Functional design of the air ventilation apparatus and overland excurions by teleosts / Karel F. Liem.

n.s. no.37(1987)

Architectures and design patterns for functional design of logic control and diagnostics in industrial automation

Recently in most of the industrial automation process an ever increasing degree of automation has been observed. This increasing is motivated by the higher requirement of systems with great performance in terms of quality of products/services generated, productivity, efficiency and low costs in the design, realization and maintenance. This trend in the growth of complex automation systems is rapidly spreading over automated manufacturing systems (AMS), where the integration of the mechanical and electronic technology, typical of the Mechatronics, is merging with other technologies such as Informatics and the communication networks. An AMS is a very complex system that can be thought constituted by a set of flexible working stations, one or more transportation systems. To understand how this machine are important in our society let considerate that every day most of us use bottles of water or soda, buy product in box like food or cigarets and so on. Another important consideration from its complexity derive from the fact that the the consortium of machine producers has estimated around 350 types of manufacturing machine. A large number of manufacturing machine industry are presented in Italy and notably packaging machine industry,in particular a great concentration of this kind of industry is located in Bologna area; for this reason the Bologna area is called “packaging valley”. Usually, the various parts of the AMS interact among them in a concurrent and asynchronous way, and coordinate the parts of the machine to obtain a desiderated overall behaviour is an hard task. Often, this is the case in large scale systems, organized in a modular and distributed manner. Even if the success of a modern AMS from a functional and behavioural point of view is still to attribute to the design choices operated in the definition of the mechanical structure and electrical electronic architecture, the system that governs the control of the plant is becoming crucial, because of the large number of duties associated to it. Apart from the activity inherent to the automation of themachine cycles, the supervisory system is called to perform other main functions such as: emulating the behaviour of traditional mechanical members thus allowing a drastic constructive simplification of the machine and a crucial functional flexibility; dynamically adapting the control strategies according to the different productive needs and to the different operational scenarios; obtaining a high quality of the final product through the verification of the correctness of the processing; addressing the operator devoted to themachine to promptly and carefully take the actions devoted to establish or restore the optimal operating conditions; managing in real time information on diagnostics, as a support of the maintenance operations of the machine. The kind of facilities that designers can directly find on themarket, in terms of software component libraries provides in fact an adequate support as regard the implementation of either top-level or bottom-level functionalities, typically pertaining to the domains of user-friendly HMIs, closed-loop regulation and motion control, fieldbus-based interconnection of remote smart devices. What is still lacking is a reference framework comprising a comprehensive set of highly reusable logic control components that, focussing on the cross-cutting functionalities characterizing the automation domain, may help the designers in the process of modelling and structuring their applications according to the specific needs. Historically, the design and verification process for complex automated industrial systems is performed in empirical way, without a clear distinction between functional and technological-implementation concepts and without a systematic method to organically deal with the complete system. Traditionally, in the field of analog and digital control design and verification through formal and simulation tools have been adopted since a long time ago, at least for multivariable and/or nonlinear controllers for complex time-driven dynamics as in the fields of vehicles, aircrafts, robots, electric drives and complex power electronics equipments. Moving to the field of logic control, typical for industrial manufacturing automation, the design and verification process is approached in a completely different way, usually very “unstructured”. No clear distinction between functions and implementations, between functional architectures and technological architectures and platforms is considered. Probably this difference is due to the different “dynamical framework”of logic control with respect to analog/digital control. As a matter of facts, in logic control discrete-events dynamics replace time-driven dynamics; hence most of the formal and mathematical tools of analog/digital control cannot be directly migrated to logic control to enlighten the distinction between functions and implementations. In addition, in the common view of application technicians, logic control design is strictly connected to the adopted implementation technology (relays in the past, software nowadays), leading again to a deep confusion among functional view and technological view. In Industrial automation software engineering, concepts as modularity, encapsulation, composability and reusability are strongly emphasized and profitably realized in the so-calledobject-oriented methodologies. Industrial automation is receiving lately this approach, as testified by some IEC standards IEC 611313, IEC 61499 which have been considered in commercial products only recently. On the other hand, in the scientific and technical literature many contributions have been already proposed to establish a suitable modelling framework for industrial automation. During last years it was possible to note a considerable growth in the exploitation of innovative concepts and technologies from ICT world in industrial automation systems. For what concerns the logic control design, Model Based Design (MBD) is being imported in industrial automation from software engineering field. Another key-point in industrial automated systems is the growth of requirements in terms of availability, reliability and safety for technological systems. In other words, the control system should not only deal with the nominal behaviour, but should also deal with other important duties, such as diagnosis and faults isolations, recovery and safety management. Indeed, together with high performance, in complex systems fault occurrences increase. This is a consequence of the fact that, as it typically occurs in reliable mechatronic systems, in complex systems such as AMS, together with reliable mechanical elements, an increasing number of electronic devices are also present, that are more vulnerable by their own nature. The diagnosis problem and the faults isolation in a generic dynamical system consists in the design of an elaboration unit that, appropriately processing the inputs and outputs of the dynamical system, is also capable of detecting incipient faults on the plant devices, reconfiguring the control system so as to guarantee satisfactory performance. The designer should be able to formally verify the product, certifying that, in its final implementation, it will perform itsrequired function guarantying the desired level of reliability and safety; the next step is that of preventing faults and eventually reconfiguring the control system so that faults are tolerated. On this topic an important improvement to formal verification of logic control, fault diagnosis and fault tolerant control results derive from Discrete Event Systems theory. The aimof this work is to define a design pattern and a control architecture to help the designer of control logic in industrial automated systems. The work starts with a brief discussion on main characteristics and description of industrial automated systems on Chapter 1. In Chapter 2 a survey on the state of the software engineering paradigm applied to industrial automation is discussed. Chapter 3 presentes a architecture for industrial automated systems based on the new concept of Generalized Actuator showing its benefits, while in Chapter 4 this architecture is refined using a novel entity, the Generalized Device in order to have a better reusability and modularity of the control logic. In Chapter 5 a new approach will be present based on Discrete Event Systems for the problemof software formal verification and an active fault tolerant control architecture using online diagnostic. Finally conclusive remarks and some ideas on new directions to explore are given. In Appendix A are briefly reported some concepts and results about Discrete Event Systems which should help the reader in understanding some crucial points in chapter 5; while in Appendix B an overview on the experimental testbed of the Laboratory of Automation of University of Bologna, is reported to validated the approach presented in chapter 3, chapter 4 and chapter 5. In Appendix C some components model used in chapter 5 for formal verification are reported.

