Design, synthesis and characterization of a hexapeptide bio-inspired by acetylcholinesterase and its interaction with pesticide dichlorvos

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Bio-inspired polymer-supported nitrido molybdenum(VI) complexes for ammonia synthesis − reactivity towards protons and electrons : EPR investigations on paramagnetic molybdenum(V) and copper(II) complexes

Die biologische Stickstofffixierung durch Molybdän-haltige Nitrogenasen sowie die Erforschung des zugrundeliegenden komplexen Mechanismus (N2-Aktivierung an Metall-Zentren, 6-fache Protonierung und Reduktion, N–N Bindungsspaltung unter Bildung von Ammoniak) ist von erheblichem Interesse. Insbesondere Molybdän-Komplexe wurden bereits erfolgreich als Modellverbindungen für die Untersuchung elementarer Einzelschritte der N2-Aktivierung eingesetzt. Durch die Verwendung von Triamidoamin-Liganden ist es Schrock et al. sogar gelungen mehrere Katalysezyklen zu durchlaufen und einen Mechanismus zu formulieren. Trotz der sterisch anspruchsvollen Substituenten in den Schrock-Komplexen ist die Umsatzrate dieses homogenen Katalysators, aufgrund Komplex-Deaktivierung infolge intermolekularer Reaktionen wie Dimerisierung und Disproportionierung, limitiert. In der vorliegenden Arbeit wurden einige dieser Herausforderungen angegangen und die aktiven Spezies auf einer Festphase immobilisiert, um intermolekulare Reaktionen durch räumliche Isolierung der Komplexe zu unterdrücken.rnEin Polymer-verankertes Analogon des Schrock Nitrido-Molybdän(VI)-Komplexes wurde auf einem neuen Reaktionsweg synthetisiert. Dieser beinhaltet nur einen einzigen Reaktionsschritt, um die funktionelle Gruppe „MoN“ einzuführen. Protonierung des immobilisierten Nitrido-Molybdän(VI)-Komplexes LMoVIN (L = Polymer-verankerter Triamidoamin-Ligand) mit 2,6-Lutidinium liefert den entsprechenden Imido-Molybdän(VI)-Komplex. Durch anschließende Ein-Elektronen-Reduktion mit Cobaltocen wird der Polymer-angebundene Imido-Molybdän(V)-Komplex erhalten, bewiesen durch EPR-Spektroskopie (g1,2,3 = 1.989, 1.929, 1.902). Durch die Immobilisierung und die effektive räumliche Separation der Reaktionszentren auf der Festphase werden bimolekulare Nebenreaktionen, die oft in homogenen Systemen auftreten, unterdrückt. Dies ermöglicht zum ersten Mal die Darstellung des Imido-Molybdän(V)-Intermediates des Schrock-Zyklus.rnEPR-Spektren des als Spin-Label eingeführten immobilisierten Nitrato-Kupfer(II)-Komplexes wurden unter verschiedenen Bedingungen (Lösungsmittel, Temperatur) aufgenommen, wobei sich eine starke Abhängigkeit zwischen der Zugänglichkeit und Reaktivität der immobilisierten Reaktionszentren und der Art des Lösungsmittels zeigte. Somit wurde die Reaktivität von LMoVIN gegenüber Protonen und Elektronen, welches zur Bildung von NH3 führt, unter Verwendung verschiedener Lösungsmittel untersucht und optimiert. Innerhalb des kugelförmigen Polymers verläuft die Protonierung und Reduktion von LMoVIN stufenweise. Aktive Zentren, die sich an der „äußeren Schale“ des Polymers befinden, sind gut zugänglich und reagieren schnell nach H+/e− Zugabe. Aktive Zentren im „Inneren des Polymers“ hingegen sind schlechter zugänglich und zeigen langsame diffusions-kontrollierte Reaktionen, wobei drei H+/e− Schritte gefolgt von einer Ligandenaustausch-Reaktion erforderlich sind, um NH3 freizusetzen: LMoVIN  LMoVNH  LMoIVNH2  LMoIIINH3 und anschließender Ligandenaustausch führt zur Freisetzung von NH3.rnIn einem weiteren Projekt wurde der Bis(ddpd)-Kupfer(II)-Komplex EPR-spektroskopisch in Hinblick auf Jahn−Teller-Verzerrung und -Dynamik untersucht. Dabei wurden die EPR-Spektren bei variabler Temperatur (70−293 K) aufgenommen. Im Festkörperspektrum bei T < 100 K erscheint der Kupfer(II)-Komplex als gestreckter Oktaeder, wohingegen das EPR-Spektrum bei höheren Temperaturen g-Werte aufzeigt, die einer pseudo-gestauchten oktaedrischen Kupfer(II)-Spezies zuzuordnen sind. Diese Tatsache wird einem intramolekularen dynamischen Jahn−Teller Phänomen zugeschrieben, welcher bei 100 K eingefroren wird.

