Functionalized Amphiphilic Block Copolymers and Complex Emulsions for Selective Sensing of Dissolved Metals at Liquid-Liquid Interfaces.

Increasing contamination in potable water supplies necessitates the development of sensing methods that provide the speed and selectivity necessary for safety. One promising method relies on recognition and detection at the liquid-liquid interface of dynamic complex emulsions. These all-liquid materials transduce changes in interfacial tensions into optical signals via the coupling of their chemical, physical, and optical properties. Thus, to introduce selectivity, it is necessary to modify the liquid-liquid interface with an interfacially stable and selective recognition unit. To this end, we report the synthesis and characterization of amphiphilic block copolymers modified with metal chelators to selectively measure the concentrations of dissolved metal ions. We find that significant reduction in interfacial tensions arises upon quantitative addition of metal ions with high affinity toward functionalized chelators. Furthermore, measurements from UV-vis spectroscopy reveal that complexation of the block copolymers with metal ions leads to an increase in surface excess and surfactant effectiveness. We also demonstrate selective detection of iron(III) cations (Fe3+) on the µM levels even through interference from other mono-, di-, or trivalent cations in complex matrices of synthetic groundwater. Our results provide a unique platform that couples selective recognition and modulation of interfacial behaviors and demonstrates a step forward in the development of the multiplexed sensing device needed to deconvolute the complicated array of contaminants that comprise real-world environmental samples.

Multiplexed and continuous microfluidic sensors using dynamic complex droplets.

Emissive complex droplets with reconfigurable morphology and dynamic optical properties offer exciting opportunities as chemical sensors due to their stimuli-responsive characteristics. In this work, we demonstrated a real-time optical sensing platform that combines poly(dimethylsiloxane) (PDMS) microfluidics and complex droplets as sensing materials. We utilized a mechanism, called directional emission, to transduce changes in interfacial tension into optical signals. We discuss the fabrication and integration of PDMS microfluidics with complex emulsions to facilitate continuous measurement of fluorescent emission and, ultimately, the interfacial tensions. Furthermore, by varying the interfacial functionalization and fluorescent dye with characteristic wavelength, we generate multiple formulations of droplets and obtain differential responses to stimuli that alter interfacial tensions (i.e., composition of surfactants, pH). Our results illustrate a proof-of-concept multiplexed and continuous sensing platform with potential applications in miniaturized, on-site environmental monitoring and biosensing.

Detection of PFAS and Fluorinated Surfactants Using Differential Behaviors at Interfaces of Complex Droplets.

Contamination of per- and polyfluoroalkyl substances (PFAS) in water supplies will continue to have serious health and environmental consequences. Despite the importance of monitoring the concentrations of PFAS at potential sites of contamination and at treatment plants, there are few suitable and rapid on-site methods. Many nonconventional techniques do not possess the necessary selectivity and sensitivity to distinguish PFAS from other surface-active components and to quantify the low concentrations in real-world conditions. Herein, we report a novel and rapid method for the detection of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) by leveraging their differential behaviors at the interfaces of emissive complex droplets. Measurement of surface and interfacial tensions via a force tensiometer reveals that PFAS preferentially self-assemble at the water-fluorocarbon oil interface (F/W) rather than the water-hydrocarbon oil interface (H/W). We also observe an opposite behavior for hydrocarbon surfactants. This difference in interfacial behavior produces distinct effects on the morphological change and optical emission of biphasic oil-in-water droplets. The change in the intensity of fluorescence emission, measured with a simple spectroscopic setup, correlates with the concentrations of PFAS. We also demonstrate that the range of detection and sensitivity can be tuned by adjusting the initial composition of the complex droplets. Our results illustrate an alternative mode of sensors that may provide a rapid and on-site detection of PFAS.

Rapid Detection of Sepsis: Recent Advances in Biomarker Sensing Platforms.