Design of New Materials for Passive Vibration Control

The aim of this contribution is to extend the techniques of composite materials design to non-linear material behaviour and apply it for design of new materials for passive vibration control. As a first step a computational tool allowing determination of macroscopic optimized one-dimensional isolator behaviour was developed. Voigt, Maxwell, standard and more complex material models can be implemented. Objective function considers minimization of the initial reaction and/or displacement peak as well as minimization of the steady-state amplitude of reaction and/or displacement. The complex stiffness approach is used to formulate the governing equations in an efficient way. Material stiffness parameters are assumed as non-linear functions of the displacement. The numerical solution is performed in the complex space. The steady-state solution in the complex space is obtained by an iterative process based on the shooting method which imposes the conditions of periodicity with respect to the known value of the period. Extension of the shooting method to the complex space is presented and verified. Non-linear behaviour of material parameters is then optimized by generic probabilistic meta-algorithm, simulated annealing. Dependence of the global optimum on several combinations of leading parameters of the simulated annealing procedure, like neighbourhood definition and annealing schedule, is also studied and analyzed. Procedure is programmed in MATLAB environment.

Control de la derivació de l'aigua de reg de Masjoan

RESUM Masjoan és una masia del segle XII on resideix la família Masferrer des del 1710. Actualment a Masjoan l’activitat principal és el cultiu i venta de plantes ornamentals, i l’explotació forestal per obtenir fusta. Pel que fa a l’aigua, tant per a la realització de l’activitat professional com per al subministrament de la casa, aquesta prové de mines d’aigua natural situades en la finca. L’objectiu d’aquest TFC ha estat dissenyar un sistema autònom per automatitzar el procés de derivació de l’aigua procedent d’una mina, i d’aquesta manera aprofitar millor els recursos naturals dels que és disposa. El desenvolupament d’aquest sistema, comprèn la selecció i configuració de sensors i actuadors, el disseny del circuit amb la realització de la placa, el disseny del sistema d’alimentació autònom, el software que controla el sistema, i dimensionar la resta d’elements de la instal•lació. Tot el sistema està controlat per un microcontrolador PIC16F876 i alimentat per un mòdul solar de 4W. En el disseny s’ha procurat, sobredimencionar les diferents etapes per possibles ampliacions o modificacions del sistema i que el circuit procures optimitzar el consum d’energia. Com a conclusions cal dir que s’han assolit els objectius proposats amb èxit. S’ha aconseguit un disseny funcional i estable que actualment es troba en funcionament.

Voimalaitoksen toiminnallinen suunnittelu

Diplomityön tavoitteena oli antaa kuva vastapainevoimalaitoksen automaation toiminnallisesta suunnittelusta ja soveltaa teoriaa suunnittelemalla toiminnallisuus vesihöyrypiirin tärkeimmille osuuksille. Työssä on esitelty tyypillinen EPCM-voimalaitosprojekti, joka toteutetaan ulkopuolisen avustajan kanssa tehdyllä yhteistyöllä. Projektin koostuu laitoksen suunnittelu-, rakennus-, asennus- sekä käyttöönottovaiheista. Huomioitavia asioita ovat mm. projektin budjetti sekä aikataulu. Valvonnalla on suuri merkitys projektin onnistumiseen. Lisäksi työssä esitellään vastapainevoimalaitoksen vesihöyrypiirin prosessi, pääsäädöt sekä automaatiojärjestelmä. Vesihöyrypiirillä tarkoitetaan syöttövesi-, höyry- ja kaukolämpöjärjestelmää. Pääsäädöillä pyritään saamaan tuotanto vastaamaan kulutusta. Voimalaitoksen painopiste on kaukolämmön tuottaminen. Automaatiojärjestelmän toiminnoilla tarkoitetaan järjestelmän suorittamia ohjauksia, säätöjä sekä hälytyksiä. Toiminnallisessa suunnittelussa tehdään toimilaitteille niin yksittäisohjaukset, säädöt kuin hälytysluettelot. Työssä tehty toiminnallinen suunnittelu keskittyy erityisesti toimilaitteiden säätöpiireihin. Säätöpiirit koostuvat tärkeimmistä prosessiin liittyvistä komponenteista ja säätömerkeistä. Toiminnallisen suunnittelun dokumentaatioita käytetään automaatiojärjestelmän sovellusohjelmoinnin pohjana.

BioSuper: A web tool for the superimposition of biomolecules and assemblies with rotational symmetry

Background Most of the proteins in the Protein Data Bank (PDB) are oligomeric complexes consisting of two or more subunits that associate by rotational or helical symmetries. Despite the myriad of superimposition tools in the literature, we could not find any able to account for rotational symmetry and display the graphical results in the web browser. Results BioSuper is a free web server that superimposes and calculates the root mean square deviation (RMSD) of protein complexes displaying rotational symmetry. To the best of our knowledge, BioSuper is the first tool of its kind that provides immediate interactive visualization of the graphical results in the browser, biomolecule generator capabilities, different levels of atom selection, sequence-dependent and structure-based superimposition types, and is the only web tool that takes into account the equivalence of atoms in side chains displaying symmetry ambiguity. BioSuper uses ICM program functionality as a core for the superimpositions and displays the results as text, HTML tables and 3D interactive molecular objects that can be visualized in the browser or in Android and iOS platforms with a free plugin. Conclusions BioSuper is a fast and functional tool that allows for pairwise superimposition of proteins and assemblies displaying rotational symmetry. The web server was created after our own frustration when attempting to superimpose flexible oligomers. We strongly believe that its user-friendly and functional design will be of great interest for structural and computational biologists who need to superimpose oligomeric proteins (or any protein). BioSuper web server is freely available to all users at http://ablab.ucsd.edu/BioSuper webcite.

