen for biomedical applications, based on the known fact that the properties of the original tissue have a significant impact on those of the final product. Performed analysis showed statistically significant age-related differences. In particular, an increase in skin thickness (+110 µm) and of wavy-like collagen fiber bundle diameter (+3 µm) besides their organization variation was observed with age. Additionally, a preferred collagen molecule orientation along two specific directions was revealed, with a higher fiber orientation degree according to age. Thermal analysis registered a shift of the endothermic peak (+1.7 °C) and an increase in the enthalpy (+3.3 J/g), while mechanical properties were found to be anisotropic, with an age-dependent brittle behavior. Water (+13%) and ash (+0.6%) contents were found to be directly proportional with age, as opposed to protein (-8%) and lipid (-10%) contents. The amino acid composition revealed a decrease in the valine, leucine, isoleucine, and threonine content and an increase in proline and hydroxyproline. Lastly, fatty acids C14:0, C15:0, C16:1, C18:2n6c, C18:3n6, C18:0, C20:3n3, and C23:0 were revealed to be upregulated, while C18:1n9c was downregulated with age.


Assuntos
Ciclídeos , Tilápia , Animais , Tilápia/metabolismo , Ciclídeos/metabolismo , Colágeno Tipo I/metabolismo , Ácidos Graxos/metabolismo , Colágeno/metabolismo , Mamíferos
4.
Chemistry ; 27(60): 14886-14898, 2021 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-34498321

RESUMO

Peptide-based hydrogels, originated by multiscale self-assembling phenomenon, have been proposed as multivalent tools in different technological areas. Structural studies and molecular dynamics simulations pointed out the capability of completely aromatic peptides to gelificate if hydrophilic and hydrophobic forces are opportunely balanced. Here, the effect produced by the introduction of a Cys residue in the heteroaromatic sequence of (FY)3 and in its PEGylated variant was evaluated. The physicochemical characterization indicates that both FYFCFYF and PEG8-FYFCFYF are able to self-assemble in supramolecular nanostructures whose basic cross-ß motif resembles the one detected in the ancestor (FY)3 assemblies. However, gelification occurs only for FYFCFYF at a concentration of 1.5 wt%. After cross-linking of cysteine residues, the hydrogel undergoes to an improvement of the rigidity compared to the parent (FY)3 assemblies as suggested by the storage modulus (G') that increases from 970 to 3360 Pa. The mechanical properties of FYFCFYF are compatible with its potential application in bone tissue regeneration. Moreover, the avalaibility of a Cys residue in the middle of the peptide sequence could allow the hydrogel derivatization with targeting moieties or with biologically relevant molecules.


Assuntos
Cisteína , Hidrogéis , Sequência de Aminoácidos , Simulação de Dinâmica Molecular , Peptídeos
5.
Nanotechnology ; 32(21)2021 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-33126233

RESUMO

Motivated by the technological relevance of tungsten oxide nanostructures as valuable materials for energy saving technology, electrochemical and electrochromic characteristics of greener processed nanostructured W18O49-based electrodes are discussed in this work. For the purpose, microwave-assisted water-dispersible W18O49nanorods have been synthesized and processed into nanostructured electrodes. An airbrushing technique has been adopted as a cost-effective large-area scalable methodology to deposit the W18O49nanorods onto conductive glass. This approach preserves the morphological and crystallographic habit of native nanorods and allows highly homogeneous transparent coating where good electronic coupling between nanowires is ensured by a mild thermal treatment (250 °C, 30 min). Morphological and structural characteristics of active material were investigated from the synthesis to the nanocrystal deposition process by transmission and scanning electron microscopy, x-ray diffraction, atomic force microscopy and Raman spectroscopy. The as-obtained nanostructured film exhibited good reversible electrochemical features through several intercalation-deintercalation cycles. The electrochromic properties were evaluated on the basis of spectro-electrochemical measurements and showed significant optical contrast in the near-infrared region and high coloration efficiency at 550 nm.

