π-Cation interactions as the origin of the weak absorption at 532 nm observed in tryptophan-containing polypeptides

We have previously reported that bovine serum albumin (BSA) and other proteins that do not contain prosthetic groups exhibited a weak light absorption in the visible, only detectable by pulsed laser-induced optoacoustic spectroscopy (LIOAS). Human serum albumin (HSA) exhibited signals 25% higher than those observed with BSA. Signals comparable to those obtained with BSA were observed with poly(L-Trp, L-Lys), poly(L-Trp, L-Arg) or poly(L-Trp, L-Orn) at pH 7.0. No signals were obtained when tryptophan was replaced by other amino acids or when free tryptophan or the tripeptide Lys-Trp-Lys was assayed ( pH 7.0). Tryptophan in HCl 5 N produced LIOAS signals similar to those produced by tryptophan-containing copolymers. Moreover, the absorption peak could be observed in a UV-VIS spectrophotometer. Therefore, the LIOAS signals obtained with BSA, HSA, and tryptophan-containing random copolymers may be attributed to a new transition of the indole moiety of their tryptophan residues when “protonated”. Tryptophan residues of proteins are known to participate in π-cation interactions, which are important in protein stability and function. As a matter of fact, HSA and BSA contain an internal tryptophan in close proximity to lysine and arginine residues and therefore suitable for π-cation interactions. The strength of this type of interaction strongly depends on distances and relative orientations of both amino acid residues. Accordingly, these interactions should be highly sensitive to conformational changes. Based on preliminary results that have shown that LIOAS signal at 532 nm depended on the aggregation state of BSA and/or on the oxidation state of its Cys-34, we postulate that the LIOAS signal observed with proteins and tryptophan-containing polypeptides are related to Trp-Lys or Trp-Arg interactions and that the intensity of the signal depends on the strength of such interactions.Fil: Roveri, Oscar Angel. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; ArgentinaFil: Braslavsky, S. E.. Max-Planck-Institute for Bioinorganic Chemistry; Alemani

Damage diagnostic technique combining machine learning approach with a sensor swarm

A Model-free approach is particularly valuable for Structural Health Monitoring because real structures are often too complex to be modelled accurately, requiring anyhow a large quantity of sensor data to be processed. In this context, this paper presents a machine learning technique that analyses data acquired by swarm of a sensor. The proposed algorithm uses unsupervised learning and is based on the use principal component analysis and symbolic data analysis: PCA extracts features from the acquired data and use them as a template for clustering. The algorithm is tested with numerical experiments. A truss bridge is modelled by a finite element model, and structural response is produced in healthy and several damaged scenarios. The present research shows also the importance of considering a sufficient number of measurements points along the structure, i.e. the swarm of sensors. This technology, which nowadays is easily attainable with the application of optical Fiber Bragg Grating strain sensors. The difficulties related to the early stage damage detection in complex structures can be skipped, especially when ambient, narrow band, moving loads are considered, enhancing the prediction capabilities of the proposed algorithm

Are fluid inclusions in gypsum reliable paleoenvironmental indicators? An assessment of the evidence from the Messinian evaporites

The paleosalinity of water from which the gypsum precipitated during the Messinian salinity crisis is a controversial issue. Recent microthermometry studies on primary fluid inclusions in gypsum provided very low salinity values not compatible with precipitation from seawater, and suggested strong mixing between seawater and nonmarine waters enriched in calcium sulfate. We applied a new microthermometric protocol on gypsum crystals from nine Mediterranean sections that were experimentally stretched to measure a larger population of fluid inclusions. The results show salinities ranging from 9 to 238 wt‰ NaCl equivalent, largely falling within the evaporation path of normal seawater. The data from previous studies were obtained mostly from those fluid inclusions capable of nucleating a stable bubble after a weak stretching, which probably correspond to those having a lower salinity acquired through post-depositional crack-and-seal processes. Our data suggest instead that the primary gypsum precipitated from a marine brine, later modified by post-trapping processes during tectonics and exhumation

