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We report the experimental realization of η6-complexes of group 6 transition metals with a single layer graphene using photo-activated reactions with organometallic compounds. The reaction progress was followed by in-situ measurements of the graphene conductivity. We observed that the chromium reagents exert the strongest effect on the electronic properties of graphene, leading to (η6-graphene)CrL [L = C6H6, (CO)3] complexes with enhanced conductivity. Thus, in the case of covalent functionalization of graphene with Cr(CO)6, the conductivity increased by a factor of 4, while the (η6- C6H6)Cr(CO)3 reagent doubled the conductivity producing the least enhancement. This mode of covalent bonding preserves the conjugation and the planarity of the graphene structure and offers a promising route for the preparation of a new class of graphitic materials functionalized with transition metals, which may find applications in optoelectronics, spintronics and magnetic nanodevices.

CVD graphene has attracted a great deal of interest from both academia and industry. The strong motivation to commercialize high quality CVD graphene films and related devices has been restricted by the lack of a cheap, efficient, clean and reliable graphene transfer process. In this article, we report a novel graphene transfer technique which provides a route to high-throughput, reliable and economical transfer of graphene without introducing large cracks and residue contamination from polymers, such as PMMA or magnetic impurities. The transferred graphene was thoroughly characterized with Raman spectroscopy, Atomic Force Microscopy, and X-ray photoelectron spectroscopy. Fabricated large area graphene-based field effect transistors exhibited high mobilities, which were about 2 times higher than those for devices prepared with graphene transferred by the conventional wet transfer method. This new graphene transfer technique has the potential to expedite the large scale industrial utilization of CVD graphene in electronics, spintronics, catalysis and energy storage.

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 &ldquo, functionalization&rdquo, 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.

We report the synthesis of vulcanized polyisoprene (SPIP) nanowires and an investigation of the electrochemical lithiation mechanism of the covalently bonded sulfur bridges in SPIP. Electrochemical analysis demonstrates that the sulfur chains in SPIP have distinct electrochemical signatures from those that are characteristic of bulk elemental sulfur. The cyclic voltammetry and galvanostatic cycling data show a distinct multistep charge-transfer process and solid-state lithium–sulfur reaction behavior, and it is clear that this new material provides a promising basis for the development of cathodes for rechargeable batteries. Chemical changes due to the lithiation process are studied using Raman and X-ray photoelectron spectroscopy, on the basis of which new lithiation mechanisms of covalently bonded sulfur are proposed.

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.

The formation of bis-hexahapto bonds between graphitic surfaces can electronically interconnect the surfaces of carbon materials containing the polybenzenoid ring system and increase the conductivity without introducing a strong perturbation to the in-plane electronic structure. In this paper, we report the use of organometallic chemistry to interconnect the surfaces of small scale graphene nanoplatelets by using a variety of metals and photochemically activated organometallic reagents.

We consider the covalent chemistry of the carbon allotropes with an emphasis on the newest member—graphene. We focus on the effect of such chemistry on the geometric and electronic structure of the functionalized materials and the way in which the conjugation is modified by such processes. We conclude that there are two limiting cases: (a) Conventional addition chemistry leading to the formation of σ-bonds to the graphitic surface in which there is full rehybridization of the derivatized carbon atoms from sp 2 to sp 3 ; thus these carbon atoms are effectively removed from conjugation and from the electronic band structure (referred to as destructive rehybridization). (b) Covalent chemisorption with formation of an organometallic hexahapto-metal bond that largely preserves the graphitic band structure (constructive rehybridization) and accompanies the formation of bis-hexahapto-metal bonds such as those in (η 6 -SWNT)Cr(η 6 -SWNT) which serve to interconnect adjacent graphitic surfaces and significantly reduces the internanotube junction resistance in SWNT networks. The formation of η 2 di-hapto bonds represent an intermediate case of covalent chemistry and is known to be important in carbon nanotubes and particularly the fullerenes but this situation has been treated in detail in previous publications.

