From Nature-Sourced Polysaccharide Particles to Advanced Functional Materials.

Polysaccharides constitute over 90% of the carbohydrate mass in nature, which makes them a promising feedstock for manufacturing sustainable materials. Polysaccharide particles (PSPs) are used as effective scavengers, carriers of chemical and biological cargos, and building blocks for the fabrication of macroscopic materials. The biocompatibility and degradability of PSPs are advantageous for their uses as biomaterials with more environmental friendliness. This review highlights the progresses in PSP applications as advanced functional materials, by describing PSP extraction, preparation, and surface functionalization with a variety of functional groups, polymers, nanoparticles, and biologically active species. This review also outlines the fabrication of PSP-derived macroscopic materials, as well as their applications in soft robotics, sensing, scavenging, water harvesting, drug delivery, and bioengineering. The paper is concluded with an outlook providing perspectives in the development and applications of PSP-derived materials.

Nanocolloidal hydrogel mimics the structure and nonlinear mechanical properties of biological fibrous networks.

Fibrous networks formed by biological polymers such as collagen or fibrin exhibit nonlinear mechanical behavior. They undergo strong stiffening in response to weak shear and elongational strains, but soften under compressional strain, in striking difference with the response to the deformation of flexible-strand networks formed by molecules. The nonlinear properties of fibrous networks are attributed to the mechanical asymmetry of the constituent filaments, for which a stretching modulus is significantly larger than the bending modulus. Studies of the nonlinear mechanical behavior are generally performed on hydrogels formed by biological polymers, which offers limited control over network architecture. Here, we report an engineered covalently cross-linked nanofibrillar hydrogel derived from cellulose nanocrystals and gelatin. The variation in hydrogel composition provided a broad-range change in its shear modulus. The hydrogel exhibited both shear-stiffening and compression-induced softening, in agreement with the predictions of the affine model. The threshold nonlinear stress and strain were universal for the hydrogels with different compositions, which suggested that nonlinear mechanical properties are general for networks formed by rigid filaments. The experimental results were in agreement with an affine model describing deformation of the network formed by rigid filaments. Our results lend insight into the structural features that govern the nonlinear biomechanics of fibrous networks and provide a platform for future studies of the biological impact of nonlinear mechanical properties.

Fibrillar Hydrogel Based on Cellulose Nanocrystals Crosslinked via Diels-Alder Reaction: Preparation and pH-Sensitive Release of Benzocaine.

A fibrillar hydrogel was obtained by covalent crosslinking via Diels-Alder reaction of two types of cellulose nanocrystals (CNCs) with furan and maleimide groups. Gelation has been studied at various ratios of components and temperatures in the range from 20 to 60 °C. It was shown that the rheological properties of the hydrogel can be optimized by varying the concentration and ratio of components. Due to the rigid structure of the CNCs, the hydrogel could be formed at a concentration of at least 5 wt%; however, it almost does not swell either in water with pH 5 or 7 or in the HBSS buffer. The introduction of aldehyde groups into the CNCs allows for the conjugation of physiologically active molecules containing primary amino groups due to the formation of imine bonds. Here, we used benzocaine as a model drug for conjugation with CNC hydrogel. The resulting drug-conjugated hydrogel demonstrated the stability of formulation at pH 7 and a pH-sensitive release of benzocaine due to the accelerated hydrolytic cleavage of the imine bond at pH < 7. The developed drug-conjugated hydrogel is promising as wound dressings for local anesthesia.

Colloidal Clusters and Networks Formed by Oppositely Charged Nanoparticles with Varying Stiffnesses.

Colloidal clusters and gels are ubiquitous in science and technology. Particle softness has a strong effect on interparticle interactions; however, our understanding of the role of this factor in the formation of colloidal clusters and gels is only beginning to evolve. Here, we report the results of experimental and simulation studies of the impact of particle softness on the assembly of clusters and networks from mixtures of oppositely charged polymer nanoparticles (NPs). Experiments were performed below or above the polymer glass transition temperature, at which the interaction potential and adhesive forces between the NPs were significantly varied. Hard NPs assembled in fractal clusters that subsequently organized in a kinetically arrested colloidal gel, while soft NPs formed dense precipitating aggregates, due to the NP deformation and the decreased interparticle distance. Importantly, interactions of hard and soft NPs led to the formation of discrete precipitating NP aggregates at a relatively low volume fraction of soft NPs. A phenomenological model was developed for interactions of oppositely charged NPs with varying softnesses. The experimental results were in agreement with molecular dynamics simulations based on the model. This work provides insight on interparticle interactions before, during, and after the formation of hard-hard, hard-soft, and soft-soft contacts and has impact for numerous applications of reversible colloidal gels, including their use as inks for additive manufacturing.

