Surface Chemistry of Amphiphilic Polysiloxane/Triethyleneglycol‐Modified Poly(pentafluorostyrene) Block Copolymer Films Before and After Water Immersion

New amphiphilic block copolymers Si‐EFSx composed of a poly(dimethyl siloxane) (Si) block and a poly(4‐(triethyleneglycol monomethyl ether)‐2,3,5,6‐tetrafluorostyrene) (EFS) block are synthesized by atom transfer radical polymerization (ATRP) starting from a bromo‐terminated Si macroinitiator. Similarly, new hydrophobic block copolymers Si‐FSy consisting of an Si block and a poly(pentafluorostyrene) (FS) block are prepared for comparison. X‐ray photoelectron spectroscopy (XPS) analysis on block copolymer films reveals that the Si block is concentrated at the polymer–air interface, while the EFS block is located in the layers underneath. The same polymer films undergo a marked surface reconstruction after immersion in water for 7 d, as probed by XPS. This phenomenon involves the exposure of the hydrophilic oxyethylenic chains to contact water. Such surface reconstruction is even more drastic when an amphiphilic block copolymer is dispersed in a cross‐linked poly(dimethyl siloxane) matrix film.

     

Surface functionalization of a poly(butylene terephthalate) (PBT) melt-blown filtration membrane by wet chemistry and photo-grafting

The surface functionalization of PBT melt-blown membrane, making up a whole filter of blood components, was achieved via two methods. Hydroxyl chain-end activation by tosylation (method A), followed by coupling of F- and ³H-tagged molecules (probes), led to 1% of surface derivatization (XPS) and 290 pmol/cm² of lysine fixation (LSC). Deposition of O-succinimidyl 4-(p-azido-phenyl)butanoate ("molecular clip") and 2 h irradiation at 254 nm led to the implanting of activated ester functions, randomly on the polymer surface (method B). Further coupling of F- and ³H-probes by wet chemistry gave highly functionalized surface (4% by XPS and 1000 pmol/cm² by LSC). However, control experiments showed that about 80% of the surface derivatization resulted from the UV treatment alone. Thus, the effect of UV irradiation on PBT membrane was systematically studied and analyzed by XPS, contact angle measurements, GPC and surface reactivity assays. The optimized conditions of "molecular clip" photo-grafting (negligible polymer photo-oxidation/photo-degradation) led to the covalent fixation of 45 pmol/cm² of ³H-probe. Throughout our study, the behaviour of PBT melt-blown membrane was compared to PBT film and PET track-etched membrane similarly treated. Lastly, the method B was applied to couple GRGDS peptide on the PBT membrane; this material showed improved properties of leukocyte depletion in buffy coat filtration experiments.     

Electronic Structure and Surface Properties of Copper Thiocyanate: A Promising Hole Transport Material for Organic Photovoltaic Cells

Considering the significance of hexagonal copper thiocyanate (β-CuSCN) in several optoelectronic technologies and applications, it is essential to investigate its electronic structure and surface properties. Herein, we have employed density functional theory (DFT) calculations to characterise the band structure, density of states, and the energy-dependent X-ray photoelectron (XPS) valence band spectra at variable excitation energies of β-CuSCN. The surface properties in the absence and presence of dimethyl sulfoxide (DMSO), a solvent additive for improving perovskite solar cells’ power conversion efficiency, have also been systematically characterised. β-CuSCN is shown to be an indirect band gap material (E_g = 3.68 eV) with the valence band edge demonstrated to change from being dominated by Cu-3d at soft X-ray ionisation photon energies to Cu-3p at hard X-ray ionisation photon energies. The adsorption energy of dimethyl sulfoxide (DMSO) on the (100) and (110) β-CuSCN surfaces is calculated at −1.12 and −0.91 eV, respectively. The presence of DMSO on the surface is shown to have a stabilisation effect, lowering the surface energy and tuning the work function of the β-CuSCN surfaces, which is desirable for organic solar cells to achieve high power conversion efficiencies.     

Surface characterization of dental Y-TZP ceramic after air abrasion treatment

Objective

The aim of this study was to characterize the surface of Y-TZP after abrasion with various airborne particles.

Methods

The Y-TZP blanks were cut into 44 discs and sintered according to the manufacturer's instructions. The specimens were treated as follows: (a) control specimens, (b) abraded with 50 μm alumina, (c) abraded with 110 μm alumina, (d) abraded with 30 μm silica-coated alumina, (e) abraded with 110 μm silica-coated alumina, (f) abraded with 110 μm alumina followed by 110 μm silica-coated alumina particles. Airborne abrasion was performed at a pressure of 2.5 bar for 15 s/cm². The Y-TZP was characterized using X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and X-ray diffraction analysis (XRD).

Results

Surface morphology of Y-TZP ceramic was changed after the airborne abrasion process compared to the control specimens. The grain boundaries disappeared and part of the airborne particles are embedded and/or rested on the ceramic surfaces. The elemental composition of the Y-TZP surface after the airborne abrasion process depended on the type and size of these particles. The concentration of Si resulted higher after the airborne abrasion process with 110 μm alumina followed by 110 μm silica-coated alumina particles in comparison to the specimens abraded with 110 μm silica-coated alumina particles. The ratio of elements normalized by yttrium for these specimens was: [Zr]/[Y]/[Al]/[Si] = 15.2/1.0/26.0/73.6, respectively.

Conclusion

The change of grain topography occurred during each impact process. Silica nano-particles covered not only loosely the abraded ceramic surface after abrasion process, but the release of kinetic energy in form of thermal energy resulted in melting of the ceramic surface and in the formation of zirconium silicate.     

