Heparin-containing block copolymers, Part I: Surface characterization

Newly synthesized heparin-containing block copolymers, consisting of a hydrophobic block of polystyrene (PS), a hydrophilic spacer-block of poly(ethylene oxide) (PEO) and covalently bound heparin (Hep) as bioactive block, were coated on aluminium, glass, polydimethylsiloxane (PDMS), PS or Biomer substrates. Surfaces of coated materials were characterized by transmission electron microscopy (TEM), contact angle measurements and X-ray photoelectron spectroscopy for chemical analysis (XPS). It was demonstrated by TEM that thin films of PS-PEO and PS-PEO-Hep block copolymers consisted of heterogeneous microphase separated structures. Using sessile-drop and Wilhelmy plate dynamic contact angle measurements, insight was provided into the hydrophilicity of the surfaces of the coatings. Measurements with hydrated coatings of PS-PEO and PS-PEO-Hep block copolymers revealed that the surfaces became more hydrophilic during immersion in water, due to relaxation/reorientation, or swelling of PEO or PEO-Hep domains, respectively. XPS results for PS, PEO, heparin and PS-PEO as powder agreed well with qualitative and quantitative predictions. XPS results for films of PS-PEO and PS-PEO-Hep block copolymers showed enrichments of PEO in the top layers of the coatings. This effect was more pronounced for hydrated surfaces. Only small amounts of heparin were detected at the surface of coatings of PS-PEO-Hep block copolymers

Correlative Microscopy of Morphology and Luminescence of Cu porphyrin aggregates

Transfer of energy and information through molecule aggregates requires as one important building block anisotropic, cable-like structures. Knowledge on the spatial correlation of luminescence and morphology represents a prerequisite in the understanding of internal processes and will be important for architecting suitable landscapes. In this context we study the morphology, fluorescence and phosphorescence of molecule aggregate structures on surfaces in a spatially correlative way. We consider as two morphologies, lengthy strands and isotropic islands. It turns out that phosphorescence is quite strong compared to fluorescence and the spatial variation of the observed intensities is largely in line with the amount of dye. However in proportion, the strands exhibit more fluorescence than the isotropic islands suggesting weaker non-radiative channels. The ratio fluorescence to phosphorescence appears to be correlated with the degree of aggregation or internal order. The heights at which luminescence saturates is explained in the context of attenuation and emission multireflection, inside the dye. This is supported by correlative photoemission electron microscopy which is more sensitive to the surface region. The lengthy structures exhibit a pronounced polarization dependence of the luminescence with a relative dichroism up to about 60%, revealing substantial perpendicular orientation preference of the molecules with respect to the substrate and parallel with respect to the strands

Directed Molecular Stacking for Engineered Fluorescent Three-Dimensional Reduced Graphene Oxide and Coronene Frameworks

[EN] Three‐dimensional fluorescent graphene frameworks with controlled porous morphologies are of significant importance for practical applications reliant on controlled structural and electronic properties, such as organic electronics and photochemistry. Here we report a synthetically accessible approach concerning directed aromatic stacking interactions to give rise to new fluorogenic 3D frameworks with tuneable porosities achieved through molecular variations. The binding interactions between the graphene‐like domains present in the in situ‐formed reduced graphene oxide (rGO) with functional porphyrin molecules lead to new hybrids via an unprecedented solvothermal reaction. Functional free‐base porphyrins featuring perfluorinated aryl groups or hexyl chains at their meso‐ and β‐positions were employed in turn to act as directing entities for the assembly of new graphene‐based and foam‐like frameworks and of their corresponding coronene‐based hybrids. Investigations in the dispersed phase and in thin‐film by XPS, SEM and FLIM shed light onto the nature of the aromatic stacking within functional rGO frameworks (denoted rGOFs) which was then modelled semi‐empirically and by DFT calculations. The pore sizes of the new emerging reduced graphene oxide hybrids are tuneable at the molecular level and mediated by the bonding forces with the functional porphyrins acting as the “molecular glue”. Single crystal X‐ray crystallography described the stacking of a perfluorinated porphyrin with coronene, which can be employed as a molecular model for understanding the local aromatic stacking order and charge transfer interactions within these rGOFs for the first time. This opens up a new route to controllable 3D framework morphologies and pore size from the Ångstrom to the micrometre scale. Theoretical modelling showed that the porosity of these materials is mainly due to the controlled inter‐planar distance between the rGO, coronene or graphene sheets. The host‐guest chemistry involves the porphyrins acting as guests held through π‐π stacking, as demonstrated by XPS. The objective of this study is also to shed light into the fundamental localised electronic and energy transfer properties in these new molecularly engineered porous and fluorogenic architectures, aiming in turn to understand how functional porphyrins may exert stacking control over the notoriously disordered local structure present in porous reduced graphene oxide fragments. By tuning the porosity and the distance between the graphene sheets using aromatic stacking with porphyrins, it is also possible to tune the electronic structure of the final nanohybrid material, as indicated by FLIM experiments on thin films. Such nanohybrids with highly controlled pores dimensions and morphologies open the way to new design and assembly of storage devices and applications incorporating π‐conjugated molecules and materials and their π‐stacks may be relevant towards selective separation membranes, water purification and biosensing applications.S.I.P. and S.W.B. thank The Royal Society and STFC for funding. B.Y.M. thanks the University of Bath for a studentship (ORS). D.G.C. thanks the Fundación General CSIC for funding (ComFuturo Program). Dr. Jose A. Ribeiro Martins, Professors Jeremy K. M. Sanders and Paul Raithby are acknowledged for training, helpful discussions and porphyrin supramolecular chemistry. The S.I.P. group thanks the EPSRC for funding to the Centre of Graphene Science (EP/K017160/1) and to the Centre for Doctoral Training in Sustainable Chemical Technologies (EP/L016354/1). The authors thank EPSRC National Service for Mass Spectrometry at Swansea and EPSRC National Service for Crystallography at Southampton for data collection. The authors also acknowledge the ERC for the Consolidator Grant O2SENSE (617107, 2014–2019)