Formal methods for industrial critical systems, preface to the special section

[EN] This special issue contains improved versions of selected papers from the workshops on Formal Methods for Industrial Critical Systems (FMICS) held in Eindhoven, The Netherlands, in November 2009 and in Antwerp, Belgium, in September 2010. These were, respectively, the 14th and 15th of a series of international workshops organized by an open working group supported by ERCIM (European Research Consortium for Informatics and Mathematics) that promotes research in all aspects of formal methods (see details in http://www.inrialpes.fr/vasy/fmics/). The FMICS workshops that have produced this special issue considered papers describing original, previously unpublished research and not simultaneously submitted for publication elsewhere, and dealing with the following themes: Design, specification, code generation and testing based on formal methods. Methods, techniques and tools to support automated analysis, certification, debugging, learning, optimization and transformation of complex, distributed, real-time and embedded systems. Verification and validation methods that address shortcomings of existing methods with respect to their industrial applicability (e.g., scalability and usability issues). Tools for the development of formal design descriptions. Case studies and experience reports on industrial applications of formal methods, focusing on lessons learned or new research directions. Impact and costs of the adoption of formal methods. Application of formal methods in standardization and industrial forums. The selected papers are the result of several evaluation steps. In response to the call for papers, FMICS 2009 received 24 papers and FMICS 2010 received 33 papers, with 10 and 14 accepted, respectively, which were published by Springer- Verlag in the series Lecture Notes in Computer Science (volumes 5825 [1] and 6371 [2]). Each paper was reviewed by at least three anonymous referees which provided full written evaluations. After the workshops, the authors of 10 papers were invited to submit extended journal versions to this special issue. These papers passed two review phases, and finally 7 were accepted to be included in the journal.his work has been partially supported by the EU (FEDER) and the Spanish MEC TIN2010-21062-C02-02 project, MICINN INNCORPORA-PTQ program, and by Generalitat Valenciana, ref. PROMETEO2011/052.Alpuente Frasnedo, M.; Joubert ., C.; Kowalewski, S.; Roveri, M. (2013). Formal methods for industrial critical systems, preface to the special section. Science of Computer Programming. 78(7):775-777. doi:10.1016/j.scico.2012.05.005S77577778

Damping control of polodes, inertia and natural frequencies: Theory and application to automotive suspensions

This paper shows how tunable dampers can help control the instant centre of rotation of a 2D rigid body and its polode in planar motion, which in turn implies that the inertia tensor can also be controlled. For mechanisms equipped with some elasticity the results show that damping can also control their natural frequencies. The foundation of a general theory to control the polode is presented, exploring the chance of an optimal control formulation of the problem via a variational control principle, approached by the LQR (Linear Quadratic Regulator) method, after a suitable linearization. Application to automotive suspension linkages is presented that demonstrates the control of the instant roll centre and axis and consequently its instant roll vibration frequency to optimize the response, when excited by lateral inertia forces

OPTYRE—Real time estimation of rolling resistance for intelligent tyres

The study of the rolling tyre is a problem framed in the general context of nonlinear elasticity. The dynamics of the related phenomena is still an open topic, even though few examples and models of tyres can be found in the technical literature. The interest in the dissipation effects associated with the rolling motion is justified by their importance in fuel-saving and in the context of an eco-friendly design. However, a general lack of knowledge characterizes the phenomenon, since not even direct experience on the rolling tyre can reveal the insights of the correlated different dissipation effects, as the friction between the rubber and the road, the contact kinematics and dynamics, the tyre hysteretic behaviour and the grip. A new technology, based on fibre Bragg grating strain sensors and conceived within the OPTYRE project, is illustrated for the specific investigation of the tyre dissipation related phenomena. The remarkable power of this wireless optical system stands in the chance of directly accessing the behaviour of the inner tyre in terms of stresses when a real-condition-rolling is experimentally observed. The ad hoc developed tyre model has allowed the identification of the instant grip conditions, of the area of the contact patch and allows the estimation of the instant dissipated power, which is the focus of this paper

Expression of a catalytically inactive mutant form of glutathione peroxidase 4 (Gpx4) confers a dominant-negative effect in male fertility.