The solution phase reactions of single-walled carbon nanotubes (SWNTs) with Cr(CO)6 and benzene-Cr(CO)3 can lead to the formation of small chromium clusters. The cluster size can be varied from less than 1 nm to about 4 nm by increasing the reaction time. TEM images suggest that the clusters are deposited predominantly on the exterior walls of the nanotubes. TGA analysis was used to obtain the Cr content and carbon to chromium ratio in the Cr-complexed SWNTs. It is suggested that the carbon nanotube benzenoid structure templates the condensation of chromium atoms and facilitates the loss of carbon monoxide leading to well defined metal clusters.

The electrical conductivity of single-walled carbon nanotube (SWNT) networks is strongly enhanced by the high vacuum e-beam deposition of transition metals. In the present communication we demonstrate that it is possible to accomplish the same chemical functionalization reactions at room temperature beginning with simple organometallic precursors. We show that the photochemically induced reactions of solutions of Cr(CO)6, Cr(η6-benzene)(CO)3, and Cr(η6-benzene)2 with thin films of semiconducting, metallic and non-separated SWNT films all lead to strongly enhanced conductivities which produce consistent results for each SWNT type among the three organometallic reagents. We conclude that all three of these reactions lead to the generation of covalent (η6-SWNT)Cr(η6-SWNT) interconnects which provide conducting pathways in the SWNT films and our results broaden the applicability of the transition metal bis-hexahapto-bond as an electronically conjugating linkage between graphene surfaces.

Polymorphism is an important issue for the application of organic semiconductors in field-effect transistors due to the dependence of device performance on crystal packing. Recently an organic semiconductor, 6,13-dichloropentacene (DCP), was shown to give a field-effect mobility as high as 9 cm2 V−1 s−1 when crystallized in the form of microribbons obtained by physical vapor transport (PVT), in contrast with the much lower mobilities found in crystals grown from solution. In the present manuscript we show that the crystals grown in the vapor phase are a polymorph of the structure reported for the crystals grown from solution. Both polymorphs show a π-stacking motif but differ in the interplanar distances and the displacement of the molecules along the long axes of the molecules. The DCP PVT structure compares favorably to that of rubrene, but DCP shows a much lower mobility. Band structure calculations show that the rubrene crystal exhibits greater band dispersion than DCP even though the long-axis displacement in rubrene is much greater. We conclude that the transport properties cannot be inferred simply by the magnitude of the intrastack long-axis displacement, but requires a consideration of the relative location of the HOMO/LUMO coefficients of the neighboring molecules in the stack.

With the advent of many different forms of graphene (in addition to the long standing interest in fullerenes and carbon nanotubes), the characterization of carbon materials and their degree of conjugation is a particularly important topic in carbon science. We report the application of absorption spectroscopy and conductivity measurements to graphene derivatives and related carbon materials. Reduced graphene oxide (RGO) has been widely studied as a promising material for graphene applications because of its processability, and the same considerations apply to graphene functionalized with octadecylamine (ODA). This study utilizes a direct chemical modification of GO with ODA in the presence of dicyclohexylcarbodiimide to partially regenerate the graphene π-conjugation while producing a material (ODA-G) with excellent solubility in organic solvents. We show that the ODA-G exhibits optical absorptions, which are much stronger than those of GO, and comparable to liquid phase exfoliated graphene and reduced graphene oxide; the optical analysis is unified by the development of an analytical relationship between solid state absorption coefficients and solution state extinction coefficients, which allows the direct comparison of the electronic absorption spectroscopy of films and solutions of carbon materials. We further benchmark the regeneration of the graphenic structure in ODA-G with electrical conductivity measurements.

Porphyrins due to their unique and interesting physicochemical properties have been widely investigated as functional materials for chemical sensor fabrication. However, their poor conductivity is a major limitation toward the realization of porphyrin-based field-effect transistor/chemiresistor sensor. The issue of conductivity can be overcome by exploiting the excellent electrical property of single-walled carbon nanotubes (SWNTs) to make a SWNTs-based hybrid device in which SWNTs would act as a transducer and porphyrin as a sensory layer. The present attempt was to fabricate a SWNTs–poly(tetraphenylporphyrin) hybrid through electrochemical route and to evaluate its potential as a low-power chemiresistor sensor for sensing acetone vapor as a model for volatile organic compounds. Functionalization of SWNTs with porphyrin polymer by the electrochemical method resulted in a fuller coverage of SWNTs surface compared to a partial coverage by adsorption and thereby higher sensitivity. SWNTs were coated with po...

