Manuel A. Martins

Optical Fiber Sensing Using Quantum Dots.

Recent advances in the application of semiconductor nanocrystals, or quantum dots, as biochemical sensors are reviewed. Quantum dots have unique optical properties that make them promising alternatives to traditional dyes in many luminescence based bioanalytical techniques. An overview of the more relevant progresses in the application of quantum dots as biochemical probes is addressed. Special focus will be given to configurations where the sensing dots are incorporated in solid membranes and immobilized in optical fibers or planar waveguide platforms.

Mesoporous Silicas Modified with Dioxomolybdenum(VI) Complexes: Synthesis and Catalysis

The dioxomolybdenum(VI) fragment MoO2X2 has been confined within the ordered mesopores of pure siliceous hexagonal MCM-41 and cubic MCM-48 molecular sieves either by direct grafting (solvent impregnation) with MoO2X2(THF)2 or by using a spacer ligand [L = NC(CH2)2Si(OEt)3]. The materials have been characterised by elemental analysis, powder X-ray diffraction, N2 adsorption, IR spectroscopy, and magic-angle spinning NMR spectroscopy (13C, 29Si). All catalysts, homogeneous and heterogenised, are active in the epoxidation of cyclooctene with tert-butyl hydroperoxide.

Mannosylated dextran derivatives labeled with fac-[M(CO)₃]+ (M = (99m)Tc, Re) for specific targeting of sentinel lymph node.

Despite being widely used in the clinical setting for sentinel lymph node detection (SLND), (99m)Tc-based colloids (e.g., (99m)Tc-human serum albumin colloids) present a set of properties that are far from ideal. Aiming to design novel compounds with improved biological properties, we describe herein the first class of fully characterized (99m)Tc(CO)₃-mannosylated dextran derivatives with adequate features for SLND. Dextran derivatives, containing the same number of pendant mannose units (13) and a variable number (n) of tridentate chelators (9, n = 1; 10, n = 4, 11, n= 12), have been synthesized and fully characterized. Radiolabeled polymers of the type fac-[(99m)Tc(CO)₃(k³-L)] (12, L = 9, 13, L = 10, 14, L = 11) have been obtained quantitatively in high radiochemical purity (≥ 98%) upon reaction of the dextran derivatives with fac-[(99m)Tc(CO)₃(H₂O)₃]+. The highly stable compounds 13 and 14 were identified by comparing their HPLC chromatograms with the ones obtained for the corresponding rhenium surrogates fac-[Re(CO)₃(k³-10)] (13a) and fac-[Re(CO)₃(k³-11)] (14a), which have been characterized both at the chemical (NMR and IR spectroscopy, and HPLC) and physical level (DLS, AFM and LDV). Compounds 13a and 14a present a positive zeta potential (+ 7.1 mV, pH 7.4) and a hydrodynamic diameter in the range 8.4-8.7 nm. Scintigraphic imaging and biodistribution studies in Wistar rats have shown good accumulation in the sentinel node at 60 min postinjection (6.71 ± 2.35%, 13; and 7.53 ± 0.69%, 14), with significant retention up to 180 min. A clear delineation of the sentinel lymph node without significant washout to other regions was observed in the scintigraphic images. The popliteal extraction of 94.47 ± 2.45% for 14 at 1 h postinjection, as compared to 61.81 ± 2.4% for 13, indicated that 14 is a very promising compound to be further explored as SLN imaging agent.

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.

Biofunctionalized ferromagnetic CoPt3/polymer nanocomposites

Magnetic latexes were prepared by the encapsulation of organically capped CoPt3 nanoparticles via miniemulsion in situ radical polymerization of tert-butyl acrylate (tBA). This is the first example of a CoPt3 based polymer nanocomposite showing ferromagnetic behaviour at room temperature. Each nanocomposite particle contains a magnetic core composed of CoPt3 nanoparticles (d~7 nm, a0 = 3.848 A) encapsulated by poly(t-butyl acrylate). The CoPt3/PtBA latexes contain polyester groups that can be readily hydrolysed, rendering the surface with carboxylic functionalities and hence allowing bioconjugation. Complementary to such surface modification experiments, we report that bovine IgG antibodies can bind to the magnetic latexes, and the potential of the nanocomposites for in vitro specific bioapplications is discussed.

