Nano-enabled smart and functional materials toward human well-being and sustainable developments.

Fabrication and operation on increasingly smaller dimensions have been highly integrated with the development of smart and functional materials; they are key to many technological innovations to meet economic and societal needs. Along with many researchers worldwide, the Waterloo Institute for Nanotechnology (WIN) has long realized the synergetic interplays between nanotechnology and functional materials and designated "Smart & Functional Materials" as one of its four major research themes. Thus far, WIN researchers have utilized the properties of smart polymers, nanoparticles, and nanocomposites to develop active materials, membranes, films, adhesives, coatings, and devices with novel and improved properties and capabilities. In this review article, we aim to highlight some of the recent developments on the subject including our own research and key research literature in the context of the UN Sustainability development goals.

Liquid-templated graphene aerogel electromagnetic traps.

For decades, the inherently reflective nature of metallic electromagnetic (EM) shields and their induced secondary EM pollution have posed significant challenges for sensitive electronics. While numerous efforts have been made to develop superior EM shielding systems, the issue of reflection dominancy in metallic substrates remains unresolved. Herein, we addressed this long-lasting obstacle by pairing metallic shields with ultra-lightweight (density of 3.12-3.40 mg cm-3) elastic anti-reflection aerogels, altering their shielding mechanism from dominant reflection (reflectance >0.8) to absorption (absorbance >0.7) by trapping EM waves inside the aerogel. The aerogel EM traps were generated using interfacial complexation, yielding engineerable filamentous liquid structures. These served as templates for aerogel creation through a follow-up process of freezing and lyophilization. The engineerable lossy medium of aerogels benefits from a multi-scale porous construct with the combined action of dielectric and conduction losses, highly dissipating the EM waves and minimizing the reflections. Notably, declining the diameter of aerogel filaments promoted its absorption dominancy, rendering it a potent dissipating medium for EM waves. Pairing a metallic substrate with filamentous aerogel EM traps has resulted in an exceptionally effective absorption-dominant shielding system, achieving absorbance levels between 0.70-0.81. This system offers a shielding effectiveness of 53-89 dB within the X-band frequency range. This innovation addresses a persistent issue in shielding science related to the reflective characteristics of metallic substrates, effectively inhibiting their induced EM reflections.

Functional Janus structured liquids and aerogels.

Janus structures have unique properties due to their distinct functionalities on opposing faces, but have yet to be realized with flowing liquids. We demonstrate such Janus liquids with a customizable distribution of nanoparticles (NPs) throughout their structures by joining two aqueous streams of NP dispersions in an apolar liquid. Using this anisotropic integration platform, different magnetic, conductive, or non-responsive NPs can be spatially confined to opposite sides of the original interface using magnetic graphene oxide (mGO)/GO, Ti3C2Tx/GO, or GO suspensions. The resultant Janus liquids can be used as templates for versatile, responsive, and mechanically robust aerogels suitable for piezoresistive sensing, human motion monitoring, and electromagnetic interference (EMI) shielding with a tuned absorption mechanism. The EMI shields outperform their current counterparts in terms of wave absorption, i.e., SET ≈ 51 dB, SER ≈ 0.4 dB, and A = 0.91, due to their high porosity ranging from micro- to macro-scales along with non-interfering magnetic and conductive networks imparted by the Janus architecture.

Surfactant-Mediated Highly Conductive Cellulosic Inks for High-Resolution 3D Printing of Robust and Structured Electromagnetic Interference Shielding Aerogels.