Control de la derivació de l'aigua de reg de Masjoan

RESUM Masjoan és una masia del segle XII on resideix la família Masferrer des del 1710. Actualment a Masjoan l’activitat principal és el cultiu i venta de plantes ornamentals, i l’explotació forestal per obtenir fusta. Pel que fa a l’aigua, tant per a la realització de l’activitat professional com per al subministrament de la casa, aquesta prové de mines d’aigua natural situades en la finca. L’objectiu d’aquest TFC ha estat dissenyar un sistema autònom per automatitzar el procés de derivació de l’aigua procedent d’una mina, i d’aquesta manera aprofitar millor els recursos naturals dels que és disposa. El desenvolupament d’aquest sistema, comprèn la selecció i configuració de sensors i actuadors, el disseny del circuit amb la realització de la placa, el disseny del sistema d’alimentació autònom, el software que controla el sistema, i dimensionar la resta d’elements de la instal•lació. Tot el sistema està controlat per un microcontrolador PIC16F876 i alimentat per un mòdul solar de 4W. En el disseny s’ha procurat, sobredimencionar les diferents etapes per possibles ampliacions o modificacions del sistema i que el circuit procures optimitzar el consum d’energia. Com a conclusions cal dir que s’han assolit els objectius proposats amb èxit. S’ha aconseguit un disseny funcional i estable que actualment es troba en funcionament.

Competencia multicultural en educación artística. Contextos y perspectivas de futuro en la formación de las maestras y los maestros

Entendemos que desde el área de Educación Artística podemos trabajar el arte de cientos de culturas y en cualquier momento de la historia, un aspecto que nos permite sensibilizar al alumnado hacia la comprensión de las distintas manifestaciones que adquiere un mismo aspecto cultural, el arte, como fenómeno universal. Hemos centrado el objetivo principal de nuestra investigación en la exploración de los caminos y las posibilidades que nos ofrece la educación artística en relación a la diversidad (cultural, de clase, minusvalía, de edad, raza, de género, etc.). Partíamos de la percepción que, en el ámbito de la educación artística y de la cultura en general, existe una tendencia que describe los hechos artísticos y las prácticas estéticas a partir de unas categorías únicas y universalmente válidas. Estas provocan a menudo el olvido de algunos valores específicos y sobre todo la falta de reconocimiento de otras propuestas artísticas igual de interesantes (oficios artísticos, arte de las/os niñas/os, arte popular, artesanias, etc. Hemos buscado caminos que nos conduzcan a asumir una visión contemporánea del hecho artístico y una concepción incluyente del arte (diseño, indumentaria, decoración, artes funcionales, arte popular, arte de las mujeres, net art, gastronomia, etc.). Entendemos que la educación es el lugar desde donde avanzar hacia otra forma de mirar y comprender el mundo. Una visión que, desde el arte, facilite elementos para el encuentro y las relaciones sociales, donde la propia diferencia y la conservación "crítica" de las propias identidades culturales sean celebradas desde la convicción del verdadero enriquecimiento cultural. Estas consideraciones y la ausencia de un marco teórico previo que nos permitiera analizar, desarrollar y evaluar la perspectiva multicultural en la educación artística fueron la causa y la coyuntura para dirigir este trabajo hacia lo que podríamos llamar "educador artístico culturalmente competente" (Andrus, 2001). En esa perspectiva de comptencia es donde hemos ubicado nuestro trabajo, así como en las necesidades de formación de las maestras y los maestros, con la convicción de que cualquier mejora en la etapa educativa donde estos actúan, redundará en todo el proceso educativo.