Can wild ungulate carcasses provide enough biomass to maintain avian scavenger populations? An empirical assessment using a bio-inspired computational model

Background The reduction in the amount of food available for European avian scavengers as a consequence of restrictive public health policies is a concern for managers and conservationists. Since 2002, the application of several sanitary regulations has limited the availability of feeding resources provided by domestic carcasses, but theoretical studies assessing whether the availability of food resources provided by wild ungulates are enough to cover energetic requirements are lacking. Methodology/Findings We assessed food provided by a wild ungulate population in two areas of NE Spain inhabited by three vulture species and developed a P System computational model to assess the effects of the carrion resources provided on their population dynamics. We compared the real population trend with to a hypothetical scenario in which only food provided by wild ungulates was available. Simulation testing of the model suggests that wild ungulates constitute an important food resource in the Pyrenees and the vulture population inhabiting this area could grow if only the food provided by wild ungulates would be available. On the contrary, in the Pre-Pyrenees there is insufficient food to cover the energy requirements of avian scavenger guilds, declining sharply if biomass from domestic animals would not be available. Conclusions/Significance Our results suggest that public health legislation can modify scavenger population trends if a large number of domestic ungulate carcasses disappear from the mountains. In this case, food provided by wild ungulates could be not enough and supplementary feeding could be necessary if other alternative food resources are not available (i.e. the reintroduction of wild ungulates), preferably in European Mediterranean scenarios sharing similar and socio-economic conditions where there are low densities of wild ungulates. Managers should anticipate the conservation actions required by assessing food availability and the possible scenarios in order to make the most suitable decisions.

A lung-on-chip array with an integrated bio-inspired respiration mechanism

We report about a lung-on-chip array that mimics the pulmonary parenchymal environment, including the thin, alveolar barrier and the three-dimensional cyclic strain induced by the breathing movements. A micro-diaphragm used to stretch the alveolar barrier is inspired by the in-vivo diaphragm, the main muscle responsible for inspiration. The design of this device aims not only at best reproducing the in-vivo conditions found in the lung parenchyma, but also at making its handling easy and robust. An innovative concept, based on the reversible bonding of the device, is presented that enables to accurately control the concentration of cells cultured on the membrane by easily accessing both sides of the membranes. The functionality of the alveolar barrier could be restored by co-culturing epithelial and endothelial cells that formed tight monolayers on each side of a thin, porous and stretchable membrane. We showed that cyclic stretch significantly affects the permeability properties of epithelial cell layers. Furthermore, we could also demonstrate that the strain influences the metabolic activity and the cytokine secretion of primary human pulmonary alveolar epithelial cells obtained from patients. These results demonstrate the potential of this device and confirm the importance of the mechanical strain induced by the breathing in pulmonary research.

