Roughness Factors of Electrodeposited Nanostructured Copper Foams.

Copper-based electrocatalytic materials play a critical role in various electrocatalytic processes, including the electroreduction of carbon dioxide and nitrate. Three-dimensional nanostructured electrodes are particularly advantageous for electrocatalytic applications due to their large surface area, which facilitates charge transfer and mass transport. However, the real surface area (RSA) of electrocatalysts is a crucial parameter that is often overlooked in experimental studies of high-surface-area copper electrodes. In this study, we investigate the roughness factors of electrodeposited copper foams with varying thicknesses and morphologies, obtained using the hydrogen bubble dynamic template technique. Underpotential deposition (UPD) of metal adatoms is one of the most reliable methods for estimating the RSA of highly dispersed catalysts. We aim to illustrate the applicability of UPD of lead for the determination of the RSA of copper deposits with hierarchical porosity. To find the appropriate experimental conditions that allow for efficient minimization of the limitations related to the slow diffusion of lead ions in the pores of the material and background currents of the reduction of traces of oxygen, we explore the effect of lead ion concentration, stirring rate, scan rate, monolayer deposition time and solution pH on the accuracy of RSA estimates. Under the optimized measurement conditions, Pb UPD allowed to estimate roughness factors as high as 400 for 100 µm thick foams, which translates into a specific surface area of ~6 m2·g-1. The proposed measurement protocol may be further applied to estimate the RSA of copper deposits with similar or higher roughness.

Transformation of Specific Dispersion Interactions between Cellulose and Polyacrylonitrile in Solutions into Covalent Interactions in Fibers.

Morphological transformations in emulsions of cellulose and polyacrylonitrile (PAN) ternary copolymers containing acrylonitrile, methyl acrylate, and methylsulfonate comonomers in N-methylmorpholine-N-oxide were studied over the entire range of concentrations depending on temperature and intensity of the deformation action. Based on the morphological and rheological features of the system, the temperature-concentration range of spinnability of mixed solutions was determined, and composite fibers were spun. The fibers are characterized by a heterogeneous fibrillar texture. Studies of the structure of the fibers, carried out using X-ray diffraction analysis, revealed a decrease in cellulose crystallinity with an increase in the content of PAN. The study of the thermal properties of the obtained fibers, carried out using DSC, and chemical transformations in them in a wide temperature range by high-temperature diffuse reflection IR spectroscopy made it possible to reveal a new intense exothermic peak on the thermograms at 360 °C, which according to the IR spectra corresponds to the transformation of intermacromolecular physical interactions of the PAN and cellulose into covalent bonds between polymers. In addition, the ester groups found during the thermal treatment of the PAN part of the composite fibers in the pyrolysis zone can have a key effect on the process of their further carbonization.

Effect of Bacterial Cellulose Plasma Treatment on the Biological Activity of Ag Nanoparticles Deposited Using Magnetron Deposition.

New functional medical materials with antibacterial activity based on biocompatible bacterial cellulose (BC) and Ag nanoparticles (Ag NPs) were obtained. Bacterial cellulose films were prepared by stationary liquid-phase cultivation of the Gluconacetobacter hansenii strain GH-1/2008 in Hestrin-Schramm medium with glucose as a carbon source. To functionalize the surface and immobilize Ag NPs deposited by magnetron sputtering, BC films were treated with low-pressure oxygen-nitrogen plasma. The composition and structure of the nanomaterials were studied using transmission (TEM) and scanning (SEM) electron microscopy and X-ray photoelectron spectroscopy (XPS). Using electron microscopy, it was shown that on the surface of the fibrils that make up the network of bacterial cellulose, Ag particles are stabilized in the form of aggregates 5-35 nm in size. The XPS C 1s spectra show that after the deposition of Ag NPs, the relative intensities of the C-OH and O-C-O bonds are significantly reduced. This may indicate the destruction of BC oxypyran rings and the oxidation of alcohol groups. In the Ag 3d5/2 spectrum, two states at 368.4 and 369.7 eV with relative intensities of 0.86 and 0.14 are distinguished, which are assigned to Ag0 state and Ag acetate, respectively. Nanocomposites based on plasma-treated BC and Ag nanoparticles deposited by magnetron sputtering (BCP-Ag) exhibited antimicrobial activity against Aspergillus niger, S. aureus and Bacillus subtilis.