Programação no ensino de matemática utilizando Processing 2: Um estudo das relações formalizadas por alunos do ensino fundamental com baixo rendimento em matemática

Pós-graduação em Educação para a Ciência - FC

Perfil de playas sustentadas : estudio hidrodinámico y experimental : directrices de diseño

Las playas sustentadas por medio de un pie sumergido son una atractiva alternativa de diseño de regeneración de playas especialmente cuando las condiciones física del emplazamiento o las características de la arena nativa y de préstamo producen perfiles de alimentación que no se intersectan. La observación y propuesta de este tipo de solución data de los años 1960’s, así como la experiencia internacional en la construcción de este tipo de playas. Sin embargo, a pesar de su utilización y los estudios en campo y laboratorio, no se dispone de criterios ingenieriles que apoyen el diseño de las mismas. Esta tesis consiste en un análisis experimental del perfil de playas sustentadas en un pie sumergido (o colgadas) que se concreta en una propuesta de directrices de diseño general que permiten estimar la ubicación y características geométricas del pie sumergido frente a un oleaje y material que constituye la playa determinados. En la tesis se describe el experimento bidimensional realizado en el modelo físico de fondo móvil, donde se combinan cinco tipos de oleaje con tres configuraciones del pie sumergido (“Sin estructura”, configuración baja o “Estructura 1” y configuración alta o “Estructura 2”), se presentan los resultados obtenidos y se realiza una discusión detallada de las implicaciones de los resultados desde el punto de vista hidrodinámico utilizando monomios adimensionales. Se ha realizado un análisis detallado del estado del arte sobre playas colgadas, presentando el concepto y las experiencias de realizaciones en distintos países. Se ha realizado una cuidadosa revisión de la literatura publicada sobre estudios experimentales de playas colgadas, modelos teóricos y otras cuestiones auxiliares, necesarias para la formulación de la metodología de la tesis. El estudio realizado se ha estructurado en dos fases. En la primera fase se ha realizado una experimentación en un modelo físico de fondo móvil construido en las instalaciones del Centro de Estudios de Puertos y Costas (CEPYC) del Centro de Estudios y Experimentación de Obras Públicas (CEDEX), consistente en un canal de 36 m de longitud, 3 m de anchura y 1.5 m de altura, provisto de un generador de oleaje de tipo pistón. Se ha diseñado una campaña de 15 ensayos, que se obtienen sometiendo a cinco tipos de oleaje tres configuraciones distintas de playa colgada. En los ensayos se ha medido el perfil de playa en distintos instantes hasta llegar al equilibrio, determinando a partir de esos datos el retroceso de la línea de costa y el volumen de sedimentos perdido. El tiempo total efectivo de ensayo asciende a casi 650 horas, y el número de perfiles de evolución de playa obtenidos totaliza 229. En la segunda fase se ha abordado el análisis de los resultados obtenidos con la finalidad de comprender el fenómeno, identificar las variables de las que depende y proponer unas directrices ingenieriles de diseño. Se ha estudiado el efecto de la altura de ola, del periodo del oleaje, del francobordo adimensional y del parámetro de Dean, constatándose la dificultad de comprensión del funcionamiento de estas obras ya que pueden ser beneficiosas, perjudiciales o inocuas según los casos. También se ha estudiado la respuesta del perfil de playa en función de otros monomios adimensionales, tales como el número de Reynolds o el de Froude. En el análisis se ha elegido el monomio “plunger” como el más significativo, encontrando relaciones de éste con el peralte de oleaje, la anchura de coronación adimensional, la altura del pie de playa adimensional y el parámetro de Dean. Finalmente, se propone un método de diseño de cuatro pasos que permite realizar un primer encaje del diseño funcional de la playa sustentada frente a un oleaje de características determinadas. Las contribuciones más significativas desde el punto de vista científico son: - La obtención del juego de resultados experimentales. - La caracterización del comportamiento de las playas sustentadas. - Las relaciones propuestas entre el monomio plunger y las distintas variables explicativas seleccionadas, que permiten predecir el comportamiento de la obra. - El método de diseño propuesto, en cuatro pasos, para este tipo de esquemas de defensa de costas. Perched beaches are an attractive beach