The Latest Advances in Ink-Based Nanogenerators: From Materials to Applications.

Nanogenerators possess the capability to harvest faint energy from the environment. Among them, thermoelectric (TE), triboelectric, piezoelectric (PE), and moisture-enabled nanogenerators represent promising approaches to micro-nano energy collection. These nanogenerators have seen considerable progress in material optimization and structural design. Printing technology has facilitated the large-scale manufacturing of nanogenerators. Although inks can be compatible with most traditional functional materials, this inevitably leads to a decrease in the electrical performance of the materials, necessitating control over the rheological properties of the inks. Furthermore, printing technology offers increased structural design flexibility. This review provides a comprehensive framework for ink-based nanogenerators, encompassing ink material optimization and device structural design, including improvements in ink performance, control of rheological properties, and efficient energy harvesting structures. Additionally, it highlights ink-based nanogenerators that incorporate textile technology and hybrid energy technologies, reviewing their latest advancements in energy collection and self-powered sensing. The discussion also addresses the main challenges faced and future directions for development.

Recent advances in photoresponsive printing inks for security encoding applications.

Counterfeiting of banknotes, important documents, and branded goods continues to be a major worldwide problem for governments, businesses, and consumers. This problem has serious financial, security, and health implications. Due to their stability for printing on various substrates, the photochromic anticounterfeiting inks have received important interest. There have been various photochromic agents, such as polymer nanoparticles, quantum and carbon dots, and organic and inorganic fluorophores and luminophores, which have been broadly used for antiforging applications. In comparison to organic agents, inorganic photochromic materials have better stability under reversible/long-term light illumination. Recently, the remarkable optical characteristics and chemical stability of photoluminescent and photochromic agents have led to their extensive usage anticounterfeiting products. There have been also several strategies to tackle the rising problem of counterfeiting. Both of solvent-based and water-based inks have been developed for security encoding purposes. Additionally, the printing methods, including screen printing, labeling, stamping, inkjet printing, and handwriting, that have been used to apply anticounterfeiting inks onto various surfaces are discussed. The limitations of photoluminescent and photochromic agents and the potential for their future preparation to combat counterfeiting were discussed. This review would benefit academic researchers and industrial developers who are interested in the area of security printing.

Laser-printed paper ELISA and hydroxyapatite immobilization for colorimetric congenital anomalies screening in saliva.

BACKGROUND: Alpha-fetoprotein (AFP) is a fetal protein that can indicate congenital anomalies such as Down syndrome and spinal canal blockage when detected at abnormal levels in pregnant women. Current AFP detection methods rely on invasive blood or serum samples, which require sophisticated equipment. From the many solutions proposed, colorimetric paper-based assays excel in point-of-care settings. The concept of paper-based ELISA (p-ELISA) enhances traditional methods, aligning with the ASSURED criteria for diagnostics in resource-limited regions. Despite success in microfluidic paper-based assay devices, laser printing remains underexplored for p-ELISA. Additionally, modifying the paper surface provides an additional layer of sensitivity enhancement. RESULTS: In this study, we developed a novel laser-printed paper-based ELISA (LP-pELISA) for rapid, sensitive, and noninvasive detection of AFP in saliva samples. The LP-pELISA platform was fabricated by printing hydrophobic barriers on filter paper using a laser printer, followed by depositing hydroxyapatite (HAp) as an immobilization material for the antibodies. The colorimetric detection was achieved using AuNPs functionalized with anti-AFP antibodies and silver nitrate enhancement. The LP-pELISA exhibited a linear response for AFP detection in both buffer and saliva samples over a range of 1.0-800 ng mL-1, with a limit of detection (LOD) reaching 1.0 ng mL-1. The assay also demonstrated good selectivity, repeatability, reproducibility, and stability. The LP-pELISA was further validated by testing spiked human saliva samples, showing its potential for point-of-care diagnosis of congenital disabilities. SIGNIFICANCE: The LP-pELISA is a noninvasive platform showcasing simplicity, cost-effectiveness, and user-friendliness, utilizing laser printing, hydroxyapatite modification, and saliva samples to efficiently detect AFP. Beyond its application for AFP, this method's versatility extends to other biomarkers, positioning it as a catalyst for the evolution of paper-based biosensors. The LP-pELISA holds promise as a transformative tool for point-of-care diagnostics, fostering advancements in healthcare with its innovative technology.

