Charge transfer dynamics on the surface of single-wall carbon nanotube sheets is investigated using in situ Raman spectroscopy in order to understand the actuation mechanism of an electrochemical actuator and to determine associated parameters. We built an actuator from single-wall carbon nanotube mat and studied its actuation in several alkali metal (Li, Na, and K) and alkaline earth (Ca) halide and sulfate solutions in order to clarify the role of counterion as mobile ions in the film. The variation of bonding with applied potential was monitored using in situ Raman spectroscopy. This is because Raman can detect changes in C–C bond length: the radial breathing mode at ∼190 cm−1 varies inversely with the nanotube diameter, and the G band at ∼1590 cm−1 varies with the axial bond length. In addition, the intensities of both the modes vary with the emptying/depleting or filling of the bonding and antibonding states due to electrochemical charge injection. We discussed the variation of peak height and wave numbers of these modes providing valuable information concerning electrochemical charge injection on the carbon nanotube mat surface. We found in-plane microscopic compressive strain (∼−0.25%) and the equivalent charge transfer per carbon atom (fc∼−0.005) as an upper bound for the actuators studied hereby. It is demonstrated that though the present analysis does comply with the proposition for the actuation principle made earlier, the quantitative estimates are significantly lower if compared with those of reported values. Furthermore, the extent of variation, i.e., coupled electro-chemo-mechanical response of single-wall carbon nanotubes (SWNT) mat depended upon the type of counterion used (Group I versus Group II). The cyclic voltammetry and ac electrochemical impedance spectroscopy results were described briefly, which help to demonstrate well-developed capacitive behavior of SWNT mat and to estimate the specific capacitances as well. Summarizing, the impact of these findings on the suitability of such material for use in electrochemical devices such as actuators is emphasized.

Much has been learned from the use of resonance Raman spectroscopy and high-resolution transmission electron microscopy techniques about the micro-/nanoscopic structure of various nanostructured carbons. However, they still possess some features that are not entirely understood particularly in terms of topological characteristics, which go beyond making a distinction with just the geometrical structure at nanoscale. To effectively utilize the potential of these materials for technological needs, understanding both the geometrical and topological structure and perhaps relating these attributes to physical (optical/electronic, lattice vibrational) properties become indispensable. Here, we make an attempt to describe the differences between various nanostructures and provide geometrical and topological property assessment semiquantitatively by monitoring the phonon spectra using resonance Raman spectroscopy thereby also capturing the electronic spectra. We elucidate the notion of global topology and curvature for a range of technologically important nanoscale carbons including tubular (single-, double-and multiwalled nanotubes, peapod), spherical (hypo-and hyperfullerenes, onion-like carbon) and complex (nanocones, nanohorns, nanodisks and nanorings) geometries. To demonstrate the proof-of-concept, we determined the variation in the prominent Raman bands of the respective materials, represented as D, G and D * (the overtone of D) bands, as a possible topological or curvature trend due to their sensitivity toward structural modification. The latter arises from local topological defects such as pentagons giving rise to curved nanocarbons. In this study, we provide systematics of their variation with respect to their geometric forms and compare with highly oriented pyrolytic graphite and monolayer graphene since the nanocarbons discussed are their derivatives. Once established, this knowledge will provide a powerful machinery to understand newer nanocarbons and indeed point to an unprecedented emergent paradigm of global topology/curvature → property → functionality relationship. We emphasize that these concepts are applicable to other topologically distinct nanomaterials, which include boron-nitride (BN) nanotubes and nanotori, helical gold nanotubes and Möbius conjugated organics. Copyright

