Graphene and metal-organic framework hybrids for high-performance sensors for lung cancer biomarker detection supported by machine learning augmentation.

Conventional diagnostic methods for lung cancer, based on breath analysis using gas chromatography and mass spectrometry, have limitations for fast screening due to their limited availability, operational complexity, and high cost. As potential replacement, among several low-cost and portable methods, chemoresistive sensors for the detection of volatile organic compounds (VOCs) that represent biomarkers of lung cancer were explored as promising solutions, which unfortunately still face challenges. To address the key problems of these sensors, such as low sensitivity, high response time, and poor selectivity, this study presents the design of new chemoresistive sensors based on hybridised porous zeolitic imidazolate (ZIF-8) based metal-organic frameworks (MOFs) and laser-scribed graphene (LSG) structures, inspired by the architecture of the human lung. The sensing performance of the fabricated ZIF-8@LSG hybrid sensors was characterised using four dominant VOC biomarkers, including acetone, ethanol, methanol, and formaldehyde, which are identified as metabolomic signatures in lung cancer patients' exhaled breath. The results using simulated breath samples showed that the sensors exhibited excellent performance for a set of these biomarkers, including fast response (2-3 seconds), a wide detection range (0.8 ppm to 50 ppm), a low detection limit (0.8 ppm), and high selectivity, all obtained at room temperature. Intelligent machine learning (ML) recognition using the multilayer perceptron (MLP)-based classification algorithm was further employed to enhance the capability of these sensors, achieving an exceptional accuracy (approximately 96.5%) for the four targeted VOCs over the tested range (0.8-10 ppm). The developed hybridised nanomaterials, combined with the ML methodology, showcase robust identification of lung cancer biomarkers in simulated breath samples containing multiple biomarkers and a promising solution for their further improvements toward practical applications.

Inhibition of α-glucosidase activity by curcumin loaded on ZnO@rGO nanocarrier for potential treatment of diabetes mellitus.

Curcumin (Cur) is an acidic polyphenol with some effects on α-glucosidase (α-Glu), but Cur has disadvantages such as being a weak target, lacking passing the blood-brain barrier and having low bioavailability. To enhance the curative effect of Cur, the hybrid composed of ZnO nanoparticles decorated on rGO was used to load Cur (ZnO@rGO-Cur). The use of the multispectral method and enzyme inhibition kinetics analysis certify the inhibitory effect and interaction mechanism of ZnO@rGO-Cur with α-Glu. The static quenching of α-Glu with both Cur and ZnO@rGO-Cur is primarily driven by hydrogen bond and van der Waals interactions. The conformation-changing ability by binding to the neighbouring phenolic hydroxyl group of Cur increased their ability to alter the secondary structure of α-Glu, resulting in the inhibition of enzyme activity. The inhibition constant (Ki, Cur > Kis,ZnO@rGO-Cur ) showed that the inhibition effect of ZnO@rGO-Cur on α-Glu was larger than that of Cur. The CCK-8 experiments proved that ZnO@rGO nanocomposites have good biocompatibility. These results suggest that the therapeutic potential of ZnO@rGO-Cur composite is an emerging nanocarrier platform for drug delivery systems for the potential treatment of diabetes mellitus.

Recent advances of silk fibroin materials: From molecular modification and matrix enhancement to possible encapsulation-related functional food applications.

Silk fibroin materials are emergingly explored for food applications due to their inherent properties including safe oral consumption, biocompatibility, gelatinization, antioxidant performance, and mechanical properties. However, silk fibroin possesses drawbacks like brittleness owing to its inherent specific composition and structure, which limit their applications in this field. This review discusses current progress about molecular modification methods on silk fibroin such as extraction, blending, self-assembly, enzymatic catalysis, etc., to address these limitations and improve their physical/chemical properties. It also summarizes matrix enhancement strategies including freeze drying, spray drying, electrospinning/electrospraying, microfluidic spinning/wheel spinning, desolvation and supercritical fluid, to generate nano-, submicron-, micron-, or bulk-scale materials. It finally highlights the food applications of silk fibroin materials, including nutraceutical improvement, emulsions, enzyme immobilization and 3D/4D printing. This review also provides insights on potential opportunities (like safe modification, toxicity risk evaluation, and digestion conditions) and possibilities (like digital additive manufacturing) in functional food industry.