Low-cost inkjet-printed nanostructured biosensor based on CRISPR/Cas12a system for pathogen detection.

The escalating global incidence of infectious diseases caused by pathogenic bacteria, especially in developing countries, emphasises the urgent need for rapid and portable pathogen detection devices. This study introduces a sensitive and specific electrochemical biosensing platform utilising cost-effective electrodes fabricated by inkjet-printing gold and silver nanoparticles on a plastic substrate. The biosensor exploits the CRISPR/Cas12a system for detecting a specific DNA sequence selected from the genome of the target pathogen. Upon detection, the trans-activity of Cas12a/gRNA is triggered, leading to the cleavage of rationally designed single-strand DNA reporters (linear and hairpin) labelled with methylene blue (ssDNA-MB) and bound to the electrode surface. In principle, this sensing mechanism can be adapted to any bacterium by choosing a proper guide RNA to target a specific sequence of its DNA. The biosensor's performance was assessed for two representative pathogens (a Gram-negative, Escherichia coli, and a Gram-positive, Staphylococcus aureus), and results obtained with inkjet-printed gold electrodes were compared with those obtained by commercial screen-printed gold electrodes. Our results show that the use of inkjet-printed nanostructured gold electrodes, which provide a large surface area, in combination with the use of hairpin reporters containing a poly-T loop can increase the sensitivity of the assay corresponding to a signal variation of 86%. DNA targets amplified from various clinically isolated bacteria, have been tested and demonstrate the potential of the proposed platform for point-of-need applications.

Pharmaceutical applications and requirements of resins for printing by digital light processing (DLP).

The digital light processing (DLP) printer has proven to be effective in biomedical and pharmaceutical applications, as its printing method does not induce shear and a strong temperature on the resin. In addition, the DLP printer has good resolution and print quality, which makes it possible to print complex structures with a customized shape, being used for various purposes ranging from jewelry application to biomedical and pharmaceutical areas. The big disadvantage of DLP is the lack of a biocompatible and non-toxic resin on the market. To overcome this limitation, an ideal resin for biomedical and pharmaceutical use is needed. The resin must have appropriate properties, so that the desired format is printed when with a determined wavelength is applied. Thus, the aim of this work is to bring the basic characteristics of the resins used by this printing method and the minimum requirements to start printing by DLP for pharmaceutical and biomedical applications. The DLP method has proven to be effective in obtaining pharmaceutical devices such as drug delivery systems. Furthermore, this technology allows the printing of devices of ideal size, shape and dosage, providing the patient with personalized treatment.

Extrusion Printing of Surface-Functionalized Metal-Organic Framework Inks for a High-Performance Wearable Volatile Organic Compound Sensor.