Polypyrrole (PPy) in the family of p-conjugated polymers is a potential candidate for microscopic actuators, electrochromic devices, batteries, and drug delivery systems. We report the controlled syntheses of PPy micro/nanocontainers through electrochemical generation of H 2 bubbles from a surfactant cum electrolyte b-NSA (b-naphthalene sulfonic acid) stabilized on the working electrode, followed by electrochemical polymerization of monomer (pyrrole) around the wall of the micelles serving as template. It is noticed that the density, shape, caliber, and thickness of self-assembled PPy micro/nanocontainers can be regulated by electrochemical potential window for H 2 bubbles and number of cyclic voltammetric scans for the electropolymerization of pyrrole. Sodium chlorate and perchlorate are used to synthesize conventional PPy films. By changing the dopant structure, one can control the microscopic structure and physical properties, which are analyzed using multiple microscopic techniques and X-ray diffraction (XRD), infrared, vis Raman and X-ray photoelectron spectroscopic analytical tools. In light of this information, an exhaustive description of the material is attained. Experimental results show that the films consist of spherical/globular surface morphology and cup-/bowl-like structures, which becomes lantern-like with increasing cyclic voltammetry scans. The bowl diameter and caliber and room temperature conductivities range 0.05-60 µm, 5-50 µm and 2 × 10 −2 -20 S cm −1 , respectively. Raman spectroscopy (RS) helps to identify the oxidized PPy; polaron and bipolaron states and thus a detailed molecular structure. The results also showed that the relative conjugation length increases with decreasing size of the morphological feature. Moreover, these studies enhanced the understanding of bubble nucleation at the solid-electrolyte interface.

Synthesis of vertically aligned small diameter (single- and double-wall) carbon nanotube films on thermally oxidized n+-Si(001) wafers, with acetylene diluted with ammonia gas mixture using a microwave plasma-assisted chemical vapor deposition technique, is reported. Experiments show that by continuous reduction in the thickness of the iron catalyst film to ∼0.3–0.5nm, or alternately, smaller catalyst particles produces hollow concentric tubes with a fewer number of walls. Double- and single-wall carbon nanotubes with diameters ranging from 1 to 5nm were identified using transmission electron microscopy and Raman spectroscopy. A relatively higher deposition temperature (∼850°C) in conjunction with a controlled catalyst and rapid growth (<40s) allowed for the growth of well-graphitized, high areal density (∼1012-1013∕cm2) nanotubes with reduced amorphous carbon and iron. Our results also indicate that the base growth is the most appropriate model to describe the growth mechanism for the nanotube films.

One subunit of the prokaryotic voltage-gated potassium ion channel from Aeropyrum pernix (KvAP) is comprised of six transmembrane α helices, of which S1–S4 form the voltage-sensor domain (VSD) and S5 and S6 contribute to the pore domain (PD) of the functional homotetramer. However, the mechanism of electromechanical coupling interconverting the closed-to-open (i.e., nonconducting-to-K+-conducting) states remains undetermined. Here, we have vectorially oriented the detergent (OG)-solubilized VSD in single monolayers by two independent approaches, namely “directed-assembly” and “self-assembly,” to achieve a high in-plane density. Both utilize Ni coordination chemistry to tether the protein to an alkylated inorganic surface via its C-terminal His6 tag. Subsequently, the detergent is replaced by phospholipid (POPC) via exchange, intended to reconstitute a phospholipid bilayer environment for the protein. X-ray interferometry, in which interference with a multilayer reference structure is used to both enhance and phase the specular x-ray reflectivity from the tethered single membrane, was used to determine directly the electron density profile structures of the VSD protein solvated by detergent versus phospholipid, and with either a moist He (moderate hydration) or bulk aqueous buffer (high hydration) environment to preserve a native structure conformation. Difference electron density profiles, with respect to the multilayer substrate itself, for the VSD-OG monolayer and VSD-POPC membranes at both the solid-vapor and solid-liquid interfaces, reveal the profile structures of the VSD protein dominating these profiles and further indicate a successful reconstitution of a lipid bilayer environment. The self-assembly approach was similarly extended to the intact full-length KvAP channel for comparison. The spatial extent and asymmetry in the profile structures of both proteins confirm their unidirectional vectorial orientation within the reconstituted membrane and indicate retention of the protein’s folded three-dimensional tertiary structure upon completion of membrane bilayer reconstitution. Moreover, the resulting high in-plane density of vectorially oriented protein within a fully hydrated single phospholipid bilayer membrane at the solid-liquid interface will enable investigation of their conformational states as a function of the transmembrane electric potential.