Design, characterization and applications of nanocolloidal hydrogels.

Nanocolloidal gels (NCGs) are an emerging class of soft matter, in which nanoparticles act as building blocks of the colloidal network. Chemical or physical crosslinking enables NCG synthesis and assembly from a broad range of nanoparticles, polymers, and low-molecular weight molecules. The synergistic properties of NCGs are governed by nanoparticle composition, dimensions and shape, the mechanism of nanoparticle bonding, and the NCG architecture, as well as the nature of molecular crosslinkers. Nanocolloidal gels find applications in soft robotics, bioengineering, optically active coatings and sensors, optoelectronic devices, and absorbents. This review summarizes currently scattered aspects of NCG formation, properties, characterization, and applications. We describe the diversity of NCG building blocks, discuss the mechanisms of NCG formation, review characterization techniques, outline NCG fabrication and processing methods, and highlight most common NCG applications. The review is concluded with the discussion of perspectives in the design and development of NCGs.

Recent Advances in Hydrogels via Diels-Alder Crosslinking: Design and Applications.

The Diels-Alder (DA) reaction is a promising tool for obtaining covalently crosslinked hydrogels due to its reaction bioorthogonality, the absence of by-products, and the application of mild conditions without a catalyst. The resulting hydrogels are in demand for use in various fields of materials science and biomedicine. While the dynamic nature of the cycloaddition of diene and dienophile has previously been used extensively for the fabrication of self-healing materials, it has only recently spread to the expansion of the functional properties of polymer gels for bioapplications. This review describes strategies and recent examples of obtaining hydrogels based on the DA reaction, demonstrating that the emerging functional properties go beyond self-healing. The types of classifications of hydrogels are listed, depending on the type of reaction and the nature of the components. Examples of obtaining hydrogels based on the normal and inverse electron-demand DA reaction, as well as the application of hydrogels for cell culture, drug delivery, injectable gels, and wound dressings, are considered. In conclusion, possible developmental directions are discussed, including the use of diene-dienophile pairs with a low temperature for the reversal of DA reaction, the modification of nanoparticles by diene and/or dienophile fragments, and new applications such as ink for 3D printing, sensing hydrogels, etc.

Fibrillar biocompatible colloidal gels based on cellulose nanocrystals and poly(N-isopropylacrylamide) for direct ink writing.

HYPOTHESIS: Hydrogels based on cellulose nanocrystals (CNC) have attracted great interest because of their sustainability, biocompatibility, mechanical strength and fibrillar structure. Gelation of colloidal particles can be induced by the introduction of polymers. Existing examples include gels based on CNC and derivatives of cellulose or poly(vinyl alcohol), however, gel structure and their application for extrusion printing were not shown. Hence, we rationalize formation of colloidal gels based on mixture of poly(N-isopropylacrylamide) (PNIPAM) and CNC and control their structure and mechanical properties by variation of components ratio. EXPERIMENTS: State diagram for colloidal system based on mixture of PNIPAM and CNC were established at 25 and 37 °C. Biocompatibility, fiber diameter and rheological properties of the gels were studied for different PNIPAM/CNC ratio. FINDINGS: We show that depending on the ratio between PNIPAM and CNC, colloidal system could be in sol or gel state at 25 °C and at gel state or phase separated at 37 °C. Physically crosslinked hydrogels were thermosensitive and could reversibly change it transparency from translucent to opaque in biologically relevant temperature range. These colloidal hydrogels were biocompatible, had fibrillar structure and demonstrate shear-thinning behavior, which makes them a promising material for bioapplications related to extrusion printing.

Stimulus-Responsive Transport Properties of Nanocolloidal Hydrogels.