Bio-inspired FPGA Architecture for Self-Calibration of an Image Compression Core based on Wavelet Transforms in Embedded Systems

A generic bio-inspired adaptive architecture for image compression suitable to be implemented in embedded systems is presented. The architecture allows the system to be tuned during its calibration phase. An evolutionary algorithm is responsible of making the system evolve towards the required performance. A prototype has been implemented in a Xilinx Virtex-5 FPGA featuring an adaptive wavelet transform core directed at improving image compression for specific types of images. An Evolution Strategy has been chosen as the search algorithm and its typical genetic operators adapted to allow for a hardware friendly implementation. HW/SW partitioning issues are also considered after a high level description of the algorithm is profiled which validates the proposed resource allocation in the device fabric. To check the robustness of the system and its adaptation capabilities, different types of images have been selected as validation patterns. A direct application of such a system is its deployment in an unknown environment during design time, letting the calibration phase adjust the system parameters so that it performs efcient image compression. Also, this prototype implementation may serve as an accelerator for the automatic design of evolved transform coefficients which are later on synthesized and implemented in a non-adaptive system in the final implementation device, whether it is a HW or SW based computing device. The architecture has been built in a modular way so that it can be easily extended to adapt other types of image processing cores. Details on this pluggable component point of view are also given in the paper.

Bio-inspired enhancement of reputation systems for intelligent environments

Providing security to the emerging field of ambient intelligence will be difficult if we rely only on existing techniques, given their dynamic and heterogeneous nature. Moreover, security demands of these systems are expected to grow, as many applications will require accurate context modeling. In this work we propose an enhancement to the reputation systems traditionally deployed for securing these systems. Different anomaly detectors are combined using the immunological paradigm to optimize reputation system performance in response to evolving security requirements. As an example, the experiments show how a combination of detectors based on unsupervised techniques (self-organizing maps and genetic algorithms) can help to significantly reduce the global response time of the reputation system. The proposed solution offers many benefits: scalability, fast response to adversarial activities, ability to detect unknown attacks, high adaptability, and high ability in detecting and confining attacks. For these reasons, we believe that our solution is capable of coping with the dynamism of ambient intelligence systems and the growing requirements of security demands.

Simulating Metabolic Processes Using an Architecture Based on Networks of Bio-inspired Processors.

In this work, we propose the Networks of Evolutionary Processors (NEP) [2] as a computational model to solve problems related with biological phenomena. In our first approximation, we simulate biological processes related with cellular signaling and their implications in the metabolism, by using an architecture based on NEP (NEP architecture) and their specializations: Networks of Polarized Evolutionary Processors (NPEP) [1] and NEP Transducers (NEPT) [3]. In particular, we use this architecture to simulate the interplay between cellular processes related with the metabolism as the Krebs cycle and the malate-aspartate shuttle pathway (MAS) both being altered by signaling by calcium.

An Architecture forRepresenting Biological Processes based on Networks of Bio-inspired Processors

n this paper we propose the use of Networks of Bio-inspired Processors (NBP) to model some biological phenomena within a computational framework. In particular, we propose the use of an extension of NBP named Network Evolutionary Processors Transducers to simulate chemical transformations of substances. Within a biological process, chemical transformations of substances are basic operations in the change of the state of the cell. Previously, it has been proved that NBP are computationally complete, that is, they are able to solve NP complete problems in linear time, using massively parallel computations. In addition, we propose a multilayer architecture that will allow us to design models of biological processes related to cellular communication as well as their implications in the metabolic pathways. Subsequently, these models can be applied not only to biological-cellular instances but, possibly, also to configure instances of interactive processes in many other fields like population interactions, ecological trophic networks, in dustrial ecosystems, etc.

A simulation environment for bio-inspired heterogeneous chained modular robots

This paper presents a new simulation environment aimed at heterogeneous chained modular robots. This simulator allows testing the feasibility of the design, checking how modules are going to perform in the field and verifying hardware, electronics and communication designs before the prototype is built, saving time and resources. The paper shows how the simulator is built and how it can be set up to adapt to new designs. It also gives some examples of its use showing different heterogeneous modular robots running in different environments.