The selenoenzyme Gpx4 is essential for early embryogenesis and cell viability for its unique function to prevent phospholipid oxidation. Recently, the cytosolic form of Gpx4 was identified as an upstream regulator of a novel form of non-apoptotic cell death, called ferroptosis, whereas the mitochondrial isoform of Gpx4 (mGpx4) was previously shown to be crucial for male fertility. Here, we generated and analyzed mice with targeted mutation of the active site selenocysteine (Sec) of Gpx4 (Gpx4_U46S). Mice homozygous for Gpx4_U46S died at the same embryonic stage (E7.5) as Gpx4-/- embryos as expected. Surprisingly, male mice heterozygous for Gpx4_U46S presented subfertility. Subfertility was manifested in a reduced number of litters from heterozygous breedings and an impairment of spermatozoa to fertilize oocytes in vitro. Morphologically, sperm isolated from heterozygous Gpx4_U46S mice revealed many structural abnormalities particularly in the spermatozoan midpiece due to improper oxidation and polymerization of sperm capsular proteins and malformation of the mitochondrial capsule surrounding and stabilizing sperm mitochondria. These findings are reminiscent of sperm isolated from selenium-deprived rodents or from mice specifically lacking mGpx4. Due to a strongly facilitated incorporation of Ser in the polypeptide chain as compared to Sec at the UGA codon, expression of the catalytically inactive Gpx4_U46S was found to be strongly increased. Since the stability of the mitochondrial capsule of mature spermatozoa depends on the moonlighting function of Gpx4 both as an enzyme oxidizing capsular protein thiols and being a structural protein, tightly controlled expression of functional Gpx4 emerges being key for full male fertility

Protein crystallization on nucleating surfaces inspired by biomineralization

n/

Remarks on the Messinian evaporites of Zakynthos Island (Ionian Sea, Eastern Mediterranean)