Ionic Liquid Boosting the Electrochemical Stability of a Poly(1,3-dioxolane) Gel Electrolyte for High-voltage Solid-State Lithium Batteries.

Poor interfacial contact between solid-state electrolytes and electrodes limits high-voltage performance of solid-state lithium batteries. A new gel electrolyte is proposed via in-situ polymerization, incorporating fluoroethylene carbonate (FEC) solvent and ionic liquid1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide (PP14 TFSI). This combination synergistically enhances Li ion transport, achieving a transfer number of 0.58 and improved electrochemical performance. FEC protects the Al current collectors from LiPF6 corrosion and promotes a protective interfacial layer formation. PP14 TFSI improves interfacial contact and provides stable components. An interface layer of fluorine and nitrogen composites forms, preventing side reactions. LiCoO2 ||PPE||Li cell exhibits robust cycling stability at 4.45 V, retaining ~80 % capacity after 200 cycles at room temperature with 0.2 C and 1 C rates, showing increased coulombic efficiency. NCM811||PPE||Li cell also displays exceptional cycling. In-situ polymerization and FEC-ionic liquid coordination enable high-voltage solid-state lithium metal batteries for practical use.

Direct Atomic-Scale Insight into the Precipitation Formation at the Lanthanum Hydroxide Nanoparticle/Solution Interface.

Understanding precipitation formation at lanthanum hydroxide (La(OH)3) nanoparticle-solution interfaces plays a crucial role in catalysis, adsorption, and electrochemical energy storage applications. Liquid-phase transmission electron microscopy enables powerful visualization with high resolution. However, direct atomic-scale imaging of the interfacial metal (hydro)oxide nanostructure in solutions has been a major challenge due to their beam-driven dissolution. Combining focused ion beam and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, we present an atomic-scale study of precipitation formation at La(OH)3 nanoparticle interfaces after reaction with phosphate. The structure transformation is observed to occur at high- and low-crystalline La(OH)3 nanoparticle surfaces. Low-crystalline La(OH)3 mostly transformed and high-crystalline ones partly converted to LaPO4 precipitations on the outer surface. The long-term structure evolution shows the low transformation of high-crystalline La(OH)3 nanoparticles to LaPO4 precipitation. Because precipitation at solid-solution interfaces is common in nature and industry, these results could provide valuable references for their atomic-scale observation.

Modulation of MG-63 Osteogenic Response on Mechano-Bactericidal Micronanostructured Titanium Surfaces.

Despite recent advances in the development of orthopedic devices, implant-related failures that occur as a result of poor osseointegration and nosocomial infection are frequent. In this study, we developed a multiscale titanium (Ti) surface topography that promotes both osteogenic and mechano-bactericidal activity using a simple two-step fabrication approach. The response of MG-63 osteoblast-like cells and antibacterial activity toward Pseudomonas aeruginosa and Staphylococcus aureus bacteria was compared for two distinct micronanoarchitectures of differing surface roughness created by acid etching, using either hydrochloric acid (HCl) or sulfuric acid (H2SO4), followed by hydrothermal treatment, henceforth referred to as either MN-HCl or MN-H2SO4. The MN-HCl surfaces were characterized by an average surface microroughness (Sa) of 0.8 ± 0.1 µm covered by blade-like nanosheets of 10 ± 2.1 nm thickness, whereas the MN-H2SO4 surfaces exhibited a greater Sa value of 5.8 ± 0.6 µm, with a network of nanosheets of 20 ± 2.6 nm thickness. Both micronanostructured surfaces promoted enhanced MG-63 attachment and differentiation; however, cell proliferation was only significantly increased on MN-HCl surfaces. In addition, the MN-HCl surface exhibited increased levels of bactericidal activity, with only 0.6% of the P. aeruginosa cells and approximately 5% S. aureus cells remaining viable after 24 h when compared to control surfaces. Thus, we propose the modulation of surface roughness and architecture on the micro- and nanoscale to achieve efficient manipulation of osteogenic cell response combined with mechanical antibacterial activity. The outcomes of this study provide significant insight into the further development of advanced multifunctional orthopedic implant surfaces.