Sepsis is a major cause of mortality among hospitalized patients worldwide. Rapid diagnosis is critical as early treatments have been demonstrated to improve survival. Despite the importance of early detection, current technologies and clinical methods are often insufficient due to their lack of the necessary speed, selectivity, or sensitivity. The development of rapid sensing platforms that target sepsis-related biomarkers could significantly improve the outcomes of patients. This Mini-Review focuses on the recent advances in rapid diagnosis of soluble biomarkers in blood with the emphasis on different configurations of point-of-care (POC) instruments. Specifically, it first describes the commonly targeted biomarkers and the mechanisms by which they are detected. Then, it highlights the recently developed sensors that aim to reduce the total time of diagnosis without sacrificing selectivity and limit of detection. These sensors are categorized based on their distinct sensing and transduction mechanisms. Finally, it concludes with a brief outlook over future developments of multiplexed sensors.

Fluorescent Janus emulsions for biosensing of Listeria monocytogenes.

Here we report a sensing method for Listeria monocytogenes based on the agglutination of all-liquid Janus emulsions. This two-dye assay enables the rapid detection of trace Listeria in less than 2 h via an emissive signal produced in response to Listeria binding. The biorecognition interface between the Janus emulsions is assembled by attaching antibodies to a functional surfactant polymer with a tetrazine/transcyclooctene click reaction. The strong binding between Listeria and the Listeria antibody located at the hydrocarbon surface of the emulsions results in the tilting of the Janus structure from its equilibrium position to produce emission that would ordinarily be obscured by a blocking dye. This method provides rapid and inexpensive Listeria detection with high sensitivity (<100 CFU/mL in 2 h) that can be paired with many antibody or related recognition elements to create a new class of biosensors.

Dynamic Complex Emulsions as Amplifiers for On-Chip Photonic Cavity-Enhanced Resonators.

Despite the recent emergence of microcavity resonators as label-free biological and chemical sensors, practical applications still require simple and robust methods to impart chemical selectivity and reduce the cost of fabrication. We introduce the use of hydrocarbon-in-fluorocarbon-in-water (HC/FC/W) double emulsions as a liquid top cladding that expands the versatility of optical resonators as chemical sensors. The all-liquid complex emulsions are tunable droplets that undergo dynamic and reversible morphological transformations in response to a change in the chemical environment (e.g., exposure to targeted analytes). This chemical-morphological coupling drastically modifies the effective refractive index, allowing the complex emulsions to act as a chemical transducer and signal amplifier. We detect this large change in the refractive index by tracking the shift of the enveloped resonant spectrum of a silicon nitride (Si3N4) racetrack resonator-based sensor, which correlates well with a change in the morphology of the complex droplets. This combination of soft materials (dynamic complex emulsions) and hard materials (on-chip resonators) provides a unique platform for liquid-phase, real-time, and continuous detection of chemicals and biomolecules for miniaturized and remote, environmental, medical, and wearable sensing applications.

Precision pH Sensor Based on WO3 Nanofiber-Polymer Composites and Differential Amplification.

We report a new type of potentiometric pH sensor with sensitivity exceeding the theoretical Nernstian behavior (-59.1 mV/pH). For the pH-sensitive electrode, 1D tungsten oxide (WO3) nanofibers (NFs) were prepared to obtain large surface area and high porosity. These NFs were then stabilized in a reactive porous chloromethylated triptycene poly(ether sulfone) (Cl-TPES) binder, to facilitate proton diffusion into the polymer membrane. The measurements were performed with a differential amplifier using matched MOSFETs and providing a 10-fold amplified signal over a simple potentiometric determination. A high pH sensitivity of -377.5 mV/pH and a linearity of 0.9847 were achieved over the pH range of 6.90-8.94. Improved signal-to-noise ratios with large EMF signal changes of 175 mV were obtained in artificial seawater ranging pH 8.07-7.64 (ΔpH = 0.43), which demonstrates a practical application for pH monitoring in ocean environments.

Chemiresistive Sensor Array and Machine Learning Classification of Food.

Successful identification of complex odors by sensor arrays remains a challenging problem. Herein, we report robust, category-specific multiclass-time series classification using an array of 20 carbon nanotube-based chemical sensors. We differentiate between samples of cheese, liquor, and edible oil based on their odor. In a two-stage machine-learning approach, we first obtain an optimal subset of sensors specific to each category and then validate this subset using an independent and expanded data set. We determined the optimal selectors via independent selector classification accuracy, as well as a combinatorial scan of all 4845 possible four selector combinations. We performed sample classification using two models-a k-nearest neighbors model and a random forest model trained on extracted features. This protocol led to high classification accuracy in the independent test sets for five cheese and five liquor samples (accuracies of 91% and 78%, respectively) and only a slightly lower (73%) accuracy on a five edible oil data set.

