Covalent Surface Modification Effects on Single‐Walled Carbon Nanotubes for Targeted Sensing and Optical Imaging

Optical nanoscale technologies often implement covalent or noncovalent strategies for the modification of nanoparticles, whereby both functionalizations are leveraged for multimodal applications but can affect the intrinsic fluorescence of nanoparticles. Specifically, single‐walled carbon nanotubes (SWCNTs) can enable real‐time imaging and cellular delivery; however, the introduction of covalent SWCNT sidewall functionalizations often attenuates SWCNT fluorescence. Recent advances in SWCNT covalent functionalization chemistries preserve the SWCNT's pristine graphitic lattice and intrinsic fluorescence, and here, such covalently functionalized SWCNTs maintain intrinsic fluorescence‐based molecular recognition of neurotransmitter and protein analytes. The covalently modified SWCNT nanosensor preserves its fluorescence response towards its analyte for certain nanosensors, presumably dependent on the intermolecular interactions between SWCNTs or the steric hindrance introduced by the covalent functionalization that hinders noncovalent interactions with the SWCNT surface. These SWCNT nanosensors are further functionalized via their covalent handles with a targeting ligand, biotin, to self‐assemble on passivated microscopy slides, and these dual‐functionalized SWCNT materials are explored for future use in multiplexed sensing and imaging applications.     

Recent Advances and Opportunities of Active Materials for Haptic Technologies in Virtual and Augmented Reality

Virtual reality and augmented reality (VR/AR) are evolving. The market demands and innovation efforts call for a shift in the key VR/AR technologies and engaging people virtually. Tele-haptics with multimodal and bilateral interactions are emerging as the future of the VR/AR industry. By transmitting and receiving haptic sensations wirelessly, tele-haptics allow human-to-human interactions beyond the traditional VR/AR interactions. The core technologies for tele-haptics include multimodal tactile sensing and feedback based on highly advanced sensors and actuators. Recent developments of haptic innovations based on active materials show that active materials can significantly contribute to addressing the needs and challenges for the current and future VR/AR technologies. Thus, this paper intends to review the current status and opportunities of active material-based haptic technology with a focus on VR/AR applications. It first provides an overview of the current VR/AR applications of active materials for haptic sensing and actuation. It then highlights the state-of-the-art haptic interfaces that are relevant to the materials with an aim to provide perspectives on the role of active materials and their potential integration in haptic devices. This paper concludes with the perspective and outlook of immersive multimodal tele-haptic interaction technologies.     

Tailored Graphitic Carbon Nitride Nanostructures: Synthesis,Modification, and Sensing Applications

Various beneficial properties of graphitic carbon nitride (g‐CN) have been discovered during the promotion of its visible‐light‐driven photocatalytic activity for water splitting. These properties enable g‐CN working as a sensing signal transducer with multiple output modes. In this review, state‐of‐the‐art sensing applications of tailored g‐CN nanostructures in the recent years are presented. Initially, g‐CN nanoarchitectures featuring large surface areas, abundance of active sites, and high dispersity in water are presented along with their preparation methods. Then, sensing applications of these g‐CN nanoarchitectures are described in sequence of the immobilization of recognition elements; semiconductor and electron donating properties derive signaling transduction modes, and efficient approaches for improving sensing performances. The review is concluded with a summary and some perspectives on the challenges and future possibilities of this research field.     

Patterned Arrays of Supramolecular Microcapsules

Micropatterning of hydrogel has brought innovative outcomes in fundamental and applied material sciences. Previous approaches have mainly been dedicated to fabricate arrays of bulk hydrogel beads, which have inherent challenges including loading ability, scalability, specificity, and versatility. Here, a methodology is presented to create hollow microcapsule arrays from sessile microdroplets. The difference in wettability between hydrophilic and hydrophobic surfaces enables self‐partitioning of liquid into microdroplet arrays, serving as microreservoirs to load complementarily functionalized host–guest polymers, cucurbit[8]uril‐threaded highly branched polyrotaxanes (HBP‐CB[8]) and naphthyl‐functionalized hydroxyethyl cellulose (HEC‐Np). The interfacial dynamic complexation between positively charged HBP‐CB[8] and HEC‐Np occurs in the presence of negatively charged surfactants, resulting in condensed supramolecular hydrogel skins. The hydrogel microcapsules are uniform in size and are developed to encapsulate target cargos in a robust and well‐defined manner. Moreover, the microcapsule substrates are further used for surface enhanced Raman spectroscopy sensing upon loading of gold nanoparticles. This facile assembly of microcapsule arrays has potential applications in controlled cargo delivery, bio‐sensing, high‐throughput analysis, and sorting.     

