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Meyyappan, M.

Publications and source records attributed to Meyyappan, M..

At least 19 records

Trends in Carbon, Oxygen, and Nitrogen Core in the X-ray Absorption Spectroscopy of Carbon Nanomaterials: A Guide for the Perplexed

Successful deployment of carbon nanomaterials in many applications, such as sensing, energy storage, and catalysis, relies on the selection, synthesis, and tailoring of the surface properties. Predictive analysis of the behavior is difficult without detailed knowledge of the differences between various carbon nanomaterials and their surface functionalization, thus leaving the selection process to traditional trial-and-error work. The present characterization fills this knowledge gap for carbon nanomaterial surface properties with respect to chemical states and functionalization. We present an overview of the chemical trends that can be extracted from soft X-ray absorption spectroscopy (XAS) spectra on an extended set of nonideal carbon nanomaterials as a function of sp 2 bonded carbon and bond ordering. In particular, the surface chemical state, the presence of long-range order in the carbon matrix, and a qualitative estimation of the amount of oxygen and nitrogen and their respective functional group formation on the material surface, together with the detailed material fabrication parameters, are reported. The results expand our understanding of carbon nanomaterial functionalization, which can support material selection in practice, provided that the specifications of the application are known.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrating Carbon Nanomaterials with Metals for Bio-sensing Applications

Age structure in most developed countries is changing fast as the average lifespan is increasing significantly, calling for solutions to provide improved treatments for age-related neurological diseases and disorders. In order to address these problems, a reliable way of recording information about neurotransmitters from in vitro and in vivo applications is needed to better understand neurological diseases and disorders as well as currently used treatments. Likewise, recent developments in medicine, especially with the opioid crisis, are demanding a swift move to personalized medicine to administer patient needs rather than population-wide averages. In order to enable the so-called personalized medicine, it is necessary to be able to do measurements in vivo and in real time. These actions require sensitive and selective detection of different analytes from very demanding environments. Current state-of-the-art materials are unable to provide sensitive and selective detection of neurotransmitters as well as the required time resolution needed for drug molecules at a reasonable cost. To meet these challenges, we have utilized different metals to grow carbon nanomaterials and applied them for sensing applications showing that there are clear differences in their electrochemical properties based on the selected catalyst metal. Additionally, we have combined atomistic simulations to support optimizing materials for experiments and to gain further understanding of the atomistic level reactions between different analytes and the sensor surface. With carbon nanostructures grown from Ni and Al + Co + Fe hybrid, we can detect dopamine, ascorbic acid, and uric acid simultaneously. On the other hand, nanostructures grown from platinum provide a feasible platform for detection of H 2 O 2 making them suitable candidates for enzymatic biosensors for detection of glutamate, for example. Tetrahedral amorphous carbon electrodes have an ability to detect morphine, paracetamol, tramadol, and O-desmethyltramadol. With carbon nanomaterial-based sensors, it is possible to reach metal-like properties in sensing applications using only a fraction of the metal as seed for the material growth. We have also seen that by using nanodiamonds as growth catalyst for carbon nanofibers, it is not possible to detect dopamine and ascorbic acid simultaneously, although the morphology of the resulting nanofibers is similar to the ones grown using Ni. This further indicates the importance of the metal selection for specific applications. However, Ni as a continuous layer or as separate islands does not provide adequate performance. Thus, it appears that metal nanoparticles combined with fiber-like morphology are needed for optimized sensor performance for neurotransmitter detection. This opens up a new research approach of application-specific nanomaterials, where carefully selected metals are integrated with carbon nanomaterials to match the needs of the sensing application in question.

59 BASIC BIOLOGICAL SCIENCES↗

Plasma jet based in situ reduction of copper oxide in direct write printing

Printing of nanostructured films with tailored oxidation state and electronic structure can have far reaching applications in several areas including printable electronics, optoelectronics, solar cells, catalytic conversion, and others. Widely used inkjet/aerosol/screen printing techniques require pre- and postprocessing for enhanced adhesion and tailoring of the chemical state of the thin film. Herein, we demonstrate atmospheric pressure plasma jet printing with unique capability to print and tune in situ the electronic properties and surface morphology of nanomaterials. Plasma printing of copper thin films with tailored oxidation state from an inexpensive copper oxide precursor is demonstrated and characterized using x-ray absorption spectroscopy, Raman spectroscopy, and electrical measurements.

