Synthesis of CaCO3 supported nano zero-valent iron-nickel nanocomposite (nZVI-Ni@CaCO3) and its application for trichloroethylene removal in persulfate activated system.

Nano zero-valent (nZVI) based composite have been widely utilized in environmental remediation. However, the rapid agglomeration and quick deactivation of nZVI limited its application on large scale. In this work, CaCO3 supported nZVI-Ni catalyst, namely nZVI-Ni@CaCO3 was prepared and used for the efficient removal of trichloroethylene (TCE) in PS oxidation process. The successful disbursement of nZVI-Ni on CaCO3 support material not only increased the surface area of nZVI-Ni@CaCO3 (69.45 m2/g) with respect to CaCO3 (5.92 m2/g) and bare nZVI (13.29 m2/g) but also improved the catalytic activity. XRD, XPS and FTIR analysis confirmed the successful formation of nZVI-Ni@CaCO3 nanoparticles. The nZVI-Ni@CaCO3 nanoparticles combined with PS had achieved complete removal of TCE (99.8%) with dosage of 36 mg/L and 1.34 mM respectively. These results showed that the use of CaCO3 as support material for nZVI-Ni could have significant influence on contaminant removal process. Scavenging and EPR tests validated the existence of SO4•-, OH• and O2•- radicals in PS/nZVI-Ni@CaCO3 system and highlighted the dominant role of SO4•- radicals in TCE removal process. HCO3- ions and humic acid have shown adverse effect on TCE removal due to radical scavenging and buffering effect. Owing to improved catalytic activity and easy preparation, the nZVI-Ni@CaCO3 nanoparticles could be served as an alternative strategy for environmental remediation.

Synthesizing pectin-crosslinked gum ghatti hydrogel for efficient adsorptive removal of malachite green.

Pectin-crosslinked gum ghatti hydrogel (PGH) has been synthesized utilizing pectin and gum ghatti through an uncomplicated and inexpensive copolymerization method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM-elemental mapping), Brunauer-Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS) characterization techniques have been employed to determine various structural, chemical and compositional characteristics of fabricated PGH. Three different weight ratios (1:1, 2:1, or 1:2 for pectin and gum ghatti, respectively) were employed to synthesize three distinct types of PGH. Swelling studies has been done to determine the best ratios for PGH fabrication. PGH has been assessed as an adsorbent for the removal of malachite green dye from aqueous solutions. The effects of PGH dosage (100-400 mg/L), dye concentration (10-160 mg/L), pH (2-9 pH), adsorption time (0-480 min), and temperature (25-55 °C) has been examined through batch solutions. According to Langmuir isotherm analysis, the maximum adsorption capacity is 658.1 mg/g. By using pseudo-second-order kinetics and the Freundlich adsorption isotherm, the adsorption process could be well explained. After five consecutive cycles, PGH had an adsorption percentage of 86.917 % for the malachite green dye. It is safe for the environment and may be used to remove malachite green (MG) dye from aqueous solutions.

Rapid self-assembly of self-healable and transferable liquid metal epidermis.

Healable electronic skins, an essential component for future soft robotics, implantable bioelectronics, and smart wearable systems, necessitate self-healable and pliable materials that exhibit functionality at intricate interfaces. Although a plethora of self-healable materials have been developed, the fabrication of highly conformal biocompatible functional materials on complex biological surfaces remains a formidable challenge. Inspired by regenerative properties of skin, we present the self-assembled transfer-printable liquid metal epidermis (SALME), which possesses autonomous self-healing capabilities at the oil-water interface. SALME comprises a layer of surfactant-grafted liquid metal nanodroplets that spontaneously assemble at the oil-water interface within a few seconds. This unique self-assembly property facilitates rapid restoration (<10 s) of SALME following mechanical damage. In addition to its self-healing ability, SALME exhibits excellent shear resistance and can be seamlessly transferred to arbitrary hydrophilic/hydrophobic curved surfaces. The transferred SALME effectively preserves submicron-scale surface textures on biological substrates, thus displaying tremendous potential for future epidermal bioelectronics.

ISX9 loaded thermoresponsive nanoparticles for hair follicle regrowth.

