48 research outputs found

    Structure, Photophysics and the Order-Disorder Transition to the Beta Phase in Poly(9,9-(di -n,n-octyl)fluorene)

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    X-ray diffraction, UV-vis absorption and photoluminescence (PL) spectroscopy have been used to study the well-known order-disorder transition (ODT) to the beta phase in poly(9,9-(di n,n-octyl)fluorene)) (PF8) thin film samples through combination of time-dependent and temperature-dependent measurements. The ODT is well described by a simple Avrami picture of one-dimensional nucleation and growth but crystallization, on cooling, proceeds only after molecular-level conformational relaxation to the so called beta phase. Rapid thermal quenching is employed for PF8 studies of pure alpha phase samples while extended low-temperature annealing is used for improved beta phase formation. Low temperature PL studies reveal sharp Franck-Condon type emission bands and, in the beta phase, two distinguishable vibronic sub-bands with energies of approximately 199 and 158 meV at 25 K. This improved molecular level structural order leads to a more complete analysis of the higher-order vibronic bands. A net Huang-Rhys coupling parameter of just under 0.7 is typically observed but the relative contributions by the two distinguishable vibronic sub-bands exhibit an anomalous temperature dependence. The PL studies also identify strongly correlated behavior between the relative beta phase 0-0 PL peak position and peak width. This relationship is modeled under the assumption that emission represents excitons in thermodynamic equilibrium from states at the bottom of a quasi-one-dimensional exciton band. The crystalline phase, as observed in annealed thin-film samples, has scattering peaks which are incompatible with a simple hexagonal packing of the PF8 chains.Comment: Submitted to PRB, 12 files; 1 tex, 1 bbl, 10 eps figure

    Polymer Crystallization in 25 nm Spheres

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    Crystallization within the discrete spheres of a block copolymer mesophase was studied by time-resolved x-ray scattering. The cubic packing of microdomains, established by self-assembly in the melt, is preserved throughout crystallization by strong interblock segregation even though the amorphous matrix block is well above its glass transition temperature. Homogeneous nucleation within each sphere yields isothermal crystallizations which follow first-order kinetics, contrasting with the sigmoidal kinetics normally exhibited in the quiescent crystallization of bulk polymers.Comment: accepted for publication in Physical Review Letters, 2/28/2000; scheduled for 5/1/2000 issu

    STAMINA: Bioinformatics Platform for Monitoring and Mitigating Pandemic Outbreaks

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    Data Availability Statement: All data driven applications used the our world in data COVID-19 datasets, complimented by proprietary datasets share by the STAMINA consortium.Copyright © 2022 by the authors. This paper presents the components and integrated outcome of a system that aims to achieve early detection, monitoring and mitigation of pandemic outbreaks. The architecture of the platform aims at providing a number of pandemic-response-related services, on a modular basis, that allows for the easy customization of the platform to address user’s needs per case. This customization is achieved through its ability to deploy only the necessary, loosely coupled services and tools for each case, and by providing a common authentication, data storage and data exchange infrastructure. This way, the platform can provide the necessary services without the burden of additional services that are not of use in the current deployment (e.g., predictive models for pathogens that are not endemic to the deployment area). All the decisions taken for the communication and integration of the tools that compose the platform adhere to this basic principle. The tools presented here as well as their integration is part of the project STAMINA.The paper presented is based on research undertaken as part of the European Commission-funded project STAMINA (Grant Agreement 883441)

    A digital platform for cross-sector collaborative value networks in the circular economy

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    In recent years there has been a growing interest in Circular Economy (CE), which promises to reduce waste and improve sustainability. The promise of CE is to change the conventional "take-make-dispose"that causes massive waste flows based on the integration of demanufacturing and remanufacturing processes within value chains. This integration requires breaking the "silos"of the circular chain to establish new collaborative and sustainable value networks. The paper introduces a novel digital platform for the CE, which is currently under development in the H2020 DigiPrime project. The platform is destined to facilitate seamless and trusted information exchange across circular actors, while offering a range of value-added services that enable manufacturers, remanufactures, recyclers and other actors to gain insights in the status of recycling and waste management processes. The latter facilitates the implementation of zero waste processes, along with the assessment of the performance of the circular chain. The paper introduces the architecture of the digital platform, along with its data modelling, exchange and data traceability mechanisms. It also presents a CE use case used to validate the platform

    The technology of transdermal delivery nanosystems: from design and development to preclinical studies