6.
Soft Matter ; 16(30): 7006-7017, 2020 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-32638818

RESUMO

Over the last few years, hydrogels have been proposed for many biomedical applications, including drug delivery systems and scaffolds for tissue engineering. In particular, peptides have been envisioned as excellent candidates for the development of hydrogel materials, due to their intrinsic biocompatibility, ease of handling, and intrinsic biodegradability. Recently, we developed a novel hybrid polymer-peptide conjugate, PEG8-(FY)3, which is able to self-assemble into a self-supporting soft hydrogel over dry and wet surfaces as demonstrated by molecular dynamics simulation. Here, we describe the synthesis and supramolecular organization of six novel hexapeptides rationally designed by punctual chemical modification of the primary peptide sequence of the ancestor peptide (FY)3. Non-coded amino acids were incorporated by replacing the phenylalanine residue with naphthylalanine (Nal) and tyrosine with dopamine (Dopa). We also studied the effect of the modification of the side chain and the corresponding PEGylated peptide analogues, on the structural and mechanical properties of the hydrogel. Secondary structure, morphology and rheological properties of all the peptide-based materials were assessed by various biophysical tools. The in vitro biocompatibility of the supramolecular nanostructures was also evaluated on fibroblast cell lines. We conclude that the PEG8-(Nal-Dopa)3 hydrogel possesses the right properties to serve as a scaffold and support cell growth.


Assuntos
Hidrogéis , Nanoestruturas , Peptídeos , Estrutura Secundária de Proteína , Engenharia Tecidual
7.
Molecules ; 25(12)2020 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-32604749

RESUMO

Fabrication of heterostructures by merging two or more materials in a single object. The domains at the nanoscale represent a viable strategy to purposely address materials' properties for applications in several fields such as catalysis, biomedicine, and energy conversion. In this case, solution-phase seeded growth and the hot-injection method are ingeniously combined to fabricate TiO2/PbS heterostructures. The interest in such hybrid nanostructures arises from their absorption properties that make them advantageous candidates as solar cell materials for more efficient solar light harvesting and improved light conversion. Due to the strong lattice mismatch between TiO2 and PbS, the yield of the hybrid structure and the control over its properties are challenging. In this study, a systematic investigation of the heterostructure synthesis as a function of the experimental conditions (such as seeds' surface chemistry, reaction temperature, and precursor concentration), its topology, structural properties, and optical properties are carried out. The morphological and chemical characterizations confirm the formation of small dots of PbS by decorating the oleylamine surface capped TiO2 nanocrystals under temperature control. Remarkably, structural characterization points out that the formation of heterostructures is accompanied by modification of the crystallinity of the TiO2 domain, which is mainly ascribed to lattice distortion. This result is also confirmed by photoluminescence spectroscopy, which shows intense emission in the visible range. This originated from self-trapped excitons, defects, and trap emissive states.


Assuntos
Chumbo/química , Pontos Quânticos/química , Sulfetos/química , Titânio/química , Nanopartículas/ultraestrutura , Energia Solar , Propriedades de Superfície
8.
Soft Matter ; 15(3): 487-496, 2019 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-30601569

RESUMO

Short peptides or single amino acids are interesting building blocks for fabrication of hydrogels, frequently used as extracellular matrix-mimicking scaffolds for cell growth in tissue engineering. The combination of two or more peptide hydrogelators could allow obtaining different materials exhibiting new architectures, tunable mechanical properties, high stability and improved biofunctionality. Here we report on the synthesis, formulation and multi-scale characterization of peptide-based mixed hydrogels formed by the low molecular weight Fmoc-FF (Nα-fluorenylmethyloxycarbonyl diphenylalanine) hydrogelator and of the PEG8-(FY)3 hexapeptide, containing three repetitions of the Phe-Tyr motif and a PEG moiety at its N-terminus. Mixed hydrogels were also prepared by replacing PEG8-(FY)3 with its analogue (FY)3, without the PEG moiety. Rheology analysis confirmed the improved mechanical features of the multicomponent gels prepared at two different ratios (2/1 or 1/1, v/v). However, the presence of the hydrophilic PEG polymeric moiety causes a slowing down of the gel kinetic formation (from 42 to 18 minutes) and a decrease of the gel rigidity (G' from 9 to 6 kPa). Preliminary in vitro biocompatibility and cell adhesion assays performed on Chinese hamster ovarian (CHO) cells suggest a potential employment of these multicomponent hydrogels as exogenous scaffold materials for tissue engineering.