Wearable sensors hold immense potential for real-time and non-destructive sensing of volatile organic compounds (VOCs), requiring both efficient sensing performance and robust mechanical properties. However, conventional colorimetric sensor arrays, acting as artificial olfactory systems for highly selective VOC profiling, often fail to meet these requirements simultaneously. Here, a high-performance wearable sensor array for VOC visual detection is proposed by extrusion printing of hybrid inks containing surface-functionalized sensing materials. Surface-modified hydrophobic polydimethylsiloxane (PDMS) improves the humidity resistance and VOC sensitivity of PDMS-coated dye/metal-organic frameworks (MOFs) composites. It also enhances their dispersion within liquid PDMS matrix, thereby promoting the hybrid liquid as high-quality extrusion-printing inks. The inks enable direct and precise printing on diverse substrates, forming a uniform and high particle-loading (70 wt%) film. The printed film on a flexible PDMS substrate demonstrates satisfactory flexibility and stretchability while retaining excellent sensing performance from dye/MOFs@PDMS particles. Further, the printed sensor array exhibits enhanced sensitivity to sub-ppm VOC levels, remarkable resistance to high relative humidity (RH) of 90%, and the differentiation ability for eight distinct VOCs. Finally, the wearable sensor proves practical by in situ monitoring of wheat scab-related VOC biomarkers. This study presents a versatile strategy for designing effective wearable gas sensors with widespread applications.

Graphene derivative-based ink advances inkjet printing technology for fabrication of electrochemical sensors and biosensors.

The field of biosensing would significantly benefit from a disruptive technology enabling flexible manufacturing of uniform electrodes. Inkjet printing holds promise for this, although realizing full electrode manufacturing with this technology remains challenging. We introduce a nitrogen-doped carboxylated graphene ink (NGA-ink) compatible with commercially available printing technologies. The water-based and additive-free NGA-ink was utilized to produce fully inkjet-printed electrodes (IPEs), which demonstrated successful electrochemical detection of the important neurotransmitter dopamine. The cost-effectiveness of NGA-ink combined with a total cost per electrode of $0.10 renders it a practical solution for customized electrode manufacturing. Furthermore, the high carboxyl group content of NGA-ink (13 wt%) presents opportunities for biomolecule immobilization, paving the way for the development of advanced state-of-the-art biosensors. This study highlights the potential of NGA inkjet-printed electrodes in revolutionizing sensor technology, offering an affordable, scalable alternative to conventional electrochemical systems.

Enzyme Immobilization by Inkjet Printing on Reagentless Biosensors for Electrochemical Phosphate Detection.

Enzyme-based biosensors commonly utilize the drop-casting method for their surface modification. However, the drawbacks of this technique, such as low reproducibility, coffee ring effects, and challenges in mass production, hinder its application. To overcome these limitations, we propose a novel surface functionalization strategy of enzyme crosslinking via inkjet printing for reagentless enzyme-based biosensors. This method includes printing three functional layers onto a screen-printed electrode: the enzyme layer, crosslinking layer, and protective layer. Nanomaterials and substrates are preloaded together during our inkjet printing. Inkjet-printed electrodes feature a uniform enzyme deposition, ensuring high reproducibility and superior electrochemical performance compared to traditional drop-casted ones. The resultant biosensors display high sensitivity, as well as a broad linear response in the physiological range of the serum phosphate. This enzyme crosslinking method has the potential to extend into various enzyme-based biosensors through altering functional layer components.

A water transfer printing method for contact lenses surface 2D MXene modification to resist bacterial infection and inflammation.

Contact lenses (CLs) are prone to adhesion and invasion by pollutants and pathogenic bacteria, leading to infection and inflammatory diseases. However, the functionalization of CL (biological functions such as anti-fouling, antibacterial, and anti-inflammatory) and maintaining its transparency still face great challenges. In this work, as a member of the MXenes family, vanadium carbide (V2C) is modified onto CL via a water transfer printing method after the formation of a tightly arranged uniform film at the water surface under the action of the Marangoni effect. The coating interface is stable owing to the electrostatic forces. The V2C-modified CL (V2C@CL) maintains optical clarity while providing good biocompatibility, strong antioxidant properties, and anti-inflammatory activities. In vitro antibacterial experiments indicate that V2C@CL shows excellent performance in bacterial anti-adhesion, sterilization, and anti-biofilm formation. Last, V2C@CL displays notable advantages of bacteria elimination and inflammation removal in infectious keratitis treatment.

