Sara Fateixa

κ-Carrageenan hydrogel nanocomposites with release behavior mediated by morphological distinct Au nanofillers.

In this work we investigate the effect of spherical and rod-shaped Au nanoparticles (NPs) in the microstructure, thermomechanical and release properties of thermosensitive κ-carrageenan hydrogels. Thermal and mechanical analyses of the composites revealed that the Au NPs reinforce the structure of the hydrogel and the mechanism of gel reinforcement is discussed. The effect of the NPs on the microstructure and strength of the hydrogel had implications in the mechanism of controlled release as demonstrated by in vitro release studies using a drug model (methylene blue: MB). Noteworthy, the mechanism of MB release followed either a diffusion or polymer relaxation mechanism, depending on the morphology of the Au NPs incorporated in the hydrogel. Consequently, κ-carrageenan hydrogels containing Au NPs exhibited not only optical features modulated by the fillers morphology, but also showed a behavior as drug carriers that can be also adjusted by Au NPs characteristics.

Biofunctionalized magnetic hydrogel nanospheres of magnetite and κ-carrageenan

Magnetic hydrogel kappa-carrageenan nanospheres were successfully prepared via water-in-oil (w/o) microemulsions combined with thermally induced gelation of the polysaccharide. The size of the nanospheres (an average diameter of about 50 and 75 nm) was modulated by varying the concentration of surfactant. The nanospheres contained superparamagnetic magnetite nanoparticles (average diameter 8 nm), previously prepared by co-precipitation within the biopolymer. Carboxyl groups, at a concentration of about 4 mmol g(-1), were successfully grafted at the surface of these magnetic nanospheres via carboxymethylation of the kappa-carrageenan. The carboxylated nanospheres were shown to be thermo-sensitive in the 37-45 degrees C temperature range, indicating their potential as thermally controlled delivery systems for drugs and/or magnetic particles at physiological temperatures. Finally, preliminary results have been obtained for IgG antibody conjugation of the carboxylated nanospheres and the potential of these systems for bio-applications is discussed.

Shaping Gold Nanocomposites with Tunable Optical Properties

We report the synthesis of morphological uniform composites using miniemulsions of poly(tert-butyl acrylate) or poly(styrene) containing organically capped gold nanocrystals (NCs). The optical features of such hybrid structures are dominated by plasmonic effects and depend critically on the morphology of the resulting nanocomposite. In particular, we demonstrate the ability to tune the overall optical response in the visible spectral region by varying the Au NCs arrangement within the polymer matrix, and therefore the interparticle plasmon coupling, using Au NCs resulting from the same batch of synthesis. This is a consequence of two well-known effects on the optical properties of Au particles: the variation of the surrounding dielectric refractive index and interparticle plasmonic coupling. The research reported here shows a general strategy to produce optical responsive nanocomposites via control of the morphology of submicrometric polymer particles containing metal nanocrystals and thus is an alternative to the more common strategy of size tuning metal nanoparticles used as nanofillers.

SERS study on adenine using a Ag/poly(t-butylacrylate) nanocomposite

Enhancement of Raman signals of the nucleobase adenine on an Ag based composite was studied using the 1064 nm laser line. The composite comprise emulsions of Ag nanoparticles encapsulated in poly(t-butylacrylate) (PtBA) beads that act as substrate for the Surface-Enhanced Raman Scattering (SERS) of adenine. For this system, Raman enhancement was observed for the ring-stretching vibrational mode of adenine after aggregation of the Ag/poly(t-butylacrylate) emulsion and isolation of the solid composite. This is a convenient and alternative analytical approach to SERS monitoring of solutions of adenine over the more common use of pure Ag colloids. As a consequence, this research contributes to develop innovative studies on DNA fragments using polymeric platforms that can act as highly sensitive SERS substrates.

Anti-fungal activity of SiO2/Ag2S nanocomposites against Aspergillus niger.

Submicron particles of amorphous SiO(2) have been used to grow Ag(2)S nanophases at their surfaces. SEM and TEM analysis showed morphological well-defined nanocomposite particles consisting of Ag(2)S nanocrystals dispersed over the silica surfaces. These SiO(2)/Ag(2)S nanocomposites were investigated as anti-fungal agents against Aspergillus niger in different experimental conditions, including as nanofillers in cellulosic fibres. The anti-fungal activity in these composite systems is suggested to result from a synergistic effect due to Ag(2)S anti-fungal centres and the SiO(2) surfaces in promoting the adsorption of the fungus.

A general strategy to prepare SERS active filter membranes for extraction and detection of pesticides in water

An important feature in the fabrication of surface-enhanced Raman scattering (SERS) platforms is, together with the high efficiency, to allow the rapid collection and analysis of a vestigial analyte. Conventional substrates based on rigid solid materials or metal hydrosols are not suitable for sample extraction, limiting their application in areas such as water quality monitoring. Herein, we have developed a strategy to fabricate SERS active substrates (Ag/LCP) based on liquid-crystal polymer (LCP) textile fibers decorated with Ag nanoparticles (NPs). Two distinct methods for substrate preparation envisaging the SERS detection of the pesticide thiram have been explored in this research. In a first stage, we have investigated the usefulness of both approaches using ethanolic solutions of the pesticide thiram, and after real samples spiked with thiram were used to explore the analysis in real environment. The SERS analysis of thiram dissolved in Aveiro Estuary water and in fruit juices have provided enhancement factors of 1.67 × 107 and 3.86 × 105, respectively, using the Ag/LCP composites. Noteworthy, in the latter case, the detection limit (0.024 ppm) achieved is lower than the maximal residue limit (MRL) of 5 ppm in fruit, as prescribed by European regulations (EU) 2016/1. Moreover, the selectivity of the SERS substrates for different pesticides was also evaluated, analyzing distinct pesticides such as paraquat and sodium diethyldithiocarbamate. SERS active Ag/LCP/PA filter membranes were also prepared using Ag/LCP composites supported by a polyamide (PA) filter, which can be an easy alternative to prepare simple, highly efficient and low-cost SERS active filter membranes for water analysis.