Design and Fabrication of Membranes Based on PAN Copolymer Obtained from Solutions in N-methylmorpholine-N-oxide.

An original method is proposed for preparing highly concentrated solutions of PAN copolymer in N-methylmorpholine-N-oxide (NMMO) and forming membranes for nanofiltration from these solutions. The high activity of the solvent with respect to the polymer provides short preparation time of spinning solutions in comparison with PAN solutions obtained in other solvents. The use of the rheological approach made it possible to find the optimal concentration for obtaining membranes. The formation of PAN membranes from the obtained solutions is proposed by the rolling method. The morphology of the formed membranes depends on the method of removing the precipitant from the sample. The features of the formed morphology of PAN membranes were studied by scanning electron microscopy. It was revealed that the use of water as a rigid precipitant leads to the formation of a homogeneous and symmetric morphology in the membrane. The average pore sizes in the membrane have been obtained by porosimetry. The study of the separating properties of PAN membranes revealed noteworthy values of the permeability and rejection for the anionic dyes Orange II and Remazol Brilliant Blue (74 and 97%, respectively). The mechanical properties of PAN membranes from solutions in NMMO are not inferior to analogs formed from commercially used direct solvents.

Evaluation of the Efficiency of Photoelectrochemical Activity Enhancement for the Nanostructured LaFeO3 Photocathode by Surface Passivation and Co-Catalyst Deposition.

Perovskite-type lanthanum iron oxide, LaFeO3, is a promising photocathode material that can achieve water splitting under visible light. However, the performance of this photoelectrode material is limited by significant electron-hole recombination. In this work, we explore different strategies to optimize the activity of a nanostructured porous LaFeO3 film, which demonstrates enhanced photoelectrocatalytic activity due to the reduced diffusion length of the charge carriers. We found that surface passivation is not an efficient approach for enhancing the photoelectrochemical performance of LaFeO3, as it is sufficiently stable under photoelectrocatalytic conditions. Instead, the deposition of a Pt co-catalyst was shown to be essential for maximizing the photoelectrochemical activity both in hydrogen evolution and oxygen reduction reactions. Illumination-induced band edge unpinning was found to be a major challenge for the further development of LaFeO3 photocathodes for water-splitting applications.

Fabrication of moldable chitosan gels via thermally induced phase separation in aqueous alcohol solutions.

Wide application of chitosan in modern technologies is limited by the lack of reliable and low-cost techniques to prepare size-tuned constructs with a complex surface morphology, improved optical and mechanical properties. We report a new simple method for preparation of transparent thermoreversible chitosan alcogels from chitosan/H2O/ethanol ternary systems. This method, termed "low temperature thermally induced phase separation under non-freezing conditions" (LT-TIPS-NF), fine tunes gelation by adjusting only temperature (from 5 to -25 °C) and varying the initial content of chitosan (from 0.5 to 2.0 wt%) and ethanol (from 28.5 to 47.5 vol%). Transparent non-swelling final constructs of complex shape are prepared by fixing the pre-formed alcogels with a base solution. The size of the gel constructs is limited only by the dimensions of the mold and the cooling chamber. The LT-TIPS-NF is applicable both in injection molding and 3D printing techniques. The in vitro and in vivo experiments show the absence of prominent cytotoxicity and well-defined cell adhesion on the obtained hydrogels. Thus, this facile and scalable technique provides the multifunctional chitosan gel preparation with easily controlled properties exploiting inexpensive, renewable, and environmentally friendly source polysaccharide. These materials have prospects for a variety of uses, especially for biomedical applications.

A Role of Coagulant in Structure Formation of Fibers and Films Spun from Cellulose Solutions.