We report the formation of chromium clusters on the outer walls of single-walled carbon nanotubes (SWNTs). The clusters were obtained by reacting purified SWNTs with chromium hexacarbonyl in dibutyl ether at 100 degrees C. The functionalized SWNTs were characterized by thermogravimetic analysis, XPS, and high-resolution TEM. The curvature of the SWNTs and the high mobility of the chromium moieties on graphitic surfaces allow the growth of the metal clusters and we propose a mechanism for their formation.

In this Perspective, we present an overview of recent fundamental studies on the nature of the interaction between individual metal atoms and metal clusters and the conjugated surfaces of graphene and carbon nanotube with a particular focus on the electronic structure and chemical bonding at the metal–graphene interface. We discuss the relevance of organometallic complexes of graphitic materials to the development of a fundamental understanding of these interactions and their application in atomtronics as atomic interconnects, high mobility organometallic transistor devices, high-frequency electronic devices, organometallic catalysis (hydrogen fuel generation by photocatalytic water splitting, fuel cells, hydrogenation), spintronics, memory devices, and the next generation energy devices. We touch on chemical vapor deposition (CVD) graphene grown on metals, the reactivity of its surface, and its use as a template for asymmetric graphene functionalization chemistry (ultrathin Janus discs). We highlight som...

We report the synthesis and properties of a series of spiro-bis(3,4,6,7-tetrachalcogenide-substituted-phenalenyl)boron salts and two of the corresponding tetrathioalkyl-substituted spiro-bis(phenalenyl)boron radicals [tetrathiomethyl (10) and tetrathioethyl (11)] in which all of the active positions of the phenalenyl (PLY) nucleus are functionalized. In the solid state, radicals 10 and 11 exist as a weak π-dimers due to the steric congestion of the thioalkyl groups in the superimposed PLY units. As a result, the spins are localized in the isolated (nonsuperimposed) PLY rings, and the structure, magnetic susceptibility measurements, and band structure calculations confirm that these PLY units are unable to undergo strong intermolecular interaction as a result of the orientation of the thioalkyl groups.

A simple two-terminal device containing a semiconducting single-walled-nanotube thin-film is reported that generates an extremely high density of holes when it comes in contact with an ionic liquid, inducing strong electromodulation of the interband and excitonic transitions as a result of the position-dependent shift of the single-walled-nanotube Fermi level.

In this Account, we discuss the chemistry of graphitic materials with particular reference to three reactions studied by our research group: (1) aryl radical addition, from diazonium precursors, (2) Diels-Alder pericyclic reactions, and (3) organometallic complexation with transition metals. We provide a unified treatment of these reactions in terms of the degenerate valence and conduction bands of graphene at the Dirac point and the relationship of their orbital coefficients to the HOMO and LUMO of benzene and to the Clar structures of graphene. In the case of the aryl radical addition and the Diels-Alder reactions, there is full rehybridization of the derivatized carbon atoms in graphene from sp(2) to sp(3), which removes these carbon atoms from conjugation and from the electronic band structure of graphene (referred to as destructive rehybridization). The radical addition process requires an electron transfer step followed by the formation of a σ-bond and the creation of a π-radical in the graphene lattice, and thus, there is the potential for unequal degrees of functionalization in the A and B sublattices and the possibility of ferromagnetism and superparamagnetism in the reaction products. With regard to metal functionalization, we distinguish four limiting cases: (a) weak physisorption, (b) ionic chemisorption, in which there is charge transfer to the graphitic structure and preservation of the conjugation and band structure, (c) covalent chemisorption, in which there is strong rehybridization of the graphitic band structure, and (d) covalent chemisorption with formation of an organometallic hexahapto-metal bond that largely preserves the graphitic band structure (constructive rehybridization). The constructive rehybridization that accompanies the formation of bis-hexahapto-metal bonds, such as those in (η(6)-SWNT)Cr(η(6)-SWNT), interconnects adjacent graphitic surfaces and significantly reduces the internanotube junction resistance in single-walled carbon nanotube (SWNT) networks. The conversion of sp(2) hybridized carbon atoms to sp(3) can introduce a band gap into graphene, influence the electronic scattering, and create dielectric regions in a graphene wafer. However, the organometallic hexahapto (η(6)) functionalization of the two-dimensional (2D) graphene π-surface with transition metals provides a new way to modify graphitic structures that does not saturate the functionalized carbon atoms and, by preserving their structural integrity, maintains the delocalization in these extended periodic π-electron systems and offers the possibility of three-dimensional (3D) interconnections between adjacent graphene sheets. These structures may find applications in interconnects, 3D-electronics, organometallic catalysis, atomic spintronics and in the fabrication of new electronic materials.