Assuntos
Fluorenos/química , Hidrogéis/síntese química , Oligopeptídeos/química , Fenilalanina/análogos & derivados , Alicerces Teciduais/química , Animais , Células CHO , Cricetinae , Cricetulus , Dipeptídeos , Fenilalanina/química , Reologia , Alicerces Teciduais/efeitos adversos
9.
Chemistry ; 24(26): 6804-6817, 2018 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-29504716

RESUMO

Phenylalanine-based nanostructures have attracted the attention of the material science community for their functional properties. These properties strongly depend on the hierarchic organization of the nanostructure that in turn can be finely tuned by punctual chemical modifications of the building blocks. Herein, we investigate how the partial or the complete replacement of the Phe residues in PEG8 -(Phe)6 (PEG8 -F6) with tyrosines to generate PEG8 -(Phe-Tyr)3 (PEG8 -(FY)3) or PEG8 -(Tyr)6 (PEG8 -Y6) affects the structural/functional properties of the nanomaterial formed by the parental compound. Moreover, the effect of the PEG derivatization was evaluated through the characterization of the peptides without the PEG moiety (Tyr)6 (Y6) and (Phe-Tyr)3 ((FY)3). Both PEG8 -Y6 and PEG8 -(FY)3 can self-assemble in water at micromolar concentrations in ß-sheet-rich nanostructures. However, WAXS diffraction patterns of these compounds present significant differences. PEG8 -(FY)3 shows a 2D WAXS oriented fiber diffraction profile characterized by the concomitant presence of a 4.7 Šmeridional and a 12.5 Šequatorial reflection that are generally associated with cross-ß structure. On the other hand, the pattern of PEG8 -Y6 is characterized by the presence of circles typically observed in the presence of PEG crystallization. Molecular modeling and dynamics provide an atomic structural model of the peptide spine of these compounds that is in good agreement with WAXS experimental data. Gelation phenomenon was only detected for PEG8 -(FY)3 above a concentration of 1.0 wt % as confirmed by storage (G'≈100 Pa) and loss (G''≈28 Pa) moduli in rheological studies. The cell viability on CHO cells of this soft hydrogel was certified to be 90 % after 24 hours of incubation.


Assuntos
Amiloide/química , Oligopeptídeos/química , Tirosina/química , Animais , Materiais Biocompatíveis/síntese química , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Células CHO , Sobrevivência Celular/efeitos dos fármacos , Cricetinae , Cricetulus , Simulação de Dinâmica Molecular , Oligopeptídeos/síntese química , Oligopeptídeos/farmacologia , Estrutura Secundária de Proteína , Reologia , Espectrometria de Fluorescência , Difração de Raios X
10.
Chemphyschem ; 19(13): 1635-1642, 2018 07 05.
Artigo em Inglês | MEDLINE | ID: mdl-29542851

RESUMO

Over the years, a large number of multidisciplinary investigations has unveiled that the self-assembly of short peptides and even of individual amino acids can generate a variety of different biomaterials. In this framework, we have recently reported that polyethylene glycol (PEG) conjugates of short homopeptides, containing aromatic amino acids such as phenylalanine (Phe, F) and naphthylalanine (Nal), are able to form elongated fibrillary aggregates having interesting chemical and physical properties. We here extend these analyses characterizing the self-assembling propensity of PEG6 -W4, a PEG adduct of the tetra-tryptophan (W4) sequence. A comprehensive structural characterization of PEG6 -W4 was obtained, both in solution and at the solid state, through the combination of spectroscopic, microscopic, X-ray scattering and computational techniques. Collectively, these studies demonstrate that this peptide is able to self-assemble in fibrillary networks characterized by a cross ß-structure spine. The present findings clearly demonstrate that aromatic residues display a general propensity to induce self-aggregation phenomenon, despite the significant differences in the physicochemical properties of their side chains.