A Reusable Interface Constructed by 3‐Aminophenylboronic Acid‐Functionalized Multiwalled Carbon Nanotubes for Cell Capture,Release, and Cytosensing

A newly developed electrochemical cell sensor for the determination of K562 leukemia cells using 3‐aminophenylboronic acid (APBA)‐functionalized multiwalled carbon nanotubes (MWCNTs) films is demonstrated. The films are generated by the covalent coupling between the ? NH₂ groups in APBA and the ? COOH group in the acid‐oxidized MWCNTs. As a result of the sugar‐specific affinity interactions, the K562 leukemia cells are firmly bound to the APBA‐functionalized MWCNTs film via boronic acid groups. Compared to electropolymerized APBA films, the presence of MWCNTs not only provides abundant boronic acid domains for cell capture, their high electrical conductivity also makes the film suitable for electrochemical sensing applications. The resulting modified electrodes are tested as cell detection sensors. This work presents a promising platform for effective cell capture and constructing reusable cytosensors.     

An Asymmetric Iron‐Based Redox‐Active System for Electrochemical Separation of Ions in Aqueous Media

Electrochemically mediated redox‐active processes are gaining momentum as a promising liquid‐phase separation technology. Compared to conventional systems, they offer potential benefits, such as smaller energy footprints, nondestructive operation, reversibility, and tunability for specific analyte removal, with clear applications to societal and industrial challenges like water treatment and chemical synthesis. An asymmetric Faradaic cell heterogeneously functionalized with a metallopolymer at the anode and a hexacyanoferrate material at the cathode is presented for the first time. The redox‐active species' iron centers enhance the electrosorption of heavy metal oxyanions with up to 98% removal in the ppb range, and offer tunable operating windows as low as ≈0.1 V at ≈1 A m^?2. By avoiding water splitting, the hexacyanoferrate cathode imparts additional advantages, namely a four‐fold reduction in adsorption energy requirements, full suppression of solution pH increase, and the ability to capture redox‐active catalytic anions such as polyoxometalates without altering their bulk oxidation state. This hybrid framework of a polymeric ferrocene anode and crystalline hexacyanoferrate cathode allows for simultaneous and synergistic uptake of anions and cations, respectively, creating a new asymmetric scheme for water‐based separations, with foreseeable future extension to fields such as ion‐sensing, energy storage, and electrocatalysis.     

Computational Chemistry‐Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups

Computational chemistry‐guided designs of chemoresponsive liquid crystals (LCs) with pyridine or pyrimidine groups that bind to metal‐cation‐functionalized surfaces to provide improved selective responses to targeted vapor species (dimethylmethylphosphonate (DMMP)) over nontargeted species (water) are reported. The LC designs against experiments are tested by synthesizing 4‐(4‐pentyl‐phenyl)‐pyridine and 5‐(4‐pentyl‐phenyl)‐pyrimidine and quantifying LC responses to DMMP and water. Consistent with the computations, pyridine‐containing LCs bind to metal‐cation‐functionalized surfaces too strongly to permit a response to either DMMP or water whereas pyrimidine‐containing LCs undergo a surface‐driven orientational transition in response to DMMP without interference from water. The computation predictions are not strongly dependent on assumptions regarding the degree of coordination of the metal ions but are limited in their ability to predict LC responses when using cations with mostly empty d orbitals. Overall, this work identifies a promising new class of chemoresponsive LCs based on pyrimidine that exhibits enhanced tolerance to water, a result that is important because water is a ubiquitous and particularly challenging chemical interferent in chemical sensing strategies based on LCs. The work also provides further evidence of the transformative utility of computational chemistry methods to design LC materials that exhibit selective orientational responses in specific chemical environments.     

Complex‐Shaped Cellulose Composites Made by Wet Densification of 3D Printed Scaffolds

Cellulose is an attractive material resource for the fabrication of sustainable functional products, but its processing into structures with complex architecture and high cellulose content remains challenging. Such limitation has prevented cellulose‐based synthetic materials from reaching the level of structural control and mechanical properties observed in their biological counterparts, such as wood and plant tissues. To address this issue, a simple approach is reported to manufacture complex‐shaped cellulose‐based composites, in which the shaping capabilities of 3D printing technologies are combined with a wet densification process that increases the concentration of cellulose in the final printed material. Densification is achieved by exchanging the liquid of the wet printed material with a poor solvent mixture that induces attractive interactions between cellulose particles. The effect of the solvent mixture on the final cellulose concentration is rationalized using solubility parameters that quantify the attractive interparticle interactions. Using X‐ray diffraction analysis and mechanical tests, 3D printed composites obtained through this process are shown to exhibit highly aligned microstructures and mechanical properties significantly higher than those obtained by earlier additively manufactured cellulose‐based materials. These features enable the fabrication of cellulose‐rich synthetic structures that more closely resemble the exquisite designs found in biological materials grown by plants in nature.     

