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.

Utilization of microalgal-bacterial energy nexus improves CO2 sequestration and remediation of wastewater pollutants for beneficial environmental services.

Carbon dioxide (CO2) emissions from the combustion of fossil fuels and coal are primary contributors of greenhouse gases leading to global climate change and warming. The toxicity of heavy metals and metalloids in the environment threatens ecological functionality, diversity and global human life. The ability of microalgae to thrive in harsh environments such as industrial wastewater, polluted lakes, and contaminated seawaters presents new, environmentally friendly, and less expensive CO2 remediation solutions. Numerous microalgal species grown in wastewater for industrial purposes may absorb and convert nitrogen, phosphorus, and organic matter into proteins, oil, and carbohydrates. In any multi-faceted micro-ecological system, the role of bacteria and their interactions with microalgae can be harnessed appropriately to enhance microalgae performance in either wastewater treatment or algal production systems. This algal-bacterial energy nexus review focuses on examining the processes used in the capture, storage, and biological fixation of CO2 by various microalgal species, as well as the optimized production of microalgae in open and closed cultivation systems. Microalgal production depends on different biotic and abiotic variables to ultimately deliver a high yield of microalgal biomass.

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.

Oscillations in modulus in solutions of graphene oxide and reduced graphene oxide with grafted poly-N-isopropylamide.

In a material consisting of graphene oxide or reduced graphene oxide and poly-N-isopropylamide (PNIPAM) in an aqueous solution, a new type of rheological behaviour is found. When subjecting the material to a short and relatively small deformation pulse, the modulus, which is observed by small deformations in the linear-viscoelastic or very slightly nonlinear range, oscillates with periodicities between 100 and several 1000 seconds; however, in many cases, it also increases systematically. The periodicity depends on the filler content and the sample preparation method (in situ polymerisation vs. blending). When subjecting the material to high nonlinear deformations (γ0 = 100-300%), the resulting linear viscoelastic behaviour changes from a periodic oscillation to a quick recovery of the original data, followed by a decrease and a subsequent increase beyond the value of the modulus of the material prior to the deformation pulse.

Hydrogen bonding in aprotic solvents, a new strategy for gelation of bioinspired catecholic copolymers with N-isopropylamide.

Copolymers of N-isopropylacrylamide (NIPAM) and dopamine methacrylate can establish a reversible, self-healing 3D network in aprotic solvents based on hydrogen bonding. The reactivity and hydrogen bonding formation of catechol groups in copolymer chains are studied by UV-vis and (1) H NMR spectroscopy, while reversibility from sol to gel and inverse as well as self-healing properties are tested rheologically. The produced reversible organogel can self-encapsulate physically interacting or chemically bonded solutes such as drugs due to thermosensitivity of the used copolymer. This system offers dual-targeted and controlled drug delivery and release-by slowing down release kinetics by supramolecular bonding of the drug and by reducing diffusion rates due to modulus increase.

Graphene oxide/carbon nanotube composite hydrogels-versatile materials for microbial fuel cell applications.

Carbonaceous nanocomposite hydrogels are prepared with an aid of a suspension polymerization method and are used as anodes in microbial fuel cells (MFCs). (Poly N-Isopropylacrylamide) (PNIPAM) hydrogels filled with electrically conductive carbonaceous nanomaterials exhibit significantly higher MFC efficiencies than the unfilled hydrogel. The observed morphological images clearly show the homogeneous dispersion of carbon nanotubes (CNTs) and graphene oxide (GO) in the PNIPAM matrix. The complex formation of CNTs and GO with NIPAM is evidenced from the structural characterizations. The effectual MFC performances are influenced by combining the materials of interest (GO and CNTs) and are attributed to the high surface area, number of active sites, and improved electron-transfer processes. The obtained higher MFC efficiencies associated with an excellent durability of the prepared hydrogels open up new possibilities for MFC anode applications.

Network formation in graphene oxide composites with surface grafted PNIPAM chains in aqueous solution characterized by rheological experiments.

Poly N-isopropyl acrylamide (PNI) radically polymerized in aqueous solution in the presence of graphene oxide (GO) can significantly change the properties of the resulting solution from a regular polymer solution to a soft solid with a GO content of only 0.176 wt% (3 wt% with respect to PNI). However, these properties require the presence of both grafting and supramolecular interactions between polymer chains and hydrophilic groups on GO (-OH, -COOH), proven by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray diffraction and spectroscopy (XRD) and Raman spectra. While very low GO-contents (below 0.05 wt%) only lead to a labile structure, which can be disassembled by shear, higher contents yield composites with solid-like characteristics. This is clearly evident from the rheological behaviour, which changes significantly at a GO content around 0.15 wt%. Intensive shearing destroys the weak network, which cannot reform quickly at lower GO-concentrations, while at intermediate concentrations, restructuring is fast. GO-contents of 0.176 wt% lead to a material behaviour, which almost perfectly recovers from small deformations (creep and creep recovery compliance almost match) but larger deformations lead to permanent damage to the sample.

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.

Recent progress in bio-mediated synthesis and applications of engineered nanomaterials for sustainable agriculture.

The ever-increasing demand for agricultural food products, medicine, and other commercial sectors requires new technologies for agricultural practices and promoting the optimum utilization of natural resources. The application of engineered nanomaterials (ENMs) enhance the biomass production and yield of food crop while resisting harmful environmental stresses. Bio-mediated synthesis of ENMs are time-efficient, low-cost, environmentally friendly, green technology. The precedence of using a bio-mediated route over conventional precursors for ENM synthesis is non-toxic and readily available. It possesses many active agents that can facilitate the reduction and stabilization processes during nanoparticle formation. This review presents recent developments in bio-mediated ENMs and green synthesis techniques using plants, algae, fungi, and bacteria, including significant contributions to identifying major ENM applications in agriculture with potential impacts on sustainability, such as the role of different ENMs in agriculture and their impact on different plant species. The review also covers the advantages and disadvantages of different ENMs and potential future research in this field.

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.

Concentration Effect over Thermoresponse Derived from Organometallic Compounds of Functionalized Poly(N-isopropylacrylamide-co-dopamine Methacrylamide).

The functionalization of smart polymers is opening a new perspective in catalysis, drug carriers and biosensors, due to the fact that they can modulate the response regarding conventional devices. This smart response could be affected by the presence of organometallic complexes in terms of interactions which could affect the physical chemical properties. In this sense, the thermoresponsive behavior of copolymers based on N-isopropylacrylamide (NIPAM) could be affected due to the presence of hydrophobic groups and concentration effect. In this work, the functionalization of a copolymer based on NIPAM and dopamine methacrylamide with different amounts of bis(cyclopentadienyl)titanium (IV) dichloride was carried out. The resulting materials were characterized, showing a clear idea about the mechanism of functionalization through FTIR spectroscopy. The thermoresponsive behavior was also studied for various polymeric solutions in water by UV-vis spectroscopy and calorimetry. The hydrophobic interactions promoted by the organometallic complex could affect the transition associated with the lower critical solution temperature (LCST), specifically, the segments composed by pure NIPAM. That fact would explain the reduction of the width of the LCST-transition, contrary to what could be expected. In addition, the hydrophobicity was tested by the contact angle and also DNA interactions.

Mussel-inspired pH-triggered reversible foamed multi-responsive gel--the surprising effect of water.

Novel covalent gels were prepared by complexation of polymer-bound catechols with NaBH4 at pH ≈ 9. These gels can absorb humidity, which changes the catechol-borate covalent bonds from irreversible to reversible. Furthermore, humidity induces self-healing, proven by rheological data.