Polymer electrolytes are an important component of many electrochemical devices. Researchers have carried out a significant work for the development of polymer electrolytes. This paper reviews the recent developments in the area of polymer electrolytes using aqueous and nonaqueous-based natural polymers for developing a cheaper, ecofriendly, biodegradable, and widely used electrolytes as a substitute for existing synthetic polymer electrolytes. This paper also encompasses the merits and demerits of the different natural polymers used by the researcher. There is a scope to develop a nonaqueous-based natural polymer electrolyte as an alternate for synthetic polymer electrolyte for batteries and other electronic devices.

Carbon electrodes are widely used in electrochemistry due to their low cost, wide potential window, and low and stable background noise. Carbon-fiber electrodes (CFE) are commonly used to electrochemically measure "quantal" catecholamine release via exocytosis from individual cells, but it is difficult to integrate CFEs into lab-on-a-chip devices. Here we report the development of nitrogen doped diamond-like carbon (DLC:N) microelectrodes on a chip to monitor quantal release of catecholamines from cells. Advantages of DLC:N microelectrodes are that they are batch producible at low cost, and are harder and more durable than graphite films. The DLC:N microelectrodes were prepared by a magnetron sputtering process with nitrogen doping. The 30 μm by 40 μm DLC:N microelectrodes were patterned onto microscope glass slides by photolithography and lift-off technology. The properties of the DLC:N microelectrodes were characterized by AFM, Raman spectroscopy and cyclic voltammetry. Quantal catecholamine release was recorded amperometrically from bovine adrenal chromaffin cells on the DLC:N microelectrodes. Amperometric spikes due to quantal release of catecholamines were similar in amplitude and area as those recorded using CFEs and the background current and noise levels of microchip DLC:N electrodes were also comparable to CFEs. Therefore, DLC:N microelectrodes are suitable for microchip-based high-throughput measurement of quantal exocytosis with applications in basic research, drug discovery and cell-based biosensors.

Graphene quantum dots (GQDs), derived from functionalized graphene precursors are graphene sheets a few nanometers in the lateral dimension having a several-layer thickness. They are zero-dimensional materials with quantum confinement and edge site effects. Intense research interest in GQDs is attributed to their unique physicochemical phenomena arising from the sp2-bonded carbon nanocore surrounded with edged plane functional moieties. In this work, GQDs are synthesized by both solvothermal and hydrothermal techniques, with the optimal size of 5 nm determined using high-resolution transmission electron microscopy, with additional UV-Vis absorption and fluorescence spectroscopy, revealing electronic band signatures in the blue-violet region. Their potential in fundamental (direct electron transfer) and applied (enzyme-based glucose biosensor) electrochemistry has been practically realized. Glucose oxidase (GOx) was immobilized on glassy carbon (GC) electrodes modified with GQDs and functionalized graphene (graphene oxide and reduced form). The cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy are used for characterizing the direct electron transfer kinetics and electrocatalytical biosensing. The well-defined quasi-reversible redox peaks were observed under various electrochemical environment and conditions (pH, concentration, scan rate) to determine the diffusion coefficient (D) and first-order electron transfer rate (kET). The cyclic voltammetry curves showed homogeneous ion transport behavior for GQD and other graphene-based samples with D ranging between 8.45 × 10−9 m2 s−1 and 3 × 10−8 m2 s−1 following the order of GO < rGO < GQD < GQD (with FcMeOH as redox probe) < GOx/rGO < GOx/GO < HRP/GQDs < GOx/GQDs. The developed GOx-GQDs biosensor responds efficiently and linearly to the presence of glucose over concentrations ranging between 10 μM and 3 mM with a limit of detection of 1.35 μM and sensitivity of 0.00769 μA μM−1·cm−2 as compared with rGO (0.025 μA μM−1 cm−2, 4.16 μM) and GO (0.064 μA μM−1 cm−2, 4.82 μM) nanosheets. The relatively high performance and stability of GQDs is attributed to a sufficiently large surface-to-volume ratio, excellent biocompatibility, abundant hydrophilic edges, and a partially hydrophobic plane that favors GOx adsorption on the electrode surface and versatile architectures to ensure rapid charge transfer and electron/ion conduction (<10 ms). We also carried out similar studies with other enzymatic protein biomolecules on electrode surfaces prepared from GQD precursors for electrochemical comparison, thus opening up potential sensing applications in medicine as well as bio-nanotechnology.