Technological fusion of emerging three-dimensional (3D) printing of aerogels with gel processing enables the fabrication of lightweight and functional materials for diverse applications. However, 3D-printed constructs via direct ink writing for fabricating electrically conductive structured biobased aerogels suffer several limitations, including poor electrical conductivity, inferior mechanical strength, and low printing resolution. This work addresses these limitations via molecular engineering of conductive hydrogels. The hydrogel inks, namely, CNC/PEDOT-DBSA, featured a unique formulation containing well-dispersed cellulose nanocrystal decorated by a poly(3,4-ethylene dioxythiophene) (PEDOT) domain combined with dodecylbenzene sulfonic acid (DBSA). The rheological properties were precisely engineered by manipulating the solid content and the intermolecular interactions among the constituents, resulting in 3D-printed structures with excellent resolution. More importantly, the resultant aerogels following freeze-drying exhibited a high electrical conductivity (110 ± 12 S m-1), outstanding mechanical properties (Young's modulus of 6.98 MPa), and fire-resistance properties. These robust aerogels were employed to address pressing global concerns about electromagnetic pollution with a specific shielding effectiveness of 4983.4 dB cm2 g-1. Importantly, it was shown that the shielding mechanism of the 3D printed aerogels could be manipulated by their geometrical features, unraveling the undeniable role of additive manufacturing in materials design.

Liquid-Templating Aerogels.

Modern materials science has witnessed the era of advanced fabrication methods to engineer functionality from the nano- to macroscales. Versatile fabrication and additive manufacturing methods are developed, but the ability to design a material for a given application is still limited. Here, a novel strategy that enables target-oriented manufacturing of ultra-lightweight aerogels with on-demand characteristics is introduced. The process relies on controllable liquid templating through interfacial complexation to generate tunable, stimuli-responsive 3D-structured (multiphase) filamentous liquid templates. The methodology involves nanoscale chemistry and microscale assembly of nanoparticles (NPs) at liquid-liquid interfaces to produce hierarchical macroscopic aerogels featuring multiscale porosity, ultralow density (3.05-3.41 mg cm-3 ), and high compressibility (90%) combined with elastic resilience and instant shape recovery. The challenges are overcome facing ultra-lightweight aerogels, including poor mechanical integrity and the inability to form predefined 3D constructs with on-demand functionality, for a multitude of applications. The controllable nature of the coined methodology enables tunable electromagnetic interference shielding with high specific shielding effectiveness (39 893 dB cm2 g-1 ), and one of the highest-ever reported oil-absorption capacities (487 times the initial weight of aerogel for chloroform), to be obtained. These properties originate from the engineerable nature of liquid templating, pushing the boundaries of lightweight materials to systematic function design and applications.

Chitosan-based emulgel and xerogel film containing Thymus pubescens essential oil as a potential wound dressing.

Controlling the wound exudates accompanied by microbial wound infections has still remained as one the most challenging clinical issues. Herein, a chitosan/gelatin/polyvinyl alcohol xerogel film containing Thymus pubescens essential oil is fabricated for antimicrobial wound dressing application. The chemical and physical characteristics of the devised formulation is characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscope, and tensile tests. Moreover, swelling capability, water vapour transmission rate, water contact angle, solubility, moisture content, and release properties are also studied. The antimicrobial and antibiofilm tests are performed using the broth microdilution and XTT assay, respectively. The produced formulation shows excellent antimicrobial efficacy against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Candida species. It is also demonstrated that the obtained film can reduce (∼80 %) Candida albicans biofilm formation, and its biocompatibility is confirmed with MTT (∼100 %) and hemolysis tests. The antimicrobial activity can be correlated to the microbial membrane attraction for Candida albicans cells, illustrated by flow cytometry. This proposed film with appropriate mechanical strength, high swelling capacity in different pH values (∼200-700 %), controlled release property, and antimicrobial and antioxidant activities as well as biocompatibility can be used as a promising candidate for antimicrobial wound dressing applications.

Super-Macroporous Lightweight Materials Templated from Bicontinuous Intra-Phase Jammed Emulsion Gels Based on Nanochitin.