A General Route for Growing Metal Sulfides onto Graphene Oxide and Exfoliated Graphite Oxide

Graphene-based materials are elective materials for a number of technologies due to their unique properties. Also, semiconductor nanocrystals have been extensively explored due to their size-dependent properties that make them useful for several applications. By coupling both types of materials, new applications are envisaged that explore the synergistic properties in such hybrid nanostructures. This research reports a general wet chemistry method to prepare graphene oxide (GO) sheets decorated with nanophases of semiconductor metal sulfides. This method allows the in situ growth of metal sulfides onto GO by using metal dialkyldithiocarbamate complexes as single-molecule precursors. In particular, the role of GO as heterogeneous substrate for the growth of semiconductor nanocrystals was investigated by using Raman spectroscopic and imaging methods. The method was further extended to other graphene-based materials, which are easily prepared in a larger scale, such as exfoliated graphite oxide (EGO).

Novel sintering-free scaffolds obtained by additive manufacturing for concurrent bone regeneration and drug delivery: Proof of concept

Advances on the fabrication of sintering-free biphasic calcium phosphate (BCP)/natural polymer composite scaffolds using robocasting as additive manufacturing technique are presented in the present work. Inks with high amounts of BCP powders (45 vol%) containing different HA/β-TCP ratios, in presence of crosslinked polymer, were successfully fine-tuned for extrusion by robocasting. The non-existence of sintering step opened the possibility to obtain drug loaded scaffolds by adding levofloxacin to the extrudable inks. The drug presence induced slightly changes on the rheological behaviour of the inks, more emphasized for the BCP compositions with higher amounts of β-TCP, and consequently, on the microstructure and on the mechanical properties of the final scaffolds. The strong interaction of β-TCP with chitosan difficult the preparation of suitable rheological inks for printing. Drug delivery studies revealed a fast release of levofloxacin with a high burst of drug within the first 30 min. Levofloxacin loaded samples also presented bacteria growth inhibition ability, proving that antibiotic was not degraded during the fabrication process and its bactericidal efficacy was preserved. From the results obtained, the composite scaffolds containing higher amounts of HA (around 80% HA/20% β-TCP) constitute a promising bi-functional synthetic bone substitute for simultaneous local bone regeneration and infection treatments.

Hybrids Based on Graphene Oxide and Porphyrin as Tools for Detection and Stabilization of DNA G-Quadruplexes

Telomerase inhibition has been an important strategy in cancer therapies, but for which effective drugs are still required. Here, noncovalent hybrid nanoplatforms containing the tetracationic 5,10,15,20-tetrakis(1-methyl-pyridinium-4-yl)porphyrin (TMPyP) and graphene oxide (GO) were prepared for promoting telomerase inhibition through the selective detection and stabilization of DNA guanine-quadruplex (G-Q) structures. Upon binding TMPyP to the GO sheets, the typical absorption bands of porphyrin have been red-shifted and the fluorescence emission was quenched. Raman mapping was used for the first time to provide new insights into the role of the electrostatic and π–π stacking interactions in the formation of such hybrids. The selective recovery of fluorescence observed during the titration of TMPyP@GO with G-Q, resembles a selective “turn-off–on” fluorescence sensor for the detection of G-Q, paving the way for a new class of antitumor drugs.

Surface-Enhanced Raman Scattering Spectral Imaging for the Attomolar Range Detection of Crystal Violet in Contaminated Water

A series of nanocomposites based on polyamide (NL16, PA) filter membranes containing metal nanoparticles (NPs) have been prepared by filtration under reduced pressure of the metal colloids. The ensuing materials were then investigated as substrates for surface-enhanced Raman scattering (SERS) imaging studies envisaging the spectroscopic detection of vestigial organic pollutants dissolved in contaminated water. The organic dye crystal violet (CV) was used here as a model pollutant because it is a hazardous compound present in certain effluent waters. Moreover this compound is well-known for its strong SERS activity, which is clearly advantageous in the context of material development for SERS. Indeed, several preparative strategies were employed to prepare PA-based composites, and the impact on SERS detection was investigated. These include the use of chemical and morphological distinct plasmonic NPs (Ag, Au), a variable metal load and changing the order of addition of the analytical specimens. These studies demonstrate that the parameters employed in the fabrication of the SERS substrates have a strong impact on the Raman signal enhancement. The use of Raman imaging during the fabrication process allows establishing improvements that translate to better performances of the substrates in the analyte detection. The results have been interpreted by considering an integrated set of operational parameters that include the affinity of CV molecules to the substrate, amount and dispersion of NPs in the PA membranes, and the detection method. Noteworthy the use of SERS analysis assisted with Raman imaging allowed achieving a detection limit for CV as low as 100 aM in ultrapure water and 10 fM in real samples.