Replacing the aqueous coagulation bath with an alcoholic one during spinning cellulose fibers (films) from solutions in N-methylmorpholine-N-oxide leads to a radical restructuring of the hydrogen bonds net of cellulose and, as a result, to a change in the structure and properties of the resulting material. By the method of optical interferometry, it was possible to identify the intrinsic features of the interaction of the solvent and isomeric alcohols and to construct phase diagrams of binary systems describing the crystalline equilibrium. Knowledge of the phase states of the system at different temperatures renders it possible to exclude the process of solvent crystallization and conduct the spinning in pseudo-homogeneous conditions. The structure and morphology of samples were studied using X-ray diffraction and scanning electron microscopy methods for a specific coagulant. When the solution under certain conditions is coagulated at contact with alcohol, the solvent may be in a glassy state, whereas, when at coagulation in water, an amorphous-crystalline structure is formed. The structural features of cellulose films obtained by coagulation of solutions with water and alcohols help to select potential engineering or functional materials (textile, packaging, membranes, etc.), in which their qualities will manifest to the best extent.

Bacterial Cellulose (Komagataeibacter rhaeticus) Biocomposites and Their Cytocompatibility.

A series of novel polysaccharide-based biocomposites was obtained by impregnation of bacterial cellulose produced by Komagataeibacter rhaeticus (BC) with the solutions of negatively charged polysaccharides-hyaluronan (HA), sodium alginate (ALG), or κ-carrageenan (CAR)-and subsequently with positively charged chitosan (CS). The penetration of the polysaccharide solutions into the BC network and their interaction to form a polyelectrolyte complex changed the architecture of the BC network. The structure, morphology, and properties of the biocomposites depended on the type of impregnated anionic polysaccharides, and those polysaccharides in turn determined the nature of the interaction with CS. The porosity and swelling of the composites increased in the order: BC-ALG-CS > BC-HA-CS > BC-CAR-CS. The composites show higher biocompatibility with mesenchymal stem cells than the original BC sample, with the BC-ALG-CS composite showing the best characteristics.

A versatile platform for bioimaging based on colominic acid-decorated upconversion nanoparticles.

Lanthanide-doped upconversion nanoparticles (UCNPs) are promising bioimaging agents that emit light under near infra-red excitation, capable of penetrating deep in biotissues with a high signal-to-noise ratio. Their successful implementation is principally associated with surface functionalization. Here, we report on UCNP surface modification with highly hydrophilic, endogenous, non-toxic, non-immunogenic colominic acid, conferring "stealth" properties. We proposed surface functionalization of UCNPs based on a two-step strategy, which consists of hydrophilization with polyethyleneimine and attachment of colominic acid by electrostatic or covalent bond formation. Analysis revealed that regardless of the nature of the bond, colominic acid acted as a non-cytotoxic UCNP surface coating with low nonspecific blood protein adsorption. UCNP-colominic acid nanocomplexes exhibited low uptake by macrophages in vitro, which plays an active role in inflammatory reactions. We demonstrated the superiority of colominic acid compared to polyethylene glycol coating in terms of the prolonged circulation time in the bloodstream of small animals when injected intravenously. The colominic acid coating made it possible to prolong the UCNP circulation time up to 3 h. This led to the efficient UCNP accumulation in the inflammation site due to microvascular remodeling, accompanied by an enhanced uptake and retention effect. UCNP-assisted imaging of inflammation in the whole-body mode as well as local visualization of blood vessels were acquired in vivo. These collective findings validate the functional significance of UCNP decoration with colominic acid for their application in bioimaging.

SEM and TEM for structure and properties characterization of bacterial cellulose/hydroxyapatite composites.

Preparation of composites with different properties and gradient of components is aimed at better performance of materials for bone substitution. Bacterial cellulose-hydroxyapatite (BC-HAP) composites with various mass ratio of the components (BC-25HAP, BC-4HAP, and BC-HAP) were prepared by a novel method of growing HAP nanocrystals (the linear size ≤30 nm) in water solutions in the presence of the BC gel-film micro-fragments. Varying the BC-HAP ratios leads to a gradual change of the physical properties of the materials. It was found that an increase in the BC content results in a decrease of the HAP crystal length and specific surface area, porosity, and pore volume while the values of density and Young's modulus values increase. SCANNING 38:757-765, 2016. © 2016 Wiley Periodicals, Inc.