Applications of polymer hydrogels in separation technologies, environmental remediation, and drug delivery require control of hydrogel transport properties that are largely governed by the pore dimensions. Stimulus-responsive change in pore size offers the capability to change gel's transport properties "on demand". Here, we report a nanocolloidal hydrogel that exhibits temperature-controlled increase in pore size and, as a result, enhanced transport of encapsulated species from the gel. The hydrogel was formed by the covalent cross-linking of aldehyde-modified cellulose nanocrystals and chitosan carrying end-grafted poly(N-isopropylacrylamide) (pNIPAm) molecules. Owing to the temperature-mediated coil-to-globule transition of pNIPAm grafts, they acted as a temperature-responsive "gate" in the hydrogel. At elevated temperature, the size of the pores showed up to a 4-fold increase, with no significant changes in volume, in contrast with conventional pNIPAm-derived gels exhibiting a reduction in both pore size and volume in similar conditions. Temperature-mediated transport properties of the gel were explored by studying diffusion of nanoparticles with different dimensions from the gel, leading to the established correlation between the kinetics of diffusion-governed nanoparticle release and the ratio nanoparticle dimensions-to-pore size. The proposed approach to stimulus-responsive control of hydrogel transport properties has many applications, including their use in nanomedicine and tissue engineering.

Recent Progress of 3D Printing of Polymer Electrolyte Membrane-Based Fuel Cells for Clean Energy Generation.

This review summarizes recent advances in the application of 3D printing (additive manufacturing) for the fabrication of various components of hydrogen fuel cells with a polymer electrolyte membrane (HFC-PEMs). This type of fuel cell is an example of green renewable energy, but its active implementation into the real industry is fraught with a number of problems, including rapid degradation and low efficiency. The application of 3D printing is promising for improvement in HFC-PEM performance due to the possibility of creating complex geometric shapes, the exact location of components on the substrate, as well as the low-cost and simplicity of the process. This review examines the use of various 3D printing techniques, such as inkjet printing, fused deposition modeling (FDM) and stereolithography, for the production/modification of electrodes, gas diffusion and catalyst layers, as well as bipolar plates. In conclusion, the challenges and possible solutions of the identified drawbacks for further development in this field of research are discussed. It is expected that this review article will benefit both representatives of applied science interested in specific engineering solutions and fundamental science aimed at studying the processes occurring in the fuel cell.

Modification of Commercial 3D Fused Deposition Modeling Printer for Extrusion Printing of Hydrogels.

In this paper, we report a simple modification of a commercially available printer with fused deposition modeling (FDM) technology for the implementation of extrusion printing of hydrogels. The main difference between an FDM printer and a gel-extrusion printer is their material propulsion system, which has to deal with ether a solid rod or liquid. By application of plastic 3D printing on an FDM printer, specific details, namely, the plunger system and parts of the gel supply system, were produced and combined with a modified printer. Two types of printing of polymer hydrogels were optimized: droplet and filament modes. The rheological ranges suitable for printing for each method were indicated, and the resolution of the samples obtained and the algorithms for creating g-code via Python scripts were given. We have shown the possibility of droplet printing of microspheres with a diameter of 100 microns and a distance between spheres of 200 microns, as well as filament printing of lines with a thickness of 300-2000 microns, which is appropriate accuracy in comparison with commercial printers. This method, in addition to scientific groups, will be especially promising for educational tasks (as a practical work for engineering students or for the introduction of 3D printing into school classes) and industrial groups, as a way to implement 3D extrusion printing of composite polymer hydrogels in a time- and cost-effective way.

Printing Structurally Anisotropic Biocompatible Fibrillar Hydrogel for Guided Cell Alignment.

Many fibrous biological tissues exhibit structural anisotropy due to the alignment of fibers in the extracellular matrix. To study the impact of such anisotropy on cell proliferation, orientation, and mobility, it is important to recapitulate and achieve control over the structure of man-made hydrogel scaffolds for cell culture. Here, we report a chemically crosslinked fibrous hydrogel due to the reaction between aldehyde-modified cellulose nanofibers and gelatin. We explored two ways to induce structural anisotropy in this gel by extruding the hydrogel precursor through two different printheads. The cellulose nanofibers in the hydrogel ink underwent shear-induced alignment during extrusion and retained it in the chemically crosslinked hydrogel. The degree of anisotropy was controlled by the ink composition and extrusion flow rate. The structural anisotropy of the hydrogel extruded through a nozzle affected the orientation of human dermal fibroblasts that were either seeded on the hydrogel surface or encapsulated in the extruded hydrogel. The reported straightforward approach to constructing fibrillar hydrogel scaffolds with structural anisotropy can be used in studies of the biological impact of tissue anisotropy.