There is a high demand for an optimal drug delivery system to treat androgenetic alopecia. Topical application of ISX9, which is a neurogenesis inducer, has been found to stimulate hair follicle (HF) regrowth by upregulating the Wnt/ß-catenin signaling pathway, an essential pathway involved in initiating HF growth and development. In the present study, a temperature-sensitive, biopolymer-based, biocompatible, and eco-friendly drug-delivery system was synthesized. This system comprised chitosan-grafted poly(glycidyl methacrylate-co-N-isopropyl acrylamide) (Poly(GMA-co-NIPAAm)@CS-PGNCS) as the shell component and PF127 as the core polymer. The hydrophobic nature of the PF127 block copolymer efficiently dissolved the partially water-soluble drug, ISX9, and the thermos-responsive shell polymer effectively released the drug at a definite skin temperature. The optimized spherical nanoparticles demonstrated the lowest critical solution temperature (LCST) at 32 ± 2 °C with a diameter of 100-250 nm, which delivered encapsulated ISX9 with greater precision than topical ISX9. In a series of in vivo experiments, we demonstrated that ISX9-coated TBNPs upregulated the expression of ß-catenin, active ß-catenin, Wnt target genes, stemness marker genes, proliferating cell nuclear antigen, HF stem cell markers, and HF markers including VEGF, TGF, and IGF-1 more effectively than topical ISX9. These results suggest that TBNPs could be employed as a platform for effective transdermal delivery of various hydrophobic drugs.

Tailoring Homogeneous Hydrogel Nanospheres by Facile Ultra-Sonication Assisted Cross-Linked Copolymerization for Rhodamine B Dye Adsorption.

The present paper describes the design of shape-oriented hydrogel nanospheres using a facile ultrasonication-supported crosslinked copolymerization technique. The effect of variable monomer concentration on the homogeneity of hydrogel nanospheres was investigated. The chitosan-cl-poly(MMA) hydrogel nanospheres were well characterized using various techniques such as FTIR, XRD, TGA, SEM, and TEM. The chitosan-cl-poly(MMA) hydrogel nanospheres were studied for their swelling behavior and could potentially be used as a novel adsorbent for rhodamine B dye remediation from aqueous media. The study found that utilizing chitosan-cl-poly(MMA) nanohydrogel spheres at the optimal pH 5 increased RhB dye adsorption capacity from 7.9 to 17.8 mg/g (pH 2 to 5), followed by a slight reduction. Furthermore, when nanohydrogel concentration increased, adsorption capacity dropped from 18.03 to 2.8 mg/g, but adsorption percentage climbed from 90.2% to 97.8%. At an initial dye concentration of 140 mg/L, rhodamine B adsorption achieved 204.3 mg/g in 60 min. The rhodamine B dye adsorption study includes adsorption kinetics, isotherm, and thermodynamics analyses. The interpretation of the adsorption study revealed that Langmuir isotherms fit best with a qmax value of 276.26 mg/g, which is in close approximation with the experimental value, whereas pseudo-second-order kinetics explains the adsorption process rate. The interaction of RhB dye with chitosan-cl-poly(MMA) hydrogel nanospheres involves multiple forces such as electrostatic interactions, hydrogen bonding, van der Waals forces, etc.

Recent advances in perovskite-based Z-scheme and S-scheme heterojunctions for photocatalytic CO2 reduction.

The dramatic rise in carbon dioxide levels in the atmosphere caused by the continuous use of carbon fuels continues to have a significant impact on environmental degradation and the disappearance of energy reserves. Past few years have seen a significant increase in the interest in photocatalytic carbon dioxide reduction because of its ability to lower CO2 releases from the burning of fossil fuels while also producing fuels and important chemical products. Because of their excellent catalytic efficiency, great uniformity, lengthy charge diffusion layers and texture flexibility that enable accurate band gap and band line optimization, perovskite-based nanomaterials are perhaps the most advantageous among the numerous semiconductors proficient in accelerating CO2 conversion under visible light. Firstly, a brief insight into photocatalytic CO2 conversion mechanism and structural features of perovskites are discussed. Further the classification and selection of perovskites for Z and S-scheme heterojunctions and their role in photocatalytic CO2 reduction analysed. The efficient modification and engineering of heterojunctions via co-catalyst loading, morphology control and vacancy introduction have been comprehensively reviewed. Third, the state-of-the-art achievements of perovskite-based Z-scheme and S-scheme heterojunctions are systematically summarized and discussed. Finally, the challenges, bottlenecks and future perspectives are discussed to provide a pathway for applying perovskite-based heterojunctions for solar-to-chemical energy conversion.

