Structural Characterization of Colloidal Core-shell Polymer-based Nanoparticles Using Small-angle X-ray Scattering

Colloidal particle complexes are often characterized by small angle X-ray scattering (SAXS) techniques. The present work demonstrates SAXS analysis of inhomogeneous core-shell nanoparticles with complex shell morphologies. Different experimental techniques such as variation of particle composition and contrast variation method, and analytical techniques such as Monte Carlo simulation and indirect Fourier transformation are applied to obtain structural parameters of polymer-based core-shell nanoparticles. It is shown that the SAXS results are consistent with other measurements performed by electron microscopy, atomic force microscopy, dynamic light scattering, thermogravimetry, helium pycnometry and BET. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3477

Change in Prosody as an Alternative: Evidence from Acquisition

This study contributes to the issue of syntax-prosody-semantics interaction in child speech. It focuses on the prosodic realization of contextually-defined direct objects in a language allowing object scrambling. The empirical data are collected from 3-4-year-old children acquiring Ukrainian. The children’s speech samples were analyzed in order to find contrast between the prosody of sentences with various syntactic and semantic properties. The results show that child intonation is variable, but mostly predictable. The most evident contrast was detected for the structures with pronouns: when children failed to scramble pronouns, they still marked them prosodically by destressing. It can be concluded, then, that 3-4-year-old children are able to establish context relatedness for pronouns, and in order to mark their special status they can use one of two ‘options’ available in the grammar: syntactic movement or prosodic recontouring

Aligning self-assembled gelators by drying under shear

We show how drying under shear can be used to prepare aligned fibres and worm-like micelles from low molecular weight gelators. Shearing followed by drying leads to the dealignment before the water can be removed; continuous shear whilst drying is required to maintain the alignment. Combining a slow pH change with continuous shear allows alignment of the gelling fibres, which can then be dried

Enthalpic incompatibility between two steric stabilizer blocks provides control over the vesicle size distribution during polymerization-induced self-assembly in aqueous media

Over the past two decades, block copolymer vesicles have been widely used by many research groups to encapsulate small molecule drugs, genetic material, nanoparticles or enzymes. They have also been used to design examples of autonomous self-propelled nanoparticles. Traditionally, such vesicles are prepared via post-polymerization processing using a water-miscible co-solvent such as DMF or THF. However, such protocols are invariably conducted in dilute solution, which is a significant disadvantage. In addition, the vesicle size distribution is often quite broad, whereas aqueous dispersions of relatively small vesicles with narrow size distributions are highly desirable for potential biomedical applications. Alternatively, concentrated dispersions of block copolymer vesicles can be directly prepared via polymerization-induced self-assembly (PISA). Moreover, using a binary mixture of a relatively long and a relatively short steric stabilizer block enables the convenient PISA synthesis of relatively small vesicles with reasonably narrow size distributions in alcoholic media (C. Gonzato et al., JACS, 2014, 136, 11100–11106). Unfortunately, this approach has not yet been demonstrated for aqueous media, which would be much more attractive for commercial applications. Herein we show that this important technical objective can be achieved by judicious use of two chemically distinct, enthalpically incompatible steric stabilizer blocks, which ensures the desired microphase separation across the vesicle membrane. This leads to the formation of well-defined vesicles of around 200 nm diameter (size polydispersity = 13–16%) in aqueous media at 10% w/w solids as judged by transmission electron microscopy, dynamic light scattering and small-angle X-ray scattering

RAFT Dispersion Alternating Copolymerization of Styrene with N-Phenylmaleimide: Morphology Control and Application as an Aqueous Foam Stabilizer