Timesaving microwave assisted synthesis of insulin amyloid fibrils with enhanced nanofiber aspect ratio.

Insulin amyloid fibrils with enhanced aspect ratio, were prepared using a timesaving microwave assisted (MW) methodology, reducing the incubation time from 13 to 2h. The fibrillation process was followed indirectly by Thioflavin T Fluorescence and UV-vis analysis, by measuring the amount of β-sheets formed and the insulin present in solution, respectively. TEM and AFM analysis revealed that the insulin fibrils obtained through the MW method, have very similar lengths but are much thinner than the ones obtained using the conventional method (CM). Additionally, it was verified that the nature of the peptides present in the final insulin fibrils was not affected by microwave irradiation. These morphological differences might reflect on noticeably enhanced mechanical and optical properties that can exploited on the development of advanced bionanomaterials.

Os nanomateriais e a descoberta de novos mundos na bancada do químico

In recent years there has been great progress in the field of nanotechnology largely driven by research into nanomaterials. Chemistry appears in this context for its relevant role in the synthesis and surface modification of nanomaterials. This review article discusses fundamental concepts related to the synthesis and properties of inorganic nanoparticles with diverse properties. Aspects related to unique size dependent optical and magnetic properties are discussed and the chemistry involved in the preparation of nanomaterials reviewed. Fundamental aspects of the chemical modification of nanoparticles envisaging potential applications for these materials are also addressed.

Neutron diffraction and magnetism of CoO antiferromagnetic nanoparticles

We report a study on neutron diffraction and magnetic properties ol cobalt oxide CoO antiferromagnetic nanoparticles with different sizes. The nanoparticles are composed by a structurally and magnetically ordered core and a structurally ordered and magnetically disordered shell with a thickness of about 2 nm. The ordered core has cell parameters, moments direction and modulus similar to those of bulk CoO. Small differences found are attributed to an increase of the oxidation of the nanoparticles with the decrease of size. A remanent moment Mr can be induced in CoO nanoparticles by crossing the transition temperature in the presence of a magnetic field, while the magnetic structure of the antiferromagnetically ordered moments of the nanoparticles core remains unchanged after field cooling within the experimental precision, suggesting that Mr arises in the magnetically disordered shell.

Refinement by interpretation in Pi-institutions

The paper discusses the role of interpretations, understood as multifunctions that preserve and reflect logical consequence, as refinement witnesses in the general setting of pi-institutions. This leads to a smooth generalization of the refinement-by-interpretation approach, recently introduced by the authors in more specific contexts. As a second, yet related contribution a basis is provided to build up a refinement calculus of structured specifications in and across arbitrary pi-institutions.

Bisimilarity and refinement for hybrid(ised) logics

The complexity of modern software systems entails the need for reconfiguration mechanisms governing the dynamic evolution of their execution configurations in response to both external stimulus or internal performance measures. Formally, such systems may be represented by transition systems whose nodes correspond to the different configurations they may assume. Therefore, each node is endowed with, for example, an algebra, or a first-order structure, to precisely characterise the semantics of the services provided in the corresponding configuration. Hybrid logics, which add to the modal description of transition structures the ability to refer to specific states, offer a generic framework to approach the specification and design of this sort of systems. Therefore, the quest for suitable notions of equivalence and refinement between models of hybrid logic specifications becomes fundamental to any design discipline adopting this perspective. This paper contributes to this effort from a distinctive point of view: instead of focussing on a specific hybrid logic, the paper introduces notions of bisimilarity and refinement for hybridised logics, i.e. standard specification logics (e.g. propositional, equational, fuzzy, etc) to which modal and hybrid features were added in a systematic way.