nourishment design alternative especially when either the site conditions or the characteristics of both the native and the borrow sand lead to a non-intersecting profile The observation and suggestion of the use of this type of coastal defence scheme dates back to the 1960’s, as well as the international experience in the construction of this type of beaches. However, in spite of its use and the field and laboratory studies performed to-date, no design engineering guidance is available to support its design. This dissertation is based on the experimental work performed on a movable bed physical model and the use of dimensionless parameters in analyzing the results to provide general functional design guidance that allow the designer, at a particular stretch of coast - to estimate the location and geometric characteristics of the submerged sill as well as to estimate the suitable sand size to be used in the nourishment. This dissertation consists on an experimental analysis of perched beaches by means of a submerged sill, leading to the proposal of general design guidance that allows to estimate the location and geometric characteristics of the submerged sill when facing a wave condition and for a given beach material. The experimental work performed on a bi-dimensional movable bed physical model, where five types of wave conditions are combined with three configurations of the submerged sill (“No structure”, low structure or “Structure 1”, and high structure or “Structure 2”) is described, results are presented, and a detailed discussion of the results - from the hydrodynamic point of view – of the implications of the results by using dimensionless parameters is carried out. A detailed state of the art analysis about perched beaches has been performed, presenting the “perched beach concept” and the case studies of different countries. Besides, a careful revision of the literature about experimental studies on perched beaches, theoretical models, and other topics deemed necessary to formulate the methodology of this work has been completed. The study has been divided into two phases. Within the first phase, experiments on a movable-bed physical model have been developed. The physical model has been built in the Centro de Estudios de Puertos y Costas (CEPYC) facilities, Centro de Estudios y Experimentación de Obras Públicas (CEDEX). The wave flume is 36 m long, 3 m wide and 1.5 m high, and has a piston-type regular wave generator available. The test plan consisted of 15 tests resulting from five wave conditions attacking three different configurations of the perched beach. During the development of the tests, the beach profile has been surveyed at different intervals until equilibrium has been reached according to these measurements. Retreat of the shoreline and relative loss of sediment in volume have been obtained from the measurements. The total effective test time reaches nearly 650 hours, whereas the total number of beach evolution profiles measured amounts to 229. On the second phase, attention is focused on the analysis of results with the aim of understanding the phenomenon, identifying the governing variables and proposing engineering design guidelines. The effect of the wave height, the wave period, the dimensionless freeboard and of the Dean parameter have been analyzed. It has been pointed out the difficulty in understanding the way perched beaches work since they turned out to be beneficial, neutral or harmful according to wave conditions and structure configuration. Besides, the beach profile response as a function of other dimensionless parameters, such as Reynolds number or Froude number, has been studied. In this analysis, the “plunger” parameter has been selected as the most representative, and relationships between the plunger parameter and the wave steepness, the dimensionless crest width, the dimensionless crest height, and the Dean parameter have been identified. Finally, an engineering 4-step design method has been proposed, that allows for the preliminary functional design of the perched beach for a given wave condition. The most relevant contributions from the scientific point of view have been: - The acquisition of a consistent set of experimental results. - The characterization of the behavior of perched beaches. - The proposed relationships between the plunger parameter and the different explanatory variables selected, that allow for the prediction of the beach behavior. - The proposed design method, four-step method, for this type of coastal defense schemes.

