Krings, B.
2009.
{Global restructuring and its effects on occupations: towards a new division of labor?}, Dec , Number 12/2009: Universidade Nova de Lisboa, IET/CICS.NOVA-Interdisciplinary Centre on Social Sciences, Faculty of Science and Technology
AbstractThe following contribution considers whether global restructuring creates new forms of the division of labor. On the basis of empirical data from a comparative project in 14 European countries, the author supports the hypothesis that in addition to the ongoing process of the internationalization of work, there are ‘hidden’ effects at the local level. From the perspective of three occupational clusters, dynamics can be observed which have differing impacts on the occupational groups. Thus, there is a simultaneous process of restructuring and redefining skills, labor processes and the working organization which forms the daily reality of working men and women.
Baptista, {PV}.
2009.
Cancer nanotechnology - Prospects for cancer diagnostics and therapy, aug. Current Cancer Therapy Reviews. 5:80–88., Number 2: Bentham Science Publishers
AbstractNanotechnology is a multidisciplinary field that brings together diverse fields of research and development such as engineering, biology, physics and chemistry. Formal definitions of nanotechnology refer to man-made devices, components and structures in the 1-100 nm range in at least one dimension. Advances in nanoscience are having a significant impact on many scientific fields, boosting the development of a variety of important technologies. Nanotechnology offers an unprecedented opportunity to interact with cancer cells in real time at the molecular and cellular scale. Because of their small size, nanoscale devices can readily interact with biomolecules on both the surface of cells and inside of cells. The concerted development of nanoscale devices, structures and components have provided essential breakthroughs in monitoring and fighting cancer at the earliest stages of the cancer process. Nanotechnology offers a wealth of tools that may provide researchers with new and innovative ways to diagnose and treat cancer - new imaging agents; systems for real-time assessments of therapeutic and surgical efficacy; multifunctional, targeted devices capable of bypassing biological barriers to deliver multiple therapeutic agents directly to cancer cells and tissues that play a critical role in cancer growth and metastasis; agents that can monitor predictive molecular changes allowing for preventive action against precancerous cells becoming malignant; minimizing costs for multiplex analysis. Nanotechnology, if properly integrated with conventional cancer research, may provide extraordinary prospects towards better diagnosis and effective therapy.
Giestas, L, Petrov V, Baptista {PV}, Lima {JC}.
2009.
General FRET-based coding for application in multiplexing methods, aug. Photochemical & Photobiological Sciences. 8:1130–1138., Number 8: Springer
AbstractFRET can be used as a strategy to assign different simultaneous events in the same sample but {"}cross-talk{"} problems are a limitation. Here we present a contribution for the better understanding of the {"}cross-talk{"} in FRET experiments that include several pairs in the same sample. Using oligonucleotide probes labeled with fluorescent dyes which can be selectively excited at a specific wavelength, and using target oligonucleotides tagged with a fluorescent dye with specific characteristics that allow only it to emit light upon selective excitation of a specific probe by energy transfer (FRET), we aim to identify the exact probe-target hybridized pair. When using three donors to probe the presence of complementary targets, only 20% of possible donor/acceptor combinations give straightforward signals readily identifiable with the sample composition, while in the remaining cases severe cross-excitation prevents the direct identification of the sample composition. To correctly resolve the samples identity, we developed a theoretical model that enables the unequivocal attribution of a sample composition to a given set of fluorescence signals, in the presence of three donors.
Conrath, K, Pereira AS, Martins CE, Timoteo CG, Tavares P, Spinelli S, Kinne J, Flaudrops C, Cambillau C, Muyldermans S, Moura I, Moura JJG, Tegoni M, Desmyter A.
2009.
Camelid nanobodies raised against an integral membrane enzyme, nitric oxide reductase, Apr. PROTEIN SCIENCE. {18}:{619-628}., Number {3}
AbstractNitric Oxide Reductase (NOR) is an integral membrane protein performing the reduction of NO to N(2)O. NOR is composed of two subunits: the large one (NorB) is a bundle of 12 transmembrane helices (TMH). It contains a b type heme and a binuclear iron site, which is believed to be the catalytic site, comprising a heme b and a non-hemic iron. The small subunit (NorC) harbors a cytochrome c and is attached to the membrane through a unique TMH. With the aim to perform structural and functional studies of NOR, we have immunized dromedaries with NOR and produced several antibody fragments of the heavy chain (VHHs, also known as nanobodies (TM)). These fragments have been used to develop a faster NOR purification procedure, to proceed to crystallization assays and to analyze the electron transfer of electron donors. BIAcore experiments have revealed that up to three VHHs can bind concomitantly to NOR with affinities in the nanomolar range. This is the first example of the use of VHHs with an integral membrane protein. Our results indicate that VHHs are able to recognize with high affinity distinct epitopes on this class of proteins, and can be used as versatile and valuable tool for purification, functional study and crystallization of integral membrane proteins.