Bio-inspired carbon electro-catalysis for the oxygen reduction reaction

We report the synthesis, characterisation and catalytic performance of two nature-inspired biomass-derived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste (lobster shells) or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a pore agent, creating increased surface area and pore volume, though considerably higher in artificial lobster samples due to the better homogeneity of the components. Various characterisation techniques revealed the presence of a considerable amount of hydroxyapatite left in the real lobster samples after acid washing and a low content of carbon (23%), nitrogen and sulphur (<1%), limiting the surface area to 23 m2/g, and consequently resulting in rather poor catalytic activity. However, artificial lobster samples, with a surface area of ≈200 m2/g and a nitrogen doping of 2%, showed a promising onset potential, very similar to a commercially available platinum catalyst, with better methanol tolerance, though with lower stability in long time testing over 10,000 s.

A flexible bio-inspired hierarchical model for analyzing musical timbre

A flexible and multipurpose bio-inspired hierarchical model for analyzing musical timbre is presented in this paper. Inspired by findings in the fields of neuroscience, computational neuroscience, and psychoacoustics, not only does the model extract spectral and temporal characteristics of a signal, but it also analyzes amplitude modulations on different timescales. It uses a cochlear filter bank to resolve the spectral components of a sound, lateral inhibition to enhance spectral resolution, and a modulation filter bank to extract the global temporal envelope and roughness of the sound from amplitude modulations. The model was evaluated in three applications. First, it was used to simulate subjective data from two roughness experiments. Second, it was used for musical instrument classification using the k-NN algorithm and a Bayesian network. Third, it was applied to find the features that characterize sounds whose timbres were labeled in an audiovisual experiment. The successful application of the proposed model in these diverse tasks revealed its potential in capturing timbral information.

A biomechanically optimized knitted stent using a bio-inspired design approach

Vascular implants have always been a key area of research in medical textiles. Knitted structures have been proven to be suitable for stent applications on the basis of their looped mesh geometry, structural flexibility and ease of manufacturing. However, there are biomechanical constraints of plain knit constructions that can result in clinical complications after implantation and hence cannot be ignored. This study reports a new segmented knit design inspired by structural metamerism observed in the body design of some invertebrate animals. Metamerism is the phenomenon of having a linear series of body segments fundamentally similar in structure, but assigned to perform different functions. It was hypothesized that utilization of this simple and yet effective biological design approach in stent construction could improve the degree of control for optimizing stent biomechanical properties. The proposed segmented stent was constructed by incorporating an elastic filament component into a polyethylene terephthalate knitted stent at specific intervals along its length, also known as the ‘Plating Technique’. This technique generates a structure with alternately arranged stiff and elastic knitted sections which equip the stent with vital structural support and volumetric compliance properties, respectively. The stent design parameters (filament diameter, loop length, segmentation plan) were optimized to achieve significantly better biomechanical performance (bending flexibility, compression resistance, volumetric expansion, longitudinal extensibility) than a plain knit stent.

PhysarumSpreader: a new bio-Inspired methodology for identifying influential spreaders in complex networks

Identifying influential spreaders in networks, which contributes to optimizing the use of available resources and efficient spreading of information, is of great theoretical significance and practical value. A random-walk-based algorithm LeaderRank has been shown as an effective and efficient method in recognizing leaders in social network, which even outperforms the well-known PageRank method. As LeaderRank is initially developed for binary directed networks, further extensions should be studied in weighted networks. In this paper, a generalized algorithm PhysarumSpreader is proposed by combining LeaderRank with a positive feedback mechanism inspired from an amoeboid organism called Physarum Polycephalum. By taking edge weights into consideration and adding the positive feedback mechanism, PhysarumSpreader is applicable in both directed and undirected networks with weights. By taking two real networks for examples, the effectiveness of the proposed method is demonstrated by comparing with other standard centrality measures.

Fly-eye inspired superhydrophobic anti-fogging inorganic nanostructures

Fly-eye bio-inspired inorganic nanostructures are synthesized via a two-step self-assembly approach, which have low contact angle hysteresis and excellent anti-fogging properties, and are promising candidates for anti-freezing/fogging materials to be applied in extreme and hazardous environments.