11.
Soft Matter ; 14(40): 8219-8230, 2018 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-30265271

RESUMO

The ability of peptides to self-assemble represents a valuable tool for the development of biomaterials of biotechnological and/or biomedical interest. Diphenylalanine homodimer (FF) and its analogues are among the most promising systems in this field. The longest Phe-based building block hitherto characterized is pentaphenylalanine (F5). We studied the aggregation propensity and the structural/morphological features of assemblies of zwitterionic hexaphenylalanine H+-F6-O- and of three variants characterized by different charged states of the terminal ends (Ac-F6-Amide, H+-F6-Amide and Ac-F6-O-). As previously observed for PEGylated hexaphenylalanine (PEG8-F6), all F6 variants show a strong tendency to form ß-rich assemblies in which the structural motif is constituted by antiparallel ß-strands in the cross-ß framework. Extensive replica exchange molecular dynamics simulations carried out on a pairs of F6 peptides indicate that the antiparallel ß-structure of the final assemblies is likely dictated by the preferred association modes of the individual chains in the very early stages of the aggregation process. Our data suggest that even very small F6 peptides are properly pre-organized and prone to the build-up of the final assembly.

12.
Phys Chem Chem Phys ; 20(16): 11396-11404, 2018 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-29645032

RESUMO

Thanks to their high stability, good optoelectronic and extraordinary electrochromic properties, tungsten oxides are among the most valuable yet underexploited materials for energy conversion applications. Herein, colloidal one-dimensional carved nanocrystals of reduced tungsten trioxide (WO3-x) are successfully integrated, for the first time, as a hole-transporting layer (HTL) into CH3NH3PbI3 perovskite solar cells with a planar inverted device architecture. Importantly, the use of such preformed nanocrystals guarantees the facile solution-cast-only deposition of a homogeneous WO3-x thin film at room temperature, allowing achievement of the highest power conversion efficiency ever reported for perovskite solar cells incorporating raw and un-doped tungsten oxide based HTL.

13.
Biochim Biophys Acta Proteins Proteom ; 1865(2): 176-185, 2017 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-27865970

RESUMO

Nucleophosmin (NPM1) is a multifunctional protein involved in a variety of biological processes including the pathogenesis of several human malignancies and is the most frequently mutated gene in Acute Myeloid Leukemia (AML). To deepen the role of protein regions in its biological activities, lately we reported on the structural behavior of dissected C-terminal domain (CTD) helical fragments. Unexpectedly the H2 (residues 264-277) and H3 AML-mutated regions showed a remarkable tendency to form amyloid-like assemblies with fibrillar morphology and ß-sheet structure that resulted as toxic when exposed to human neuroblastoma cells. More recently NPM1 was found to be highly expressed and toxic in neurons of mouse models of Huntington's disease (HD). Here we investigate the role of each residue in the ß-strand aggregation process of H2 region of NPM1 by performing a systematic alanine scan of its sequence and structural and kinetic analyses of aggregation of derived peptides by means of Circular Dichorism (CD) and Thioflavin T (Th-T) assay. These solution state investigations pointed out the crucial role exerted by the basic amyloidogenic stretch of H2 (264-271) and to shed light on the initial and main interactions involved in fibril formation we performed studies on fibrils deriving from the related Ala peptides through the analysis of fibrils with birefringence of polarized optical microscopy and wide-angle X-ray scattering (WAXS). This analysis suggested that the presence of branched Ile269 conferred preferential packing patterns that, instead, appeared geometrically hampered by the aromatic side-chain of Phe268. Present investigations could be useful to deepen the knowledge of AML molecular mechanisms and the role of cytoplasmatic aggregates of NPM1c+.


Assuntos
Amiloide/metabolismo , Proteínas Amiloidogênicas/metabolismo , Proteínas Nucleares/metabolismo , Agregação Patológica de Proteínas/metabolismo , Peptídeos beta-Amiloides/metabolismo , Amiloidose/metabolismo , Cinética , Nucleofosmina , Conformação Proteica , Conformação Proteica em Folha beta , Domínios Proteicos , Estrutura Secundária de Proteína , Difração de Raios X/métodos
14.
Chemistry ; 23(36): 8741-8748, 2017 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-28508550