Non-equilibrium multiphase systems are formed by mixing two immiscible nanoparticle dispersions, leading to bicontinuous emulsions that template cryogels with interconnected, tortuous channels. Herein, a renewable, rod-like biocolloid (chitin nanocrystals, ChNC) is used to kinetically arrest bicontinuous morphologies. Specifically, it is found that ChNC stabilizes intra-phase jammed bicontinuous systems at an ultra-low particle concentration (as low as 0.6 wt.%), leading to tailorable morphologies. The synergistic effects of ChNC high aspect ratio, intrinsic stiffness, and interparticle interactions produce hydrogelation and, upon drying, lead to open channels bearing dual characteristic sizes, suitably integrated into robust bicontinuous ultra-lightweight solids. Overall, it demonstrates the successful formation of ChNC-jammed bicontinuous emulsions and a facile emulsion templating route to synthesize chitin cryogels that form unique super-macroporous networks.

Direct milling: Efficient, facile, and green method for processing fibrillated cellulose/polymeric nanocomposites with boosted thermomechanical and rheological performance.

Bringing biobased nanomaterials into polymer manufacturing is essential to enhance polymers' properties and address the challenges posed by plastic waste. Using polymers such as polyamide 6 (PA6) in advanced industries, e.g., automotive sector, has been impeded as a direct consequence of their inability to meet the required mechanical properties. Herein, we utilize bio-based cellulose nanofibers (CNFs) to enhance the properties of PA6 by green processing, with no footprint on the environment. We address the issue of the dispersion of the nanofillers in polymeric matrices and demonstrate direct milling (cryo-milling and planetary ball milling) to facilitate a thorough integration of the components. Nanocomposites incorporating 1.0 wt% CNF, processed by pre-milling followed by compression molding, are shown to possess a storage modulus of 3.8 ± 0.2 GPa, Young's modulus of 2.9 ± 0.2 GPa, and ultimate tensile strength of 63 ± 3 MPa (all measured at room temperature). To show the superiority of direct milling in achieving these properties, other frequent approaches used to disperse CNF in polymers, such as solvent casting and hand mixing, are meticulously investigated and compared for the performance of their resulting specimens. The ball-milling method is demonstrated to provide PA6-CNF nanocomposites with excellent performance, better than solvent casting, with no associated environmental concerns.

Encapsulation of Zataria multiflora essential oil in polyvinyl alcohol/chitosan/gelatin thermo-responsive hydrogel: Synthesis, physico-chemical properties, and biological investigations.

Zataria multiflora essential oil is a natural volatile plant product whose therapeutic applications require a delivery platform. Biomaterial-based hydrogels have been extensively used in biomedical applications, and they are promising platforms to encapsulate essential oils. Among different hydrogels, intelligent hydrogels have recently attracted many interests because of their response to environmental stimuli such as temperature. Herein, Zataria multiflora essential oil is encapsulated in a polyvinyl alcohol/chitosan/gelatin hydrogel as a positive thermo-responsive and antifungal platform. According to the optical microscopic image, the encapsulated spherical essential oil droplets reveal a mean size of 1.10 ± 0.64 µm, which are in consistent with the SEM imaging results. Encapsulation efficacy and loading capacity are 98.66 % and 12.98 %, respectively. These results confirm the successful efficient encapsulation of the Zataria multiflora essential oil within the hydrogel. The chemical compositions of the Zataria multiflora essential oil and the fabricated hydrogel are analyzed by gas chromatography-mass spectroscopy (GC-MS) and Fourier transform infrared (FTIR) techniques. It is found that thymol (44.30 %) and γ-terpinene (22.62 %) are the main constituents of the Zataria multiflora essential oil. The produced hydrogel inhibits the metabolic activity of Candida albicans biofilms (∼60-80 %), which can be related to the antifungal activity of the essential oil constituents and chitosan. Based on the rheological results, the produced thermo-responsive hydrogel shows a gel-sol viscoelastic transition at a temperature of 24.5 °C. This transition leads to a facile release of the loaded essential oil. The release test depicts that about 30 % of Zataria multiflora essential oil is released during the first 16 min. In addition, 2, 5-diphenyl-2H-tetrazolium bromide (MTT) assay demonstrates that the designed thermo-sensitive formulation is biocompatible with high cell viability (over 96 %). The fabricated hydrogel can be deemed as a potential intelligent drug delivery platform for controlling cutaneous candidiasis due to antifungal effectiveness and less toxicity, which can be a promising alternative to traditional drug delivery systems.