Sensor to Electronics Applications of Graphene Oxide through AZO Grafting.

Graphene is a two-dimensional (2D) material with a single atomic crystal structure of carbon that has the potential to create next-generation devices for photonic, optoelectronic, thermoelectric, sensing, wearable electronics, etc., owing to its excellent electron mobility, large surface-to-volume ratio, adjustable optics, and high mechanical strength. In contrast, owing to their light-induced conformations, fast response, photochemical stability, and surface-relief structures, azobenzene (AZO) polymers have been used as temperature sensors and photo-switchable molecules and are recognized as excellent candidates for a new generation of light-controllable molecular electronics. They can withstand trans-cis isomerization by conducting light irradiation or heating but have poor photon lifetime and energy density and are prone to agglomeration even at mild doping levels, reducing their optical sensitivity. Graphene derivatives, including graphene oxide (GO) and reduced graphene oxide (RGO), are an excellent platform that, combined with AZO-based polymers, could generate a new type of hybrid structure with interesting properties of ordered molecules. AZO derivatives may modify the energy density, optical responsiveness, and photon storage capacity, potentially preventing aggregation and strengthening the AZO complexes. They are potential candidates for sensors, photocatalysts, photodetectors, photocurrent switching, and other optical applications. This review aimed to provide an overview of the recent progress in graphene-related 2D materials (Gr2MS) and AZO polymer AZO-GO/RGO hybrid structures and their synthesis and applications. The review concludes with remarks based on the findings of this study.

International Interlaboratory Comparison of Thermogravimetric Analysis of Graphene-Related Two-Dimensional Materials.

Research on graphene-related two-dimensional (2D) materials (GR2Ms) in recent years is strongly moving from academia to industrial sectors with many new developed products and devices on the market. Characterization and quality control of the GR2Ms and their properties are critical for growing industrial translation, which requires the development of appropriate and reliable analytical methods. These challenges are recognized by International Organization for Standardization (ISO 229) and International Electrotechnical Commission (IEC 113) committees to facilitate the development of these methods and standards which are currently in progress. Toward these efforts, the aim of this study was to perform an international interlaboratory comparison (ILC), conducted under Versailles Project on Advanced Materials and Standards (VAMAS) Technical Working Area (TWA) 41 "Graphene and Related 2D Materials" to evaluate the performance (reproducibility and confidence) of the thermogravimetric analysis (TGA) method as a potential new method for chemical characterization of GR2Ms. Three different types of representative and industrially manufactured GR2Ms samples, namely, pristine few-layer graphene (FLG), graphene oxide (GO), and reduced graphene oxide (rGO), were used and supplied to ILC participants to complete the study. The TGA method performance was evaluated by a series of measurements of selected parameters of the chemical and physical properties of these GR2Ms including the number of mass loss steps, thermal stability, temperature of maximum mass change rate (Tp) for each decomposition step, and the mass contents (%) of moisture, oxygen groups, carbon, and impurities (organic and non-combustible residue). TGA measurements determining these parameters were performed using the provided optimized TGA protocol on the same GR2Ms by 12 participants across academia, industry stakeholders, and national metrology institutes. This paper presents these results with corresponding statistical analysis showing low standard deviation and statistical conformity across all participants that confirm that the TGA method can be satisfactorily used for characterization of these parameters and the chemical characterization and quality control of GR2Ms. The common measurement uncertainty for each parameter, key contribution factors were identified with explanations and recommendations for their elimination and improvements toward their implementation for the development of the ISO/IEC standard for chemical characterization of GR2Ms.

From Biowaste to Lab-Bench: Low-Cost Magnetic Iron Oxide Nanoparticles for RNA Extraction and SARS-CoV-2 Diagnostics.