From Fluorescence-Transfer-Lightening-Printing-Assisted Conductive Adhesive Nanocomposite Hydrogels toward Wearable Interactive Optical Information-Electronic Strain Sensors.

The interactive flexible device, which monitors the human motion in optical and electrical synergistic modes, has attracted growing attention recently. The incorporation of information attribute within the optical signal is deemed advantageous for improving the interactive efficiency. Therefore, the development of wearable optical information-electronic strain sensors holds substantial promise, but integrating and synergizing various functions and realizing strain-mediated information transformation keep challenging. Herein, an amylopectin (AP) modified nanoclay/polyacrylamide-based nanocomposite (NC) hydrogel and an aggregation-induced-emission-active ink are fabricated. Through the fluorescence-transfer printing of the ink onto the hydrogel film in different strains with nested multiple symbolic information, a wearable interactive fluorescent information-electronic strain sensor is developed. In the sensor, the nanoclay plays a synergistic "one-stone-three-birds" role, contributing to "lightening" fluorescence (≈80 times emission intensity enhancement), ionic conductivity, and excellent stretchability (>1000%). The sensor has high biocompatibility, resilience (elastic recovery ratio: 97.8%), and strain sensitivity (gauge factor (GF): 10.9). Additionally, the AP endows the sensor with skin adhesiveness. The sensor can achieve electrical monitoring of human joint movements while displaying interactive fluorescent information transformation. This research poses an efficient strategy to develop multifunctional materials and provides a general platform for achieving next-generation interactive devices with prospective applications in wearable devices, human-machine interfaces, and artificial intelligence.

Digitally Controlled Printing of Bioink Barriers for Paper-Based Analytical Devices: An Environmentally Friendly One-Step Approach.

The patterning of hydrophilic paper with hydrophobic materials has emerged as an interesting method for the fabrication of paper-based devices (PADs). Herein, we demonstrate a digitally automated, easy, low-cost, eco-friendly, and readily available method to create highly hydrophobic barriers on paper that can be promptly employed with PADs by simply using a bioink made with rosin, a commercially available natural resin obtained from conifer trees. The bioink can be easily delivered with the use of a ballpoint pen to produce water- and organic solvent-resistant barriers, showing superior properties when compared to other methods such as wax-printing or permanent markers. The approach enables the pen to be attached to a commercially available cutting printer to perform the semiautomated fabrication of hydrophobic barriers for PADs. With the aid of digitally controlled optimization, together with features of machine learning and design of experiments, we show a thorough investigation on the barrier strength that can be further adjusted to the desired application's needs. Then, we explored the barrier sturdiness across various uses, such as wide range aqueous pH sensing and the harsh acidic/organic conditions needed for the colorimetric detection of cholecalciferol.

Printable and flexible integrated sensing systems for wireless healthcare.

The rapid development of wearable sensing devices and artificial intelligence has enabled portable and wireless tracking of human health, fulfilling the promise of digitalized healthcare applications. To achieve versatile design and integration of multi-functional modules including sensors and data transmission units onto various flexible platforms, printable technologies emerged as some of the most promising strategies. This review first introduces the commonly utilized printing technologies, followed by discussion of the printable ink formulations and flexible substrates to ensure reliable device fabrication and system integration. The advances of printable sensors for body status monitoring are then discussed. Moreover, the integration of wireless data transmission via printable approaches is also presented. Finally, the challenges in achieving printable sensing devices and wireless integrated systems with competitive performances are considered, so as to realize their practical applications for personalized healthcare.

Customizable orodispersible films: Inkjet printing and data matrix encoding for personalized hydrocortisone dosing.