Rheology of graphene oxide stabilized Pickering emulsions.

Pickering emulgels stabilized by graphene oxide (GO) with didodecyldimethylammonium bromide (DDAB) as an auxiliary surfactant and liquid paraffin as the oil phase have proved to be an excellent 3D printable ink. This paper elucidates the structure of such emulgels by a combination of microscopy before and after intensive shear as well as broadband dielectric spectroscopy and rheology in the linear and nonlinear regime. An increase of the DDAB surfactant and GO-contents leads to a systematic increase of modulus and viscosity, a reduction of the limits of the nonlinear regime and a more complicated variation of the normal forces, with negative normal forces at high shear rate  for low GO-contents and positive normal forces at high GO-contents. The interfacial jamming behavior studied by morphology, rheology and dielectric spectroscopy is explained based on droplet deformation, jamming and recovery phenomena.

Understanding Gel-Powers: Exploring Rheological Marvels of Acrylamide/Sodium Alginate Double-Network Hydrogels.

This study investigates the rheological properties of dual-network hydrogels based on acrylamide and sodium alginate under large deformations. The concentration of calcium ions affects the nonlinear behavior, and all gel samples exhibit strain hardening, shear thickening, and shear densification. The paper focuses on systematic variation of the alginate concentration-which serves as second network building blocks-and the Ca2+-concentration-which shows how strongly they are connected. The precursor solutions show a typical viscoelastic solution behavior depending on alginate content and pH. The gels are highly elastic solids with only relatively small viscoelastic components, i.e., their creep and creep recovery behavior are indicative of the solid state after only a very short time while the linear viscoelastic phase angles are very small. The onset of the nonlinear regime decreases significantly when closing the second network (alginate) upon adding Ca2+, while at the same time the nonlinearity parameters (Q0, I3/I1, S, T, e3/e1, and v3/v1) increase significantly. Further, the tensile properties are significantly improved by closing the alginate network by Ca2+ at intermediate concentrations.

High Dielectric Poly(vinylidene fluoride)-Based Polymer Enables Uniform Lithium-Ion Transport in Solid-State Ionogel Electrolytes.

Ionic liquids (ILs)-incorporated solid-state polymer electrolytes (iono-SPEs) have high ionic conductivities but show non-uniform Li+ transport in different phases. This work greatly promotes Li+ transport in polymer phases by employing a poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE), PTC] as the framework of ILs to prepare iono-SPEs. Unlike PVDF, PTC with suitable polarity shows weaker adsorption energy on IL cations, reducing their possibility of occupying Li+ -hopping sites. The significantly higher dielectric constant of PTC than PVDF facilitates the dissociation of Li-anions clusters. These two factors motivate Li+ transport along PTC chains, narrowing the difference in Li+ transport among varied phases. The LiFePO4 /PTC iono-SPE/Li cells cycle steadily with capacity retention of 91.5 % after 1000 cycles at 1 C and 25 °C. This work paves a new way to induce uniform Li+ flux in iono-SPEs through polarity and dielectric design of polymer matrix.

Study of the synergistic influence of zwitterionic interactions and graphene oxide on water diffusion mechanism and mechanical properties in hybrid hydrogel network.

Hybrid hydrogels based on n-isopropylacrylamide, zwitterionic comonomer, and graphene oxide were synthesized to study their physical and mechanical properties. The compositional variation largely influenced the swelling characteristics of the hybrid hydrogels compared to mechanical properties, i.e., elongation and compression. Additionally, Rheometric swelling measurements on the swollen hydrogels were performed until they reached equilibrium showed a very low phase angle δ indicating strong covalent network, which intrun increases with increasing content of zwitterions and GO. Swelling kinetics were studied and found to follow Fickian dynamics, albeit zwitterion-containing gels showed a peculiar 2-step swelling pattern. Interestingly, differences in the swelling mechanism are also clear for the hydrogels with 2D GO (Graphene oxide) nano-fillers from its 1D nano-filler CNTs (Carbon nanotubes). In elongation, the samples break in a brittle fashion at Hencky strains εmax around 0.4-0.65 with the maximum stress being observed for samples with high Zw-content and 0.2% GO, which can be explained by the stress-rising properties of sharp edges of GO. In contrast, the data in compression profits from higher GO-contents as crack growth is less important in this deformation mode. This work will contribute to future composite gel applications.