Multi-Stimuli Dually-Responsive Intelligent Woven Structures with Local Programmability for Biomimetic Applications.

This work focuses on multi-stimuli-responsive materials with distinctive abilities, that is, color-changing and shape-memory. Using metallic composite yarns and polymeric/thermochromic microcapsule composite fibers, processed via a melt-spinning technique, an electrothermally multi-responsive fabric is woven. The resulting smart-fabric transfers from a predefined structure to an original shape while changing color upon heating or applying an electric field, making it appealing for advanced applications. The shape-memory and color-changing features of the fabric can be controlled by rationally controlling the micro-scale design of the individual fibers in the structure. Thus, the fibers' microstructural features are optimized to achieve excellent color-changing behavior along with shape fixity and recovery ratios of 99.95% and 79.2%, respectively. More importantly, the fabric's dual-response by electric field can be achieved by a low voltage of 5 V, which is smaller than the previously reported values. Above and beyond, the fabric is able to be meticulously activated by selectively applying a controlled voltage to any part of the fabric. The precise local responsiveness can be bestowed upon the fabric by readily controlling its macro-scale design. A biomimetic dragonfly with the shape-memory and color-changing dual-response ability is successfully fabricated, broadening the design and fabrication horizon of groundbreaking smart materials with multiple functions.

Mapping 3D Printability of Ionically Cross-Linked Cellulose Nanocrystal Inks: Architecting from Nano- to Macroscale Structures.

Engineering the rheological properties of colloidal inks is one of the main challenges in achieving high-fidelity 3D printing. Herein, we provide a comprehensive study on the rheological behavior of inks based on cellulose nanocrystals (CNCs) in the presence of given salts to enable high-quality 3D printing. The rheological properties of the CNC suspensions are tailored by considering the nature of the electrolyte (i.e., 10 types of salts featuring different ion sizes, charge numbers, and inter- and intra-molecular interactions) at various concentrations (25-100 mM). A high printing fidelity is achieved in a narrow CNC and salt concentration range, significantly depending on the salt type. The structure-property relationship is explored in a "3D-printing" space (2D map), introducing a guideline for researchers active in this field. To further unravel the effect of salt type on morphological properties, CNC aerogels are developed by freeze-drying the printed structures. The results illustrate that enhancing viscoelastic properties render a denser structure featuring smaller pores.

A solution-processable and highly flexible conductor of a fluoroelastomer FKM and carbon nanotubes with tuned electrical conductivity and mechanical performance.

The use of fluoroelastomer nanocomposites for flexible electronics is increasing due to their high deformability and recoverability. Often, a high amount of conductive nanofillers and crosslinking agents is required to improve their mechanical performance, which unfavorably affects the electrical percolation threshold and conductivity due to dispersion issues. Herein, we developed a unique solution mixing (SM) technique by a fine-tuned formulation to obtain well-dispersed carbon nanotubes (CNTs) in fluoroelastomer FKM for both low and high CNT concentrations (0.2 phr and 3 phr). Effective nano-network formation was confirmed by transmission electron microscopy (TEM) and oscillatory shear rheological tests. Compared to the melt mixing (MM) process, the stretchability of neat FKM improves to 503% in the SM process versus 430% in the MM process. The electrical conductivity of the SM samples percolates at significantly lower filler concentrations (i.e., 0.35 phr in SM vs. 0.45 phr in MM) with a maximum value of 7 × 10-1 S cm-1 for 3 phr. Overall, the 2 phr CNT/FKM nanocomposite fabricated by SM exceeds those of carbon-based FKM conductors reported in the literature. The enhanced electrical and mechanical properties include an electrical conductivity of 3 × 10-1 S cm-1, a strain-to-failure of 300%, and a tensile strength at break of 12 MPa. This process is a promising approach for fabricating fluoroelastomer nanocomposites of a mechanically robust and stable stretchable conductor for various wearable electronic devices.

