A Study of Deployable Structures Based on Nature Inspired Curved-Crease Folding.

Fascinating 3D shapes arise when a thin planar sheet is folded without stretching, tearing or cutting. The elegance amplifies when the fold/crease is changed from a straight line to a curve, due to the association of plastic deformation via folding and elastic deformation via bending. This results in the curved crease working as a hinge support providing deployability to the surface which is of significant interest in industrial engineering and architectural design. Consequently, finding a stable form of curved crease becomes pivotal in the development of deployable structures. This work proposes a novel way to evaluate such curves by taking inspiration from biomimicry. For this purpose, growth mechanism in plants was observed and an analogous model was developed to create a discrete curve of fold. A parametric model was developed for digital construction of the folded models. Test cases were formulated to compare the behavior of different folded models under various loading conditions. A simplified way to visualize the obtained results is proposed using visual programming tools. The models were further translated into physical prototypes with the aid of 3D printing, hybrid and cured-composite systems, where different mechanisms were adopted to achieve the folds. The prototypes were further tested under constrained boundary and compressive loading conditions, with results validating the analytical model.

A Study of Free-Form Shape Rationalization Using Biomimicry as Inspiration.

Bridging the gap between the material and geometrical aspects of a structure is critical in lightweight construction. Throughout the history of structural development, shape rationalization has been of prime focus for designers and architects, with biological forms being a major source of inspiration. In this work, an attempt is made to integrate different phases of design, construction, and fabrication under a single framework of parametric modeling with the help of visual programming. The idea is to offer a novel free-form shape rationalization process that can be realized with unidirectional materials. Taking inspiration from the growth of a plant, we established a relationship between form and force, which can be translated into different shapes using mathematical operators. Different prototypes of generated shapes were constructed using a combination of existing manufacturing processes to test the validity of the concept in both isotropic and anisotropic material domains. Moreover, for each material/manufacturing combination, generated geometrical shapes were compared with other equivalent and more conventional geometrical constructions, with compressive load-test results being the qualitative measure for each use case. Eventually, a 6-axis robot emulator was integrated with the setup, and corresponding adjustments were made such that a true free-form geometry could be visualized in a 3D space, thus closing the loop of digital fabrication.

Investigation of an Impedimetric LaSrMnO3-Au/Y2O3-ZrO2-Al2O3 Composite NOx Sensor.

Composite NOx sensors were fabricated by combining partially and fully stabilized yttria-doped zirconia with alumina forming a composite electrolyte, Y2O3-ZrO2-Al2O3, and strontium-doped lanthanum manganese oxide mixed with gold to form the composite sensing electrode, La0.8 Sr0.2MnO3-Au. A surface chemistry analysis of the composite sensor was conducted to interpret defects and the structural phases present at the Y2O3-ZrO2-Al2O3 electrolyte, as well as the charge conduction mechanism at the LaSrMnO3-Au electrode surface. Based on the surface chemistry analysis, ionic and electronic transport properties, and microstructural features of sensor components, the working principle was described for NOx sensing at the composite sensor. The role of the composite materials on the NOx sensing response, cross-sensitivity to O2, H2O, CO, CO2, and CH4, and the response/recovery rates relative to sensor accuracy were characterized by operating the composite NOx sensors via the impedimetric method. The composite sensors were operated at temperatures ranging from 575 to 675 °C in dry and humidified gas environments with NO and NO2 concentrations varying from 0 to 100 ppm, where the balance gas was N2. It was found that the microstructure of the composite NOx sensor electrolyte and sensing electrode had a significant effect on interfacial reactions at the triple phase boundary, as well as the density of active sites for oxygen reactions. Overall, the composite NOx sensor microstructure enabled a high NOx sensing response, along with low cross-sensitivity to O2, CO, CO2, and CH4, and promoted NO detection down to 2 ppm.

Stimuli-Responsive Templated Polymer as a Target Receptor for a Conformation-based Electrochemical Sensing Platform.