42 ENGINEERING↗

Plasma Jet Printing and in Situ Reduction of Highly Acidic Graphene Oxide

Miniaturization of electronic devices and the advancement of Internet of Things pose exciting challenges to develop technologies for patterned deposition of functional nanomaterials. Printed and flexible electronic devices and energy storage devices can be embedded onto clothing or other flexible surfaces. Graphene oxide (GO) has gained much attention in printed electronics due its solution processability, robustness, and high electrical conductivity in the reduced state. We introduce an approach to print GO films from highly acidic suspensions with in situ reduction using an atmospheric pressure plasma jet. Low-temperature plasma of a He and H 2 mixture was used successfully to reduce a highly acidic GO suspension (pH < 2) in situ during deposition. This technique overcomes the multiple intermediate steps required to increase the conductivity of deposited GO. X-ray spectroscopic studies confirmed that the reaction intermediates and the concentration of oxygen functionalities bonded to GO have been reduced significantly by this approach without any additional steps. Moreover, the reduced GO films showed enhanced conductivity. Hence, this technique has a strong potential for printing conducting patterns of GO for a range of large-scale applications.

42 ENGINEERING↗

Efficacy of atmospheric pressure dielectric barrier discharge for inactivating airborne pathogens

Atmospheric pressure plasmas have gained attention in recent years for several environmental applications. This technology could potentially be used to deactivate airborne microorganisms, surface-bound microorganisms, and biofilms. Here, the authors explore the efficacy of the atmospheric pressure dielectric barrier discharge (DBD) to inactivate airborne Staphylococcus epidermidis and Aspergillus niger that are opportunistic pathogens associated with nosocomial infections. This technology uses air as the source of gas and does not require any process gas such as helium, argon, nitrogen, or hydrogen. Moreover, the effect of DBD was studied on aerosolized S. epidermidis and aerosolized A. niger spores via scanning electron microscopy (SEM). The morphology observed on the SEM micrographs showed deformations in the cellular structure of both microorganisms. Cell structure damage upon interaction with the DBD suggests leakage of vital cellular materials, which is a key mechanism for microbial inactivation. The chemical structure of the cell surface of S. epidermidis was also analyzed by near edge x-ray absorption fine structure spectroscopy before and after DBD exposure. Our results from surface analysis revealed that reactive oxygen species from the DBD discharge contributed to alterations on the chemistry of the cell membrane/cell wall of S. epidermidis.

59 BASIC BIOLOGICAL SCIENCES↗

What does nitric acid really do to carbon nanofibers? [What nitric acid really does to carbon nanofibers]

Understanding the chemical nature of the surface of carbon nanofibers (CNF) is critical in assessing their fundamental properties and tailoring them for the right application. To gain such knowledge, we present here a detailed X-ray adsorption spectroscopy (XAS) study accompanied by high resolution transmission electron microscopy (TEM) micrographs of two morphologically different CNF pairs (tetrahedral amorphous carbon (ta-C) grown “open structured” fibers and traditional bamboo-like “closed structured” fibers), where the surface chemical properties and structural features of the fibers are investigated in depth and the effects of nitric acid treatment on the fibers are revealed. The morphology of the fiber and/or the original seed- and adhesion layers markedly affect the response of the fibers to the acid treatment. Results also show that the nitric acid treatment increases the observed sp 2 intensity and modifies the two types of fibers to become more-alike both structurally and with respect to their oxygen functionalities. Furthermore, the XAS and HRTEM results confirm that a short nitric acid treatment does not remove the Ni catalyst particle but, instead, oxidizes their surfaces, especially in the case of ta-C grown fibers.

36 MATERIALS SCIENCE↗

Atmospheric Pressure Plasma Jet as a Dry Alternative to Inkjet Printing in Flexible Electronics

We have developed an atmospheric pressure plasma jet printing system that works at room temperature to 50 deg C unlike conventional aerosol assisted techniques which require a high temperature sintering step to obtain desired thin films. Multiple jets can be configured to increase throughput or to deposit multiple materials, and the jet(s) can be moved across large areas using a x-y stage. The plasma jet has been used to deposit carbon nanotubes, graphene, silver nanowires, copper nanoparticles and other materials on substrates such as paper, cotton, plastic and thin metal foils.

Printable electronics↗

Plasma jet printing for flexible substrates

Recent interest in flexible electronics and wearable devices has created a demand for fast and highly repeatable printing processes suitable for device manufacturing. Robust printing technology is critical for the integration of sensors and other devices on flexible substrates such as paper and textile. An atmospheric pressure plasma-based printing process has been developed to deposit different types of nanomaterials on flexible substrates. Multiwalled carbon nanotubes were deposited on paper to demonstrate site-selective deposition as well as direct printing without any type of patterning. Plasma-printed nanotubes were compared with non-plasma-printed samples under similar gas flow and other experimental conditions and found to be denser with higher conductivity. The utility of the nanotubes on the paper substrate as a biosensor and chemical sensor was demonstrated by the detection of dopamine, a neurotransmitter, and ammonia, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Morphological and chemical changes of aerosolized E. coli treated with a dielectric barrier discharge

