Origin of the Giant Enhanced Raman Scattering by Sulfur Chains Encapsulated inside Single-Wall Carbon Nanotubes.

In this work, we explain the origin and the mechanism responsible for the strong enhancement of the Raman signal of sulfur chains encapsulated by single-wall carbon nanotubes by running resonance Raman measurements in a wide range of excitation energies for two nanotube samples with different diameter distributions. The Raman signal associated with the vibrational modes of the sulfur chain is observed when it is confined by small-diameter metallic nanotubes. Moreover, a strong enhancement of the Raman signal is observed for excitation energies corresponding to the formation of excited nanotube-chain-hybrid electronic states. Our hypothesis was further tested by high pressure Raman measurements and confirmed by density functional theory calculations of the electronic density of states of hybrid systems formed by sulfur chains encapsulated by different types of single-wall carbon nanotubes.

Chemically Functionalized Water-Soluble Single-Walled Carbon Nanotubes Obstruct Vesicular/Plasmalemmal Recycling in Astrocytes Down-Stream of Calcium Ions.

We used single-walled carbon nanotubes chemically functionalized with polyethylene glycol (SWCNT-PEG) to assess the effects of this nanomaterial on astrocytic endocytosis and exocytosis. We observed that the SWCNT-PEG do not affect the adenosine triphosphate (ATP)-evoked Ca2+ elevations in astrocytes but significantly reduce the Ca2+-dependent glutamate release. There was a significant decrease in the endocytic load of the recycling dye during constitutive and ATP-evoked recycling. Furthermore, SWCNT-PEG hampered ATP-evoked exocytotic release of the loaded recycling dye. Thus, by functionally obstructing evoked vesicular recycling, SWCNT-PEG reduced glutamate release from astrocytes via regulated exocytosis. These effects implicate SWCNT-PEG as a modulator of Ca2+-dependent exocytosis in astrocytes downstream of Ca2+, likely at the level of vesicle fusion with/pinching off the plasma membrane.

Confined Lithium-Sulfur Reactions in Narrow-Diameter Carbon Nanotubes Reveal Enhanced Electrochemical Reactivity.

We demonstrate an unusual electrochemical reaction of sulfur with lithium upon encapsulation in narrow-diameter (subnanometer) single-walled carbon nanotubes (SWNTs). Our study provides mechanistic insight on the synergistic effects of sulfur confinement and Li+ ion solvation properties that culminate in a new mechanism of these sub-nanoscale-enabled reactions (which cannot be solely attributed to the lithiation-delithiation of conventional sulfur). Two types of SWNTs with distinct diameters, produced by electric arc (EA-SWNTs, average diameter 1.55 nm) or high-pressure carbon monoxide (HiPco-SWNTs, average diameter 1.0 nm), are investigated with two comparable electrolyte systems based on tetraethylene glycol dimethyl ether (TEGDME) and 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5). Electrochemical analyses indicate that a conventional solution-phase Li-S reaction occurs in EA-SWNTs, which can be attributed to the smaller solvated [Li(TEGDME)]+ and [Li(15-crown-5)]+ ions within the EA-SWNT diameter. In stark contrast, the Li-S confined in narrower diameter HiPco-SWNTs exhibits unusual electrochemical behavior that can be attributed to a solid-state reaction enabled by the smaller HiPco-SWNT diameter compared to the size of solvated Li+ ions. Our results of the electrochemical analyses are corroborated and supported with various spectroscopic analyses including operando Raman, X-ray photoelectron spectroscopy, and first-principles calculations from density functional theory. Taken together, our findings demonstrate that the controlled solid-state lithiation-delithiation of sulfur and an enhanced electrochemical reactivity can be achieved by sub-nanoscale encapsulation and one-dimensional confinement in narrow-diameter SWNTs.

Effects of Chemically-Functionalized Single-Walled Carbon Nanotubes on the Morphology and Vitality of D54MG Human Glioblastoma Cells.