Detailed mapping of the Neogene deposits on Zakynthos Island shows that the Messinian primary evaporite basins, formed over Ionian basement, are delimited by the westernmost outcrop of the Triassic evaporitic diapirs, located west of the Kalamaki-Argasi Messinian gypsum unit. The post-Miocene external Ionian thrust is emplaced west of the Triassic diapirs. Planktonic foraminifera biostratigraphy indicates that primary evaporite accumulation took place probably during the first stage of the Messinian salinity crisis (5.96-5.60 Ma), in shallower parts of a foreland basin, formed over the Pre-Apulian and the Ionian zone basement. Establishment of these depositional environments, before the Ionian thrust emplacement, was probably due to the particularities of the foreland basin, which extended from the external Ionian to the internal Pre-Apulian zone. Field observations, borehole data and an onshore seismic profile show that the Neogene sediments over the Pre-Apulian basement correspond to the foredeep through forebulge domain of the foreland basin, as it is documented from their spatial thickness distribution. In contrast, the Neogene sediments over the Ionian basement correspond to the wedge top of the foreland basin, which was less subsiding, as it is deduced by their reduced thickness. This lower subsidence rate was the result of the concurrent diapiric movements of the Ionian Triassic evaporites. In Agios Sostis area, located over Pre-Apulian basement, the Neogene sequence is intercalated by decametre-thick resedimented blocks consisting of shallow water selenite. To the southeast, this mass-wasting Messinian gypsum passes to mainly gypsum turbidite. In Kalamaki-Argasi area, located over Ionian basement, the shallow water environment led to the deposition of the observed primary gypsum. Erosion of the primary gypsum of both forebulge and wedge top supplied the foreland basin’s depocenter with gypsum turbidites. Η λεπτομερής χαρτογράφηση των Νεογενών αποθέσεων της Ζακύνθου δείχνει ότι οι λεκάνες πρωτογενούς Μεσσήνιας εβαποριτικής απόθεσης, που σχηματίστηκαν πάνω σε Ιόνιο υπόβαθρο, οριοθετούνται από τη δυτικότερη εμφάνιση των Τριαδικών εβαποριτικών διάπειρων (δυτικά της Μεσσήνιας ενότητας γύψου Καλαμάκι-Αργάσι). Η μετα-Μειοκαινική εξωτερική Ιόνια επώθηση τοποθετείται δυτικά αυτών των Τριαδικών διάπειρων. Βιοστρωματογραφική ανάλυση των συναθροίσεων πλαγκτονικών τρηματοφόρων στα Νεογενή ιζήματα δείχνει ότι η συσσώρευση πρωτογενούς εβαπορίτη έλαβε χώρα πιθανά κατά το πρώτο στάδιο της κρίσης αλμυρότητας του Μεσσηνίου (5.96-5.60 Εκατ.χρ.), στα αβαθέστερα τμήματα της λεκάνης προχώρας, η οποία σχηματίστηκε πάνω στο Προ-Απούλιο και Ιόνιο αλπικό υπόβαθρο. Ο σχηματισμός των περιβαλλόντων ιζηματογένεσης, πριν από την Ιόνια επώθηση, πιθανά οφείλεται στις ιδιαιτερότητες της λεκάνης προχώρας, η οποία εκείνο το διάστημα εκτείνονταν από την εξωτερική Ιόνια ως την εσωτερική Προ-Απούλια ζώνη. Νέα δεδομένα υπαίθρου, σε συνδυασμό με τη βιοστρωματογραφία, τα στοιχεία γεωτρήσεων και μία διαθέσιμη σεισμική τομή δείχνουν ότι τα Νεογενή ιζήματα πάνω στο Προ-Απούλιο υπόβαθρο αντιστοιχούν στον τμήμα της λεκάνης προχώρας, από το προβύθισμα (foredeep) ως την πρόσθια ανύψωση (forebulge), όπως αυτό διαπιστώνεται από την χωρική κατανομή του πάχους τους. Αντίθετα, τα Νεογενή ιζήματα πάνω στο Ιόνιο υπόβαθρο αντιστοιχούν στο τμήμα της λεκάνης προχώρας που βρίσκεται πάνω στο μετωπικό πρίσμα της ορογένεσης (wedge top), το οποίο βυθίζονταν λιγότερο όπως συνάγεται από το ελαττωμένο πάχος των ιζημάτων. Ο μικρότερος ρυθμός βύθισης οφείλεται στις διαπειρικές κινήσεις των Τριαδικών εβαποριτών. Στη Νεογενή ακολουθία, που βρίσκεται πάνω σε Προ-Απούλιο υπόβαθρο (περιοχή Άγιος Σώστης), παρεμβάλλονται επανιζηματοποιημένα μπλοκ δεκαμετρικού πάχους αποτελούμενα από σεληνίτη μικρού βάθους απόθεσης. Προς νότο, αυτή η βαρυτικά μεταφερόμενη μάζα της Μεσσήνιας γύψου μεταπίπτει κυρίως σε τουρβιδιτική γύψο. Στην περιοχή Καλαμάκι-Αργάσι που βρίσκεται πάνω σε Ιόνιο υπόβαθρο, το αβαθές περιβάλλον οδήγησε στην απόθεση της παρατηρούμενης πρωτογενούς γύψου. Η διάβρωση της πρωτογενούς γύψου τόσο της πρόσθιας ανύψωσης όσο και του μετωπικού πρίσματος επώθησης τροφοδότησαν το προβύθισμα της λεκάνης προχώρας με τουρβιδίτες γύψου