Characterization of Graphite Oxide and Reduced Graphene Oxide Obtained from Different Graphite Precursors and Oxidized by Different Methods Using Raman Spectroscopy Statistical Analysis

In this paper, various graphite oxide (GO) and reduced graphene oxide (rGO) preparation methods are analyzed. The obtained materials differed in their properties, including (among others) their oxygen contents. The chemical and structural properties of graphite, graphite oxides, and reduced graphene oxides were previously investigated using Raman spectroscopy (RS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). In this paper, hierarchical clustering analysis (HCA) and analysis of variance (ANOVA) were used to trace the directions of changes of the selected parameters relative to a preparation method of such oxides. We showed that the oxidation methods affected the physicochemical properties of the final products. The aim of the research was the statistical analysis of the selected properties in order to use this information to design graphene oxide materials with properties relevant for specific applications (i.e., in gas sensors).     

Nanoporous SiLK® Dielectric Films Prepared from Free‐Radical Graft Polymerization and Thermolysis

Summary: Thermally‐initiated free‐radical graft polymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA) with the ozone‐pretreated SiLK® precursor was carried out. The chemical composition and structure of the graft copolymers were characterized by NMR and X‐ray photoelectron spectroscopy (XPS). Nanoporous low dielectric constant (κ) SiLK films were prepared by solution spin‐casting of the graft copolymers on the Si(100) substrates, followed by thermally‐induced cycloaddition and cross‐linking of the SiLK precursor and thermal decomposition of the labile PEGMA side chains. The nanoporous SiLK films so‐obtained had well‐preserved SiLK backbones and pore size in the range of 10–15 nm. The refractive index (RI) of resulting films has decreased to 1.47, from 1.62 for the pristine (non‐porous) SiLK dielectric film. A dielectric constant of about 2.2 was achieved from thermolysis of the SiLK graft copolymer containing about 15.2 wt.‐% of the PEGMA side chains.

Preparation of the nanoporous SiLK dielectric film.     

Effect of surface coating on the biodistribution profile of gold nanoparticles in the rat

Successful application of gold nanoparticles (AuNPs) in biomedicine requires extensive safety assessment for which biokinetic studies are crucial.We evaluated the biodistribution of AuNPs (∼20 nm) with different surface coatings: citrate, 11-MUA and 3 pentapeptides, CALNN, CALND and CALNS, after i.v. administration to rats (0.6-1 mg Au/kg). Biodistribution was evaluated based on Au tissue content measured by GFAAS.Citrate-AuNPs were rapidly removed from circulation with 60% of the injected dose depositing in the liver. Thirty minutes post-injection, the lungs presented about 6% of the injected dose with levels decreasing to 0.7% at 24 h. Gold levels in the spleen were of 2.6%. After 24 h, liver presented the highest Au level, followed by spleen and blood.A similar biodistribution profile was observed for MUA-coated AuNPs compared to Cit-AuNPs at 24 h post-injection, while significantly higher levels of peptide-capped AuNPs were found in the liver (74-86%) accompanied by a corresponding decrease in blood levels.TEM analysis of liver slices showed AuNPs in Kupffer cells and hepatocytes, trapped inside endosomes.Our data demonstrate that AuNPs are rapidly distributed and that the liver is the preferential accumulation organ. Peptide capping significantly increased hepatic uptake, showing the influence of AuNPs functionalization in biodistribution.     

Adsorption of pharmaceutical excipients onto microcrystals of siramesine hydrochloride: Effects on physicochemical properties

A common challenge in the development of new drug substances is poor dissolution characteristics caused by low aqueous solubility. In this study, microcrystals with optimized physicochemical properties were prepared by precipitation in the presence of excipients, which adsorbed to the particle surface and altered particle size, morphology, and dissolution rate. The poorly water-soluble drug siramesine hydrochloride was precipitated by the antisolvent method in the presence of each of various polymeric and surface active excipients. Powder dissolution studies of six of the resulting particle systems showed a significant increase in percent dissolved after 15 min compared to the starting material.A quantitative determination of the amount of excipient adsorbed to the surface of the drug particles proved that only a very small amount of excipient was needed to exert a marked effect on particle properties. The adsorbed amount of excipient constituted less than 1.4% (w/w) of the total particle weight, and thus powders of very high drug loads were obtained. Sodium lauryl sulphate (SLS), hydroxypropyl methylcellulose (HPMC), and hydroxypropyl cellulose (HPC), which exhibited the greatest degree of adsorption, also had the greatest effect on the physicochemical properties of the particles. X-ray Photoelectron Spectroscopy (XPS) analysis of the surface composition and scanning electron microscopy studies on particle morphology suggested that the excipients adsorbed to specific faces of the crystals.     

In Situ Hall Effect Monitoring of Vacuum Annealing of In2O3:H Thin Films

Hydrogen doped In₂O₃ thin films were prepared by room temperature sputter deposition with the addition of H₂O to the sputter gas. By subsequent vacuum annealing, the films obtain high mobility up to 90 cm²/Vs. The films were analyzed in situ by X-ray photoelectron spectroscopy (XPS) and ex situ by X-ray diffraction (XRD), optical transmission and Hall effect measurements. Furthermore, we present results from in situ Hall effect measurements during vacuum annealing of In₂O₃:H films, revealing distinct dependence of carrier concentration and mobility with time at different annealing temperatures. We suggest hydrogen passivation of grain boundaries as the main reason for the high mobility obtained with In₂O₃:H films.