The gold standard for diagnostics of SARS-CoV-2 (COVID-19) virus is based on real-time polymerase chain reaction (RT-PCR) using centralized PCR facilities and commercial viral RNA extraction kits. One of the key components of these kits are magnetic beads composed of silica coated magnetic iron oxide (Fe2O3 or Fe3O4) nanoparticles, needed for the selective extraction of RNA. At the beginning of the pandemic in 2019, due to a high demand across the world there were severe shortages of many reagents and consumables, including these magnetic beads required for testing for SARS-CoV-2. Laboratories needed to source these products elsewhere, preferably at a comparable or lower cost. Here, we describe the development of a simple, low-cost and scalable preparation of magnetic nanoparticles (MNPs) from biowaste and demonstrate their successful application in viral RNA extraction and the detection of COVID-19. These MNPs have a unique nanoplatelet shape with a high surface area, which are beneficial features, expected to provide improved RNA adsorption, better dispersion and processing ability compared with commercial spherical magnetic beads. Their performance in COVID-19 RNA extraction was evaluated in comparison with commercial magnetic beads and the results presented here showed comparable results for high throughput PCR analysis. The presented magnetic nanoplatelets generated from biomass waste are safe, low-cost, simple to produce in large scale and could provide a significantly reduced cost of nucleic acid extraction for SARS-CoV-2 and other DNA and RNA viruses.

Efficient removal of Cd2+ by diatom frustules self-modified in situ with intercellular organic components.

The organic modification of three-dimensional porous diatom frustules (biosilica) and their fossils (diatomite) is promising in heavy metal adsorption. However, the preparation of such materials involves complex processes, high costs, and environmental hazards. In this study, organic-biosilica composites based on in situ self-modification of diatoms were prepared by freeze-drying pretreatment. Freeze-drying resulted in the release of the intercellular organic components of diatoms, followed by loading on the surface of their diatom frustules. The bio-adsorbent exhibits outstanding Cd2+ adsorption capacity (up to 220.3 mg/g). The adsorption isotherms fitted the Langmuir model and the maximum adsorption capacity was 4 times greater than that of diatom biosilica (54.1 mg/g). The adsorption kinetics of Cd2+ was adequately described by a pseudo-second-order model and reached equilibrium within 30 min. By combining focused ion beam thinning with transmission electron microscopy-energy dispersive X-ray spectroscopy, the internal structure of the composite and the Cd2+ distribution were investigated. The results showed that the organic matter of the composite adsorbed approximately 10 times more Cd2+ than inorganic biosilica. The adsorption mechanism was dominated by complexation between the abundant organic functional groups (amide, carboxyl, and amino groups) on the surfaces of composite and Cd2+. The bio-adsorbent was demonstrated to have wide applicability in the presence of competitive cations (Na+, K+, Ca2+, and Mg2+) and under a wide range of pH (3-10) conditions. Thus, the self-modification of diatoms offers a promising organic-inorganic composite for heavy metal remediation.

Magnetic enrichment of immuno-specific extracellular vesicles for mass spectrometry using biofilm-derived iron oxide nanowires.

Immuno-specific enrichment of extracellular vesicles (EVs) can provide important information into cellular pathways underpinning various pathologies and for non-invasive diagnostics, including mass spectrometry-based analyses. Herein, we report an optimised protocol for immuno-magnetic enrichment of specific EV subtypes and their subsequent processing with liquid chromatography-tandem mass spectrometry (LC-MS/MS). Specifically, we conjugated placental alkaline phosphatase (PLAP) antibodies to magnetic iron oxide nanowires (NWs) derived from bacterial biofilms and demonstrated the utility of this approach by enriching placenta-specific EVs (containing PLAP) from cell culture media. We demonstrate efficient PLAP+ve EV enrichment for both NW-PLAP and Dynabeads™-PLAP, with high PLAP protein recovery (83.7 ± 8.9% and 83.2 ± 5.9%, respectively), high particle-to-protein ratio (7.5 ± 0.7 × 109 and 7.1 ± 1.2 × 109, respectively), and low non-specific binding of non-target EVs (7 ± 3.2% and 5.4 ± 2.2%, respectively). Furthermore, our optimized EV enrichment and processing approach identified 2518 and 2545 protein groups with LC-MS/MS for NW-PLAP and Dynabead™-PLAP, respectively, with excellent reproducibility (Pearson correlation 0.986 and 0.988). These findings demonstrate that naturally occurring iron oxide NWs have comparable performance to current gold standard immune-magnetic beads. The optimized immuno-specific EV enrichment for LC-MS/MS method provides a low-cost and highly-scalable yet efficient, high-throughput approach for quality EV proteomic studies.

