Advancing Glucose Sensing Through Auto-Fluorescent Polymer Brushes: From Surface Design to Nano-Arrays.

Designing smart (bio)interfaces with the capability to sense and react to changes in local environments offers intriguing possibilities for new surface-based sensing devices and technologies. Polymer brushes make ideal materials to design such adaptive and responsive interfaces given their large variety of functional and structural possibilities as well as their outstanding abilities to respond to physical, chemical, and biological stimuli. Herein, a practical sensory interface for glucose detection based on auto-fluorescent polymer brushes decorated with phenylboronic acid (PBA) receptors is presented. The glucose-responsive luminescent surfaces, which are capable of translating conformational transitions triggered by pH variations and binding events into fluorescent readouts without the need for fluorescent dyes, are grown from both nanopatterned and non-patterned substrates. Two-photon laser scanning confocal microscopy and atomic force microscopy (AFM) analyses reveal the relationship between the brush conformation and glucose concentration and confirm that the phenylboronic acid functionalized brushes can bind glucose over a range of physiologically relevant concentrations in a reversible manner. The combination of auto-fluorescent polymer brushes with synthetic receptors presents a promising avenue for designing innovative and robust sensing systems, which are essential for various biomedical applications, among other uses.

Learning from nature: binary cooperative complementary nanomaterials.

In this Review, nature-inspired binary cooperative complementary nanomaterials (BCCNMs), consisting of two components with entirely opposite physiochemical properties at the nanoscale, are presented as a novel concept for the building of promising materials. Once the distance between the two nanoscopic components is comparable to the characteristic length of some physical interactions, the cooperation between these complementary building blocks becomes dominant and endows the macroscopic materials with novel and superior properties. The first implementation of the BCCNMs is the design of bio-inspired smart materials with superwettability and their reversible switching between different wetting states in response to various kinds of external stimuli. Coincidentally, recent studies on other types of functional nanomaterials contribute more examples to support the idea of BCCNMs, which suggests a potential yet comprehensive range of future applications in both materials science and engineering.

Smart Polymer Surfaces with Complex Wrinkled Patterns: Reversible, Non-Planar, Gradient, and Hierarchical Structures.

This review summarizes the relevant developments in preparing wrinkled structures with variable characteristics. These include the formation of smart interfaces with reversible wrinkle formation, the construction of wrinkles in non-planar supports, or, more interestingly, the development of complex hierarchically structured wrinkled patterns. Smart wrinkled surfaces obtained using light-responsive, pH-responsive, temperature-responsive, and electromagnetic-responsive polymers are thoroughly described. These systems control the formation of wrinkles in particular surface positions and the reversible construction of planar-wrinkled surfaces. This know-how of non-planar substrates has been recently extended to other structures, thus forming wrinkled patterns on solid, hollow spheres, cylinders, and cylindrical tubes. Finally, this bibliographic analysis also presents some illustrative examples of the potential of wrinkle formation to create more complex patterns, including gradient structures and hierarchically multiscale-ordered wrinkles. The orientation and the wrinkle characteristics (amplitude and period) can also be modulated according to the requested application.

A Flexible Artificial Sensory Nerve Enabled by Nanoparticle-Assembled Synaptic Devices for Neuromorphic Tactile Recognition.

Tactile perception enabled by somatosensory system in human is essential for dexterous tool usage, communication, and interaction. Imparting tactile recognition functions to advanced robots and interactive systems can potentially improve their cognition and intelligence. Here, a flexible artificial sensory nerve that mimics the tactile sensing, neural coding, and synaptic processing functions in human sensory nerve is developed to achieve neuromorphic tactile recognition at device level without relying on algorithms or computing resources. An interfacial self-assembly technique, which produces uniform and defect-less thin film of semiconductor nanoparticles on arbitrary substrates, is employed to prepare the flexible synaptic device. The neural facilitation and sensory memory characteristics of the proton-gating synaptic device enable this system to identify material hardness during robotic grasping and recognize tapping patterns during tactile interaction in a continuous, real-time, high-accuracy manner, demonstrating neuromorphic intelligence and recognition capabilities. This artificial sensory nerve produced in wearable and portable form can be readily integrated with advanced robots and smart human-machine interfaces for implementing human-like tactile cognition in neuromorphic electronics toward robotic and wearable applications.