Fumed Silica-Based Suspensions for Shear Thickening Applications: A Full-Scale Rheological Study.

Understanding shear thickening fluids (STFs) is critically important in a broad spectrum of fields ranging from biology to military. STFs are referred to the suspension of solid particles in an inert carrier liquid. Customizing the thickening behavior is vital for obtaining desired properties. Hence, comprehending shear thickening mechanisms is necessary to fully understand the factors affecting the shear thickening response of the STFs. Herein, we systematically investigate the effects of a wide range of parameters, from inherent properties of the constituents, including size and surface chemistry of the suspended particles, to practical conditions such as temperature and shear history, on the shear thickening behavior of fumed silica nanoparticles (NPs)-based suspensions in a polyethylene glycol (PEG) medium. Accordingly, increasing the hydrophobicity of the silica NPs or decreasing the NP size transforms the suspensions from sol to gel. The sol systems exhibit a strong shear thickening response, while shear thinning behavior is prominent in the strong gel systems. Hybridization of different silica NPs is also leveraged to tune the shear thickening behavior. In addition, we showcase the decisive role of operating temperature or shear history on the shear thickening behavior of suspensions. For instance, in terms of the shear history, above a critical value of preshear, the shear thickening behavior occurs at lower shear rates for STFs containing hydrophilic NPs. It is believed that the provided insights in this study can pave the way for developing advanced STFs with prescribed features.

Structured Ultra-Flyweight Aerogels by Interfacial Complexation: Self-Assembly Enabling Multiscale Designs.

The rapid co-assembly of graphene oxide (GO) nanosheets and a surfactant at the oil/water (O/W) interface is harnessed to develop a new class of soft materials comprising continuous, multilayer, interpenetrated, and tubular structures. The process uses a microfluidic approach that enables interfacial complexation of two-phase systems, herein, termed as "liquid streaming" (LS). LS is demonstrated as a general method to design multifunctional soft materials of specific hierarchical order and morphology, conveniently controlled by the nature of the oil phase and extrusion's injection pressure, print-head speed, and nozzle diameter. The as-obtained LS systems can be readily converted into ultra-flyweight aerogels displaying worm-like morphologies with multiscale porosities (micro- and macro-scaled). The presence of reduced GO nanosheets in such large surface area systems renders materials with outstanding mechanical compressibility and tailorable electrical activity. This platform for engineering soft materials and solid constructs opens up new horizons toward advanced functionality and tunability, as demonstrated here for ultralight printed conductive circuits and electromagnetic interference shields.

Synthesis, Applications, and Prospects of Graphene Quantum Dots: A Comprehensive Review.

Graphene quantum dot (GQD) is one of the youngest superstars of the carbon family. Since its emergence in 2008, GQD has attracted a great deal of attention due to its unique optoelectrical properties. Non-zero bandgap, the ability to accommodate functional groups and dopants, excellent dispersibility, highly tunable properties, and biocompatibility are among the most important characteristics of GQDs. To date, GQDs have displayed significant momentum in numerous fields such as energy devices, catalysis, sensing, photodynamic and photothermal therapy, drug delivery, and bioimaging. As this field is rapidly evolving, there is a strong need to identify the emerging challenges of GQDs in recent advances, mainly because some novel applications and numerous innovations on the ease of synthesis of GQDs are not systematically reviewed in earlier studies. This feature article provides a comparative and balanced discussion of recent advances in synthesis, properties, and applications of GQDs. Besides, current challenges and future prospects of these emerging carbon-based nanomaterials are also highlighted. The outlook provided in this review points out that the future of GQD research is boundless, particularly if upcoming studies focus on the ease of purification and eco-friendly synthesis along with improving the photoluminescence quantum yield and production yield of GQDs.

A Simple Approach to Control the Physical and Chemical Features of Custom-Synthesized N-Doped Carbon Nanotubes and the Extent of Their Network Formation in Polymers: The Importance of Catalyst to Substrate Ratio.