Graphene woven fabric-polydimethylsiloxane piezoresistive films for smart multi-stimuli responses.

The outstanding properties of graphene, including its electromechanical property, could be engineered for wearable electronic sensor platforms. The tubular graphene weaved into a mesh or graphene woven fabrics (GWF) has been reported as one of the most sensitive materials for deformation detection, as well as a promising temperature sensor. Herein, we present the performance of our developed flexible, stretchable, and multiple sensitive sensors fabricated from GWF embedded in polydimethylsiloxane (PDMS) film substrate. The GWF/PDMS sensor shows a pressure sensitivity of 0.0142 kPa-1 in a wide linearity range of 0-20 kPa, an outstanding Gauge factor (GF) of 582 at a strain of 6.2 %, and a very high positive sensitivity of 0.0238 °C-1 in the temperature range of 25-80 °C. A practical application as a high sensitivity air pressure sensor able to measure low pressures (in the range of Pa to kPa) was also demonstrated. This sensor platform having desirable performance characteristics is an excellent candidate for wearable devices in the healthcare sector.

Converting Chrysotile Nanotubes into Magnesium Oxide and Hydroxide Using Lanthanum Oxycarbonate Hybridization and Alkaline Treatment for Efficient Phosphate Adsorption.

Magnesium oxide and hydroxide nanomaterials comprise a class of promising advanced functional metal nanomaterials whose use in environmental and material applications is increasing. Several strategies to synthesize these nanomaterials have been described but are unsustainable and uneconomic. This work reports on a processing strategy that turns natural magnesium-rich chrysotile into magnesium oxide and hydroxide nanoparticles via nanoparticle hybridization and an alkaline process while enabling La-based nanoparticles to coat the chrysotile nanotube surfaces. The adsorbent's resulting hybrid nanostructure had an outstanding capacity for phosphate uptake (135.2 mg P g-1) and enhanced regeneration performance. Furthermore, the adsorbent featured wide applicability with respect to the coexistence of competitive anions and a broad range of pH conditions, and its high-performance phosphate removal from sewage effluent was also demonstrated. Spectroscopic and microscopic analyses revealed the scavenging ability of phosphate by the La-based and Mg-based nanoparticles and the multiple capture mechanisms involved, including surface complexation and ion exchange. This proposed approach expands chrysotile's potential use as a magnesium-rich nanomaterial and harbors great promise for the removal of pollutants in a variety of real-world settings.

New insights on energetic properties of graphene oxide (GO) materials and their safety and environmental risks.

Graphene oxide (GO) has been recognized as a thermally unstable and energetic material, but surprisingly its environmental and safety risks were not fully explored, defined, and regulated. In this study, systematic explosivity and flammability characterizations of commercial GO materials were conducted to evaluate the influence of key parameters such as physical forms (paste, powders, films, and aerogels), temperature, heating rate, mass, and heating environment, as well as their potential safety and environmental impacts. Results based on thermogravimetric analysis (TGA) showed that GO in paste and powder forms have lower temperature thresholds (>180-192 °C) to initiate micro-explosions compared to GO film and aerogels (> 205 °C and 213 °C) regardless of the environment (inert, air, or oxygen). The observed explosive behavior can be explained by thermal runaway reactions as a result of thermal deoxygenation and decomposition of oxygen functional groups. Flammability rating and limiting oxygen index (LOI) results confirmed that GO films are flammable materials that can spontaneously propagate flame in a low oxygen environment (~11 %). These results provided new insights about potential safety and environmental risks of GO materials, which somehow were not considered, suggesting urgent actions to improve current safety protocols for labeling, handling, transporting, and storage practices from manufacturers to the end-users.