We report a new nonaqueous polymerization-induced self-assembly (PISA) formulation based on the reversible addition−fragmentation chain transfer (RAFT) dispersion alternating copolymerization of styrene with N-phenylmaleimide using a nonionic poly(N,N-dimethylacrylamide) stabilizer in a 50/50 w/w ethanol/methyl ethyl ketone (MEK) mixture. The MEK cosolvent is significantly less toxic than the 1,4-dioxane cosolvent reported previously [Yang, P.; et al. Macromolecules 2013, 46, 8545−8556]. The core-forming alternating copolymer block has a relatively high glass transition temperature (Tg), which leads to vesicular morphologies being observed during PISA, as well as the more typical sphere and worm phases. Each of these copolymer morphologies has been characterized by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) studies. TEM studies reveal micrometer-sized elliptical particles with internal structure, with SAXS analysis suggesting an oligolamellar vesicle morphology. This structure differs from that previously reported for a closely related PISA formulation utilizing a poly(methacrylic acid) stabilizer block for which unilamellar platelet-like particles are observed by TEM and SAXS. This suggests that interlamellar interactions are governed by the nature of the steric stabilizer layer. Moreover, using the MEK cosolvent also enables access to a unilamellar vesicular morphology, despite the high Tg of the alternating copolymer coreforming block. This was achieved by simply conducting the PISA synthesis at a higher temperature for a longer reaction time (80 °C for 24 h). Presumably, MEK solvates the core-forming block more than the previously utilized 1,4-dioxane cosolvent, which leads to greater chain mobility. Finally, preliminary experiments indicate that the worms are much more efficient stabilizers for aqueous foams than either the spheres or the oligolamellar elliptical vesicles

The Application of Fuzzy Logic for Rating of Suppliers for the Firm

Cílem této diplomové práce je navrhnout vhodnou metodu pro vyhodnocení dodavatelů průmyslových větráku pro společnost První brněnská strojírna a.s. (PBS Brno). Společnost existuje více než 200 let na trhu a má více než 100 dodavatelů po celém světě. Proto je potřeba navrhnout adekvátní systém hodnocení dodavatelů. Pro vyhodnocení budou použité programy MS Excel a MATLAB.Aim of this diploma thesis is to recommend appropriate method how to evaluate suppliers of industrial fans for První brněnská strojírna a.s. (PBS Brno). The company has already existed for more than 200 years and has more than 100 suppliers all over the world. Therefore, there is need for adequate evaluation method. For the evaluation MS Excel and MATLAB programs will be used.

Financing of Business Activities

Bakalářská práce řeší způsoby financování pořízení dlouhodobého hmotného majetku pro konkrétní firmu. Teoretická část objasňuje jednotlivé pojmy z oblasti financí. V praktické časti je představena společnost a majetek, jehož pořízení řeším. Dále srovnám všechny možnosti financování tohoto dlouhodobého majetku. Cílem práce je vybrat nejlepší způsob financování investice pro firmu.The Bachelor thesis deals with the funding methods of fixed assets acquisition for the company. Theoretic part explain the terminology of the financial sphere. In the practical part company and the acquisited asset are introduced. Next is the comparison of all the fuding methods of that acquisition. The work´s aim is to choose the best way for the company to fund the investment.

Flow-induced crystallisation of polymers from aqueous solution

Synthetic polymers are thoroughly embedded in the modern society and their consumption grows annually. Efficient routes to their production and processing have never been more important. In this respect, silk protein fibrillation is superior to conventional polymer processing, not only by achieving outstanding physical properties of materials, such as high tensile strength and toughness, but also improved process energy efficiency. Natural silk solidifies in response to flow of the liquid using conformation-dependent intermolecular interactions to desolvate (denature) protein chains. This mechanism is reproduced here by an aqueous poly(ethylene oxide) (PEO) solution, which solidifies at ambient conditions when subjected to flow. The transition requires that an energy threshold is exceeded by the flow conditions, which disrupts a protective hydration shell around polymer molecules, releasing them from a metastable state into the thermodynamically favoured crystalline state. This mechanism requires vastly lower energy inputs and demonstrates an alternative route for polymer processing

Structural and mechanistic studies of the pyridoxal 5’-phosphate-dependent enzyme serine palmitoyltransferase