Consequences of metamorphosis for the locomotor performance and thermal physiology of the newt Triturus critatus

During metamorphosis, most amphibians undergo rapid shifts in their morphology that allow them to move from an aquatic to a more terrestrial existence. Two important challenges associated with this shift in habitat are the necessity to switch from an aquatic to terrestrial mode of locomotion and changes in the thermal environment. In this study, I investigated the consequences of metamorphosis to the burst swimming and running performance of the European newt Triturus cristatus to determine the nature and magnitude of any locomotor trade-offs that occur across life-history stages. In addition, I investigated whether there were any shifts in the thermal dependence of performance between life-history stages of T. cristatus to compensate for changes in their thermal environment during metamorphosis. A trade-off between swimming and running performance was detected across life-history stages, with metamorphosis resulting in a simultaneous decrease in swimming and increase in running performance. Although the terrestrial habitat of postmetamorphic stages of the newt T. cristatus experienced greater daily fluctuations in temperature than the aquatic habitat of the larval stage, no differences in thermal sensitivity of locomotor performance were detected between the larval aquatic and postmetamorphic stages. The absence of variation across life-history stages of T. cristatus may indicate that thermal sensitivity may be a conservative trait across ontogenetic stages in amphibians, but further studies are required to investigate this assertion.

Cluster scheduling and load balancing via TCP options

This paper describes an experiment in designing, implementing and testing a Transport layer cluster scheduling and dispatching architecture. The motivation for the experiment was the hypothesis that a Transport layer clustering solution may offer advantantages over the existing industry-standard Network layer and Data Link Layer approaches. The critical success factors initially established to guide and evaluate the experiment were reduced dispatcher work load, reduced dispatcher internal state memory requirements, distributed denial of service resilience, and cluster software design simplicity. The functional design stage of the experiment produced a Transport layer strategy for scheduling and load balancing based on the specification of two new TCP options. Implementation required the introduction of the newly specified TCP options into the Linux (2.4) kernel. The implementation produced an extended Linux Socket API to facilitate user-process access to the additional TCP capability. The testing stage of the experiment confirmed the operational efficiency of the solution.

Design and study of self-assembled functional organic and hybrid systems for biological applications