Coupling Natural Halloysite Nanotubes and Bimetallic Pt-Au Alloy Nanoparticles for Highly Efficient and Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid.

The aerobic oxidation of 5-hydroxymethylfurfural (HMF), a key platform compound derived from biomass, to 2,5-furandicarboxylic acid (FDCA) is a highly important reaction in the production of green and sustainable chemicals. Here, we developed a highly efficient and stable halloysite-supported Pt-Au alloy catalyst for the selective oxidation of HMF to FDCA. The catalyst was synthesized through the organosilane functionalization of halloysite nanotubes, followed by the in situ formation and dispersion of Pt-Au alloy nanoparticles on the internal and external surfaces of nanotubes. The composition, morphology, and structure of the prepared catalyst were characterized. The catalyst with the optimal composition of Pt/Au molar ratio of 1/4 and metal loading of 1.5 wt % exhibited outstanding catalytic activity for the oxidation of HMF to FDCA using O2 as an oxidant with 100% conversion of HMF and 99% selectivity of FDCA. This excellent catalytic performance is mainly attributed to the high dispersion and alloying effects of bimetallic nanoparticles, which promoted the activation of reactants or intermediates and further improved FDCA selectivity. Furthermore, the halloysite-supported Pt/Au bimetallic catalyst showed high stability and reusability. This study provides a promising strategy by combining clay mineral halloysite and bimetallic alloys for developing efficient catalysts with high FDCA selectivity and stability for the oxidation of HMF to FDCA.

Tailoring Additively Manufactured Titanium Implants for Short-Time Pediatric Implantations with Enhanced Bactericidal Activity.

Paediatric titanium (Ti) implants are used for the short-term fixation of fractures, after which they are removed. However, bone overgrowth on the implant surface can complicate their removal. The current Ti implants research focuses on improving their osseointegration and antibacterial properties for long-term use while overlooking the requirements of temporary implants. This paper presents the engineering of additively manufactured Ti implants with antibacterial properties and prevention of bone cell overgrowth. 3D-printed implants were fabricated followed by electrochemical anodization to generate vertically aligned titania nanotubes (TNTs) on the surface with specific diameters (∼100 nm) to reduce cell attachment and proliferation. To achieve enhanced antibacterial performance, TNTs were coated with gallium nitrate as antibacterial agent. The physicochemical characteristics of these implants assessed by the attachment, growth and viability of osteoblastic MG-63 cells showed significantly reduced cell attachment and proliferation, confirming the ability of TNTs surface to avoid cell overgrowth. Gallium coated TNTs showed strong antibacterial activity against S. aureus and P. aeruginosa with reduced bacterial attachment and high rates of bacterial death. Thus a new approach for the engineering of temporary Ti implants with enhanced bactericidal properties with reduced bone cell attachment is demonstrated as a new strategy toward a new generation of short-term implants in paediatrics.

Advancing of 3D-Printed Titanium Implants with Combined Antibacterial Protection Using Ultrasharp Nanostructured Surface and Gallium-Releasing Agents.

This paper presents the development of advanced Ti implants with enhanced antibacterial activity. The implants were engineered using additive manufacturing three-dimensional (3D) printing technology followed by surface modification with electrochemical anodization and hydrothermal etching, to create unique hierarchical micro/nanosurface topographies of microspheres covered with sharp nanopillars that can mechanically kill bacteria in contact with the surface. To achieve enhanced antibacterial performance, fabricated Ti implant models were loaded with gallium nitrate as an antibacterial agent. The antibacterial efficacy of the fabricated substrates with the combined action of sharp nanopillars and locally releasing gallium ions (Ga3+) was evaluated toward Staphylococcus aureus and Pseudomonas aeruginosa. Results confirm the significant antibacterial performance of Ga3+-loaded substrates with a 100% eradication of bacteria. The nanopillars significantly reduced bacterial attachment and prevented biofilm formation while also killing any bacteria remaining on the surface. Furthermore, 3D-printed surfaces with microspheres of diameter 5-30 µm and interspaces of 12-35 µm favored the attachment of osteoblast-like MG-63 cells, as confirmed via the assessment of their attachment, proliferation, and viability. This study provides important progress toward engineering of next-generation 3D-printed implants, that combine surface chemistry and structure to achieve a highly efficacious antibacterial surface with dual cytocompatibility to overcome the limitations of conventional Ti implants.