Engineering Protein-Based Parts for Genetic Devices in Mammalian Cells.

Synthetic biology has been advancing cellular and molecular biology studies through the design of synthetic circuits capable to examine diverse endogenously or exogenously driven regulatory pathways. While early genetic devices were engineered to be insulated from intracellular crosstalk, more recently the need of achieving dynamic control of cellular behavior has led to the development of smart interfaces that connect signal information (sensor) to desired output activation (actuator). Sensor-actuator circuits can respond to diverse inputs, including small molecules, exogenous and endogenous mRNA, noncoding RNA (i.e., miRNA), and proteins to regulate downstream events, transcriptionally, posttranscriptionally, and translationally. These devices require attentive engineering to either create complex chimeric proteins or modify protein structures to be amenable to the specific circuits' architecture and/or purpose.In this chapter, we describe how to implement two different protein-based devices in mammalian cells: (1) a modular platform that sense and respond to disease-associated proteins and (2) a protein-based system that allows simultaneous regulation of RNA translation and protein activity, via RNA-protein and newly engineered protein-protein interactions.

Electroresponsive Polyelectrolyte Brushes Studied by Self-Consistent Field Theory.

End-grafting of polyelectrolyte chains to conducting substrates offers an opportunity to fabricate electro-responsive surfaces capable of changing their physical/chemical properties (adhesion, wettability) in response to applied electrical voltage. We use a self-consistent field numerical approach to compare the equilibrium properties of tethered strong and weak (pH-sensitive) polyelectrolytes to applied electrical field in both salt-free and salt-containing solutions. We demonstrate that both strong and weak polyelectrolyte brushes exhibit segregation of polyions in two populations if the surface is oppositely charged with respect to the brush. This segregation gives rise to complex patterns in the dependence of the brush thickness on salt concentration. We demonstrate that adjustable ionization of weak polyelectrolytes weakens their conformational response in terms of the dependence of brush thickness on the amplitude of the applied voltage.

Carbon Nanotubes Arranged As Smart Interfaces in Lipid Langmuir-Blodgett Films Enhancing the Enzymatic Properties of Penicillinase for Biosensing Applications.

In this paper, carbon nanotubes (CNTs) were incorporated in penicillinase-phospholipid Langmuir and Langmuir-Blodgett (LB) films to enhance the enzyme catalytic properties. Adsorption of the penicillinase and CNTs at dimyristoylphosphatidic acid (DMPA) monolayers at the air-water interface was investigated by surface pressure-area isotherms, vibrational spectroscopy, and Brewster angle microscopy. The floating monolayers were transferred to solid supports through the LB technique, forming mixed DMPA-CNTs-PEN films, which were investigated by quartz crystal microbalance, vibrational spectroscopy, and atomic force microscopy. Enzyme activity was studied with UV-vis spectroscopy and the feasibility of the supramolecular device nanostructured as ultrathin films were essayed in a capacitive electrolyte-insulator-semiconductor (EIS) sensor device. The presence of CNTs in the enzyme-lipid LB film not only tuned the catalytic activity of penicillinase but also helped conserve its enzyme activity after weeks, showing increased values of activity. Viability as penicillin sensor was demonstrated with capacitance/voltage and constant capacitance measurements, exhibiting regular and distinctive output signals over all concentrations used in this work. These results may be related not only to the nanostructured system provided by the film, but also to the synergism between the compounds on the active layer, leading to a surface morphology that allowed a fast analyte diffusion because of an adequate molecular accommodation, which also preserved the penicillinase activity. This work therefore demonstrates the feasibility of employing LB films composed of lipids, CNTs, and enzymes as EIS devices for biosensing applications.