The use of highly crosslinked molecularly imprinted polymers as a synthetic target receptor has the limitations of restricted accessibility to the binding sites resulting in slow response time. Moreover, such artificial receptors often require additional transduction mechanisms to translate target binding events into measurable signals. Here, we propose the development of a single-chain stimuli-responsive templated polymer, without using any covalent interchain crosslinkers, as a target recognition element. The synthesized polymer chain exhibits preferential binding with the target molecule with which the polymer is templated. Moreover, upon specific target recognition, the polymer undergoes conformation change induced by its particular stimuli responsiveness, namely the target binding event. Such templated single-chain polymers can be attached to the electrode surface to implement a label-free electrochemical sensing platform. A target analyte, 4-nitrophenol (4-NP), was used as a template to synthesize a poly-N-isopropylacrylamide (PNIPAM)-based copolymer chain which was anchored to the electrode to be used as a selective receptor for 4-NP. The electrode surface chemistry analysis and the electrochemical impedance study reveal that the polymer concentration, the interchain interactions, and the Hofmeister effect play a major role in influencing the rate of polymer grafting as well as the morphology of the polymers grafted to the electrode. We also show that the specific binding between 4-NP and the copolymer results in a substantial change in the charge transfer kinetics at the electrode signifying the polymer conformation change.

A Single-chain Templated Polymer-based Target Receptor as a New Platform for Label-free Selective Electrochemical Sensing.

We report a novel single-chain polymer-based chemical receptor that can be used for the label-free electrochemical detection of an analyte with high selectivity. The polymer was developed using poly-N-isopropylacrylamide (pNIPAM) as a backbone structure in addition to other functional monomers that are used to imprint the template molecule 4-nitrophenol. The polymer also contains a redox reporting monomers (ferrocene) which create a change in the electrochemical signal upon molecular recognition. We hypothesize that the analyte binding to the receptor causes the polymer conformation change from the extended to the collapsed phase. After anchoring the polymer-based receptors onto the surfaces of the gold electrode, when exposed to the analyte, the changes in the electrochemical signals were observed which confirmed the selective target binding as well as the polymer conformation change as a result.

NON-ENZYMATIC ELECTROCHEMICAL DETECTION OF GLUTAMATE USING TEMPLATED POLYMER-BASED TARGET RECEPTORS.

We present a novel electrochemical biosensing platform for the detection of neurotransmitter glutamate using templated polymer-based target receptors. Our sensing approach demonstrates, for the first time, a non-enzymatic approach without the need of glutamate oxidase, leading to a more specific and rapid response. The proposed detection principle is based on the following two claims: (1) our templated polymer-based receptor results in specific molecular recognition of the target glutamate and, (2) upon target binding, the polymer undergoes a conformation change which can then be measured via electrochemical techniques. This sensing platform has the potential to provide direct monitoring of a variety of non-electroactive species and to eliminate the incorporation of enzymes thereby providing a simpler and more robust alternative to enzyme-based sensors.

Surface Fouling of Ultrananocrystalline Diamond Microelectrodes during Dopamine Detection: Improving Lifetime via Electrochemical Cycling.

In this work, we report the electrochemical response of a boron-doped ultrananocrystalline diamond (BDUNCD) microelectrode during long-term dopamine (DA) detection. Specifically, changes to its electrochemical activity and electroactive area due to DA byproducts and surface oxidation are studied via scanning electron microscopy, energy dispersive spectroscopy, electrochemical impedance spectroscopy, and silver deposition imaging (SDI). The fouling studies with amperometry (AM) and fast scan cyclic voltammetry (FSCV) methods suggest that the microelectrodes are heavily fouled due to poor DA-dopamine- o-quinone cyclization rates followed by a combination of polymer formation and major changes in their surface chemistry. SDI data confirms the presence of the insulating polymer with sparsely distributed tiny electroactive regions. This resulted in severely distorted DA signals and a 90% loss in signal starting as early as 3 h for AM and a 56% loss at 6.5 h for FSCV. This underscores the need for cleaning of the fouled microelectrodes if they have to be used long-term. Out of the three in vivo suitable electrochemical cycling cleaning waveforms investigated, the standard waveform (-0.4 V to +1.0 V) provides the best cleaned surface with a fully retained voltammogram shape, no hysteresis, no DA signal loss (a 90 ± 0.72 nA increase), and the smallest charge transfer resistance value of 0.4 ± 0.02 MΩ even after 6.5 h of monitoring. Most importantly, this is the same waveform that is widely used for in vivo detection with carbon fiber microelectrodes. Future work to test these microelectrodes for more than 24 h of DA detection is anticipated.