The aim of this study was to exploit the versatility of inkjet printing to develop flexible doses of drug-loaded orodispersible films that encoded information in a data matrix pattern, and to introduce a specialised data matrix-generator software specifically focused on the healthcare sector. Pharma-inks (drug-loaded inks) containing hydrocortisone (HC) were developed and characterised based on their rheological properties and drug content. Different strategies were investigated to improve HC solubility: formation of ß-cyclodextrin complexes, Soluplus® based micelles, and the use of co-solvent systems. The software automatically adapted the data matrix size and identified the number of layers for printing. HC content deposited in each film layer was measured, and it was found that the proportion of co-solvent used directly affected the drug solubility and simultaneously played a role in the modification of the viscosity and surface tension of the inks. The formation of ß-cyclodextrin complexes improved the drug quantity deposited in each layer. On the contrary, micelle-based inks were not suitable for printing. Orodispersible films containing flexible and low doses of personalised HC were successfully prepared, and the development of a code generator software oriented to medical use provided an additional, innovative, and revolutionary advantage to personalised medicine safety and accessibility.

4D printing for biomedical applications.

While three-dimensional (3D) printing excels at fabricating static constructs, it fails to emulate the dynamic behavior of native tissues or the temporal programmability desired for medical devices. Four-dimensional (4D) printing is an advanced additive manufacturing technology capable of fabricating constructs that can undergo pre-programmed changes in shape, property, or functionality when exposed to specific stimuli. In this Perspective, we summarize the advances in materials chemistry, 3D printing strategies, and post-printing methodologies that collectively facilitate the realization of temporal dynamics within 4D-printed soft materials (hydrogels, shape-memory polymers, liquid crystalline elastomers), ceramics, and metals. We also discuss and present insights about the diverse biomedical applications of 4D printing, including tissue engineering and regenerative medicine, drug delivery, in vitro models, and medical devices. Finally, we discuss the current challenges and emphasize the importance of an application-driven design approach to enable the clinical translation and widespread adoption of 4D printing.

Ultra-Sensitive and Stable Multiplexed Biosensors Array in Fully Printed and Integrated Platforms for Reliable Perspiration Analysis.

Electrochemical biosensors have emerged as one of the promising tools for tracking human body physiological dynamics via non-invasive perspiration analysis. However, it remains a key challenge to integrate multiplexed sensors in a highly controllable and reproducible manner to achieve long-term reliable biosensing, especially on flexible platforms. Herein, a fully inkjet printed and integrated multiplexed biosensing patch with remarkably high stability and sensitivity is reported for the first time. These desirable characteristics are enabled by the unique interpenetrating interface design and precise control over active materials mass loading, owing to the optimized ink formulations and droplet-assisted printing processes. The sensors deliver sensitivities of 313.28 µA mm-1 cm-2 for glucose and 0.87 µA mm-1 cm-2 for alcohol sensing with minimal drift over 30 h, which are among the best in the literature. The integrated patch can be used for reliable and wireless diet monitoring or medical intervention via epidermal analysis and would inspire the advances of wearable devices for intelligent healthcare applications.

Research progress in the degradation of printing and dyeing wastewater using chitosan based composite photocatalytic materials.

The surge in economic growth has spurred the expansion of the textile industry, resulting in a continuous rise in the discharge of printing and dyeing wastewater. In contrast, the photocatalytic method harnesses light energy to degrade pollutants, boasting low energy consumption and high efficiency. Nevertheless, traditional photocatalysts suffer from limited light responsiveness, inadequate adsorption capabilities, susceptibility to agglomeration, and hydrophilicity, thereby curtailing their practical utility. Consequently, integrating appropriate carriers with traditional photocatalysts becomes imperative. The combination of chitosan and semiconductor materials stands out by reducing band gap energy, augmenting reactive sites, mitigating carrier recombination, bolstering structural stability, and notably advancing the photocatalytic degradation of printing and dyeing wastewater. This study embarks on an exploration by initially elucidating the technical principles, merits, and demerits of prevailing printing and dyeing wastewater treatment methodologies, with a focal emphasis on the photocatalytic approach. It delineates the constraints encountered by traditional photocatalysts in practical scenarios. Subsequently, it comprehensively encapsulates the research advancements and elucidates the reaction mechanisms underlying chitosan based composite materials employed in treating printing and dyeing wastewater. Finally, this work casts a forward-looking perspective on the future research trajectory of chitosan based photocatalysts, particularly in the realm of industrial applications.