Sphingolipids (SLs) are complex lipid-derived structures that are essential components of cell membranes in eukaryotes and some bacteria. SLs and their complex derivatives ceramides are known to be involved in multiple processes such as the formation of lipid rafts, cell signalling and membrane trafficking. The first step of SL biosynthesis is universal to all sphingolipid-producing organisms from bacteria to humans and is catalysed by the enzyme serine palmitoyltransferase (SPT). SPT is a member of the alpha-oxoamine synthase (AOS) family of pyridoxal- 5’-phosphate-dependent enzymes. All AOS family enzymes retain a high degree of structural homology and catalyse the decarboxylative Claisen-like condensation of amino acids with thioester substrates. The SPT enzyme catalyses the formation of the universal SL precursor, 3-ketodihydrosphingosine (KDS), by condensation of L-serine and coenzyme A-derived palmitic acid. Being the key controller in SL biosynthesis, SPT plays a big role in regulating natural and pathological processes. A lot of research interest has been recently generated by SLs isolated from bacterial members of the human microbiome and their roles in human health. Increasing evidence suggests that some of these SLs possess immunoregulatory effects and can have a direct impact on the immunity of the host. Bacteroides fragilis is a commensal gut-dwelling bacterium that belongs to a few human microbionts known to produce unique iso-branched sphingolipids (isoSLs); these have been shown to influence the human iNKT cell count. The production of SLs in B.fragilis is completely regulated by a gene product BF2461. In this work, BF2461 was expressed and purified; using a combination of UV-vis spectrometry, enzymatic assays, mass spectrometry and protein X-ray crystallography, it has been confirmed to be an SPT. The substrate specificity of the BfSPT has been assessed with a range of different chain-length substrates, including less common 15 and 17-carbon chain length coenzyme A substrates. The enzyme can produce different types of SL precursors with a preference for the 16-carbon chain substrate palmitoyl- CoA. However, at high levels of PCoA, a substrate inhibition is observed that might point to a natural control mechanism employed by the bacterium in favour of producing iso-branched SLs (isoSLs). The structure of BfSPT has been elucidated in a complex with its amino acid substrate L-serine. Search and analysis of putative SPTs from other microbiome-associated bacteria that produce isoSLs show that they share high similarity with an average amino acid conservation of 74%, suggesting they might be adapted to a particular type of substrate. In this respect, BfSPT might be the first isoSL-producing SPT to be structurally characterised, and the first one to have a direct impact on human health. Further structural data were obtained on protein complexes with L-cycloserine and L-penicillamine, some common inhibitors of the PLP-dependent enzymes. The structure obtained in the presence of L-penicillamine provides the first direct structural evidence of the inhibitory mechanism by a thiazolidine complex formation in the active site of a PLP-dependent enzyme. These findings shed light on certain aspects of the reaction and inhibition mechanisms of BfSPT as well as opening new prospects into researching this interesting target and its impact on the human microbiome

Loading of silica nanoparticles in block copolymer vesicles during polymerization-induced self-assembly: encapsulation efficiency and thermally-triggered release

Poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) diblock copolymer vesicles can be prepared in the form of concentrated aqueous dispersions via polymerization-induced self-assembly (PISA). In the present study, these syntheses are conducted in the presence of varying amounts of silica nanoparticles of approximately 18 nm diameter. This approach leads to encapsulation of up to hundreds of silica nanoparticles per vesicle. Silica has high electron contrast compared to the copolymer and its thermal stability enables quantification of the loading efficiency via thermogravimetric analysis. Encapsulation efficiencies can be obtained using disk centrifuge photosedimentometry, since the vesicle density increases at higher silica loadings while the mean vesicle diameter remains essentially unchanged. Small angle X-ray scattering (SAXS) is used to confirm silica encapsulation, since a structure factor is observed at q ~ 0.25 nm-1. A new two-population model provides satisfactory data fits to the SAXS patterns and allows the mean silica volume fraction within the vesicles to be determined. Finally, the thermo-responsive nature of the diblock copolymer enables thermally-triggered release of the encapsulated silica nanoparticles simply by cooling to 0-10 oC, which induces a morphological transition. These silica-loaded vesicles constitute a useful model system for understanding the encapsulation of globular proteins, enzymes or antibodies within block copolymer vesicles for potential biomedical applications. They may also serve as an active payload for self-healing hydrogels or repair of biological tissue. Finally, we also encapsulate a model globular protein, bovine serum albumin, and calculate its loading efficiency using fluorescence spectroscopy. Please click Additional Files below to see the full abstract