A Novel Microbiosensor Microarray for Continuous ex Vivo Monitoring of Gamma-Aminobutyric Acid in Real-Time.

Gamma-aminobutyric acid (GABA) is a major inhibitory neurotransmitter that is essential for normal brain function. It is involved in multiple neuronal activities, including plasticity, information processing, and network synchronization. Abnormal GABA levels result in severe brain disorders and therefore GABA has been the target of a wide range of drug therapeutics. GABA being non-electroactive is challenging to detect in real-time. To date, GABA is detected mainly via microdialysis with a high-performance liquid chromatography (HPLC) system that employs electrochemical (EC) and spectroscopic methodology. However, these systems are bulky and unsuitable for real-time continuous monitoring. As opposed to microdialysis, biosensors are easy to miniaturize and are highly suitable for in vivo studies; they selectively oxidize GABA into a secondary electroactive product (usually hydrogen peroxide, H2O2) in the presence of enzymes, which is then detected by amperometry. Unfortunately, this method requires a rather cumbersome process with prereactors and relies on externally applied reagents. Here, we report the design and implementation of a GABA microarray probe that operates on a newly conceived principle. It consists of two microbiosensors, one for glutamate (Glu) and one for GABA detection, modified with glutamate oxidase and GABASE enzymes, respectively. By simultaneously measuring and subtracting the H2O2 oxidation currents generated from these microbiosensors, GABA and Glu can be detected continuously in real-time in vitro and ex vivo and without the addition of any externally applied reagents. The detection of GABA by this probe is based upon the in-situ generation of α-ketoglutarate from the Glu oxidation that takes place at the Glu microbiosensor. A GABA sensitivity of 36 ± 2.5 pA µM-1cm-2, which is 26-fold higher than reported in the literature, and a limit of detection of 2 ± 0.12 µM were achieved in an in vitro setting. The GABA probe was successfully tested in an adult rat brain slice preparation. These results demonstrate that the developed GABA probe constitutes a novel and powerful neuroscientific tool that could be employed in the future for in vivo longitudinal studies of the combined role of GABA and Glu (a major excitatory neurotransmitter) signaling in brain disorders, such as epilepsy and traumatic brain injury, as well as in preclinical trials of potential therapeutic agents for the treatment of these disorders.

Detection of neurochemicals with enhanced sensitivity and selectivity via hybrid multiwall carbon nanotube-ultrananocrystalline diamond microelectrodes.

Abnormal neurochemical signaling is often the underlying cause of brain disorders. Electrochemical microsensors are widely used to monitor neurochemicals with high spatial-temporal resolution. However, they rely on carbon fiber microelectrodes that often limit their sensing performance. In this study, we demonstrate the potential of a hybrid multiwall carbon nanotube (MWCNT) film modified boron-doped ultrananocrystalline diamond (UNCD) microelectrode (250 µm diameter) microsensor for improved detection of dopamine (DA) in the presence of common interferents. A series of modified microelectrodes with varying film thicknesses were microfabricated by electrophoretic deposition (EPD) and characterized by scanning electron microscopy, x-ray photoelectron spectroscopy, electrochemical impedance spectroscopy (EIS) and silver deposition imaging. Using cyclic voltammetry, the 100-nm "thin" film microelectrode produced the most favorable combination of DA sensitivity value of 36 ±2% µA/µM/cm2 with a linear range of 33 nM to 1 µM and a limit of detection (LOD) of 9.5 ± 1.2% nM. The EIS spectra of these microelectrodes revealed three regions with inhomogeneous pore geometry and differing impedance values and electrochemical activity, which was found to be film thickness dependent. Using differential pulse voltammetry, the modified microelectrode showed excellent selectivity by exhibiting three distinct peaks for the DA, serotonin and excess ascorbic acid in a ternary mixture. These results provide two key benefits: first, remarkable improvements in DA sensitivity (>125-fold), selectivity (>2000-fold) and LOD (>180-fold), second, these MWCNTs can be selectively coated with a simple, scalable and low cost EPD process for highly multiplexed microsensor technologies. These advances offer considerable promise for further progress in chemical neurosciences.