RESUMO

A great interest has been recently generated by the discovery that peptide-based nanostructures (NSs) endowed with cross-ß structure may show interesting photoluminescent (PL) properties. It was shown that NSs formed by PEGylated hexaphenylalanine (PEG8 -F6, PEG=polyethylene glycol) are able to emit at 460 nm when excited at 370 or 410 nm. Here, the possibility to transfer the fluorescence of these PEG8 -F6-based NSs by foster resonance electron transfer (FRET) phenomenon to a fluorescent dye was explored. To achieve this aim, the 4-chloro-7-nitrobenzofurazan (NBD) dye was encapsulated in these NSs. Structural data in solution and in solid state, obtained by a variety of techniques (circular dichroism, Fourier-transform infrared spectroscopy, wide-angle X-ray scattering, and small-angle X-ray scattering), indicated that the organization of the peptide spine of PEG8 -F6 NS, which consists of anti-parallel ß-sheets separated by a dry interface made of interacting phenylalanine side chains, was maintained upon NBD encapsulation. The spectroscopic characterization of these NSs clearly showed a red-shift of the emission fluorescence peak both in solution and in solid state. This shift from 460 to 530 nm indicated that a FRET phenomenon from the peptide-based to the fluorophore-encapsulated NS occurred. FRET could also be detected in the PEG8 -F6 conjugate, in which the NBD was covalently bound to the amine of the compound. On the basis of these results, it is suggested that the red-shift of the intrinsic PL of NSs may be exploited in the bio-imaging field.


Assuntos
Transferência Ressonante de Energia de Fluorescência/métodos , Corantes Fluorescentes/química , Nanoestruturas/química , Peptídeos/química , Fenilalanina/química , 4-Cloro-7-nitrobenzofurazano/química , Dicroísmo Circular/métodos , Microscopia Eletrônica de Varredura/métodos , Tamanho da Partícula , Polietilenoglicóis/química , Espectrometria de Fluorescência/métodos , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Propriedades de Superfície
15.
Chemistry ; 23(56): 14039-14048, 2017 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-28782843

RESUMO

Peptides containing aromatic residues are known to exhibit spontaneous phenomena of supramolecular organization into ordered nanostructures (NSs). In this work we studied the structural behavior and optoelectronic properties of new biocompatible materials obtained by the self-assembly of a series of hexaphenylalanines (F6) modified at the N terminus by a PEG chain of different lengths. PEG12 -F6, PEG18 -F6, and PEG24 -F6 peptides were synthesized by coupling sequentially two, three, or four units of amino-carboxy-PEG6 blocks, each one containing six oxyethylene repetitions. Changes in the length and composition of the PEG chain were found to modulate the structural organization of the phenylalanine-based nanostructures. An increase in the self-aggregation tendency was observed with longer PEG chains, whereas, independently of the PEG length, the peptide NSs display cross-ß-like secondary structures with an antiparallel ß-strand arrangement. WAXS/GIWAXS diffraction patterns indicate a progressive decrease in fiber order along the series. All the PEG-F6 derivatives present blue photoluminescent (PL) emission at 460 nm, with the adduct with the longest PEG chain (PEG24 -F6) showing an additional green emission at 530 nm.

16.
Chemistry ; 22(46): 16586-16597, 2016 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-27706842

RESUMO

Despite the growing literature about diphenylalanine-based peptide materials, it still remains a challenge to delineate the theoretical insight into peptide nanostructure formation and the structural features that could permit materials with enhanced properties to be engineered. Herein, we report the synthesis of a novel peptide building block composed of six phenylalanine residues and eight PEG units, PEG8 -F6. This aromatic peptide self-assembles in water in stable and well-ordered nanostructures with optoelectronic properties. A variety of techniques, such as fluorescence, FTIR, CD, DLS, SEM, SAXS, and WAXS allowed us to correlate the photoluminescence properties of the self-assembled nanostructures with the structural organization of the peptide building block at the micro- and nanoscale. Finally, a model of hexaphenylalanine in aqueous solution by molecular dynamics simulations is presented to suggest structural and energetic factors controlling the formation of nanostructures.