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    Transdermal administration has gained much attention due to the remarkable advantages such as patient compliance, drug escape from first-pass elimination, favorable pharmacokinetic profile and prolonged release properties. However, the major limitation of these systems is the limited skin penetration of the stratum corneum, the skin's most important barrier, which protects the body from the insertion of substances from the environment. Transdermal drug delivery systems are aiming to the disruption of the stratum corneum in order for the active pharmaceutical ingredients to enter successfully the circulation. Therefore, nanoparticles are holding a great promise because they can act as effective penetration enhancers due to their small size and other physicochemical properties that will be analyzed thoroughly in this report. Apart from the investigation of the physicochemical parameters, a comparison between the different types of nanoparticles will be performed. The complexity of skin anatomy and the unclear mechanisms of penetration should be taken into consideration to reach some realistic conclusions regarding the way that the described parameters affect the skin permeability. To the best of the authors knowledge, this is among the few reports on the literature describing the technology of transdermal delivery systems and how this technology affects the biological activity. © 2021 Elsevier B.V

    Testing non-destructive spectrometric methods for the identification and distinction of archaeological pine wood tar and birch bark tar

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    Archaeological findings prove the appearance and use of birch bark tar since the Middle Palaeolithic. The production and use of birch bark tar and pine wood tar has overlapped since at least the late Neolithic, but probably for much longer. The reliable chemical identification of such archaeological tar residues can offer valuable insights into, for example, ancient technical complexity, trade and culture. In this context, the scarcity of these mainly organic residue findings in the archaeological record bears the need for non-destructive analytical tools. However, there is currently no systematic proposed way for this purpose. We aim here to verify the organic nature and test the reliability of the identification of archaeological pine wood tar and birch bark tar with a combination of SEM-EDS, FTIR microspectroscopy in reflectance mode and XRD. We examined a set of experimental adhesive replicas of pine tar and birch tar in pristine form, but also after a three-year-long weathering experiment. Additionally, we studied a set of archaeological samples, consisting of Mesolithic bone/antler points with adhering hafting residues, form the Dutch North Sea. This research shows that degradation negatively influences the reliable verification and identification of the organic residue constituents significantly. SEM-EDS as a starting point of analysis verifies the residue's organic nature, but it cannot be used to identify birch or pine tar. XRD can identify crystalline additives in the adhesive mixture, like ochre and wax, as well as phases related to the artefact's environment of burial and provenance. Micro-FTIR is also capable of verifying the organic matter of the residue constituents. The differentiation of birch and pine tars is hindered by vibrational modes occurring in neighbouring wavenumbers for both tars, and by the limited research on degradation markers indicative of thermal treatment to prove tar production. Until reference collections also account for degradation and include a wide variety of adhesives, results of FTIR collected in reflectance mode are best treated with some caution.Team Joris DikTeam Amarante BottgerDelft Aerospace Structures and Materials LaboratoryGroup Alderlieste

    A multi-analytical approach reveals flexible compound adhesive technology at Steenbokfontein Cave, Western Cape

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    Evidence of different compound resin-based adhesives is present in South Africa from at least 77000 years ago. Ancient glue production is considered one of the oldest known highly complex technologies, requiring advanced technological and mental abilities. However, our current knowledge of adhesive materials, recipes, and uses in South Africa is limited by the lack of in-depth analysis and molecular characterization of residues. To deepen our knowledge of past adhesive technology, we performed a detailed multi-analytical analysis (use-wear, XRD, μ-CT, IR spectroscopy, GC-MS) of 30 Later Stone Age tools with adhesive remains from Steenbokfontein Cave, South Africa. At the site, tools made of various rocks were hafted with compound adhesives, and we identified three recipes: 1) resin/tar of Widdringtonia or Podocarpus species combined with hematite; 2) resin/tar of Widdringtonia or Podocarpus species mixed with hematite and another plant exudate; 3) resin/tar without hematite. The studied scrapers were used in hide-working activities, and the studied cutting tools were used to work animal and soft plant matters. All scrapers display evidence of intense resharpening and were discarded when no longer useable. The combination of different methods for residue analysis reveals the flexibility of adhesive technology at Steenbokfontein. Despite the consistent use of conifer resin/tar throughout the sequence, we observed that other ingredients were added or excluded independently of the tools’ raw materials and functions. Our results highlight the long-lasting tradition of using adhesive material from conifer species but also the adaptability and flexibility of adhesive traditions. The systematic application of this multi-analytical approach to Pleistocene adhesives will be useful to better characterise adhesive traditions and enhance the debate on the technological, cognitive, and behavioural implications of this technology.Team Joris DikGeo-engineeringTeam Amarante Bottge
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