Fully Printed Light‐Emitting Electrochemical Cells Utilizing Biocompatible Materials

The use of biomaterials and bioinspired concepts in electronics will enable the fabrication of transient and disposable technologies within areas ranging from smart packaging and advertisement to healthcare applications. In this work, the use of a nonhalogenated biodegradable solid polymer electrolyte based on poly(ε‐caprolactone‐co‐trimethylene carbonate) and tetrabutylammonium bis‐oxalato borate in light‐emitting electrochemical cells (LECs) is presented. It is shown that the spin‐cast devices exhibit current efficiencies of ≈2 cd A^?1 with luminance over ≈12 000 cd m^?2, an order of magnitude higher than previous bio‐based LECs. By a combination of industrially relevant techniques (i.e., inkjet printing and blade coating), the fabrication of LEC devices on a cellulose‐based flexible biodegradable substrate showing lifetimes compatible with transient applications is demonstrated. The presented results have direct implications toward the industrial manufacturing of biomaterial‐based light‐emitting devices with potential use in future biodegradable/biocompatible electronics.     

Triangular Elastomeric Stamps for Optical Applications: Near‐Field Phase Shift Photolithography, 3D Proximity Field Patterning,Embossed Antireflective Coatings,and SERS Sensing

The use of a decal transfer lithography technique to fabricate elastomeric stamps with triangular cross‐sections, specifically triangular prisms and cones, is described. These stamps are used in demonstrations for several prototypical optical applications, including the fabrication of multiheight 3D photoresist patterns with near zero‐width features using near‐field phase shift lithography, fabrication of periodic porous polymer structures by maskless proximity field nanopatterning, embossing thin‐film antireflection coatings for improved device performance, and efficient fabrication of substrates for surface‐enhanced Raman spectroscopic sensing. The applications illustrate the utility of the triangular poly(dimethylsiloxane) decals for a wide variety of optics‐centric applications, particularly those that exploit the ability of the designed geometries and materials combinations to manipulate light–matter interactions in a predictable and controllable manner.     

Light‐Emitting Electrochemical Cells Based on Color‐Tunable Inorganic Colloidal Quantum Dots

Large‐area, ultrathin light‐emitting devices currently inspire architects and interior and automotive designers all over the world. Light‐emitting electrochemical cells (LECs) and quantum dot light‐emitting diodes (QD‐LEDs) belong to the most promising next‐generation device concepts for future flexible and large‐area lighting technologies. Both concepts incorporate solution‐based fabrication techniques, which makes them attractive for low cost applications based on, for example, roll‐to‐roll fabrication or inkjet printing. However, both concepts have unique benefits that justify their appeal. LECs comprise ionic species in the active layer, which leads to the omission of additional organic charge injection and transport layers and reactive cathode materials, thus LECs impress with their simple device architecture. QD‐LEDs impress with purity and opulence of available colors: colloidal quantum dots (QDs) are semiconducting nanocrystals that show high yield light emission, which can be easily tuned over the whole visible spectrum by material composition and size. Emerging technologies that unite the potential of both concepts (LEC and QD‐LED) are covered, either by extending a typical LEC architecture with additional QDs, or by replacing the entire organic LEC emitter with QDs or perovskite nanocrystals, still keeping the easy LEC setup featured by the incorporation of mobile ions.     

Large‐Area,Flexible Broadband Photodetector Based on ZnS–MoS2 Hybrid on Paper Substrate

Flexible broadband photodetectors based on 2D MoS₂ have gained significant attention due to their superior light absorption and increased light sensitivity. However, pristine MoS₂ has absorption only in visible and near IR spectrum. This paper reports a paper‐based broadband photodetector having ZnS–MoS₂ hybrids as active sensing material fabricated using a simple, cost effective two‐step hydrothermal method wherein trilayer MoS₂ is grown on cellulose paper followed by the growth of ZnS on MoS₂. Optimization in terms of process parameters is done to yield uniform trilayer MoS₂ on cellulose paper. UV sensing property of ZnS and broadband absorption of MoS₂ in visible and IR, broadens the range from UV to near IR. ZnS plays the dual role for absorption in UV and in the generation of local electric fields, thereby increasing the sensitivity of the sensor. The fabricated photodetector exhibits a higher responsivity toward the visible light when compared to UV and IR light. Detailed studies in terms of energy band diagram are presented to understand the charge transport mechanism. This represents the first demonstration of a paper‐based flexible broadband photodetector with excellent photoresponsivity and high bending capability that can be used for wearable electronics, flexible security, and surveillance systems, etc.     