The unique properties of single-walled carbon nanotubes (SWCNTs) have made them interesting candidates for applications in biomedicine. There are diverse chemical groups that can be attached to SWCNTs in order for these tiny tubes to gain various functionalities, for example, water solubility. Due to the availability of these "functionalization" approaches, SWCNTs are seen as agents for a potential anti-cancer therapy. In this context, we tested different chemically-functionalized forms of SWCNTs to determine which modifications make them better combatants against glioblastoma (astrocytoma grade IV), the deadliest brain cancer. We investigated the effects that two types of water soluble SWCNTs, functionalized with polyethylene glycol (SWCNT-PEG) or tetrahydrofurfuryl-terminated polyethylene glycol (SWCNT-PEG-THFF), have on the morphology and vitality, that is, cell adhesion, proliferation and death rate, of the D54MG human glioblastoma cells in culture. We found that SWCNT-PEG-THFF solute, when added to culture media, makes D54MG cells less round (measured as a significant decrease, by ~23%, in the form factor). This morphological change was induced by the PEG-THFF functional group, but not the SWCNT backbone itself. We also found that SWCNT-PEG-THFF solute reduces the proliferation rate of D54MG cells while increasing the rate of cell death. The functional groups PEG and PEG-THFF, on the other hand, reduce the cell death rate of D54MG human glioma cells. These data indicate that the process of functionalization of SWCNTs for potential use as glioma therapeutics may affect their biological effects.

Visible-Blind UV Photodetector Based on Single-Walled Carbon Nanotube Thin Film/ZnO Vertical Heterostructures.

Ultraviolet (UV) photodetectors based on heterojunctions of conventional (Ge, Si, and GaAs) and wide bandgap semiconductors have been recently demonstrated, but achieving high UV sensitivity and visible-blind photodetection still remains a challenge. Here, we utilized a semitransparent film of p-type semiconducting single-walled carbon nanotubes (SC-SWNTs) with an energy gap of 0.68 ± 0.07 eV in combination with a molecular beam epitaxy grown n-ZnO layer to build a vertical p-SC-SWNT/n-ZnO heterojunction-based UV photodetector. The resulting device shows a current rectification ratio of 103, a current photoresponsivity up to 400 A/W in the UV spectral range from 370 to 230 nm, and a low dark current. The detector is practically visible-blind with the UV-to-visible photoresponsivity ratio of 105 due to extremely short photocarrier lifetimes in the one-dimensional SWNTs because of strong electron-phonon interactions leading to exciton formation. In this vertical configuration, UV radiation penetrates the top semitransparent SC-SWNT layer with low losses (10-20%) and excites photocarriers within the n-ZnO layer in close proximity to the p-SC-SWNT/n-ZnO interface, where electron-hole pairs are efficiently separated by a high built-in electric field associated with the heterojunction.

Sublimation-assisted graphene transfer technique based on small polyaromatic hydrocarbons.

Advances in the chemical vapor deposition (CVD) growth of graphene have made this material a very attractive candidate for a number of applications including transparent conductors, electronics, optoeletronics, biomedical devices and energy storage. The CVD method requires transfer of graphene on a desired substrate and this is most commonly accomplished with polymers. The removal of polymer carriers is achieved with organic solvents or thermal treatment which makes this approach inappropriate for application to plastic thin films such as polyethylene terephthalate substrates. An ultraclean graphene transfer method under mild conditions is highly desired. In this article, we report a naphthalene-assisted graphene transfer technique which provides a reliable route to residue-free transfer of graphene to both hard and flexible substrates. The quality of the transferred graphene was characterized with atomic force microscopy, scanning electron microscopy, and Raman spectroscopy. Field effect transistors, based on the naphthalene-transfered graphene, were fabricated and characterized. This work has the potential to broaden the applications of CVD graphene in fields where ultraclean graphene and mild graphene transfer conditions are required.

Fast Electrochromic Device Based on Single-Walled Carbon Nanotube Thin Films.

Optical properties of electrochromic materials can be controlled by the application of an electric field allowing recent development of new applications such as smart windows technology for indoor climate control and energy conservation. We report the fabrication of a single-walled nanotube (SWNT) thin film based electro-optical modulator controlled by ionic liquid polarization in which the active electrochromic layer is made of a film of semiconducting (SC-) SWNTs and the counter-electrode is composed of a film of metallic (MT-) SWNTs. Optimization of this electro-optical cell allows the operations with an optical modulation depth of 3.7 dB and a response time in the millisecond range, which is thousands of times faster than typical electrolyte-controlled devices. In addition, a dual electro-optical device was built utilizing electro-optically active SC-SWNT films for each electrode that allowed increasing modulation depth of 6.7 dB while preserving the speed of the response.

Comparative Reaction Diagrams for the SN(2) Reaction Formulated According to the Leffler Analysis and the Hammond Postulate.

