Novel Melt Transurethane Process for Cycloaliphatic Polyurethanes and Their Self-Organization for Nano-Materials

In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

Systematics of properties of the electron gas in deep-etched quantum wires

An efficient method is developed for an iterative solution of the Poisson and Schro¿dinger equations, which allows systematic studies of the properties of the electron gas in linear deep-etched quantum wires. A much simpler two-dimensional (2D) approximation is developed that accurately reproduces the results of the 3D calculations. A 2D Thomas-Fermi approximation is then derived, and shown to give a good account of average properties. Further, we prove that an analytic form due to Shikin et al. is a good approximation to the electron density given by the self-consistent methods.

Influence of the pseudopotential on the properties of liquid rubidium at 315 K

The influence of the pseudopotential on both the structure and the self-diffusion of liquid rubidium at the melting point has been investigated by means of molecular-dynamics calculations. The model potential considered has been computed from the pseudopotential of Ashcroft, the dielectric function of Geldart and Vosko, and a Born-Mayer term. Four different values for the core radius which enters as input in the pseudopotential have been considered. In this way we have been able to observe and interpret the effect of this contribution on the properties of the liquid.

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.

Accurate Hartree-Fock-Slater calculations on small diatomic molecules with the finite-element method

We report on the self-consistent field solution of the Hartree-Fock-Slater equations using the finite-element method for the three small diatomic molecules N_2, BH and CO as examples. The quality of the results is not only better by two orders of magnitude than the fully numerical finite difference method of Laaksonen et al. but the method also requires a smaller number of grid points.

Work and economic security in the 21st century

In recent decades there has been a transformation of two central concepts of modernity – labour and the household. Ela Bhatt – the founder of the Self-Employed Women’s Association of India (SEWA), has made an important contribution to this transformation. Through the emergence of unions such as SEWA, the notion of who represents labour is being broadened; the marginalised are finding an institutional voice. Increasingly, the household is being recognised as a site of both production and reproduction. SEWA is not a traditional trade union that aims, through collective bargaining with an employer, to improve its members’ wages and working conditions as sellers of their labour power. Instead, it aims to empower women economically in the informal economy by bringing them into the mainstream economy as owners of their labour. The union dimension of SEWA builds their collective power through struggle; the cooperative dimension translates their bargaining power into the economic and social development of its members and their community. Besides, Bhatt’s approach to the self-employed was a direct challenge to the ILO’s tripartism when it was established in the early seventies. The first part of the paper provides a short biography of Ela Bhatt, describes the origins of SEWA, analyses a ‘classification struggle’ over how and who is to define what a worker is. In the second part the author considers SEWAs innovative organizing strategy and is rethinking modernity in the labour context. In the conclusion the paper discusses the lessons that can be learnt from Ela Bhatt.

Self-Assembly of Stimuli-Responsive Water-Soluble [60]Fullerene End-Capped Ampholytic Block Copolymer

Well-defined, water-soluble, pH and temperature stimuli-responsive [60]fullerene (C₆₀) containing ampholytic block copolymer of poly((methacrylic acid)-block-(2-(dimethylamino)ethyl methacrylate))-block–C₆₀ (P(MAA-b-DMAEMA)-b-C₆₀) was synthesized by the atom transfer radical polymerization (ATRP) technique. The self-assembly behaviour of the C₆₀ containing polyampholyte in aqueous solution was characterized by dynamic light scattering (DLS), and transmission electron microscopy. This amphiphilic mono-C₆₀ end-capped block copolymer shows enhanced solubility in aqueous medium at room and elevated temperatures and at low and high pH but phase-separates at intermediate pH of between 5.4 and 8.8. The self assembly of the copolymer is different from that of P(MAA-b-DMAEMA). Examination of the association behavior using DLS revealed the co-existence of unimers and aggregates at low pH at all temperatures studied, with the association being driven by the balance of hydrophobic and electrostatic interactions. Unimers and aggregates of different microstructures are also observed at high pH and at temperatures below the lower critical solution temperature (LCST) of PDMAEMA. At high pH and at temperatures above the LCST of PDMAEMA, the formation of micelles and aggregates co-existing in solution is driven by the combination of hydrophobic, electrostatic, and charge-transfer interactions.

