Search

We study the particle size distribution and phase changes of the anatase TiO2 nanopowder samples when they are subject to the plasma treatments of three different kinds of gases as nitrogen (N2), oxygen (O2), and argon (Ar). The plasma gas pressures vary as 0.1, 0.3, and 0.6 Torr. We demonstrate that the plasma treatments have an effect neither on the phase structure nor on the mean nanocrystalline size. The phase and size invariances of the samples are attributed to their nanoscale thermodynamic aspects. We find out that elevating the gas pressure in some cases creates fine-size amorphous nanoparticles with a narrow distribution. Our findings authenticate that plasma treatment affects the amorphous phase with etching particles down to a mean value of ∼3 nm. The small-angle X-ray scattering (SAXS) technique was utilized to obtain the size distribution of the nanoparticles, and the wide-angle X-ray scattering (WAXS) technique was used to probe the phase and size changes of the crystalline structure.

In situ research of materials under moderate pressures (hundreds of bar) is essential in many scientific fields. These range from gas sorption to chemical and biological processes. One industrially important discipline is the hydration of oil well cements. Existing capillary cells in this pressure range are static as they are easy to design and operate. This is convenient for the study of single-phase materials; however, powder diffraction quantitative analyses for multiphase systems cannot be performed accurately as a good powder average cannot be attained. Here, the design, construction and commissioning of a cost-effective spinning capillary cell for in situ powder X-ray diffraction is reported, for pressures currently up to 200 bar. The design addresses the importance of reducing the stress on the capillary by mechanically synchronizing the applied rotation power and alignment on both sides of the capillary while allowing the displacement of the supports needed to accommodate different capillaries sizes and to insert the sample within the tube. This cell can be utilized for multiple purposes allowing the introduction of gas or liquid from both ends of the capillary. The commissioning is reported for the hydration of a commercial oil well cement at 150 bar and 150°C. The quality of the resulting powder diffraction data has allowed in situ Rietveld quantitative phase analyses for a hydrating cement containing seven crystalline phases.

Anti-EFG1 2-OMethylRNA is an antisense oligonucleotide (ASO) that has the ability to recognize and block the EFG1 gene and to control Candida albicans filamentation. However, it is important to protect the anti-EFG1 2-OMethylRNA ASO from the environmental human body conditions and to ensure that they will be delivered to their site of action, and polyplex microparticles (MPs) represent a class of vehicles to ASO cargo with these functionalities. Thus, the goal of this work was to develop polyplexes based on porous poly(-butyrolactam) (PA4) or poly(-caprolactam) (PA6) MPs for the anti-EFG1 2-OMethylRNA ASO cargo and delivery. Two types of polyplexes were prepared with payloads of anti-EFG1 2-OMethylRNA molecules, either entrapped or immobilized on prefabricated polyamide MPs. Our data confirm that PA4 and PA6 polyplex MPs can be feasible carriers for anti-EFG1 2-OMethylRNA ASO molecules, using either the entrapment or immobilization strategies, whereby the released ASO maintains its activity against C. albicans cells., This study was supported by the Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding of the UIDB/04469/2020 unit and BioTecNorte operation (NORTE-01-0145-FEDER-000004) funded by the European Regional Development Fund under the scope of Norte2020Programa Operacional Regional do Norte and Daniela Eira Araujo [SFRH/BD/121417/2016] Ph.D. grant. The authors also acknowledge the project funding by the “02/SAICT/2017 Projetos de Investigação Científica e Desenvolvimento Tecnológico (IC&DT) POCI-01-0145-FEDER-028893”. N.V.D. and Z.Z.D. are also grateful to the Executive Commission of ALBA synchrotron for the support under the project no. 2018022726., info:eu-repo/semantics/publishedVersion

Thermoplastic polyurethanes (TPU) with varying hard segment contents (HSC) are monitored during melting and solidifying (20 K/min , Tmax = 220 ° C) by small-angle and wide-angle X-ray scattering (WAXS and SAXS). Hard segments: MDI/BD. Soft segments: PTHF1000. The neat materials are injection-molded, having small amorphous hard domains (chord length d⎯⎯h ∼ 35% show sharp Bragg peaks and larger hard domains ( d⎯⎯h > 7 nm ). When heated, small domains melt, but crystallization in the remaining large domains is not detected. Upon cooling, large agglomerates segregate first, which crystallize immediately. Segregation starts for HSC = 42% at 160 °C and for HSC = 75% at 210 °C. When HSC ≤ 30%, the morphologies before and after are similar, but afterward, many hard blocks are dissolved in the soft phase at the expense of the hard domain fraction. In heating and cooling the melts, multiple homogenization and segregation processes are observed, which are explained by the agglomeration of hard blocks of different lengths in the colloidal fluid.