This study intends to reveal the significance of the catalyst to substrate ratio (C/S) on the structural and electrical features of the carbon nanotubes and their polymeric nanocomposites. Here, nitrogen-doped carbon nanotube (N-MWNT) was synthesized via a chemical vapor deposition (CVD) method using three ratios (by weight) of iron (Fe) catalyst to aluminum oxide (Al2O3) substrate, i.e.,1/9, 1/4, and 2/3, by changing the Fe concentration, i.e., 10, 20, and 40 wt.% Fe. Therefore, the synthesized N-MWNT are labelled as (N-MWNTs)10, (N-MWNTs)20, and (N-MWNTs)40. TEM, XPS, Raman spectroscopy, and TGA characterizations revealed that C/S ratio has a significant impact on the physical and chemical properties of the nanotubes. For instance, by increasing the Fe catalyst from 10 to 40 wt.%, carbon purity increased from 60 to 90 wt.% and the length of the nanotubes increased from 1.2 to 2.6 µm. Interestingly, regarding nanotube morphology, at the highest C/S ratio, the N-MWNTs displayed an open-channel structure, while at the lowest catalyst concentration the nanotubes featured a bamboo-like structure. Afterwards, the network characteristics of the N-MWNTs in a polyvinylidene fluoride (PVDF) matrix were studied using imaging techniques, AC electrical conductivity, and linear and nonlinear rheological measurements. The nanocomposites were prepared via a melt-mixing method at various loadings of the synthesized N-MWNTs. The rheological results confirmed that (N-MWNTs)10, at 0.5-2.0 wt.%, did not form any substantial network through the PVDF matrix, thereby exhibiting an electrically insulative behavior, even at a higher concentration of 3.0 wt.%. Although the optical microscopy, TEM, and rheological results confirmed that both (N-MWNTs)20 and (N-MWNTs)40 established a continuous 3D network within the PVDF matrix, (N-MWNTs)40/PVDF nanocomposites exhibited approximately one order of magnitude higher electrical conductivity. The higher electrical conductivity of (N-MWNTs)40/PVDF nanocomposites is attributed to the intrinsic chemical features of (N-MWNTs)40, such as nitrogen content and nitrogen bonding types.

Waste to Value-Added Product: Developing Electrically Conductive Nanocomposites Using a Non-Recyclable Plastic Waste Containing Vulcanized Rubber.

This study intends to show the potential application of a non-recyclable plastic waste towards the development of electrically conductive nanocomposites. Herein, the conductive nanofiller and binding matrix are carbon nanotubes (CNT) and polystyrene (PS), respectively, and the waste material is a plastic foam consisting of mainly vulcanized nitrile butadiene rubber and polyvinyl chloride (PVC). Two nanocomposite systems, i.e., PS/Waste/CNT and PS/CNT, with different compositions were melt-blended in a mixer and characterized for electrical properties. Higher electrical conduction and improved electromagnetic interference shielding performance in PS/Waste/CNT system indicated better conductive network of CNTs. For instance, at 1.0 wt.% CNT loading, the PS/Waste/CNT nanocomposites with the plastic waste content of 30 and 50 wt.% conducted electricity 3 and 4 orders of magnitude higher than the PS/CNT nanocomposite, respectively. More importantly, incorporation of the plastic waste (50 wt.%) reduced the electrical percolation threshold by 30% in comparison with the PS/CNT nanocomposite. The enhanced network of CNTs in PS/Waste/CNT samples was attributed to double percolation morphology, evidenced by optical images and rheological tests, caused by the excluded volume effect of the plastic waste. Indeed, due to its high content of vulcanized rubber, the plastic waste did not melt during the blending process. As a result, CNTs concentrated in the PS phase, forming a denser interconnected network in PS/Waste/CNT samples.

Morphology Evolution, Molecular Simulation, Electrical Properties, and Rheology of Carbon Nanotube/Polypropylene/Polystyrene Blend Nanocomposites: Effect of Molecular Interaction between Styrene-Butadiene Block Copolymer and Carbon Nanotube.