The agreement between ipsative and normative questionnaires using compositional data analysis techniques

The main instrument used in psychological measurement is the self-report questionnaire. One of its major drawbacks however is its susceptibility to response biases. A known strategy to control these biases has been the use of so-called ipsative items. Ipsative items are items that require the respondent to make between-scale comparisons within each item. The selected option determines to which scale the weight of the answer is attributed. Consequently in questionnaires only consisting of ipsative items every respondent is allotted an equal amount, i.e. the total score, that each can distribute differently over the scales. Therefore this type of response format yields data that can be considered compositional from its inception. Methodological oriented psychologists have heavily criticized this type of item format, since the resulting data is also marked by the associated unfavourable statistical properties. Nevertheless, clinicians have kept using these questionnaires to their satisfaction. This investigation therefore aims to evaluate both positions and addresses the similarities and differences between the two data collection methods. The ultimate objective is to formulate a guideline when to use which type of item format. The comparison is based on data obtained with both an ipsative and normative version of three psychological questionnaires, which were administered to 502 first-year students in psychology according to a balanced within-subjects design. Previous research only compared the direct ipsative scale scores with the derived ipsative scale scores. The use of compositional data analysis techniques also enables one to compare derived normative score ratios with direct normative score ratios. The addition of the second comparison not only offers the advantage of a better-balanced research strategy. In principle it also allows for parametric testing in the evaluation

A Self-Scoring Exercise On APA Style, Research Language, and Referencing for Undergraduate Students

Based on examples provided by 27 graduate psychology faculty, this self-test incorporates many of the more common errors in style, language, and referencing found in student papers. Taking this self-test helps students to recognize common errors and encourages them to refer the APA Publication Manual on a regular basis. In addition, students begin to think about how to use correctly the language of psychological research. This self-test should take about 30 minutes to complete and score. It is composed of three parts: a) a mock Discussion section, where students are asked to act as editors and find the errors, p. 2 (10 minutes). b) a corrected Discussion section, where students find the errors they missed, p. 3 (5 minutes) and, c) a full description of each error with illustrations of correct usage, pp. 4-7 (15 minutes). This exercise assumes some knowledge of APA style. Thus, it is best-suited for advanced undergraduates who need to write research reports and all levels of graduate students. It may be taken at home or in class. Although the self-test is designed to be fully self-directed, instructors may wish to use it at the beginning or end of a classroom discussion on APA style. It could also be used in a pre-test-post-test fashion to evaluate students learning over the course of a term.

Using video markschemes to support self-assessment in Chemistry

A video markscheme was created using a combination of Camtasia screen capture (on a Tablet PC) and 'live action' video taken with a camcorder. The resulting video supported students in the self-assessment of an organic chemistry exercise which had been set over the Easter vacation break. Feedback was collected from the students after the exercise and was overwhelmingly positive. The video won the 2010 award for 'Most Effective Use of Video in an Educational Context' from the Assocation for Learning Technology. DOWNLOAD THE ZIP FOLDER AND EXTRACT THE FILES TO ACCESS THEM.

Analysis of the alveolar recruitment maneuvers applied at seven intensive care units

Introduction: During the past years, alveolar recruitment maneuvers (RM) have produced growing interest due to their beneficial potential in pulmonary protection, and have been introduced in clinical practice. Objective: To describe and analyze the knowledge of MR and its application at seven intensive care units in the city of Cali, Colombia. Methods and materials: Descriptive Cross-Sectional Study with an intentional sample of 64 professionals working in seven intensive care units and who apply MR. The self-completed survey was made up of thirteen questions, and the application period was two months. Results: Out of 64 professionals surveyed, 77.8% of them follow a protocol guide; 54.7% employes during RM the ideal Positive end-expiratory pressure (PEEP), which maintains a saturation > 90% and a PaO2 > 60 mmHg; 42.1% tolerates airway pressures between 35 and 50 cmH2O; 48.4% perform RM with a progressive increase of the PEEP and a low tidal volume. Conclusions: Regarding the knowledge related to RM, heterogeneity was found in the answers. There is currently no consensus about which is the most effective and secure way to implement an MR. This study can be the starting point to create awareness towards the revision of knowledge, capacities and abilities that are required to perform RM.

The dialectic of silence and remembrance in Lily Brett’s ''Things could be worse''

The dynamics of silence and remembrance in Australian writer Lily Brett’s autobiographic fiction Things Could Be Worse reflects the crisis of memory and understanding experienced by both first and second-generation Holocaust survivors within the diasporic space of contemporary Australia. It leads to issues of handling traumatic and transgenerational memory, the latter also known as postmemory (M. Hirsch), in the long aftermath of atrocities, and problematises the role of forgetting in shielding displaced identities against total dissolution of the self. This paper explores the mechanisms of remembrance and forgetting in L. Brett’s narrative by mainly focusing on two female characters, mother and daughter, whose coming to terms with (the necessary) silence, on the one hand, and articulated memories, on the other, reflects different modes of comprehending and eventually coping with individual trauma. By differentiating between several types of silence encountered in Brett’s prose (that of the voiceless victims, of survivors and their offspring, respectively), I argue that silence can equally voice and hush traumatic experience, that it is never empty, but invested with individual and collective meaning. Essentially, I contend that beside the (self-)damaging effects of silence, there are also beneficial consequences of it, in that it plays a crucial role in emplacing the displaced, rebuilding their shattered self, and contributing to their reintegration, survival and even partial healing.