Rapid Detection of Salmonella enterica via Directional Emission from Carbohydrate-Functionalized Dynamic Double Emulsions.

Reliable early-stage detection of foodborne pathogens is a global public health challenge that requires new and improved sensing strategies. Here, we demonstrate that dynamically reconfigurable fluorescent double emulsions can function as highly responsive optical sensors for the rapid detection of carbohydrates fructose, glucose, mannose, and mannan, which are involved in many biological and pathogenic phenomena. The proposed detection strategy relies on reversible reactions between boronic acid surfactants and carbohydrates at the hydrocarbon/water interface leading to a dynamic reconfiguration of the droplet morphology, which alters the angular distribution of the droplet's fluorescent light emission. We exploit this unique chemical-morphological-optical coupling to detect Salmonella enterica, a type of bacteria with a well-known binding affinity for mannose. We further demonstrate an oriented immobilization of antibodies at the droplet interface to permit higher selectivity. Our demonstrations yield a new, inexpensive, robust, and generalizable sensing strategy that can help to facilitate the early detection of foodborne pathogens.

Janus Graphene: Scalable Self-Assembly and Solution-Phase Orthogonal Functionalization.

Orthogonal functionalization of 2D materials by selective assembly at interfaces provides opportunities to create new materials with transformative properties. Challenges remain in realizing controllable, scalable surface-selective, and orthogonal functionalization. Herein, dynamic covalent assembly is reported that directs the functionalization of graphene surfaces at liquid-liquid interfaces. This process allows facile addition and segregation of chemical functionalities to impart Janus characteristics to graphenes. Specifically, dynamic covalent functionalization is accomplished via Meisenheimer complexes produced by reactions of primary amines with pendant dinitroaromatics attached to graphenes. Janus graphenes are demonstrated to be powerful surfactants that organize at water/organic, water/fluorocarbon, and organic/fluorocarbon liquid interfaces. This approach provides general access to the creation of diverse surfactant materials and promising building blocks for 2D materials.

Waveguide-based chemo- and biosensors: complex emulsions for the detection of caffeine and proteins.

We report on a new modular sensing approach in which complex emulsions serve as efficient transducers in optical evanescent field-based sensing devices. Specifically, we leverage the tunable refractive index upon chemically triggered changes in droplet morphology or orientation. Variations in the optical coupling result in readily detectable changes in the light transmitted from a waveguide.

Morphology-Dependent Luminescence in Complex Liquid Colloids.

Complex liquid colloids hold great promise as transducers in sensing applications as a result of their tunable morphology and intrinsic optical properties. Herein, we introduce meta-amino substituted green fluorescence protein chromophore (GFPc) surfactants that localize at the organic-water interface of complex multiphase liquid colloids. The meta-amino GFPc exhibits hydrogen-bonding (HB) mediated fluorescence quenching, and are nearly nonemissive in the presence of protic solvents. We demonstrate morphology-dependent fluorescence of complex liquid colloids and investigate the interplay between GFPc surfactants and other simple surfactants. This environmentally responsive surfactant allows us to observe morphological changes of complex emulsions in randomized orientations. We demonstrate utility with an enzyme activity based fluorescence "turn-ON" scheme. The latter employs an oligopeptide-linked GFPc that functions as both a surfactant and trypsin target. The cleavage of hydrophilic peptide results in a morphology change and ultimately a fluorescence turn-on. Fluorescent complex colloids represent a new approach for biosensing in liquid environments.

Carbon Nanotube Chemical Sensors.