Dynamically bonded, tough, and conductive MXene@oxidized sodium alginate: chitosan based multi-networked elastomeric hydrogels for physical motion detection.

Biopolymer-based conductive hydrogels (HGs) are promising candidates for preparing environmentally friendly flexible electronics. However, it is still a great challenge to synthesize biopolymer-based tough, self-healable, and fast strain recoverable HGs. Herein, a facile strategy is demonstrated to synthesize stretchable, self-recoverable, conductive, and tough HGs strain sensors through the formation of multi-dynamic interactions (i.e., imine bond formation, hydrogen bonds, ionic bonds, and electrostatic bonds) and strong covalent interactions between MXene (Ti3C2Tx), oxidized sodium alginate (OSA), chitosan (CS), polyacrylamide (PAAm), Fe(III) and PEDOT:PSS. Thus, obtaining dynamically and covalently bonded nanocomposite hydrogels (NCHGs) with controllable interfacial interactions exhibited a high mechanical strength (0.91 MPa), toughness (2.99 MJ/m3), stretchability (820 %), elasticity (>600 %) and conductivity (1.31 S/m). In addition, the presence of Fe(III) ions and conducting fillers endows excellent repeatability with high stability in resistance change upon bending or stretching with ultra-broad sensitivity up to 11-gauge factor and consisting lowest resistance change up to 0.5 %.

Influence of Cellulose Nanofibers on the Behavior of Pickering Emulsions. Part 1. Microscopy and Startup Flow Test.

The dispersibility of flexible polymer chains present at the emulsion's interface between the dispersed and continuous phase has obvious effects on rheology and dielectric properties of the whole emulsion. Cellulose nanofiber (CNF)-based Pickering emulsions are good systems to research these properties with respect to their microscopic phase structure, dielectric, and rheological properties by using CNF as a water-dispersible Pickering emulsifier, liquid paraffin as an oil phase, and didodecyldimethylammonium bromide (DDAB) as a cationic auxiliary surfactant. The CNF and DDAB contents were systematically varied while the water-to-paraffin oil ratio was kept constant to discern the influence of the Pickering emulsifiers. Polarized optical microscopic images reveal that the droplets tend to shrink at higher CNF content but grow bigger when increasing the DDAB content, which is proved by fluorescence analysis of the CNF dispersibility with varying DDAB content. The dielectric damping exhibits a minimum, whose value decreases with increasing DDAB and CNF content. Increasing the DDAB content promotes the solubilization of CNF in the aqueous phase, which will increase the overall viscosity and yield points. Similarly, a higher CNF content leads to a higher viscosity and yield point, but at high DDAB contents, the viscosity function exhibits an S-shape at intermediate CNF contents. To evaluate the results further, they were compared with CNF dispersions (without oil phase), which showed a surfactant effect slightly on maximum stress but strongly on yield stress τy, indicating that DDAB can promote the formation of a CNF network rather than the viscosity of the whole system. This paper provides information on how a systematical variation of the composition influences morphology and physico-chemical interactions as detected by broadband dielectric spectroscopy and rheological behavior.

Mussel-inspired biomaterials: From chemistry to clinic.

After several billions of years, nature still makes decisions on its own to identify, develop, and direct the most effective material for phenomena/challenges faced. Likewise, and inspired by the nature, we learned how to take steps in developing new technologies and materials innovations. Wet and strong adhesion by Mytilidae mussels (among which Mytilus edulis-blue mussel and Mytilus californianus-California mussel are the most well-known species) has been an inspiration in developing advanced adhesives for the moist condition. The wet adhesion phenomenon is significant in designing tissue adhesives and surgical sealants. However, a deep understanding of engaged chemical moieties, microenvironmental conditions of secreted proteins, and other contributing mechanisms for outstanding wet adhesion mussels are essential for the optimal design of wet glues. In this review, all aspects of wet adhesion of Mytilidae mussels, as well as different strategies needed for designing and fabricating wet adhesives are discussed from a chemistry point of view. Developed muscle-inspired chemistry is a versatile technique when designing not only wet adhesive, but also, in several more applications, especially in the bioengineering area. The applications of muscle-inspired biomaterials in various medical applications are summarized for future developments in the field.

Water-Soluble and -Insoluble Polymers and Biopolymers for Biomedical, Environmental, and Biological Applications.

In this Special Issue, several papers dedicated to biomedical, environmental, and biological applications have been assembled, representing different aspects of the field [...].