We report the preparation of organometallic side-wall complexes of single-walled carbon nanotubes (SWNTs) under conditions, which allow the study of both mono- and bis-hexahapto SWNT coordination compounds [(η6-SWNT)Cr(CO)3, (η6-SWNT)Cr(η6-C6H6), (η6-SWNT)2Cr]. The results are interpreted in terms of exohedral and endohedral binding of chromium to the SWNT sidewalls and ligand competition reactions suggest that endohedral binding provides a very stable and kinetically inert mode of organometallic bonding. We demonstrate that the electrical conductivity of SWNT thin films are significantly enhanced by side-wall bonding to Group 6 transition metals (M = Cr, Mo, and W), which serve to reduce the inter-carbon nanotube junction electrical resistance by the formation of SWNT interconnects [(η6-SWNT)2M].

A high energy density supercapacitor device is reported that utilizes hybrid carbon electrodes and the ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) as an electrolyte. The hybrid electrodes are prepared from reduced graphite oxide (rGO) and purified single-walled carbon nanotubes (SWCNTs). A simple casting technique gives the hybrid structure with optimum porosity and functionality that provides high energy and power densities. The combination of SWCNTs and rGO in a weight ratio of 1:1 is found to afford a specific capacitance of 222 F g−1 and an energy density of 94 Wh kg−1 at room temperature.

We report the preparation, crystallization, and solid state characterization of a new benzannulated phenalenyl radical; a distinctive feature of this molecular solid is the absence of any well defined conducting pathway(s). In the solid state, the radicals exist as π-dimer and the requisite C···C contacts between dimers are all larger than the sum of the van der Waals distances. The magnetic susceptibility measurement indicates that, in the solid state, the radical remains paramagnetic and the fraction of Curie spins is 0.55 per molecule. Pressed pellet conductivity measurements indicate a value of σRT = 0.5 × 10−6 S/cm. The conductivity value is comparable with those of similarly packed phenalenyl based neutral radicals. Copyright © 2012 John Wiley & Sons, Ltd.

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 (3Σg–) molecules which undergo polymerization to linear diradicals. Fil: Li, Guanghui. University of California; Estados Unidos Fil: Fu, Chengyin. University of California; Estados Unidos Fil: Oviedo, María Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina. University of California; Estados Unidos Fil: Chen, Mingguang. University of California; Estados Unidos Fil: Tian, Xiaojuan. University of California; Estados Unidos Fil: Bekyarova, Elena. University of California; Estados Unidos Fil: Itkis, Mikhail. University of California; Estados Unidos Fil: Wong, Bryan. University of California; Estados Unidos Fil: Guo, Juchen. University of California; Estados Unidos Fil: Haddon, Robert. University of California; Estados Unidos

Single-walled carbon nanotubes (SWCNTs) were purified by treatment with concentrated nitric acid and then subjected to Soxhlet extraction with tetrahydrofuran (THF). The THF extract of low molecular weight carboxylated carbons was derivatized with (trimethylsilyl)diazomethane and the resulting methylated material was separated with column chromatography and thin layer chromatography and several fractions were identified by GC–MS and 1H NMR. The fractions were shown to include small benzopolycarboxylic acids and organic nitro compounds.