The Hammond Postulate and the Leffler analysis have provided a cornerstone in the understanding of reaction processes in organic chemistry for over 60 years, yet quantitative applications of these methodologies over the range of reactions envisaged in the original works remain elusive. In the present paper, we analyze a series of SN2 reactions in three solvents that lead to endothermic and exothermic reaction processes, and we show that within the hybridization reaction coordinate the SN2 reaction is fully consistent with both treatments. We give new presentations of the reaction energies as a function of reaction progress, which allow the generation of unified reaction coordinate diagrams that show a linear relationship between the hybridization metric of reaction progress and the relative energies of the stationary points on the potential surface as a function of structure and solvent as originally envisaged by Leffler and Hammond.

Giant Raman Response to the Encapsulation of Sulfur in Narrow Diameter Single-Walled Carbon Nanotubes.

Encapsulation of sulfur in HiPCO-SWNTs leads to large changes in the Raman spectra with the appearance of new peaks at 319, 395, and 715 cm(-1) which originate from the sulfur species within the SWNTs, while the high frequency SWNT bands (ν > 1200 cm(-1)) are decreased in intensity. The encapsulated species also shifts the near-IR interband electronic transitions to lower energy by more than 10%. These effects seem to originate with the van der Waals interaction of the confined sulfur species with the walls of the SWNTs which are not expected to be significant in the case of the previously studied large diameter SWNTs. We suggest that sulfur in the small diameter SWNTs exists as a helical polymeric sulfur chain that enters the SWNT interior in the form of S2 ((3)Σ(g)(-)) molecules which undergo polymerization to linear diradicals.

Application of Hybrid Fillers for Improving the Through-Plane Heat Transport in Graphite Nanoplatelet-Based Thermal Interface Layers.

The in-plane alignment of graphite nanoplatelets (GNPs) in thin thermal interface material (TIM) layers suppresses the though-plane heat transport thus limiting the performance of GNPs in the geometry normally required for thermal management applications. Here we report a disruption of the GNP in-plane alignment by addition of spherical microparticles. The degree of GNP alignment was monitored by measurement of the anisotropy of electrical conductivity which is extremely sensitive to the orientation of high aspect ratio filler particles. Scanning Electron Microscopy images of TIM layer cross-sections confirmed the suppression of the in-plane alignment. The hybrid filler formulations reported herein resulted in a synergistic enhancement of the through-plane thermal conductivity of GNP/Al2O3 and GNP/Al filled TIM layers confirming that the control of GNP alignment is an important parameter in the development of highly efficient GNP and graphene-based TIMs.

Networks of semiconducting SWNTs: contribution of midgap electronic states to the electrical transport.

Single-walled carbon nanotube (SWNT) thin films provide a unique platform for the development of electronic and photonic devices because they combine the advantages of the outstanding physical properties of individual SWNTs with the capabilities of large area thin film manufacturing and patterning technologies. Flexible SWNT thin film based field-effect transistors, sensors, detectors, photovoltaic cells, and light emitting diodes have been already demonstrated, and SWNT thin film transparent, conductive coatings for large area displays and smart windows are under development. While chirally pure SWNTs are not yet commercially available, the marketing of semiconducting (SC) and metallic (MT) SWNTs has facilitated progress toward applications by making available materials of consistent electronic structure. Nevertheless the electrical transport properties of networks of separated SWNTs are inferior to those of individual SWNTs. In particular, for semiconducting SWNTs, which are the subject of this Account, the electrical transport drastically differs from the behavior of traditional semiconductors: for example, the bandgap of germanium (E = 0.66 eV) roughly matches that of individual SC-SWNTs of diameter 1.5 nm, but in the range 300-100 K, the intrinsic carrier concentration in Ge decreases by more than 10 orders of magnitude while the conductivity of a typical SC-SWNT network decreases by less than a factor of 4. Clearly this weak modulation of the conductivity hinders the application of SC-SWNT films as field effect transistors and photodetectors, and it is the purpose of this Account to analyze the mechanism of the electrical transport leading to the unusually weak temperature dependence of the electrical conductivity of such networks. Extrinsic factors such as the contribution of residual amounts of MT-SWNTs arising from incomplete separation and doping of SWNTs are evaluated. However, the observed temperature dependence of the conductivity indicates the presence of midgap electronic states in the semiconducting SWNTs, which provide a source of low-energy excitations, which can contribute to hopping conductance along the nanotubes following fluctuation induced tunneling across the internanotube junctions, which together dominate the low temperature transport and limit the resistivity of the films. At high temperatures, the intrinsic carriers thermally activated across the bandgap as in a traditional semiconductor became available for band transport. The midgap states pin the Fermi level to the middle of the bandgap, and their origin is ascribed to defects in the SWNT walls. The presence of such midgap states has been reported in connection with scanning tunneling spectroscopy experiments, Coulomb blockade observations in low temperature electrical measurements, selective electrochemical deposition imaging, tip-enhanced Raman spectroscopy, high resolution photocurrent spectroscopy, and the modeling of the electronic density of states associated with various defects. Midgap states are present in conventional semiconductors, but what is unusual in the present context is the extent of their contribution to the electrical transport in networks of semiconducting SWNTs. In this Account, we sharpen the focus on the midgap states in SC-SWNTs, their effect on the electronic properties of SC-SWNT networks, and the importance of these effects on efforts to develop electronic and photonic applications of SC-SWNTs.