Visible-light driven dual heterojunction formed between g-C3N4/BiOCl@MXene-Ti3C2 for the effective degradation of tetracycline.

In the present study, we have successfully formulated a dual heterojunction of g-C3N4/BiOCl@MXene-Ti3C2 (GCBM) which was found to be highly active in the visible region. GCBM was found to be highly efficient for the degradation of an antibiotic, tetracycline (TC) as compared to the individual constituting units; g-C3N4 and BiOCl. Maximum of 97% TC degradation rate was obtained within 90 min of visible light irradiation for initial concentration of 10 mg/L of TC. Optical analysis exhibited that the synthesized heterojunction showed high absorption in the complete spectrum. The reactive species specified by the scavenger study showed the major involvement of •O2- and •OH radicals. The charge transfer mechanism showed that 2 schemes were majorly involvement in which Z-scheme was formed between g-C3N4 and BiOCl and Schottky junction was formed between g-C3N4 and Mxene-Ti3C2. The formation of Schottky junction helped in inhibiting the back transfer of photogenerated charges and thus, helped in reducing the recombination rate. The synthesized photocatalyst was found to be highly reusable and was studied for consecutive 5 cycles that generalized the high proficiency even after repetitive cycles.

Chitosan as a Tool for Sustainable Development: A Mini Review.

New developments require innovative ecofriendly materials defined by their biocompatibility, biodegradability, and versatility. For that reason, the scientific society is focused on biopolymers such as chitosan, which is the second most abundant in the world after cellulose. These new materials should show good properties in terms of sustainability, circularity, and energy consumption during industrial applications. The idea is to replace traditional raw materials with new ecofriendly materials which contribute to keeping a high production rate but also reducing its environmental impact and the costs. The chitosan shows interesting and unique properties, thus it can be used for different purposes which contributes to the design and development of sustainable novel materials. This helps in promoting sustainability through the use of chitosan and diverse materials based on it. For example, it is a good sustainable alternative for food packaging or it can be used for sustainable agriculture. The chitosan can also reduce the pollution of other industrial processes such as paper production. This mini review collects some of the most important advances for the sustainable use of chitosan for promoting circular economy. Hence, the present review focuses on different aspects of chitosan from its synthesis to multiple applications.

Gum Acacia-Crosslinked-Poly(Acrylamide) Hydrogel Supported C3N4/BiOI Heterostructure for Remediation of Noxious Crystal Violet Dye.

Herein, we report the designing of a C3N4/BiOI heterostructure that is supported on gum acacia-crosslinked-poly(acrylamide) hydrogel to fabricate a novel nanocomposite hydrogel. The potential application of the obtained nanocomposite hydrogel to remediate crystal violet dye (CVD) in an aqueous solution was explored. The structural and functional analysis of the nanocomposite hydrogel was performed by FTIR (Fourier transform infrared spectroscopy), X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The different reaction parameters, such as CVD concentration, nanocomposite hydrogel dosage, and working pH, were optimized. The C3N4/BiOI heterostructure of the nanocomposite hydrogel depicts Z-scheme as the potential photocatalytic mechanism for the photodegradation of CVD. The degradation of CVD was also specified in terms of COD and HR-MS analysis was carried to demonstrate the major degradation pathways.

Adsorption of cationic dyes onto carrageenan and itaconic acid-based superabsorbent hydrogel: Synthesis, characterization and isotherm analysis.

Polysaccharide-based hydrogels offer a great overlook for environmental applications and help in the elimination of various noxious pollutants from the water system. Novel carrageenan and itaconic acid-based superadsorbent hydrogel having appreciable swelling properties and adsorption capacity towards Methylene blue (MB), Crystal violet (CV), and Methyl Red (MR) was synthesized by suspension polymerization technique. The swelling study showed the dependency upon the temperature in which the swelling rate increased with increasing temperature with a maximum swelling rate of 417% at 318 K. For ascertaining the maximum adsorption capacity, various influential parameters such as contact time, adsorbent dose, dye concentration, and temperature were systematically studied. Maximum adsorption capacity as calculated from the Langmuir isotherm was 2439.02, 1111.11, and 666.68 mg/g for MB, CV, and MR, respectively. Thermodynamic studies revealed the spontaneous nature of the undertaken dye adsorption experiment. Overall, the present study reveals that the synthesized superadsorbent hydrogel can be used as an efficient adsorbent for the removal of dyes from an aqueous solution.