Museums and quality, from the concept of the museum that carries out functions to the museum that provides services

Quality management Self-evaluation of the organisation Citizens/customers satisfaction Impact on society evaluation Key performance evaluation Good practices comparison (Benchmarking) Continuous improvement In professional environments, when quality assessment of museums is discussed, one immediately thinks of the honourableness of the directors and curators, the erudition and specialisation of knowledge, the diversity of the gathered material and study of the collections, the collections conservation methods and environmental control, the regularity and notoriety of the exhibitions and artists, the building’s architecture and site, the recreation of environments, the museographic equipment design. We admit that the roles and attributes listed above can contribute to the definition of a specificity of museological good practice within a hierarchised functional perspective (the museum functions) and for the classification of museums according to a scale, validated between peers, based on “installed” appreciation criteria, enforced from above downwards, according to the “prestige” of the products and of those who conceive them, but that say nothing about the effective satisfaction of the citizen/customers and the real impact on society. There is a lack of evaluation instruments that would give us a return of all that the museum is and represents in contemporary society, focused on being and on the relation with the other, in detriment of the ostentatious possession and of the doing in order to meet one’s duties. But it is only possible to evaluate something by measurement and comparison, on the basis of well defined criteria, from a common grid, implicating all of the actors in the self-evaluation, in the definition of the aims to fulfil and in the obtaining of results.

The Fundamental Rights Agency and Civil Society: Reminding the Gardeners of their Plants' Roots. EDAP 02/2012, 2012

The European Union Agency for Fundamental Rights (FRA), the EU body responsible for advising EU institutions on fundamental rights, is equipped with a Fundamental Rights Platform (FRP) to ensure an on-going and structured exchange of information and feedback between the FRA and Civil Society. When the FRA was founded in 2007, there was little pre-existing knowledge on how to design such a Platform; hence, the development of the relationship between the FRA and Civil Society over the first five years proved an interesting experiment. Although the Platform was never intended as a mechanism of democratic co-decision making, it is far more than a loose marketplace where Civil Society actors across the spectrum of fundamental rights themes gather. The Platform offers channels of consultation and exchange not only among the participants but also with the FRA. It allows for cross-pollination, ensuring informed grassroots input into FRA work and FRA expertise flow to Civil Society actors. This synergetic relationship builds upon both the self-organising forces of Civil Society and the terms of references of the FRP as defined by the FRA. The Platform allows to find a certain unity in the remarkable diversity of fundamental rights voices. To what degree, however, the Platform’s dynamics allow the transformation of sometimes ‘compartmentalised’ single human rights discussions into wider trans-sectoral and transnational debates within the Human Rights Community depends on the motivation and the interest(s) of the different Civil Society players.

The counter-propagating Rossby-wave perspective on baroclinic instability. II: Application to the Charney model

The constant-density Charney model describes the simplest unstable basic state with a planetary-vorticity gradient, which is uniform and positive, and baroclinicity that is manifest as a negative contribution to the potential-vorticity (PV) gradient at the ground and positive vertical wind shear. Together, these ingredients satisfy the necessary conditions for baroclinic instability. In Part I it was shown how baroclinic growth on a general zonal basic state can be viewed as the interaction of pairs of ‘counter-propagating Rossby waves’ (CRWs) that can be constructed from a growing normal mode and its decaying complex conjugate. In this paper the normal-mode solutions for the Charney model are studied from the CRW perspective. Clear parallels can be drawn between the most unstable modes of the Charney model and the Eady model, in which the CRWs can be derived independently of the normal modes. However, the dispersion curves for the two models are very different; the Eady model has a short-wave cut-off, while the Charney model is unstable at short wavelengths. Beyond its maximum growth rate the Charney model has a neutral point at finite wavelength (r=1). Thereafter follows a succession of unstable branches, each with weaker growth than the last, separated by neutral points at integer r—the so-called ‘Green branches’. A separate branch of westward-propagating neutral modes also originates from each neutral point. By approximating the lower CRW as a Rossby edge wave and the upper CRW structure as a single PV peak with a spread proportional to the Rossby scale height, the main features of the ‘Charney branch’ (0the normal modes. Furthermore, CRWs from this branch are seen to make a smooth transition into the boundary and interior PV structure of the neutral modes appearing at r=1. The behaviour of the other branches and neutral points is essentially the same when viewed from the CRW perspective, but with cancelling interior PV structures reducing the self and mutual interaction of the CRWs. The underlying dynamics determining the nature of all the solutions is the difference in the scale-dependence of PV inversion for boundary and interior PV anomalies, the Rossby-wave propagation mechanism and the CRW interaction. The behaviour of the Charney modes and the first neutral branch, which rely on tropospheric PV gradients, are arguably more applicable to the atmosphere than modes of the Eady model where the positive PV gradient exists only at the tropopause