Carbon nanotubes (CNTs) promise to advance a number of real-world technologies. Of these applications, they are particularly attractive for uses in chemical sensors for environmental and health monitoring. However, chemical sensors based on CNTs are often lacking in selectivity, and the elucidation of their sensing mechanisms remains challenging. This review is a comprehensive description of the parameters that give rise to the sensing capabilities of CNT-based sensors and the application of CNT-based devices in chemical sensing. This review begins with the discussion of the sensing mechanisms in CNT-based devices, the chemical methods of CNT functionalization, architectures of sensors, performance parameters, and theoretical models used to describe CNT sensors. It then discusses the expansive applications of CNT-based sensors to multiple areas including environmental monitoring, food and agriculture applications, biological sensors, and national security. The discussion of each analyte focuses on the strategies used to impart selectivity and the molecular interactions between the selector and the analyte. Finally, the review concludes with a brief outlook over future developments in the field of chemical sensors and their prospects for commercialization.

Modular Synthesis of Polymers Containing 2,5-di(thiophenyl)-N-arylpyrrole.

A modular facile route has been developed to synthesize functionalized 2,5-di(thiophen-2-yl)-1-H-arylpyrroles from readily available starting materials. These units are compatible with various polymerization conditions and are versatile building blocks for conjugated polymers. The polymers show high thermal stability and solubility in a number of solvents. Characterization of the polymers reveals a correlation between molecular packing, controllable by polymer design, and charge carrier mobility.

Insights into Magneto-Optics of Helical Conjugated Polymers.

Materials with magneto-optic (MO) properties have enabled critical fiber-optic applications and highly sensitive magnetic field sensors. While traditional MO materials are inorganic in nature, new generations of MO materials based on organic semiconducting polymers could allow increased versatility for device architectures, manufacturing options, and flexible mechanics. However, the origin of MO activity in semiconducting polymers is far from understood. In this paper, we report high MO activity observed in a chiral helical poly-3-(alkylsulfone)thiophene (P3AST), which confirms a new design for the creation of a giant Faraday effect with Verdet constants up to (7.63 ± 0.78) × 104 deg T-1 m-1 at 532 nm. We have determined that the sign of the Verdet constant and its magnitude are related to the helicity of the polymer at the measured wavelength. The Faraday rotation and the helical conformation of P3AST are modulated by thermal annealing, which is further supported by DFT calculations and MD simulations. Our results demonstrate that helical polymers exhibit enhanced Verdet constants and expand the previous design space for polythiophene MO materials that was thought to be limited to highly regular lamellar structures. The structure-property studies herein provide insights for the design of next-generation MO materials based upon semiconducting organic polymers.

Effects of flexibility and branching of side chains on the mechanical properties of low-bandgap conjugated polymers.

This paper describes effects of the flexibility, length, and branching of side chains on the mechanical properties of low-bandgap semiconducting polymers. The backbones of the polymer chains comprise a diketopyrrolopyrrole (DPP) motif flanked by two furan rings and copolymerized by Stille polycondensation with thiophene (DPP2FT). The side chains of the DPP fall into three categories: linear alkyl (C8, C14, or C16), branched alkyl (ethylhexyl, EH, or hexyldecyl, HD), and linear oligo(ethylene oxide) (EO3, EO4, or EO5). Polymers bearing C8 and C14 side chains are obtained in low yields and thus not pursued. Thermal, mechanical, and electronic properties are plotted against the number of carbon and oxygen atoms in the side chain. We obtain consistent trends in the thermal and mechanical properties for branched alkyl and linear oligo(ethylene oxide) side chains. For example, the glass transition temperature (T g) and elastic modulus decrease with increasing number of carbon and oxygen atoms, whereas the crack-onset strain increases. Among polymers with side chains of 16 carbon and oxygen atoms (C16, HD, and EO5), C16 exhibits the highest T g and the greatest susceptibility to fracture. Hole mobility, as measured in thin-film transistors, appears to be a poor predictor of electronic performance for polymers blended with [60]PCBM in bulk heterojunction (BHJ) solar cells. For example, while EO3 and EO4 exhibit the lowest mobilities (< 10-2 cm2 V-1 s-1) in thin-film transistors, solar cells made using these materials performed the best (efficiency > 2.6%) in unoptimized devices. Conversely, C16 exhibits the highest mobility (≈ 0.2 cm2 V-1 s-1) but produces poor solar cells (efficiency < 0.01%). We attribute the lack of correlation between mobility and power conversion efficiency to unfavorable morphology in the BHJ solar cells. Given the desirable properties measured for EO3 and EO4, the use of flexible oligo(ethylene oxide) side chains is a successful strategy to impart mechanical deformability to organic solar cells, without sacrificing electronic performance.