Band Structure Engineering by Substitutional Doping in Solid-State Solutions of [5-Me-PLY(O,O)]2B(1-x)Be(x) Radical Crystals.

We report the substitutional doping of solid-state spiro-bis(5-methyl-1,9-oxido-phenalenyl)boron radical ([2]2B) by co-crystallization of this radical with the corresponding spiro-bis(5-methyl-1,9-oxido-phenalenyl)beryllium compound ([2]2Be). The pure compounds crystallize in different space groups ([2]2B, P1̅, Z = 2; [2]2Be, P21/c, Z = 4) with distinct packing arrangements, yet we are able to isolate crystals of composition [2]2B(1-x)Be(x), where x = 0-0.59. The phase transition from the P1̅ to the P21/c space group occurs at x = 0.1, but the conductivities of the solid solutions are enhanced and the activation energies reduced for values of x = 0-0.25. The molecular packing is driven by the relative concentration of the spin-bearing ([2]2B) and spin-free ([2]2Be) molecules in the crystals, and the extended Hückel theory band structures show that the progressive incorporation of spin-free [2]2Be in the lattice of the [2]2B radical (overall bandwidth, W = 1.4 eV, in the pure compound) leads to very strong narrowing of the bandwidth, which reaches a minimum at [2]2Be (W = 0.3 eV). The results provide a graphic picture of the structural transformations undergone by the lattice, and at certain compositions we are able to identify distinct structures for the [2]2B and [2]2Be molecules in a single crystalline phase.

Ionic Liquid Gating of Suspended MoS2 Field Effect Transistor Devices.

We demonstrate ionic liquid (IL) gating of suspended few-layer MoS2 transistors, where ions can accumulate on both exposed surfaces. Upon application of IL, all free-standing samples consistently display more significant improvement in conductance than substrate-supported devices. The measured IL gate coupling efficiency is up to 4.6 × 10(13) cm(-2) V(-1). Electrical transport data reveal contact-dominated electrical transport properties and the Schottky emission as the underlying mechanism. By modulating IL gate voltage, the suspended MoS2 devices display metal-insulator transition. Our results demonstrate that more efficient charge induction can be achieved in suspended two-dimensional (2D) materials, which with further optimization, may enable extremely high charge density and novel phase transition.

Chemically functionalized single-walled carbon nanotubes enhance the glutamate uptake characteristics of mouse cortical astrocytes.

Using a radioactive glutamate uptake assay and immunolabeling, we report that single-walled carbon nanotubes, chemically functionalized with polyethylene glycol (SWCNT-PEG), delivered as a colloidal solute, cause an increase in the uptake of extracellular glutamate by astrocytes and an increase in the immunoreactivity of the glutamate transporter GLAST on their cell surface, which is likely a consequence of an increase in the immunoreactivity of glial fibrillary acidic protein. Additional corollary is that astrocytes exposed to SWCNT-PEG became larger and stellate, morphological characteristics of maturation and heightened activity of these glial cells. These results imply that SWCNT-PEG could potentially be used as a viable candidate for neural prosthesis applications, perhaps to alleviate the death toll of neurons due to glutamate excitotoxicity, a pathological process observed in brain and spinal cord injuries.

Effect of Lanthanide Metal Complexation on the Properties and Electronic Structure of Single-Walled Carbon Nanotube Films.