This work studied the impact of three types of styrene-butadiene (SB and SBS) block copolymers on the morphology, electrical, and rheological properties of immiscible blends of polypropylene:polystyrene (PP:PS)/multi-walled carbon nanotubes (MWCNT) with a fixed blend ratio of 70:30 vol.%. The addition of block copolymers to PP:PS/MWCNT blend nanocomposites produced a decrease in the droplet size. MWCNTs, known to induce co-continuity in PP:PS blends, did not interfere with the copolymer migration to the interface and, thus, there was morphology refinement upon addition of the copolymers. Interestingly, the addition of the block copolymers decreased the electrical resistivity of the PP:PS/1.0 vol.% MWCNT system by 5 orders of magnitude (i.e., increase in electrical conductivity). This improvement was attributed to PS Droplets-PP-Copolymer-Micelle assemblies, which accumulated MWCNTs, and formed an integrated network for electrical conduction. Molecular simulation and solubility parameters were used to predict the MWCNT localization in the immiscible blend. The simulation results showed that diblock copolymers favorably interact with the nanotubes in comparison to the triblock copolymer, PP, and PS. However, the interaction between the copolymers and PP or PS is stronger than the interaction of the copolymers and MWCNTs. Hence, the addition of copolymer also changed the localization of MWCNT from PS to PS-PP-Micelles-Interface, as observed by TEM images. In addition, in the last step of this work, we investigated the effect of the addition of copolymers on inter- and intra-cycle viscoelastic behavior of the MWCNT incorporated polymer blends. It was found that addition of the copolymers not only affects the linear viscoelasticity (e.g., increase in the value of the storage modulus) but also dramatically impacts the nonlinear viscoelastic behavior under large deformations (e.g., higher distortion of Lissajous-Bowditch plots).].

Role of temperature on bio-printability of gelatin methacryloyl bioink in two-step cross-linking strategy for tissue engineering applications.

Additive manufacturing has shown promising results in reconstructing three-dimensional (3D) living tissues for various applications, including tissue engineering, regenerative medicine, drug discovery, and high-throughput drug screening. In extrusion-based bioprinters, stable formation of filaments and high-fidelity deposition of bioinks are the primary challenges in fabrication of physiologically relevant tissue constructs. Among various bioinks, gelatin methacryloyl (GelMA) is known as a photocurable and physicochemically tunable hydrogel with a demonstrated biocompatibility and tunable biodegradation properties. The two-step crosslinking of GelMA (reversible thermal gelation and permanent photo-crosslinking) has attracted researchers to make complex tissue constructs. Despite promising results in filament formation and printability of this hydrogel, the effect of temperature on physicochemical properties, cytocompatibility, and biodegradation of the hydrogel are to be investigated. This work studies the effect of thermoreversible, physical crosslinking on printability of GelMA. The results of 3D printing of GelMA at different temperatures followed by irreversible chemical photo-crosslinking show that the decrease in temperature improves the filament formation and shape fidelity of the deposited hydrogel, particularly at the temperatures around 15 °C. Time dependant mechanical testing of the printed samples revealed that decreasing the extruding temperature increases the elastic properties of the extruded filaments. Furthermore, our novel approach in minimizing the slippage effect during rheological study enabled to measure changes in linear and non-linear viscoelastic properties of the printed samples at different temperatures. A considerable increase in storage modulus of the extruded samples printed at lower temperatures confirms their higher solid behavior. Scanning electron microscopy revealed a remarkable decrease in porosity of the extruded hydrogels by decreasing the temperature. Chemical analysis by Fourier-transform infrared spectroscopy and circular dichroism showed a direct relationship between the coil-helix transition in hydrogel macromers and its physical alterations. Finally, biodegradation and cytocompatibility of the extruded hydrogels decreased at lower extruding temperatures.

Intra-Cycle Elastic Nonlinearity of Nitrogen-Doped Carbon Nanotube/Polymer Nanocomposites under Medium Amplitude Oscillatory Shear (MAOS) Flow.

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