Development and evaluation of superconducting circuit elements

An approach to the application of high Tc ceramic superconductors to practical circuit elements was developed and demonstrated. This method, known as the rigid-conductor process (RCP), involves the combination of a pre-formed, sintered, and tested superconductor material with an appropriate, rigid substrate via an epoxy adhesive which also serves to encapsulate the element from the ambient environment. Emphasis was on the practical means to achieve functional, reliable, and reproducible components. Although all of the work described in this report involved a YBa2Cu3Osub(7-x) high Tc superconductor material, the techniques developed and conclusions reached are equally applicable to other high Tc materials

NASA Thesaurus Supplement: A three part cumulative supplement to the 1982 edition of the NASA Thesaurus (supplement 2)

The three part cumulative NASA Thesaurus Supplement to the 1982 edition of the NASA Thesaurus includes: part 1, hierarchical listing; part 2, access vocabulary, and part 3, deletions. The semiannual supplement gives complete hierarchies for new terms and includes new term indications for terms new to this supplement

Index to NASA Tech Briefs, January - June 1967

Technological innovations for January-June 1967, abstracts and subject inde

A New Phenomenon: Sub-Tg, Solid-State, Plasticity-Induced Bonding in Polymers

Polymer self-adhesion due to the interdiffusion of macromolecules has been an active area of research for several decades [70, 43, 62, 42, 72, 73, 41]. Here, we report a new phenomenon of sub-Tg, solid-state, plasticity-induced bonding; where amorphous polymeric films were bonded together in a period of time on the order of a second in the solid-state at ambient temperatures nearly 60 K below their glass transition temperature (Tg) by subjecting them to active plastic deformation. Despite the glassy regime, the bulk plastic deformation triggered the requisite molecular mobility of the polymer chains, causing interpenetration across the interfaces held in contact. Quantitative levels of adhesion and the morphologies of the fractured interfaces validated the sub-Tg, plasticity-induced, molecular mobilization causing bonding. No-bonding outcomes (i) during the compression of films in a near hydrostatic setting (which inhibited plastic flow) and (ii) between an 'elastic' and a 'plastic' film further established the explicit role of plastic deformation in this newly reported sub-Tg solid-state bonding

Vegetable oil hybrid films cross-linked at the air-water interface: formation kinetics and physical characterization

Vegetable oil based hybrid films were developed thanks to a novel solvent- and heating- free method at the air-water interface using silylated castor oil cross-linked via a sol-gel reaction. To understand the mechanism of the hybrid film formation, the reaction kinetics was studied in detail by using complementary techniques: rheology, thermogravimetric analysis, and infrared spectroscopy. The mechanical properties of the final films were investigated by nano-indentation, whereas their structure was studied using a combination of wide-angle X-ray scattering, electron diffraction, and atomic force microscopy. We found that solid and transparent films form in 24 hours and, by changing the silica precursor to castor oil ratio, their mechanical properties are tunable in the MPa-range by about a factor of twenty. In addition to that, a possible optimization of the cross-linking reaction with different catalysts was explored and finally, cytotoxicity tests were performed on fibroblasts proving the absence of film toxicity. The results of this work pave the way to a straightforward synthesis of castor-oil films with tunable mechanical properties: hybrid films cross-linked at the air-water interface combine an easy and cheap spreading protocol with the features of their thermal history optimized for possible future micro/nano drug loading, thus representing excellent candidates for the replacement of non-environment friendly petroleum-based materials

Silodosin oral films: Development, physico-mechanical properties and in vitro dissolution studies in simulated saliva

Sublingual film dosage forms for drugs used for fast symptomatic treatment have promise because they allow a rapid onset of action. The aim of this study was to prepare films of silodosin intended for sublingual administration for the symptomatic treatment of benign prostatic hyperplasia in men. Hydroxypropyl methylcellulose (HPMC) or hydroxypropyl methylcellulose acetate succinate (HPMC-AS) were used as film-forming polymers. The effects of the polymers and the surfactant tocopherol polyethylene glycol succinate (TPGS) on the physico-mechanical properties and dissolution behavior of the films in simulated saliva were investigated. The eight silodosin oral films developed (F1–F8) contained 8 mg silodosin per 6 cm2 film and HPMC or HPMC-AS in drug:polymer ratios of 1:5 or 1:3, while four also contained TPGS (0.5% w/w). The films were characterized using DSC, TGA, SEM, and PXRD and the mechanical properties were investigated by measuring tensile strength, elongation at break and Young's modulus. The mechanical properties of the films were dependent on the ratio of polymer used. The in vitro dissolution and drug release studies indicated that HPMC-AS films disintegrated more quickly than HPMC films. Silodosin was shown to be dispersed within the polymers. Despite silodosin being submicronized in the HPMC films, the dissolution and drug release rate (time for 80% release) from HPMC films was significantly faster than from HPMC-AS films. TPGS increased the drug release rate to a greater extent with HPMC than with HPMC-AS. The degree of saturation of formulation F4 was >1, which shows potential for improving oral absorption of silodosin.Peer reviewe