Supercritical CO2-assisted spray drying of strawberry-like gold-coated magnetite nanocomposites in chitosan powders for inhalation

Associate Laboratory Research Unit for Green Chemistry Clean Processes and Technologies-LAQV - (UID/QUI/50006/2013) ; UCIBIO from FCT/MEC - UID/Multi/04378/2013 ; ERDF - POCI-01-0145-FEDER-007265; FCT/MEC - SFRH/BD/51584/2011; SFRH/BPD/93982/2013 ; FCT-Lisbon - IF/00915/2014Lung cancer is one of the leading causes of death worldwide. Therefore, it is of extreme importance to develop new systems that can deliver anticancer drugs into the site of action when initiating a treatment. Recently, the use of nanotechnology and particle engineering has enabled the development of new drug delivery platforms for pulmonary delivery. In this work, POXylated strawberry-like gold-coated magnetite nanocomposites and ibuprofen (IBP) were encapsulated into a chitosan matrix using Supercritical Assisted Spray Drying (SASD). The dry powder formulations showed adequate morphology and aerodynamic performances (fine particle fraction 48%-55% and aerodynamic diameter of 2.6-2.8 μm) for deep lung deposition through the pulmonary route. Moreover, the release kinetics of IBP was also investigated showing a faster release of the drug at pH 6.8, the pH of lung cancer. POXylated strawberry-like gold-coated magnetite nanocomposites proved to have suitable sizes for cellular internalization and their fluorescent capabilities enable their future use in in vitro cell based assays. As a proof-of-concept, the reported results show that these nano-in-micro formulations could be potential drug vehicles for pulmonary administration. © 2017 by the authors.publishersversionpublishe

Synthesis and Structural Characterization of Branched Bimetallic AuPd Nanoparticles with a Highly Tunable Optical Response

Bimetallic nanostructures composed of gold (Au) and palladium (Pd) have garnered increased interest for their applications in heterogeneous catalysis. This study reports a simple strategy for manufacturing Au@Pd bimetallic branched nanoparticles (NPs), which offer a tunable optical response, using polyallylamine-stabilized branched AuNPs as template cores for Pd overgrowth. The palladium content can be altered by manipulating the concentration of PdCl4 2− and ascorbic acid (AA) that are injected, which permit an overgrowth of the Pd shell up to ca. 2 nm thick. The homogeneous distribution of Pd at the surfaces of Au NPs can be carried out regardless of their size or branching degree, which allows for an adjustment of the plasmon response in the near-infrared (NIR) spectral range. As a proof of concept, the nanoenzymatic activity of pure gold and gold−palladium NPs was compared, exploring their peroxidase-like activity in the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). The bimetallic AuPd NPs demonstrate an increase in the catalytic properties attributed to the presence of palladium at the surface of gold

Synthesis of gold functionalised nanoparticles with the eranthis hyemalis lectin and preliminary toxicological studies on caenorhabditis elegans

The lectin found in the tubers of the Winter Aconite (Eranthis hyemalis) plant (EHL) is a Type II Ribosome Inactivating Protein (RIP). Type II RIPs have shown anti-cancer properties and have great potential as therapeutic agents. Similarly, colloidal gold nanoparticles are successfully used in biomedical applications as they can be functionalised with ligands with high affinity and specificity for target cells to create therapeutic and imaging agents. Here we present the synthesis and characterization of gold nanoparticles conjugated with EHL and the results of a set of initial assays to establish whether the biological effect of EHL is altered by the conjugation. Gold nanoparticles functionalised with EHL (AuNPs@EHL) were successfully synthesised by bioconjugation with citrate gold nanoparticles (AuNPs@Citrate). The conjugates were analysed by UV-Vis spectroscopy, Dynamic Light Scattering (DLS), Zeta Potential analysis, and Transmission Electron Microscopy (TEM). Results indicate that an optimal functionalisation was achieved with the addition of 100 µL of EHL (concentration 1090 ± 40 µg/mL) over 5 mL of AuNPs (concentration [Au0] = 0.8 mM). Biological assays on the effect of AuNPs@EHL were undertaken on Caenorhabditis elegans, a free-living nematode commonly used for toxicological studies, that has previously been shown to be strongly affected by EHL. Citrate gold nanoparticles did not have any obvious effect on the nematodes. For first larval stage (L1) nematodes, AuNPs@EHL showed a lower biological effect than EHL. For L4 stage, pre-adult nematodes, both EHL alone and AuNPs@EHL delayed the onset of reproduction and reduced fecundity. These assays indicate that EHL can be conjugated to gold nanoparticles and retain elements of biocidal activity

Enhancing the teaching-research nexus in the undergraduate curriculum through assessment