The focus of self-assembly as a strategy for the synthesis has been confined largely to molecules, because of the importance of manipulating the structure of matter at the molecular scale. We have investigated the influence of temperature and pH, in addition to the concentration of the capping agent used for the formation of the nano-bio conjugates. For example, the formation of the narrower size distribution of the nanoparticles was observed with the increase in the concentration of the protein, which supports the fact that γ-globulin acts both as a controller of nucleation as well as stabiliser. As analyzed through various photophysical, biophysical and microscopic techniques such as TEM, AFM, C-AFM, SEM, DLS, OPM, CD and FTIR, we observed that the initial photoactivation of γ-globulin at pH 12 for 3 h resulted in small protein fibres of ca. Further irradiation for 24 h, led to the formation of selfassembled long fibres of the protein of ca. 5-6 nm and observation of surface plasmon resonance band at around 520 nm with the concomitant quenching of luminescence intensity at 680 nm. The observation of light triggered self-assembly of the protein and its effect on controlling the fate of the anchored nanoparticles can be compared with the naturally occurring process such as photomorphogenesis.Furthermore,our approach offers a way to understand the role played by the self-assembly of the protein in ordering and knock out of the metal nanoparticles and also in the design of nano-biohybrid materials for medicinal and optoelectronic applications. Investigation of the potential applications of NIR absorbing and water soluble squaraine dyes 1-3 for protein labeling and anti-amyloid agents forms the subject matter of the third chapter of the thesis. The study of their interactions with various proteins revealed that 1-3 showed unique interactions towards serum albumins as well as lysozyme. 69%, 71% and 49% in the absorption spectra as well as significant quenching in the fluorescence intensity of the dyes 1-3, respectively. Half-reciprocal analysis of the absorption data and isothermal titration calorimetric (ITC) analysis of the titration experiments gave a 1:1 stoichiometry for the complexes formed between the lysozyme and squaraine dyes with association constants (Kass) in the range 104-105 M-1. We have determined the changes in the free energy (ΔG) for the complex formation and the values are found to be -30.78, -32.31 and -28.58 kJmol-1, respectively for the dyes 1, 2 and 3. Furthermore, we have observed a strong induced CD (ICD) signal corresponding to the squaraine chromophore in the case of the halogenated squaraine dyes 2 and 3 at 636 and 637 nm confirming the complex formation in these cases. To understand the nature of interaction of the squaraine dyes 1-3 with lysozyme, we have investigated the interaction of dyes 1-3 with different amino acids. These results indicated that the dyes 1-3 showed significant interactions with cysteine and glutamic acid which are present in the side chains of lysozyme. In addition the temperature dependent studies have revealed that the interaction of the dye and the lysozyme are irreversible. Furthermore, we have investigated the interactions of these NIR dyes 1-3 with β- amyloid fibres derived from lysozyme to evaluate their potential as inhibitors of this biologically important protein aggregation. These β-amyloid fibrils were insoluble protein aggregates that have been associated with a range of neurodegenerative diseases, including Huntington, Alzheimer’s, Parkinson’s, and Creutzfeldt-Jakob diseases. We have synthesized amyloid fibres from lysozyme through its incubation in acidic solution below pH 4 and by allowing to form amyloid fibres at elevated temperature. To quantify the binding affinities of the squaraine dyes 1-3 with β-amyloids, we have carried out the isothermal titration calorimetric (ITC) measurements. The association constants were determined and are found to be 1.2 × 105, 3.6× 105 and 3.2 × 105 M-1 for the dyes, 1-3, respectively. To