Internet of things: Vision,applications and research challenges

The term “Internet-of-Things” is used as an umbrella keyword for covering various aspects related to the extension of the Internet and the Web into the physical realm, by means of the widespread deployment of spatially distributed devices with embedded identification, sensing and/or actuation capabilities. Internet-of-Things envisions a future in which digital and physical entities can be linked, by means of appropriate information and communication technologies, to enable a whole new class of applications and services. In this article, we present a survey of technologies, applications and research challenges for Internet-of-Things.     

Live Lymphocyte Arrays for Biosensing

Systems designed to sensitively and accurately detect whole pathogen particles, their components, or other proteins diagnostic of infection or disease are of interest as sensors for biodefense and clinical diagnostics. To this end, we examined the potential of a sensing strategy based on live T‐cell/B‐cell interactions in a biosensor chip format. An approach to fabricate patterned hydrogel microwells functionalized at their bases with antibodies to promote specific immobilization of lymphocytes was developed and used to array single T cells in a regular pattern on a substrate. A sensing platform was created by overlaying arrayed T cells with a confluent layer of antigen‐capturing B cells. In this system, a peptide analyte added to the chip was captured by B cells and physically presented to arrayed T cells by B‐cell‐surface major histocompatibility complex molecules, triggering T cells through their T‐cell receptors. T‐cell recognition of the target peptide was detected by fluorescence measurements of T‐cell intracellular calcium levels, a biochemical read‐out of T‐cell receptor triggering. We demonstrate that this approach allows rapid, sensitive detection of a model peptide analyte, and that T‐cell arrays allow for maximal T‐cell/B‐cell contacts while simultaneously optimizing single‐cell fluorescence detection for analysis of the sensor response. This approach could be of interest for the design of sensing platforms that can detect both peptide fragments and whole intact pathogens, irrespective of surface mutations that might be induced naturally or during “weaponization”.     

CMOS based capacitive sensor laboratory-on-chip: a multidisciplinary approach

In this paper, we review the recent advances of CMOS-based capacitive sensors for Lab-on-chip (LoC) applications. LoC design is a multidisciplinary approach of adapting classical biochemical assays to a miniaturized platform by exploiting advances in microelectronic and microfluidic technologies. By offering low cost and integrated devices, CMOS based LoCs could be amenable to a large number of biological and biochemical assays for disease diagnostics and biotechnology in the near future. While an exhaustive, all-encompassing review of CMOS-based LoCs is beyond the scope of this review, we have focused on the design and implementation of CMOS-based capacitive sensor LoCs for the most important biochemical applications. For each application, the corresponding biochemical sensing layer, interface circuit and microfluidic packaging technique are discussed based on the recent literature studies.     

Multifunctional AIEgens: Ready Synthesis,Tunable Emission,Mechanochromism, Mitochondrial,and Bacterial Imaging

Luminogens with aggregation‐induced emission characteristics (AIEgens) are intriguing due to its rapid expansion in various high‐tech applications. However, there is still in high demand on the development of novel AIEgens with easy preparation and functionalization, stable structures, tunable emissions, and high quantum efficiency. In this contribution, three AIEgens based on diphenyl isoquinolinium (IQ) derivatives are reported. They can be facilely synthesized and possess high structural stability, favorable visible light excitation, large Stokes shifts, high quantum yields, tunable colors, and sufficient two‐photon absorption of near‐infrared light. Importantly, they exhibit multifunctionalities. They exhibit mechanochromic property, making them capable to be applied for rewritable papers. They can also be applied in mitochondrial imaging with high specificity, cell permeability, brightness, biocompatibility, and photostability. They are promising for the applications in evaluation of mitochondrial membrane potential and image‐guided cancer cell ablation. Last, they are able to stain bacteria in a wash‐free manner. All these intriguing results suggest such readily accessible and multifunctional diphenyl IQ‐based AIEgens provide a new platform for construction of advanced materials for practical applications.     