Chemical functionalization is a promising route to band gap engineering of graphene. We chemically grafted nitrophenyl groups onto exfoliated single-layer graphene sheets in the form of substrate-supported or free-standing films. Our transport measurements demonstrate that nonsuspended functionalized graphene behaves as a granular metal, with variable range hopping transport and a mobility gap ∼0.1 eV at low temperature. For suspended graphene that allows functionalization on both surfaces, we demonstrate tuning of its electronic properties from a granular metal to a semiconductor in which transport occurs via thermal activation over a transport gap ∼80 meV from 4 to 300 K. This noninvasive and scalable functionalization technique paves the way for CMOS-compatible band gap engineering of graphene electronic devices.

We report the synthesis, crystallization, and solid-state characterization of the 3,7-ethoxy-substituted spirobiphenalenyl-boron neutral radical 22. The radical is distinguished by its low disproportionation energy and one-dimensional structure. We show that our strategy of substitution of OEt group at the active positions of the phenalenyl units changes the crystal packing from its previously known OMe analogue and the solid-state properties are dictated by the partial π-stack structure and the oxygen atoms at the 3,7-positions and can be best rationalized in terms of the resonating valence bond model. Magnetic susceptibility measurements show that in the solid state the radical remains paramagnetic but there is significant spin-spin interaction between the molecules. Band structure calculations reflect efficient overlap between the molecules along the π stack and show evidence of interactions between the spin-bearing oxygen atoms. The room temperature electrical conductivity (σ(RT)=2.0×10(-2) S cm(-1)) of 22 is higher than that observed in previously known one-dimensional phenalenyl radicals.

The carbon nanotube−polyethylene glycol (PEG) graft copolymer was synthesized by covalent functionalization of electric arc single-walled carbon nanotubes (SWNTs) with the monofunctional, tetrahydrofurfuryl-terminated polyethylene glycol PEG-THFF (MW∼200), to give a material composed of 80 wt % SWNTs. We show that the sequential processing of the resulting material by ultrasonication and high-shear mixing provides a means to disperse the SWNT-PEG-THFF macromolecules on two different length scales and leads to highly viscous solutions; at a concentration of 10 mg/mL the kinematic viscosity (ν) of an aqueous SWNT-PEG-THFF dispersion reaches a value of ν > 1000 cSt (for water ν ∼ 1 cSt). Analysis of this procedure by means of viscosity measurements and atomic force microscopy (AFM), shows that ultrasonication is effective in disrupting the SWNT bundles, while the high shear mixing disperses the individual SWNTs. The kinematic viscosity of aqueous dispersions of SWNT-PEG-THFF was measured as a function of nan...

We report the synthesis, crystallization, electrochemistry, X-ray structure and electron density distribution of a methoxy-substituted-tris-phenalenyl based neutral radical (18); the cyclic voltammogram of the compound shows that the strategy of oxygen substitution at 3,7-positions and the utilization of tris-phenalenyls within the silicon complex reduce the electrochemical disproportionation potentials. The crystal structure shows that the radical exists as a 1D π-chain of partially superimposed phenalenyl rings with intermolecular carbon⋯carbon contacts that fall within van der Waals atomic separation. A bond length–bond order regression analysis of the experimental structures shows that the electron density is distributed over two out of the three phenalenyl units.

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. Fil: Fu, Chengyin. University Of California Riverside; Estados Unidos Fil: Oviedo, María Belén. University Of California Riverside; Estados Unidos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina Fil: Zhu, Yihan. Zhejiang University Of Technology; China Fil: von Wald Cresce, Arthur. U. S. Army Research Laboratory; Estados Unidos Fil: Xu, Kang. U. S. Army Research Laboratory; Estados Unidos Fil: Li, Guanghui. University Of California Riverside; Estados Unidos Fil: Itkis, Mikhail E.. University Of California Riverside; Estados Unidos Fil: Haddon, Robert C.. University Of California Riverside; Estados Unidos Fil: Chi, Miaofang. Oak Ridge National Laboratory; Estados Unidos Fil: Han, Yu. King Abdullah University Of Science And Technology; Arabia Saudita Fil: Wong, Bryan M.. University Of California Riverside; Estados Unidos Fil: Guo, Juchen. University Of California Riverside; Estados Unidos