Red GaPAs/GaP Nanowire-Based Flexible Light-Emitting Diodes.

We demonstrate flexible red light-emitting diodes based on axial GaPAs/GaP heterostructured nanowires embedded in polydimethylsiloxane membranes with transparent electrodes involving single-walled carbon nanotubes. The GaPAs/GaP axial nanowire arrays were grown by molecular beam epitaxy, encapsulated into a polydimethylsiloxane film, and then released from the growth substrate. The fabricated free-standing membrane of light-emitting diodes with contacts of single-walled carbon nanotube films has the main electroluminescence line at 670 nm. Membrane-based light-emitting diodes (LEDs) were compared with GaPAs/GaP NW array LED devices processed directly on Si growth substrate revealing similar electroluminescence properties. Demonstrated membrane-based red LEDs are opening an avenue for flexible full color inorganic devices.

Memristive TiO2: Synthesis, Technologies, and Applications.

Titanium dioxide (TiO2) is one of the most widely used materials in resistive switching applications, including random-access memory, neuromorphic computing, biohybrid interfaces, and sensors. Most of these applications are still at an early stage of development and have technological challenges and a lack of fundamental comprehension. Furthermore, the functional memristive properties of TiO2 thin films are heavily dependent on their processing methods, including the synthesis, fabrication, and post-fabrication treatment. Here, we outline and summarize the key milestone achievements, recent advances, and challenges related to the synthesis, technology, and applications of memristive TiO2. Following a brief introduction, we provide an overview of the major areas of application of TiO2-based memristive devices and discuss their synthesis, fabrication, and post-fabrication processing, as well as their functional properties.

Ionic Polyureas-A Novel Subclass of Poly(Ionic Liquid)s for CO2 Capture.

The growing concern for climate change and global warming has given rise to investigations in various research fields, including one particular area dedicated to the creation of solid sorbents for efficient CO2 capture. In this work, a new family of poly(ionic liquid)s (PILs) comprising cationic polyureas (PURs) with tetrafluoroborate (BF4) anions has been synthesized. Condensation of various diisocyanates with novel ionic diamines and subsequent ion metathesis reaction resulted in high molar mass ionic PURs (Mw = 12 ÷ 173 × 103 g/mol) with high thermal stability (up to 260 °C), glass transition temperatures in the range of 153-286 °C and remarkable CO2 capture (10.5-24.8 mg/g at 0 °C and 1 bar). The CO2 sorption was found to be dependent on the nature of the cation and structure of the diisocyanate. The highest sorption was demonstrated by tetrafluoroborate PUR based on 4,4'-methylene-bis(cyclohexyl isocyanate) diisocyanate and aromatic diamine bearing quinuclidinium cation (24.8 mg/g at 0 °C and 1 bar). It is hoped that the present study will inspire novel design strategies for improving the sorption properties of PILs and the creation of novel effective CO2 sorbents.

Inkjet Printing Humidity Sensing Pattern Based on Self-Organizing Polystyrene Spheres.

This study is devoted to the development of photonic patterns based on polystyrene spheres (PSS) incorporated in chitosan hydrogels by inkjet printing. Using this method, high-resolution encrypted images that became visible only in high humidity were obtained. Inks based on PSS with carboxylic groups on the surface were made, and their rheological parameters (viscosity, surface tension, and ζ-potential) were optimized according to the Ohnesorge theory. The obtained value of the ζ-potential indicated the stability of the synthesized colloidal inks. The dependences of the printing parameters on the concentration of ethylene glycol in PSS dispersion, the drop spacing, the shape of the printed pattern, waveform, the temperature of the printing process, and the degree of ordering of the PSS-based photonic crystal were investigated. The scanning electronic microscope (SEM) images confirmed that the optimal self-organization of PSS was achieved at the following values of 0.4% weight fraction (wt%) carboxylic groups, the drop spacing of 50 µm, and the temperature of the printing table of 25 °C. High-resolution microstructures were obtained by drop-on-demand printing with a deposited drophead diameter of 21 µm and an accuracy of ±2 µm on silicon and glass substrates. The deposition of chitosan-based hydrogels on the obtained polystyrene photonic crystals allowed reversibly changing the order of the diffraction lattice of the photonic crystal during the swelling of the hydrogel matrix, which led to a quick optical response in the daylight. The kinetics of the appearance of the optical response of the obtained coating were discussed. The simplicity of production, the speed of image appearance, and the ability to create high-resolution patterns determine the potential applications of the proposed systems as humidity sensors or anticounterfeiting coatings.