Pina, AS, Roque ACA.
2009.
Studies on the molecular recognition between bioactive peptides and angiotensin-converting enzyme, apr. Journal of Molecular Recognition. 22:162–168., Number 2
AbstractHigh blood pressure or hypertension is a condition affecting many individuals and represents a controllable risk factor for cardiovascular diseases such as coronary heart disease and stroke. A non-pharmacological approach to manage these includes the application of food components with antihypertensive activity. Milk protein-derived peptides have been exploited as natural hypotensive agents, namely the peptides {Val-Pro-Pro} {(VPP)} and {Ile-Pro-Pro} {(IPP)}, already commercialized in functional foods as a potential alternative to synthetic drugs. These bioactive peptides inhibit in vitro and in vivo the Angiotensin I-converting enzyme {(ACE)}, a protein with an important role in blood pressure regulation. In this work, we attempted to elucidate the possible mode of interaction between the peptides and {ACE}, including mechanisms of binding to the cofactor Zn2+, and further contrast this with the known mode of inhibition exerted by synthetic drugs {(Captopril}, Enalaprilat and Lisinopril). The bioactive peptide {Ala-Leu-Pro-Met-His-Ile-Arg} {(ALPMHIR)}, also known to inhibit the enzyme {ACE} but with a lower efficiency than {VPP} and {IPP}, was utilized in the docking studies for comparison. It was observed that the best docking poses obtained for {VPP} and {IPP} were located at the {ACE} catalytic site with very high resemblance to the drugs mode of interaction, including the coordination with Zn2+. As for {ALPMHIR}, the best docking poses were located in the narrow {ACE} channel outside the catalytic site, representing higher affinity energies and fewer resemblances with the interaction established by drugs.
Pinheiro, C, Parola AJ, Pina F, Laia CAT.
2009.
Electrochromism of Crystal Violet Lactone in the presence of Fe(III)/Fe(II) redox pair, 2009. Electrochimica Acta. 54:5593-5597.
AbstractSelective interaction between Crystal Violet Lactone and Fe(3+)/Fe(2+) in methanol leads to a reversible ionochromic colour change. This interaction can be controlled electrochemically, in order to achieve reversible colour changes with high contrast between colourless and dark blue solutions. The presented system is proposed as an alternative electrochromic solution. (C) 2009 Elsevier Ltd. All rights reserved.
Petrov, V, Gomes R, Parola AJ, Pina F.
2009.
Flash photolysis and stopped flow studies of the 2'-methoxyflavylium network in aq. acidic and alkaline solution, 2009. Dyes and Pigments. 80:149-155.
AbstractThe rate and equilibrium constants of the network of chemical species involving the dye 2'-methoxyflavylium tetrafluoroborate were characterized using stopped flow and flash photolysis in both acidic and alkaline aqueous solution. The trans-chalcone is the thermodynamic stable species in acidic solutions 2 < pH < 7; irradiation of trans-chalcone at low pH leads to the corresponding coloured flavylium cation. The system reverts to its initial state in a few hours, in the dark. The kinetics of the various steps in the system were determined; flash photolysis revealed that the rate determining process of flavylium formation is the ring closure to give the corresponding hemiketal. In alkaline medium the ionized transchalcone is the stable form and clear evidence for the existence of a hemiketal species was obtained. A write-read-erase cycle can be performed with this compound. (c) 2008 Elsevier Ltd. All rights reserved.
Gomes, R, Parola AJ, Bastkowski F, Polkowska J, Klarner FG.
2009.
Host-Guest Interactions between Molecular Clips and Multistate Systems Based on Flavylium Salts, 2009. Journal of the American Chemical Society. 131:8922-8938.