17.
Chemphyschem ; 17(5): 699-709, 2016 Mar 03.
Artigo em Inglês | MEDLINE | ID: mdl-26756645

RESUMO

We have developed a general X-ray powder diffraction (XPD) methodology for the simultaneous structural and compositional characterization of inorganic nanomaterials. The approach is validated on colloidal tungsten oxide nanocrystals (WO3-x NCs), as a model polymorphic nanoscale material system. Rod-shaped WO3-x NCs with different crystal structure and stoichiometry are comparatively investigated under an inert atmosphere and after prolonged air exposure. An initial structural model for the as-synthesized NCs is preliminarily identified by means of Rietveld analysis against several reference crystal phases, followed by atomic pair distribution function (PDF) refinement of the best-matching candidates (static analysis). Subtle stoichiometry deviations from the corresponding bulk standards are revealed. NCs exposed to air at room temperature are monitored by XPD measurements at scheduled time intervals. The static PDF analysis is complemented with an investigation into the evolution of the WO3-x NC structure, performed by applying the modulation enhanced diffraction technique to the whole time series of XPD profiles (dynamical analysis). Prolonged contact with ambient air is found to cause an appreciable increase in the static disorder of the O atoms in the WO3-x NC lattice, rather than a variation in stoichiometry. The time behavior of such structural change is identified on the basis of multivariate analysis.

18.
Sci Technol Adv Mater ; 16(5): 055007, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-27877842

RESUMO

Colloidal semiconductor nanocrystals, with intense and sharp-line emission between red and near-infrared spectral regions, are of great interest for optoelectronic and bio-imaging applications. The growth of an inorganic passivation layer on nanocrystal surfaces is a common strategy to improve their chemical and optical stability and their photoluminescence quantum yield. In particular, cation exchange is a suitable approach for shell growth at the expense of the nanocrystal core size. Here, the cation exchange process is used to promote the formation of a CdS passivation layer on the surface of very small PbS nanocrystals (2.3 nm in diameter), blue shifting their optical spectra and yielding luminescent and stable nanostructures emitting in the range of 700-850 nm. Structural, morphological and compositional investigation confirms the nanocrystal size contraction after the cation-exchange process, while the PbS rock-salt crystalline phase is retained. Absorption and photoluminescence spectroscopy demonstrate the growth of a passivation layer with a decrease of the PbS core size, as inferred by the blue-shift of the excitonic peaks. The surface passivation strongly increases the photoluminescence intensity and the excited state lifetime. In addition, the nanocrystals reveal increased stability against oxidation over time. Thanks to their absorption and emission spectral range and the slow recombination dynamics, such highly luminescent nano-objects can find interesting applications in sensitized photovoltaic cells and light-emitting devices.

19.
Opt Express ; 22(10): 12200-10, 2014 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-24921340

RESUMO

We study the incubation effect during laser ablation of stainless steel with ultrashort pulses to boost the material removal efficiency at high repetition rates. The multi-shot ablation threshold fluence has been estimated for two pulse durations, 650-fs and 10-ps, in a range of repetition rates from 50 kHz to 1 MHz. Our results show that the threshold fluence decreases with the number of laser pulses N due to damage accumulation mechanisms, as expected. Moreover, approaching the MHz regime, the onset of heat accumulation enhances the incubation effect, which is in turn lower for shorter pulses at repetition rates below 600 kHz. A saturation of the threshold fluence value is shown to occur for a significantly high number of pulses, and well fitted by a modified incubation model.

20.
J Mater Chem B ; 11(12): 2638-2649, 2023 03 22.
Artigo em Inglês | MEDLINE | ID: mdl-36629337

RESUMO

Due to the pollution problem, the use of more sustainable materials with a reduced environmental impact, spanning across biocompatible and biodegradable polymers, is growing worldwide in many different fields, particularly when referring to applications in Life Sciences. Accordingly, with the aim of developing multifunctional materials for potential cosmetic/biomedical purposes, this work reports the physical and chemical characterization of chitosan-based films blended with snail slime, exhibiting antioxidant and sunscreen features. A suitable formulation for preparing free-standing chitosan platforms, mixing low molecular weight chitosan, lactic acid, glycerol, and snail slime into an appropriate ratio, is thus described. The results obtained by morphological analysis and ATR-FTIR spectroscopy, XRD, swelling analysis (also when varying pH, ionic strength, and temperature), and WVTR measurements evidence a uniform distribution of snail slime inside the chitosan network, forming more compacted structures. At first, the UV-Vis analysis is used to investigate the theoretical Sun Protection Factor, finding that these innovative platforms can be used for preventing sunburn. Then, the antioxidant features are investigated using the ABTS assay, displaying a snail slime-mediated and dose-dependent boosted activity.


Assuntos
Quitosana , Quitosana/química , Antioxidantes , Polímeros , Protetores Solares , Espectroscopia de Infravermelho com Transformada de Fourier
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