Printing of Colorful Cellulose Nanocrystalline Patterns Visible in Linearly Polarized Light.

This study addresses the inkjet printing approach for fabrication of cellulose nanocrystalline (CNC) patterns with tunable optical properties varied by the thickness of deposited layers. In particular, forming functional patterns visible only in linearly polarized light is of the primary interest. The possibility of controlling the bright iridescent color response associated with the birefringence in the chiral anisotropic structure of inkjet-printed layers of CNC with sulfo-groups (s-CNC) has been thoroughly investigated. In this connection, we have elaborated an appropriate synthesis sequence for deriving printable inks in the form of sedimentation-stable s-CNC colloids with various concentrations of solid phase and experimentally determined the optimal regimes of their inkjet printing. For this purpose, the rheological parameters and s-CNC particle concentration have also been optimized. The study is accomplished with a comprehensive optical characterization of the deposited s-CNC layers with variable thickness, drying conditions, and the polarization state. The experimental results demonstrate the feasibility of inkjet printing technology to perform the precise fabrication of optically active s-CNC patterns with variable optical properties. These results are particularly relevant for applications requiring special conditions of color demonstration in security printing for such as anticounterfeiting applications, polygraphy decoration printing, and color photo filters.

Silicon Quantum Dots: Synthesis, Encapsulation, and Application in Light-Emitting Diodes.

Silicon quantum dots (SiQDs) are semiconductor Si nanoparticles ranging from 1 to 10 nm that hold great applicative potential as optoelectronic devices and fluorescent bio-marking agents due to their ability to fluoresce blue and red light. Their biocompatibility compared to conventional toxic Group II-VI and III-V metal-based quantum dots makes their practical utilization even more attractive to prevent environmental pollution and harm to living organisms. This work focuses on their possible use for light-emitting diode (LED) manufacturing. Summarizing the main achievements over the past few years concerning different Si quantum dot synthetic methods, LED formation and characteristics, and strategies for their stabilization by microencapsulation and modification of their surface by specific ligands, this work aims to provide guidance en route to the development of the first stable Si-based light-emitting diodes.

Clinical and experimental studies of multiple sclerosis in Russia: experience of the leading national research centers.

Mechanisms of axonal damage and adaptive capacity in multiple sclerosis (MS), including cortical reorganization, have been actively studied in recent years. The lack of regenerative capabilities and the irreversibility of neurodegeneration in MS are critical factors for the optimization of MS treatment. In this study, we present the results of clinical and basic studies in the field of MS by two leading Russian centers. Clinical and neuroimaging correlations show that spinal damage in MS is accompanied by functional reorganization of the cerebral cortex, which is determined not only by the efferent component but also by the afferent component. Comparative analysis of MS treatment with both interferon ß1b (IFN-ß1b) and IFN-ß1a at a dosage of 22 µg for 3 years through subcutaneous administration and glatiramer acetate showed equally high efficiency in reducing the number of exacerbations in relapsing-remitting MS and secondary-progressive MS. We demonstrate a reduced risk of disability in relapsing-remitting MS and secondary-progressive MS patients in all groups treated with IFN-ß1 and glatiramer acetate. MS appears to be a disease that would greatly benefit from the development of personalized therapy; thus, adequate molecular predictors of myelin degradation are greatly needed. Therefore, novel ideas related to the viral hypothesis of the etiology of MS and new targets for therapeutic intervention are currently being developed. In this manuscript, we discuss findings of both clinical practice and fundamental research reflecting challenges and future directions of MS treatment in the Russian Federation.