Fractal Design for Advancing the Performance of Chemoresistive Sensors.

The rapid advancement of internet of things (IoT)-enabled applications along with connected automation in sensing technologies is the heart of future intelligent systems. The probable applications have significant implications, from chemical process monitoring to agriculture, mining, space, wearable electronics, industrial manufacturing, smart cities, and point-of-care (PoC) diagnostics. Advancing sensor performance such as sensitivity to detect trace amounts (ppb-ppm) of analytes (gas/VOCs), selectivity, portability, and low cost is critical for many of these applications. These advancements are mainly achieved by selecting and optimizing sensing materials by their surface functionalization and/or structural optimization to achieve favorable transport characteristics or chemical binding/reaction sites. Surprisingly, the sensor geometry, shapes, and patterns were not considered as critical parameters, and most of these sensors were designed by following simple planar and interdigitated electrode geometry. In this study, we introduce a new bioinspired fractal approach to design chemoresistive sensors with fractal geometry, which grasp the architecture of fern leaves represented by the geometric group of space-filling curves of fractal patterns. These fractal sensors were printed by an extrusion process on a flexible substrate (PET) using specially formulated graphene ink as a sensing material, which provided significant enhancement of the active surface area to volume ratio and allowed high-resolution fractal patterning along with a reduced current transportation path. To demonstrate the advantages and influence of fractal geometry on sensor performance, here, three different kinds of sensors were fabricated based on different fractal geometrics (Sierpinski, Peano, and Hilbert), and the sensing performance was explored toward different VOC analytes (e.g., ethanol, methanol, and acetone). Among all these fractal-designed sensors including interdigitate sensors, the Hilbert-designed printed sensor shows enhanced sensing properties in terms of fast response time (6 s for 30 ppm), response value (14%), enhanced detection range (5-100 ppm), high selectivity, and low interference to humidity (up to RH 80%) for ethanol at room temperature (20 °C). Moreover, a significant improvement of this sensor performance was observed by applying the mechanical deformation (positive bending) technique. The practical application of this sensor was successfully demonstrated by monitoring food spoilage using a commercial box of strawberries as a model. Based on these presented results, this biofractal biomimetic VOC sensor is demonstrated for a prospective application in food monitoring.

Converging 2D Nanomaterials and 3D Bioprinting Technology: State-of-the-Art, Challenges, and Potential Outlook in Biomedical Applications.

The development of next-generation of bioinks aims to fabricate anatomical size 3D scaffold with high printability and biocompatibility. Along with the progress in 3D bioprinting, 2D nanomaterials (2D NMs) prove to be emerging frontiers in the development of advanced materials owing to their extraordinary properties. Harnessing the properties of 2D NMs in 3D bioprinting technologies can revolutionize the development of bioinks by endowing new functionalities to the current bioinks. First the main contributions of 2D NMS in 3D bioprinting technologies are categorized here into six main classes: 1) reinforcement effect, 2) delivery of bioactive molecules, 3) improved electrical conductivity, 4) enhanced tissue formation, 5) photothermal effect, 6) and stronger antibacterial properties. Next, the recent advances in the use of each certain 2D NMs (1) graphene, 2) nanosilicate, 3) black phosphorus, 4) MXene, 5) transition metal dichalcogenides, 6) hexagonal boron nitride, and 7) metal-organic frameworks) in 3D bioprinting technology are critically summarized and evaluated thoroughly. Third, the role of physicochemical properties of 2D NMSs on their cytotoxicity is uncovered, with several representative examples of each studied 2D NMs. Finally, current challenges, opportunities, and outlook for the development of nanocomposite bioinks are discussed thoroughly.