This paper presents the morphological and chemical modification of the cell structure of aerosolized Escherichia coli treated with a dielectric barrier discharge (DBD). Exposure to DBD results in severe oxidation of the bacteria, leading to the formation of hydroxyl groups and carbonyl groups and a significant reduction in amine functionalities and phosphate groups. Near edge x-ray absorption fine structure(NEXAFS) measurements confirm the presence of additional oxide bonds upon DBD treatment, suggesting oxidation of the outer layer of the cell wall. Electron microscopy images show that the bacteria undergo physical distortion to varying degrees, resulting in deformation of the bacterial structure. The electromagnetic field around the DBD coil causes severe damage to the cell structure, possibly resulting in leakage of vital cellular materials. The oxidation and chemical modification of the bacterial components are evident from the Fourier transform infrared spectroscopy and NEXAFS results. The bacterial reculture experiments confirm inactivation of airborne E. coli upon treating with DBD.

59 BASIC BIOLOGICAL SCIENCES↗

Investigation of electromigration in In{sub 2}Se{sub 3} nanowire for phase change memory devices

The decomposition of In{sub 2}Se{sub 3} nanowire phase change memory devices during current-driving operation was investigated. The devices were subjected to thermal/electrical stress with current density and electric field during the reset operation at 0.24–0.38 MA/cm{sup 2} and 5.3–6.4 kV/cm, respectively. After multiple operation cycles, a change in morphology and composition of the In{sub 2}Se{sub 3} nanowire was observed and led to the device failure. The transmission electron microscopy and energy dispersive analysis indicate that electromigration causes the catastrophic failure by void formation where In atoms migrate toward the cathode and Se atoms migrate toward the anode depending on their electronegativities.

36 MATERIALS SCIENCE↗

Label-Free Detection of Cardiac Troponin-I Using Carbon Nanofiber Based Nanoelectrode Arrays

A sensor platform based on vertically aligned carbon nanofibers (CNFs) has been developed. Their inherent nanometer scale, high conductivity, wide potential window, good biocompatibility and well-defined surface chemistry make them ideal candidates as biosensor electrodes. A carbon nanofiber (CNF) multiplexed array has been fabricated with 9 sensing pads, each containing 40,000 carbon nanofibers as nanoelectrodes. Here, we report the use of vertically aligned CNF nanoelectrodes for the detection of cardiac Troponin-I for the early diagnosis of myocardial infarction. Antibody, antitroponin, probe immobilization and subsequent binding to human cardiac troponin-I were characterized using electrochemical impedance spectroscopy and cyclic voltammetry techniques. Each step of the modification process resulted in changes in electrical capacitance or resistance to charge transfer due to the changes at the electrode surface upon antibody immobilization and binding to the specific antigen. This sensor demonstrates high sensitivity, down to 0.2 ng/mL, and good selectivity making this platform a good candidate for early stage diagnosis of myocardial infarction.

cardiac output↗

Carbon Nanotube Based Nanotechnology for NASA Mission Needs and Societal Applications

Carbon nanotubes (CNT) exhibit extraordinary mechanical properties and unique electronic properties and therefore, have received much attention for more than a decade now for a variety of applications ranging from nanoelectronics, composites to meeting needs in energy, environmental and other sectors. In this talk, we focus on some near term potential of CNT applications for both NASA and other Agency/societal needs. The most promising and successful application to date is a nano chem sensor at TRL 6 that uses a 16-256 sensor array in the construction of an electronic nose. Pristine, doped, functionalized and metal-loaded SWCNTs are used as conducting materials to provide chemical variation across the individual elements of the sensor array. This miniaturized sensor has been incorporated in an iPhone for homeland security applications. Gases and vapors relevant to leak detection in crew vehicles, biomedical, mining, chemical threats, industrial spills and others have been demonstrated. SWCNTs also respond to radiation exposure via a change in conductivity and therefore, a similar strategy is being pursued to construct a radiation nose to identify radiation sources (gamma, protons, neutrons, X-ray, etc.) with their energy levels. Carbon nanofibers (CNFs) grown using plasma enhanced CVD typically are vertical, individual, freestanding structures and therefore, are ideal for construction of nanoelectrodes. A nanoelectrode array (NEA) can be the basis for an affinity-based biosensor to meet the needs in applications such as lab-on-a-chip, environmental monitoring, cancer diagnostics, biothreat monitoring, water and food safety and others. A couple of demonstrations including detection of e-coli and ricin will be discussed. The NEA is also useful for implantation in the brain for deep brain stimulation and neuroengineering applications. Miniaturization of payload such as science instrumentation and power sources is critical to reduce launch costs. High current density (greater than 100 mA/per square centimeters) field emission capabilities of CNTs can be exploited for construction of electron gun for electron microscopy and X-ray tubes for spectrometers and baggage screening. A CNT pillar array configuration has been demonstrated, not only meeting the high current density needs but more importantly providing long term emitter stability. Finally, supercapacitors hold the promise to combine the high energy density of a battery with the high power density of capacitors. Traditional graphite electrodes have not delivered this promise yet. A novel design and processing approach using MWCNTs has shown a record 550 F/g capacitance along with significant device endurance. This supercapacitor is suitable for railgun launch application for NASA, powering rovers and robots, consumer electronics and future hybrid vehicles.