Structural and morphological interplay between hard and soft phases determine the bulk properties of thermoplastic polyurethanes. Commonly employed techniques rely on different physical or chemical phenomena for characterizing the organization of domains, but detailed structural information can be difficult to derive. Here, total scattering pair distribution function (PDF) analysis is used to determine atomic-scale insights into the connectivity and molecular ordering and compared to the domain size and morphological characteristics measured by AFM, TEM, SAXS, WAXS, and solid-state NMR 1H–1H spin-diffusion. In particular, density distribution functions are highlighted as a means to bridging the gap from the domain morphology to intradomain structural ordering. High real-space resolution PDFs are shown to provide a sensitive fingerprint for indexing aromatic, aliphatic, and polymerization-induced bonding characteristics, as well as the hard phase structure, and indicate that hard phases coexist in both ordered and disordered states.

This study reports a new strategy for enzyme immobilization based on passive immobilization in neat and magnetically responsive polyamide 4 (PA4) highly porous particles. The microsized particulate supports were synthesized by low-temperature activated anionic ring-opening polymerization. The enzyme of choice was laccase from Trametes versicolor and was immobilized by either adsorption on prefabricated PA4 microparticles (PA4@iL) or by physical in situ entrapment during the PA4 synthesis (PA4@eL). The surface topography of all PA4 particulate supports and laccase conjugates, as well as their chemical and physical structure, were studied by microscopic, spectral, thermal, and synchrotron WAXS/SAXS methods. The laccase content and activity in each conjugate were determined by complementary spectral and enzyme activity measurements. PA4@eL samples displayed &gt, 93% enzyme retention after five incubation cycles in an aqueous medium, and the PA4@iL series retained ca. 60% of the laccase. The newly synthesized PA4-laccase complexes were successfully used in dyestuff decolorization aiming at potential applications in effluent remediation. All of them displayed excellent decolorization of positively charged dyestuffs reaching ~100% in 15 min. With negative dyes after 24 h the decolorization reached 55% for PA4@iL and 85% for PA4@eL. A second consecutive decolorization test revealed only a 5&ndash, 10% decrease in effectiveness indicating the reusability potential of the laccase-PA4 conjugates.

Melting and solidification of thermoplastic polyurethanes (TPU) are monitored by X-ray scattering. The colloidal character of the typical material becomes unstable as soon as the hard domains (HD) are molten. Then the scattered intensity fluctuates considerably and “lost” photons are found at small scattering angles (Tyndall effect). In this temperature regime the material is a fluid. Competing homogenization and segregation processes appear to take place, which modulate the materials colloidal character. Monitored by SAXS and WAXS, TPU elastomers are melted and re-solidified (heating rate: 20 K/min, temperatures T m a x : 220 °C, 190 °C). Strong fluctuations in scattering intensity due to varying Tyndall effect are observed in most of our experiments. Here the typical effects are demonstrated on a polyether-based TPU with a hard segment content of 30%, whose colloidal melt is stabilized by adding 0.5% graphite. In the hot quiescent melt the morphology is characterized by density undulations. HD arrangement does not grow late. Graphite stabilizes the colloidal melt. It increases both the HD melting-temperature (from 185 °C to 210 °C) and the HD formation temperature (from 90 °C to 165 °C).

Microstructure formation in individual layers during fused filament fabrication (FFF) of a Π-shaped multilayer single-walled polymer sample was studied by simultaneous measurement of small- and wide-angle X-ray scattering (SAXS and WAXS, respectively) methods employing synchrotron radiation. We investigated individual layers and the welding zone between individual layers. As a model material, we used isotactic polypropylene (iPP), which is a commodity semicrystalline polymer and has a strong potential as a feedstock material for additive manufacturing. The layers were deposited by an FFF three-dimensional (3D) printer that was custom-built to fit into the synchrotron beamline. WAXS data were utilized to determine the temperature of the irradiated volume. The polymer microstructure was characterized in terms of crystallinity and long-spacing. Avrami analysis indicates that the crystallization behavior of iPP in thin layers is rather similar to that observed in quiescent crystallization of bulk iPP, suggesting similar nucleation and growth mechanisms. Our results revealed a variation of crystallinity across the individual layers, reflecting the influence of interfaces (free surface and welding zone) on the final crystallinity of the thin layer (thickness h = 0.02 cm): the polymer is more crystalline in the bulk of the layer and less crystalline in the vicinity of the interfaces. This effect can be advantageous to facilitate the welding between the layers, i.e., to improve the overall mechanical performance of the 3D-printed object because welding between layers is expected to occur by polymer chain interdiffusion. Along the thin layer we observed a higher crystallinity near the corners attributed to a deceleration of the print head.