AbstractFlavylium salts contain the basic structure and show a pH-dependent sequence of reactions identical to natural anthocyanins, which are responsible for most of the red and blue colors of flowers and fruits. In this work we investigated the effect of the water-soluble molecular clips C1 and C2 substituted by hydrogen phosphate or sulfate groups on the stability and reactions of the flavylium salts 1-4 by the use of UV-vis absorption, fluorescence, and NMR spectroscopy as well as of the time-resolved pH jump and flash photolysis methods. Clip C1 forms highly stable host-guest complexes with the flavylium salts 1 and 2 and the quinoidal base 3A in methanol. The binding constants were determined by fluorometric titration to be log K = 4.1, 4.7, and 5.6, respectively. Large complexation-induced (1)H NMR shifts of guest signals, Delta delta(max), indicate that in the case of the flavylium salts 1 and 2 the pyrylium ring and in the case of the quinoidal base 3A the o-hydroxyquinone ring are preferentially bound inside the clip cavity. Due to the poor solubility of these host-guest complexes in water, the association constants could be only determined in highly diluted aqueous solution by UV-vis titration experiments for the complex formation of clip C1 with the flavylium salt 3AH(+) at pH = 2 and the quinoidal base 3A at pH = 5.3 to be log K = 4.9 for both complexes. Similar results were obtained for the formation of the complexes of the sulfate-substituted clip C2 with flavylium salt 4AH(+) and its quinoidal base 4A which are slightly better soluble in water (log K = 4.3 and 4.0, respectively). According to the kinetic analysis (performed by using the methods mentioned above) the thermally induced trans-cis chalcone isomerization (4Ct -> 4Cc) and the H(2)O addition to flavylium cation 4AH(+) followed by H(+) elimination leading to hemiketal 4B are both retarded in the presence of clip C2, whereas the photochemically induced trans-cis isomerization (4Ct -> 4Cc) is not affected by clip C2. The results presented here are explained with dominating hydrophobic interactions between the molecular clips and the flavylium guest molecules. The other potential interactions (ion-ion, cation-pi, pi-pi, and CH-pi), which certainly determine the structures of these host-guest complexes to a large extent, seem to be of minor importance for their stability.
Pinheiro, C, Parola AJ, Laia CAT, Camara A, Pina F.
2009.
Multiresponsive chromogenic systems operated by light and electrical inputs, 2009. New Journal of Chemistry. 33:2144-2147.
AbstractIn the framework of supramolecular chemistry, a three component system constituted by Fe(3+)/Fe(2+), crystal violet lactone (CVL) and a spiropyran (SPI) leads to three coloured states, cyan, magenta and yellow, as well as a transparent state, each independently addressable by light and electrical input. The system profits from fine speciation Fe(3+)/Fe(2+) complexes with CVL and SPI. Redox stimulus operates the metal, leading to different coloured complexes (ionochromism), while light stimulus operates the SPI component (photochromism).
Diniz, AM, Gomes R, Parola AJ, Laia CAT, Pina F.
2009.
Photochemistry of 7-Hydroxy-2-(4-hydroxystyryl)-1-benzopyrylium and Related Compounds, 2009. Journal of Physical Chemistry B. 113:719-727.
Abstract2-Styryl-1-benzopyrylium derivatives exhibit deeper hues and absorption spectra that are substantially red-shifted when compared with their 2-phenyl-1-benzopyrylium analogues. They follow the same pH and light-dependent network of chemical reactions previously described for 2-phenyl-1-benzopyrylium compounds. In this work, the photochromic properties of 7-hydroxy-2-(4-hydroxystyryl)-1-benzopyrylium chloride are reported. This compound was fully characterized by UV-vis absorption, fluorescence emission, pH jumps, and flash photolysis, and its properties were compared with the analogue 7,4'-dihydroxyflavylium (7-hydroxy-2-(4-hydroxyphenyl)-1- benzopyrylium). The trans-chalcones of both compounds lacking the hydroxyl in position 2 were synthesized and used as model compounds since they exhibit cis-trans isomerization but cannot be involved in the other processes resulting from the ring closure. The transient absorption of two triplets attributed to the chalcones Ct/Ct(-), and a tautomer was detected by nanosecond flash photolysis, independent of the existence of the 2-hydroxyl substituent. The experimental results are compatible with the main formation of cis-chalcone from the singlet state. In the case of the styryl derivatives, the fraction of triplet formed from excitation of Ct is much higher, and the fraction of isomerization is much smaller. For this reason, the photochemistry of 7-hydroxy-2-(4-hydroxystyryl)-1-benzopyrylium in water is much less efficient than that of its parent 7,4'-dihydroxyflavylium; however, in the presence of CTAB micelles, intense red colors can be obtained upon irradiation, confirming the usefulness of this family of compounds as photochromic systems.