Treatment of carbon nanotubes by oxidizing acids is extensively used to dissolve metal residues from raw nanotube samples. The effect of acid treatment on the tubes themselves is twofold: it introduces uniform carboxylic sidegroups on the tube ends and defects, and it increases the overall charge concentration on the nanotube walls, thereby p-doping the material. Wide-range optical spectroscopy is an ideal tool to characterize both effects from one type of measurement: vibrational signatures indicate the presence of the sidegroups, the increase in far-infrared absorption signals the presence of free carriers, and the disappearance of interband transitions is the consequence of the depletion of Van Hove singularities when introducing holes. We have subjected carbon nanotube samples to two kinds of acid treatment: mild (in HNO(3) vapor at room temperature) and aggressive (high-temperature reflux). We found that on mild treatment, electronic doping occurs without defect oxidation to carboxylic groups, while the aggressive procedure leads to both doping and defect oxidation. Our spectroscopic data unambiguously prove that the changes in electrical conductivity on acid doping are intrinsic, and not just a result of improving the contact between nanotubes. Refereed/Peer-reviewed

We report the preparation of the first benzannulated phenalenyl neutral radical conductor (18), and we show that the compound displays unprecedented solid state behavior: the structure is dominated by two sets of intermolecular interactions: (1) a pi-chain structure with superimposed pi-overlap of the benzannulated phenalenyls along [0 0 1], and (2) an interchain overlap involving a pair of carbon atoms (C4) along [0 1 0]. The pi-chain-type stacking motif is reminiscent of previously reported phenalenyl radicals and the room temperature structure (space group P2/c) together with the conductivity of sigma(RT) = 0.03 S/cm and the Pauli-like magnetic susceptibility are best described by the resonating valence bond (RVB) model. The interchain interaction is unstable with respect to the formation of a sigma-charge density wave (sigma-CDW) involving pairs of C4 carbon atoms between adjacent radicals and this phase is characterized by the P2(1)/c space group which involves a doubling of the unit cell along the [0 1 0] direction. The RVB and CDW phases compete for structural occupancy throughout the whole temperature range (15-293 K) with the RVB phase predominating at 15 and 293 K and the sigma-CDW phase achieving a maximum structural occupancy of about 60% at 150 K where it produces clearly discernible effects on the magnetism and conductivity.

We report a simple method to prepare individual electric arc-produced single-walled carbon nanotubes (SWNTs) in aqueous solution on a large scale through three steps of processing: refluxing in concentrated HNO(3), low speed centrifugation, and high speed centrifugation. The bulk production (10 g of starting SWNTs) results in a concentration of 0.2 mg/mL individual SWNTs stably dispersed in DI-H(2)O without any external protection. The atomic force microscopy images show that the aqueous dispersion contained approximately 80% individual SWNTs with lengths ranging from 500 nm to 1 micrometer. It is found that the stable individual SWNT dispersion has an absolute zeta potential value of approximately 72 mV with a concentration of 0.05 mg/mL at pH 5. We believe that it is this high zeta potential resulting from an electrical double layer which produces the repulsion to overcome the van der Waals attraction thereby keeping the SWNTs individually dispersed. The free-standing film prepared from the individual SWNT dispersion exhibits a 4-probe electrical conductivity of approximately 2000 S/cm and a transmittance of 60% at 550 nm.

We report the synthesis, crystallization, and solid-state characterization of spiro-bis(3,7-dimethoxy-1,9-dioxophenalenyl) boron neutral radical 17; the radical is distinguished by its oxygen functionalization and we show that our strategy of oxygen substitution at the active positions of the phenalenyl units reduces the electrochemical disproportionation potential. The crystal structure shows that the radical exists as a π-dimer at room temperature and a one-dimensional (1D) π-chain of alternating superimposed and partially superimposed phenalenyl units at 100 K. Magnetic susceptibility measurements show that in the solid state, the radical remains paramagnetic but there is significant spin−spin interaction between the molecules along the π-chains. Band structure calculations delineate the response of the electronic structure to the structural changes observed in the crystal lattice, although magnetic and conductivity measurements do not show any sign of a phase transition. The room temperature electrica...