We spectroscopically analyze the effect of e-beam deposition of lanthanide metals on the electronic structure and conductivities of films of semiconducting (SC) single-walled carbon nanotubes (SWNTs) in high vacuum. We employ near-infrared and Raman spectroscopy to interpret the changes in the electronic structure of SWNTs on exposure to small amounts of the lanthanides (Ln = Sm, Eu, Gd, Dy, Ho, Yb), based on the behavior of the reference metals (M = Li, Cr) which are taken to exemplify ionic and covalent bonding, respectively. The analysis shows that while the lanthanides are more electropositive than the transition metals, in most cases they exhibit similar conductivity behavior which we interpret in terms of the formation of covalent bis-hexahapto bonds [(η(6)-SWNT)M(η(6)-SWNT), where M = La, Nd, Gd, Dy, Ho]. However, only M = Eu, Sm, Yb show the continually increasing conductivity characteristic of Li, and this supports our contention that these metals provide the first examples of mixed covalent-ionic bis-hexahapto bonds [(η(6)-SWNT)M(η(6)-SWNT), where M = Sm, Eu, Yb].

Enhanced electrical conductivity in a substitutionally doped spiro-bis(phenalenyl)boron radical molecular solid.

We report the crystallization of a subsitutionally doped organic conductor based on a host lattice composed of spiro-bis(phenalenyl)boron radicals. Co-crystallization of solutions of spiro-bis(9-oxidophenalenone)boron radical [PLY(O,O)]2B mixed with selected amounts of spiro-bis(9-oxidophenalenone)beryllium [PLY(O,O)]2Be leads to the formation of a series of solid-state solutions of composition [PLY(O,O)]2B(1-x)Be(x). The dopant molecules [PLY(O,O)]2Be serve to introduce holes into the lattice of spins provided by the [PLY(O,O)]2B radicals and lead to a systematic increase in the conductivity while decreasing the activation energy of the conduction process and leaving the solid-state structure relatively unperturbed. While the energies of the hole sites are expected to be high, the results are consistent with the interpretation of the electronic structure of [PLY(O,O)]2B in terms of the resonating valence bond model.

Effect of atomic interconnects on percolation in single-walled carbon nanotube thin film networks.

The formation of covalent bonds to single-walled carbon nanotube (SWNT) or graphene surfaces usually leads to a decrease in the electrical conductivity and mobility as a result of the structural rehybridization of the functionalized carbon atoms from sp(2) to sp(3). In the present study, we explore the effect of metal deposition on semiconducting (SC-) and metallic (MT-) SWNT thin films in the vicinity of the percolation threshold and we are able to clearly delineate the effects of weak physisorption, ionic chemisorption with charge transfer, and covalent hexahapto (η(6)) chemisorption on these percolating networks. The results support the idea that for those metals capable of forming bis-hexahapto-bonds, the generation of covalent (η(6)-SWNT)M(η(6)-SWNT) interconnects provides a conducting pathway in the SWNT films and establishes the transition metal bis-hexahapto organometallic bond as an electronically conjugating linkage between graphene surfaces.

Changes in the morphology and proliferation of astrocytes induced by two modalities of chemically functionalized single-walled carbon nanotubes are differentially mediated by glial fibrillary acidic protein.

Alterations in glial fibrillary acidic protein (GFAP) levels accompany the changes in the morphology and proliferation of astrocytes induced by colloidal solutes and films of carbon nanotubes (CNTs). To determine if GFAP is required for the effects of CNTs on astrocytes, we used astrocytes isolated from GFAP null mice. We find that selected astrocytic changes induced by CNTs are mediated by GFAP, i.e., perimeter, shape, and cell death for solutes, and proliferation for films.

Hexahapto-lanthanide interconnects between the conjugated surfaces of single-walled carbon nanotubes.

We report the response of the electrical conductivity of semiconducting single-walled carbon nanotube (SWNT) thin films on exposure to metal vapors of the early lanthanides under high vacuum conditions. We attribute the strongly enhanced conductivities observed on deposition of samarium and europium to charge transfer from the metals to the SWNT backbone, thereby leading to the first examples of mixed covalent-ionic bis-hexahapto bonds [(η(6)-SWNT)M(η(6)-SWNT), where M = Sm, Eu].

Diels-Alder reactions of graphene: computational predictions of products and sites of reaction.

The cycloaddition reactions and noncovalent π interactions of 2,3-dimethoxybutadiene (DMBD), 9-methylanthracene (MeA), tetracyanoethylene (TCNE), and maleic anhydride (MA) with graphene models have been investigated using density functional theory (DFT) calculations. Reaction enthalpies have been obtained to assess the reactivity and selectivity of covalent and noncovalent functionalization. Results indicate that graphene edges may be functionalized by the four reagents through cycloaddition reactions, while the interior regions cannot react. Noncovalent complexation is much more favorable than cycloaddition reactions on interior bonds of graphene. The relative reactivities of different sites in graphene are related to loss of aromaticity and can be predicted using Hückel molecular orbital (HMO) localization energy calculations.