Li, Jing↗

Nanomaterials for Electronics and Optoelectronics

Nanomaterials such as carbon nanotubes(CNTs), graphene, and inorganic nanowires(INWs) have shown interesting electronic, mechanical, optical, thermal, and other properties and therefore have been pursued for a variety of applications by the nanotechnology community ranging from electronics to nanocomposites. While the first two are carbon-based materials, the INWs in the literature include silicon, germanium, III-V, II-VI, a variety of oxides, nitrides, antimonides and others. In this talk, first an overview of growth of these three classes of materials by CVD and PECVD will be presented along with results from characterization. Then applications in development of chemical sensors, biosensors, energy storage devices and novel memory architectures will be discussed.

Koehne, Jessica E.↗

Nanotechnologv Enabled Biological and Chemical Sensors

Nanotechnology is an enabling technology that will impact almost all economic sectors: one of the most important and with great potential is the health/medical sector. - Nanomaterials for drug delivery - Early warning sensors - Implantable devices - Artificial parts with improved characteristics Carbon nanotubes and nanofibers show promise for use in sensor development, electrodes and other biomedical applications.

Koehne, Jessica↗

Biochips Containing Arrays of Carbon-Nanotube Electrodes

Biochips containing arrays of nanoelectrodes based on multiwalled carbon nanotubes (MWCNTs) are being developed as means of ultrasensitive electrochemical detection of specific deoxyribonucleic acid (DNA) and messenger ribonucleic acid (mRNA) biomarkers for purposes of medical diagnosis and bioenvironmental monitoring. In mass production, these biochips could be relatively inexpensive (hence, disposable). These biochips would be integrated with computer-controlled microfluidic and microelectronic devices in automated hand-held and bench-top instruments that could be used to perform rapid in vitro genetic analyses with simplified preparation of samples. Carbon nanotubes are attractive for use as nanoelectrodes for detection of biomolecules because of their nanoscale dimensions and their chemical properties.

Li, Jun↗

Carbon-Nanotube-Based Electrodes for Biomedical Applications

A nanotube array based on vertically aligned nanotubes or carbon nanofibers has been invented for use in localized electrical stimulation and recording of electrical responses in selected regions of an animal body, especially including the brain. There are numerous established, emerging, and potential applications for localized electrical stimulation and/or recording, including treatment of Parkinson s disease, Tourette s syndrome, and chronic pain, and research on electrochemical effects involved in neurotransmission. Carbon-nanotube-based electrodes offer potential advantages over metal macroelectrodes (having diameters of the order of a millimeter) and microelectrodes (having various diameters ranging down to tens of microns) heretofore used in such applications. These advantages include the following: a) Stimuli and responses could be localized at finer scales of spatial and temporal resolution, which is at subcellular level, with fewer disturbances to, and less interference from, adjacent regions. b) There would be less risk of hemorrhage on implantation because nano-electrode-based probe tips could be configured to be less traumatic. c) Being more biocompatible than are metal electrodes, carbon-nanotube-based electrodes and arrays would be more suitable for long-term or permanent implantation. d) Unlike macro- and microelectrodes, a nano-electrode could penetrate a cell membrane with minimal disruption. Thus, for example, a nanoelectrode could be used to generate an action potential inside a neuron or in proximity of an active neuron zone. Such stimulation may be much more effective than is extra- or intracellular stimulation via a macro- or microelectrode. e) The large surface area of an array at a micron-scale footprint of non-insulated nanoelectrodes coated with a suitable electrochemically active material containing redox ingredients would make it possible to obtain a pseudocapacitance large enough to dissipate a relatively large amount of electric charge, so that a large stimulation current could be applied at a micron-scale region without exhausting the redox ingredients. f) Carbon nanotube array is more compatible with the three-dimensional network of tissues. Particularly, a better electrical-neural interface can be formed. g) A carbon nanotube array inlaid in insulating materials with only the ends exposed is an extremely sensitive electro-analysis tool that can measure the local neurotransmitter signal at extremely high sensitivity and temporal resolution.

Li, Jun↗