Stretchable and Degradable Semiconducting Block Copolymers.

This paper describes the synthesis and characterization of a class of highly stretchable and degradable semiconducting polymers. These materials are multi-block copolymers (BCPs) in which the semiconducting blocks are based on the diketopyrrolopyrrole (DPP) unit flanked by furan rings and the insulating blocks are poly(ε-caprolactone) (PCL). The combination of stiff conjugated segments with flexible aliphatic polyesters produces materials that can be stretched >100%. Remarkably, BCPs containing up to 90 wt% of insulating PCL have the same field-effect mobility as the pure semiconductor. Spectroscopic (ultraviolet-visible absorption) and morphological (atomic force microscopic) evidence suggests that the semiconducting blocks form aggregated and percolated structures with increasing content of the insulating PCL. Both PDPP and PCL segments in the BCPs degrade under simulated physiological conditions. Such materials could find use in wearable, implantable, and disposable electronic devices.

Bio-Inspired Carbon Monoxide Sensors with Voltage-Activated Sensitivity.

Carbon monoxide (CO) outcompetes oxygen when binding to the iron center of hemeproteins, leading to a reduction in blood oxygen level and acute poisoning. Harvesting the strong specific interaction between CO and the iron porphyrin provides a highly selective and customizable sensor. We report the development of chemiresistive sensors with voltage-activated sensitivity for the detection of CO comprising iron porphyrin and functionalized single-walled carbon nanotubes (F-SWCNTs). Modulation of the gate voltage offers a predicted extra dimension for sensing. Specifically, the sensors show a significant increase in sensitivity toward CO when negative gate voltage is applied. The dosimetric sensors are selective to ppm levels of CO and functional in air. UV/Vis spectroscopy, differential pulse voltammetry, and density functional theory reveal that the in situ reduction of FeIII to FeII enhances the interaction between the F-SWCNTs and CO. Our results illustrate a new mode of sensors wherein redox active recognition units are voltage-activated to give enhanced and highly specific responses.

Janus Emulsions for the Detection of Bacteria.

Janus emulsion assays that rely on carbohydrate-lectin binding for the detection of Escherichia coli bacteria are described. Surfactants containing mannose are self-assembled at the surface of Janus droplets to produce particles with lectin binding sites. Janus droplets orient in a vertical direction as a result of the difference in densities between the hydrocarbon and fluorocarbon solvents. Binding of lectin to mannose(s) causes agglutination and a tilted geometry. The distinct optical difference between naturally aligned and agglutinated Janus droplets produces signals that can be detected quantitatively. The Janus emulsion assay sensitively and selectively binds to E. coli at 104 cfu/mL and can be easily prepared with long-time stability. It provides the basis for the development of inexpensive portable devices for fast, on-site pathogen detection.

Mechanical Properties of Organic Semiconductors for Stretchable, Highly Flexible, and Mechanically Robust Electronics.

Mechanical deformability underpins many of the advantages of organic semiconductors. The mechanical properties of these materials are, however, diverse, and the molecular characteristics that permit charge transport can render the materials stiff and brittle. This review is a comprehensive description of the molecular and morphological parameters that govern the mechanical properties of organic semiconductors. Particular attention is paid to ways in which mechanical deformability and electronic performance can coexist. The review begins with a discussion of flexible and stretchable devices of all types, and in particular the unique characteristics of organic semiconductors. It then discusses the mechanical properties most relevant to deformable devices. In particular, it describes how low modulus, good adhesion, and absolute extensibility prior to fracture enable robust performance, along with mechanical "imperceptibility" if worn on the skin. A description of techniques of metrology precedes a discussion of the mechanical properties of three classes of organic semiconductors: π-conjugated polymers, small molecules, and composites. The discussion of each class of materials focuses on molecular structure and how this structure (and postdeposition processing) influences the solid-state packing structure and thus the mechanical properties. The review concludes with applications of organic semiconductor devices in which every component is intrinsically stretchable or highly flexible.