Successful linkages between teaching and research in the undergraduate curriculum are strongly dependent on academics’ ability to encourage and facilitate an inquiry based approach to learning. An assessment strategy in which students become active participants in the assessment process is crucial to facilitate the development of this inquiry based approach. Developing this so-called research-mindedness is central to helping students' to become independent learners and to be more effective professionals in their future careers. This paper describes a distributed systems approach to assessment implemented in the undergraduate module Molecular Biology. The assessment comprised a series of sequence identification, database use and analysis steps, with each student being given a different starting gene. In combination, the students analysed an entire genetic pathway. This approach allows the assignments generated to be combined and used to address a single larger question, which can be either teaching or research based. This is then fed back into the teaching. This direct link between the assessment outcomes and the learning process increases student engagement with the subject and sense of ownership of the work carried out. This approach to assessment, in which students undertake a small part of a larger task, is ideal for various technical, skills-based, assignments, such as those central to the many types of bioinformatics analyses. However, it can be adapted to various types of meta-review. The paper discusses the details for the implementation, as well as the benefits and potential pitfalls of the approach

Intramolecular excimer formation and sensing behavior of new fluorimetric probes and their interactions with metal cations and barbituric acids

A new family of compounds able to promote host-guest interactions with specific molecules (e.g., cyanuric and parabanic acids) and to coordinate metal ions, namely Zn(II) and Cu(II), has been synthesized and fully characterized. The new probes derive from the attachment of two methylaminopyrene units to the carbonyl precursor 2,6-bis(2-formylphenoxymethyl)pyridine.http://www.sciencedirect.com/science/article/B6THH-4HF5KD3-1/1/ef66847d1e019d05e2068bef93cfbd9

Long Range Electron Transfer Quenching in Polyamine Chains Bearing a Terminal Naphthalene Unit

The fluorescence emission of a naphthalene unit attached to a polyamine chain is quenched by intramolecular electron transfer from the deprotonated amines to the excited fluorophore. Measurements of the respective quenching rate constants as a function of the distance, reveal an exponential dependence with β = 0.45 Å-1. Identical measurements carried out in deuterated water have shown a similar dependence with the distance β = 0.49 Å-1 but an average reduction of the absolute values of the rate constants of ca. 1.2. The polyamine chains seem to constitute a bridge through which the electron can find a route to its movement, more efficiently than through space

Atomic scale model and electronic structure of Cu2_2O/CH3_3NH3_3PbI3_3 interfaces in perovskite solar cells

Cuprous oxide has been conceived as a potential alternative to traditional organic hole transport layers in hybrid halide perovskite-based solar cells. Device simulations predict record efficiencies using this semiconductor, but experimental results do not yet show this trend. More detailed knowledge about the Cu$_2$O/perovskite interface is mandatory to improve the photoconversion efficiency. Using density functional theory calculations, here we study the interfaces of CH$_3$NH$_3$PbI$_3$ with Cu$_2$O to assess their influence on device performance. Several atomistic models of these interfaces are provided for the first time, considering different compositions of the interface atomic planes. The interface electronic properties are discussed on the basis of the optimal theoretical situation, but in connection with the experimental realizations and device simulations. It is shown that the formation of vacancies in the Cu$_2$O terminating planes is essential to eliminate dangling bonds and trap states. The four interface models that fulfill this condition present a band alignment favorable for photovoltaic conversion. Energy of adhesion, and charge transfer across the interfaces are also studied. The termination of CH$_3$NH$_3$PbI$_3$ in PbI$_2$ atomic planes seems optimal to maximize the photoconversion efficiency.Comment: 16 pages; 8 figures. Submitted to ACS Applied Materials & Interfaces. Published after changes not included her

Ultrasonic energy for proteomics: when, where and how

Comunicaciones a congreso

Effects of N-starvation and C-source on Bradyrhizobium japonicum exopolysaccharide production and composition, and bacterial infectivity to soybean roots

The exopolysaccharide (EPS) is an extracellular molecule that in Bradyrhizobium japonicum affects bacterial efficiency to nodulate soybean. Culture conditions such as N availability, type of C-source, or culture age can modify the amount and composition of EPS. To better understand the relationship among these conditions for EPS production, we analyzed their influence on EPS in B. japonicum USDA 110 and its derived mutant ΔP22. This mutant has a deletion including the 3′ region of exoP, exoT, and the 5′ region of exoB, and produces a shorter EPS devoid of galactose. The studies were carried out in minimal media with the N-source at starving or sufficient levels, and mannitol or malate as the only C-source. Under N-starvation there was a net EPS accumulation, the levels being similar in the wild type and the mutant with malate as the C-source. By contrast, the amount of EPS diminished in N-sufficient conditions, being poyhydroxybutyrate accumulated with culture age. Hexoses composition was the same in both N-situations, either with mannitol or malate as the only C-source, in contrast to previous observations made with different strains. This result suggests that the change in EPS composition in response to the environment is not general in B. japonicum. The wild type EPS composition was 1 glucose:0.5 galactose:0.5 galacturonic acid:0.17 mannose. In ΔP22 the EPS had no galactose but had galacturonic acid, thus indicating that it was not produced from oxidation of UDP-galactose. Infectivity was lower in ΔP22 than in USDA 110. When the mutant infectivity was compared between N-starved or N-sufficient cultures, the N-starved were not less infective, despite the fact that the amounts of altered EPS produced by this mutant under N-starvation were higher than in N-sufficiency. Since this altered EPS does not bind soybean lectin, the interaction of EPS with this protein was not involved in increasing ΔP22 infectivity under N-starvation.Instituto de Biotecnología y Biología Molecula