gain more insights into the amyloid inhibiting nature of the squaraine dyes under investigations, we have carried out thioflavin assay, CD, isothermal titration calorimetry and microscopic analysis. The addition of the dyes 1-3 (5μM) led to the complete quenching in the apparent thioflavin fluorescence, thereby indicating the destabilization of β-amyloid fibres in the presence of the squaraine dyes. Further, the inhibition of the amyloid fibres by the squaraine dyes 1-3, has been evidenced though the DLS, TEM AFM and SAED, wherein we observed the complete destabilization of the amyloid fibre and transformation of the fibre into spherical particles of ca. These results demonstrate the fact that the squaraine dyes 1-3 can act as protein labeling agents as well as the inhibitors of the protein amyloidogenesis. The last chapter of the thesis describes the synthesis and investigation of selfassembly as well as bio-imaging aspects of a few novel tetraphenylethene conjugates 4-6.Expectedly, these conjugates showed significant solvatochromism and exhibited a hypsochromic shift (negative solvatochromism) as the solvent polarity increased, and these observations were justified though theoretical studies employing the B3LYP/6-31g method. We have investigated the self-assembly properties of these D-A conjugates though variation in the percentage of water in acetonitrile solution due to the formation of nanoaggregates. Further the contour map of the observed fluorescence intensity as a function of the fluorescence excitation and emission wavelength confirmed the formation of J-type aggregates in these cases. To have a better understanding of the type of self-assemblies formed from the TPE conjugates 4-6, we have carried out the morphological analysis through various microscopic techniques such as DLS, SEM and TEM. 70%, we observed rod shape architectures having ~ 780 nm in diameter and ~ 12 μM in length as evidenced through TEM and SEM analysis. We have made similar observations with the dodecyl conjugate 5 at ca. 70% and 50% water/acetonitrile mixtures, the aggregates formed from 4 and 5 were found to be highly crystalline and such structures were transformed to amorphous nature as the water fraction was increased to 99%. To evaluate the potential of the conjugate as bio-imaging agents, we have carried out their in vitro cytotoxicity and cellular uptake studies though MTT assay, flow cytometric and confocal laser scanning microscopic techniques. Thus nanoparticle of these conjugates which exhibited efficient emission, large stoke shift, good stability, biocompatibility and excellent cellular imaging properties can have potential applications for tracking cells as well as in cell-based therapies. In summary we have synthesized novel functional organic chromophores and have studied systematic investigation of self-assembly of these synthetic and biological building blocks under a variety of conditions. The investigation of interaction of water soluble NIR squaraine dyes with lysozyme indicates that these dyes can act as the protein labeling agents and the efficiency of inhibition of β-amyloid indicate, thereby their potential as anti-amyloid agents.

The Design and Synthesis of Versatile Molecular Building Blocks: Working Towards the Controlled Self-Assembly of Novel Functional Materials

Our research goals are focused on the preparation of novel molecule-based materials that possess specifically designed properties in solution or in the solid state e.g. self-assembly, magnetism, conductivity and spin crossover phenomena. Most of our systems incorporate paramagnetic transition metal ions and the search for new molecule-based magnetic materials is a prominent theme. Specific areas of research include the preparation and study of oxalate based 2D and 3D magnets, probing the versatility of octacyanometalate building blocks as precursors for new molecular magnets, and the preparation of new tetrathiafulvalene (TIF) derivatives for applications in molecular and supramolecular chemistry.