Enabling long term monitoring of dopamine using dimensionally stable ultrananocrystalline diamond microelectrodes.

Chronic dopamine (DA) monitoring is a critical enabling technology to identify the neural basis of human behavior. Carbon fiber microelectrodes (CFM), the current gold standard electrode for in vivo fast scan cyclic voltammetry (FSCV), rapidly loses sensitivity due to surface fouling during chronic neural testing. Periodic voltage excursions at elevated anodic potentials regenerate fouled CFM surfaces but they also chemically degrade the CFM surfaces. Here, we compare the dimensional stability of 150 µm boron-doped ultrananocrystalline diamond (BDUNCD) microelectrodes in 1X PBS during 'electrochemical cleaning' with a similar-sized CFM. Scanning electron microscopy and Raman spectroscopy confirm the exceptional dimensional stability of BDUNCD after 40 h of FSCV cycling (~8 million cycles). The fitting of electrochemical impedance spectroscopy data to an appropriate circuit model shows a 2x increase in charge transfer resistance and an additional RC element, which suggests oxidation of BDUNCD electrode surface. This could have likely increased the DA oxidation potential by ~34% to +308 mV. A 2x increase in BDUNCD grain capacitance and a negligible change in grain boundary impedance suggests regeneration of grains and the exposure of new grain boundaries, respectively. Overall, DA voltammogram signals were reduced by only ~20%. In contrast, the CFM is completely etched with a ~90% reduction in the DA signal using the same cleaning conditions. Thus, BDUNCD provides a robust electrode surface that is amenable to repeated and aggressive cleaning which could be used for chronic DA sensing.

Nanocrystalline Diamond Electrodes: Enabling electrochemical microsensing applications with high reliability and stability.

THE DIAMOND (D) IS ONE OF the most precious materials in the world with unmatched physical and chemical properties, such as hardness, extreme chemical stability, high thermal conductivity, the highest acoustic velocity of any material, an extremely low friction coefficient when smooth, and nearly unmatched biocompatibility [1]. The carbon (C) atoms in Ds are tetrahedrally coordinated, i.e., each C atom is bonded to four others in the D lattice. This bonding is referred to as sp 3 bonding, and the strength and configuration of these bonds provide Ds with these unmatched fundamental properties and characteristics. Realizing these properties of the D in a C-based film that can easily be integrated into functional engineering systems and deployed in many applications has been a challenge for several decades. This is of primary concern in microelectronics, sensing, and hard-coating applications.

The effect of electrode size and surface heterogeneity on electrochemical properties of ultrananocrystalline diamond microelectrode.

We report here the effect of electrode size on electrochemical properties of boron-doped ultrananocrystalline diamond (UNCD) microelectrodes using electrochemical impedance spectroscopy (EIS). By reducing microelectrode size from 250-µm to 10-µm diameter (D), the shape of impedance spectra changes from linear line to two-arcs. The fitting of experimental data to electrochemical circuit model suggests that each arc likely corresponds to UNCD grains and grain boundary phases. The two phases become separable as a result of microelectrode size reduction. In addition, for D ≤ 100-µm, microstructural and morphological defects/heterogeneities of grain boundaries and the presence of surface oxygen are also revealed in the spectra. The microelectrode size reduction specifically affect the impedance of the grain boundaries, e.g. for ultramicroelectrodes, UMEs (D ≤ 25-µm), as the grain boundary impedance increases by ~30-fold. Thus, at UMEs, the grain-grain boundary properties are revealed more sensitively in the spectra. Atomic force microscopy, scanning electron microscopy, Raman spectroscopy and surface profilometry measurements were performed to study the influence of microfabrication on surface properties. A significant increase in surface roughness after microfabrication shows that heterogeneities as observed in the spectra are not only due to intrinsic UNCD properties but also arises from microfabrication.