The synthesis of three gold(I) tripodal complexes derived from tripropargylamine and containing the water soluble phosphines PTA (1, 3,5-triaza-7-phosphaadamantane), DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) and TPPTS (triphenylphosfine-3,3',3''-trisulfonic acid trisodium salt) is here described. The three complexes are observed to give rise to the formation of supramolecular aggregates in water and very long fibers. This property has been analyzed by means of 1H-NMR spectroscopy at different concentrations and SAXS. The results point out the important role of the phosphine moieties as the main enthalpic or entropic contribution in the resulting Gibbs energy of aggregates formation. The tripodal structure of the three complexes together with the presence of gold(I) atoms make them ideal candidates to interact with hydrophobic molecules also in water. For this, the interaction with pyrene in this solvent has been evaluated with successful results in all three complexes. The highest association constant corresponds to 2 as the host. DFT studies indicates the location of pyrene in the tripodal cavity as the most stable conformation. The interaction with pyrene has been additionally studied within cholate hydrogel matrixes pointing out the stability of the resulting host:guest adducts in the different medium.

This work presents the preparation, optimization, and testing of an enzymebased optical biosensor for catechol determination. The sensing area is attached to a glass support and contains: anionic polyamide 6 (PA6) porous microparticles supporting laccase from Trametes Versicolor, embedded in a Pebax® MH1657 polymer binder that contains the optical indicator dye 3-methyl-2-benzothiazolinone hydrazone (MBTH), responsible for the optical transduction. The catechol analyte, after its enzymatic oxidation, forms o-benzoquinone that can be detected by oxidative coupling with MBTH giving rise to a colored product. The latter can be quantified easuring the UV/VIS absorbance at 500 nm. The PA6 microparticles performed as useful laccase carriers reaching high immobilization yields of up to 99.8% and preserving the enzyme catalytic activity. This permitted the reparation of a new biosensor presenting a detection limit of 11 μM and responding linearly to up to 118 μM of catechol. Biosensor applicability was tested in spiked natural water samples from river and spring. The recovery rates observed were in the range of 97–108% that proves the good accuracy of the proposed biosensor., All authors gratefully acknowledge the financial support of the project TSSiPRO NORTE-01-0145-FEDER-000015, supported by the regional operation program NORTE2020, under the Portugal 2020 Partnership Agreement, through the European Regional Development Fund, as well as the support by National Funds through Fundação para a Ciência e Tecnologia (FCT), project UID/CTM/50025/2019. Special thank is due to the ALBA synchrotron governance for financing our WAXS/SAXS experiments at NCD SWEET beamline in the framework of the approved pro posal ID 2018/022726. N. Dencheva is also grateful for the financial support of FCT in the frames of the strategic project UID/CTM/50025/2013 and the personal program contract CTTI-51/18-IPC. The authors gratefully acknowledge the support of Dr. Amélie Noel (Arkema, France) for providing a free sample of Pebax® MH 1657.

International audience; Biological macromolecules in solution interact with each other through medium-range (from a few Angstrom to a few nm) interaction potentials. These potentials control the macromolecular distribution in solution, the macromolecular phase diagram and the crystallization process. We have previously shown that small angle X-ray scattering (SAXS) is a convenient tool to characterize the resulting potential, either attractive or repulsive, and to follow the changes induced by the crystallizing agents. In the present paper SAXS and simulation methods derived from statistical mechanics are coupled to determine the best fit potentials from the comparison of experimental and theoretical intensity curves. The currently used models in the colloid field are derived from the DLVO (Derjaguin, Landau, Verwey, Overbeek) potential where three types of interactions play a major role: hard sphere and electrostatic are repulsive, van der Waals are attractive. A combination of a short-range attractive potential and a coulombic repulsive indeed correctly accounts at low ionic strength for the phase diagram as a function of pH and salt concentration. The origin of the ion specificities at high ionic strength associated with the so-called "Hofmeister series" remain, however, unclear. The whole of the data demonstrates that the colloidal approach may be applied with success to protein crystallization. (C) 1999 Elsevier Science B.V. All rights reserved.

International audience; Osmotic pressure, small-angle X-ray scattering and quasi-elastic light scattering were used to study the medium-range interaction potentials between macromolecules in solution. These potentials determine macromolecular crystallization. Calf eye lens gamma-crystallins were used as a model system with the charge, and therefore the interactions, varied with pH. The second virial coefficient was determined under the same conditions with each of the three techniques. Osmotic pressure and quasi-elastic light scattering can be used conveniently in the laboratory to rapidly test the type of interactions (either attractive or repulsive) present in the solution. The measurement is direct with osmotic pressure, whereas with quasi-elastic light scattering, the directly measured coefficient is a combination of thermodynamic and hydrodynamic terms. X-rays, which require more sophisticated equipment such as synchrotron radiation facilities, can provide more detailed information on the interparticle potentials when models are used. At low ionic strength, two potentials were found necessary to account for the temperature and pH phase diagram as a function of protein concentration. The first potential is the van der Waals attractive potential that was previously shown to account for the fluid-fluid phase separation at low temperature. The second potential is an electrostatic coulombic repulsive potential which is a function of the protein charge and thus of the pH. The interaction trail could be followed at protein concentrations as low as 10 mg ml(-1). The results as a whole are expected to be valid for all compact low molecular weight proteins at low ionic strength.

International audience