Transparent Nanopaper‐Based Flexible Organic Thin‐Film Transistor Array

Eco‐friendly and low‐cost cellulose nanofiber paper (nanopaper) is a promising candidate as a novel substrate for flexible electron device applications. Here, a thin transparent nanopaper‐based high‐mobility organic thin‐film transistor (OTFT) array is demonstrated for the first time. Nanopaper made from only native wood cellulose nanofibers has excellent thermal stability (>180 °C) and chemical durability, and a low coefficient of thermal expansion (CTE: 5–10 ppm K^‐1). These features make it possible to build an OTFT array on nanopaper using a similar process to that for an array on conventional glass. A short‐channel bottom‐contact OTFT is successfully fabricated on the nanopaper by a lithographic and solution‐based process. Owing to the smoothness of the cast‐coated nanopaper surface, a solution processed organic semiconductor film on the nanopaper comprises large crystalline domains with a size of approximately 50–100 μm, and the corresponding TFT exhibits a high hole mobility of up to 1 cm²V^‐1 s^‐1 and a small hysteresis of below 0.1 V under ambient conditions. The nanopaper‐based OTFT also had excellent flexibility and can be formed into an arbitrary shape. These combined technologies of low‐cost and eco‐friendly paper substrates and solution‐based organic TFTs are promising for use in future flexible electronics application such as flexible displays and sensors.     

Universal Colorimetric Detection of Nucleic Acids Based on Polydiacetylene (PDA) Liposomes

A universal colorimetric method for the detection of nucleic acids, based on ionic interactions by polydiacetylene (PDA) liposomes, is described. Primary and quaternary amine‐modified diacetylene monomers were synthesized and used to generate positively charged PDA liposomes. The resulting PDA sensors showed a dramatic color change from blue to red upon the addition of nucleic acids amplified by using the polymerase chain reaction (PCR) due to the stimuli caused by ionic interactions between the positively charged PDA and negatively charged phosphate backbone of the nucleic acids. The color change that takes place can be simply detected by the naked eye. Compared with quaternary amine‐functionalized PDA vesicles, the primary amine‐functionalized PDA underwent a more intense color transition under optimized conditions. By using the PDA‐based colorimetric sensor, nucleic acids amplified by common PCR reaction, whose typical concentration is around 100 nM, can be readily detected. Since implementation of this universal colorimetric method is simple, rapid and does not require any sophisticated instrumentation, it should have greatly enhanced applications as a technology for DNA diagnosis.     

Solution‐Processible Red Iridium Dendrimers based on Oligocarbazole Host Dendrons: Synthesis,Properties, and their Applications in Organic Light‐Emitting Diodes

A series of novel red‐emitting iridium dendrimers functionalized with oligocarbazole host dendrons up to the third generation ( red‐G3 ) have been synthesized by a convergent method, and their photophysical, electrochemical, and electroluminescent properties have been investigated. In addition to controlling the intermolecular interactions, oligocarbazole‐based dendrons could also participate in the electrochemical and charge‐transporting process. As a result, highly efficient electrophosphorescent devices can be fabricated by spin‐coating from chlorobenzene solution in different device configurations. The maximum external quantum efficiency (EQE) based on the non‐doped device configuration increases monotonically with increasing dendron generation. An EQE as high as 6.3% was obtained as for the third generation dendrimer red‐G3 , which is about 30 times higher than that of the prototype red‐G0 . Further optimization of the device configuration gave an EQE of 11.8% (13.0 cd A^?1, 7.2 lm W^?1) at 100 cd m^?2 with CIE coordinates of (0.65, 0.35). The state‐of‐the‐art performance indicated the potential of these oligocarbazole‐based red iridium dendrimers as solution processible emissive materials for organic light‐emitting diode applications.     

Humidity‐Tolerant Single‐Stranded DNA‐Functionalized Graphene Probe for Medical Applications of Exhaled Breath Analysis

Highly sensitive and selective chemiresistive sensors based on graphene functionalized by metals and metal oxides have attracted considerable attention in the fields of environmental monitoring and medical assessment because of their ultrasensitive gas detecting performance and cost‐effective fabrication. However, their operation, in terms of detection limit and reliability, is limited in traditional applications because of ambient humidity. Here, the enhanced sensitivity and selectivity of single‐stranded DNA‐functionalized graphene (ssDNA‐FG) sensors to NH₃ and H₂S vapors at high humidity are demonstrated and their sensing mechanism is suggested. It is found that depositing a layer of ssDNA molecules leads to effective modulation of carrier density in graphene, as a negative‐potential gating agent and the formation of an additional ion conduction path for proton hopping in the layer of hydronium ions (H₃O⁺) at high humidity (>80%). Considering that selectively responsive chemical vapors are biomarkers associated with human diseases, the obtained results strongly suggest that ssDNA‐FG sensors can be the key to developing a high‐performance exhaled breath analyzer for diagnosing halitosis and kidney disorder.