Ionogels for flexible conductive substrates and their application in biosensing.

Ionogels are highly conductive gels made from ionic liquids dispersed in a matrix made of organic or inorganic materials. Ionogels are known for high ionic conductivity, flexibility, high thermal and electrochemical stability. These characteristics make them suitable for sensing and biosensing applications. This review discusses about the two main constituents, ionic liquids and matrix, used to make ionogels and effect of these materials on the characteristics of ionogels. Here, the material properties like mechanical, electrochemical and stability are discussed for both polymer matrix and ionic liquid. We have briefly described about the fabrication methods like 3D printing, sol-gel, blade coating, spin coating, aerosol jet printing etc., used to make films or coating of these ionogels. The advantages and disadvantages of each method are also briefly summarized. Finally, the last section provides a few examples of application of flexible ionogels in areas like wearables, human-machine interface, electronic skin and detection of biological molecules.

Achieving Reliable and Ultrafast Memristors via Artificial Filaments in Silk Fibroin.

The practical implementation of memristors in neuromorphic computing and biomimetic sensing suffers from unexpected temporal and spatial variations due to the stochastic formation and rupture of conductive filaments (CFs). Here, the biocompatible silk fibroin (SF) is patterned with an on-demand nanocone array by using thermal scanning probe lithography (t-SPL) to guide and confine the growth of CFs in the silver/SF/gold (Ag/SF/Au) memristor. Benefiting from the high fabrication controllability, cycle-to-cycle (temporal) standard deviation of the set voltage for the structured memristor is significantly reduced by ≈95.5% (from 1.535 to 0.0686 V) and the device-to-device (spatial) standard deviation is also reduced to 0.0648 V. Besides, the statistical relationship between the structural nanocone design and the resultant performance is confirmed, optimizing at the small operation voltage (≈0.5 V) and current (100 nA), ultrafast switching speed (sub-100 ns), large on/off ratio (104 ), and the smallest switching slope (SS < 0.01 mV dec-1 ). Finally, the short-term plasticity and leaky integrated-and-fire behavior are emulated, and a reliable thermal nociceptor system is demonstrated for practical neuromorphic applications.

Integrated Ink Printing Paper Based Self-Powered Electrochemical Multimodal Biosensing (IFP-Multi ) with ChatGPT-Bioelectronic Interface for Personalized Healthcare Management.

Personalized healthcare management is an emerging field that requires the development of environment-friendly, integrated, and electrochemical multimodal devices. In this study, the concept of integrated paper-based biosensors (IFP-Multi ) for personalized healthcare management is introduced. By leveraging ink printing technology and a ChatGPT-bioelectronic interface, these biosensors offer ultrahigh areal-specific capacitance (74633 mF cm-2 ), excellent mechanical properties, and multifunctional sensing and humidity power generation capabilities. More importantly, the IFP-Multi devices have the potential to simulate deaf-mute vocalization and can be integrated into wearable sensors to detect muscle contractions and bending motions. Moreover, they also enable monitoring of physiological signals from various body parts, such as the throat, nape, elbow, wrist, and knee, and successfully record sharp and repeatable signals generated by muscle contractions. In addition, the IFP-Multi devices demonstrate self-powered handwriting sensing and moisture power generation for sweat-sensing applications. As a proof-of-concept, a GPT 3.5 model-based fine-tuning and prediction pipeline that utilizes recorded physiological signals through IFP-Multi is showcased, enabling artificial intelligence with multimodal sensing capabilities for personalized healthcare management. This work presents a promising and ecofriendly approach to developing paper-based electrochemical multimodal devices, paving the way for a new era of healthcare advancements.