We report the use of chemically-functionalized water soluble single-walled carbon nanotube (SWNT) graft copolymers to inhibit endocytosis. The graft copolymers were prepared by the functionalization of SWNTs with poly-ethylene glycol. When added to the culturing medium, these functionalized water soluble SWNTs were able to increase the length of various neuronal processes, neurites, as previously reported. Here we have determined that SWNTs are able to block stimulated membrane endocytosis in neurons, which could then explain the previously noted extended neurite length.

We use the suspended single-walled carbon nanotube (SWNT) thin film technology to assemble the first prototype of an integrated optoelectronic SWNT device, a SWNT optocoupler in which a SWNT emitter and a SWNT detector couple two electrical circuits by the transmission of a signal through the optical channel. Our experiments show that the integrated SWNT emitter/SWNT detector is an ideal couple in which the broadband wavelength character of the emission matches the broadband detection capabilities.

A thin film of single-wall carbon nanotubes (SWNTs) and SWNT−multiwall carbon nanotube (MWNT) hybrids loaded with Pt have been evaluated as the cathode catalyst layer in proton exchange membrane fuel cells. The optimum Pt loading and thickness for SWNT films is found to be in the range of 20−100 µg Pt/cm2 and 0.3−1.4 µm, respectively. In this optimum range, Pt-SWNT thin films show excellent proton conductivity and are able to reach peak performance without additional nafion in the catalyst layer. Cathode-specific mass activity of Pt on a SWNT support is found to decrease as the Pt loading and thickness increase due to mass transfer limitations. Addition of Pt-MWNTs to Pt-SWNT thin films is found to increase the mass transport characteristics and cathode-specific mass activity. A SWNT−MWNT hybrid support shows three times higher mass activity than a SWNT support at about the same power output, and the optimum hybrid is found for a blend composed of 20−30 µgPt/cm2 on SWNTs and 5−10 µgPt/cm2 on MWNTs.

We report the preparation, crystallization, and solid-state characterization of the first member of a new family of tris(1,9-disubstituted phenalenyl)silicon neutral radicals. In the solid state, the radical packs as weak partial pi-dimers with intermolecular carbon...carbon contacts that fall at the van der Waals atomic separation. Magnetic susceptibility measurements indicate approximately 0.7 Curie spins per molecule from room temperature down to 50 K, below which antiferromagnetic coupling becomes apparent; the compound has a room-temperature single-crystal conductivity of sigmaRT = 2.4 x 10(-6) S cm(-1).

Low color, flexible, space-durable polyimide films with inherent and robust electrical conductivity to dissipate electrostatic charge (ESC) have been under investigation as part of a materials development activity for future NASA space missions. The use of single-walled carbon nanotubes (SWCNTs) is one means of achieving this goal. Even though the concentration of SWCNTs needed to achieve ESC dissipation is typically low, it is dependent upon purity, size, dispersion and functionalization. In this study, SWCNTs prepared by the electric arc discharge method were used to synthesize nanocomposites using the LaRCTM CP2 backbone as the matrix. Pristine and functionalized SWCNTs were mixed with an alkoxysilane terminated amide acid of LaRC TM CP2 and the soluble imide form of the polymer and the resultant nanocomposites evaluated for mechanical, thermal and electrical properties. Due to the preparative conditions for the pristine and functionalized SWCNTs, the average aspect ratio for both was comparable. This permitted the assessment of SWCNT functionalization with respect to various interactions (e.g. van der Waals, hydrogen bonding, covalent bond formation, etc.) with the matrix and the macroscopic effects upon nanocomposite properties. The results of the study are described.

Soluble graphene layers were formed by reacting graphite fluoride with alkyl lithium reagents. IR spectral studies confirmed the covalent attachment of alkyl chains to the graphene layers. Raman scattering and XRD studies of the starting materials and products revealed that the chemical process partially restores the sp2 carbon network. The solubility and extinction coefficient were determined by UV–vis-near infrared spectroscopy. Annealing of bulk samples further extends the sp2 lattice due to dealkylation as followed by Raman, XRD and mid-infrared spectroscopy. The present study demonstrates a one-step chemical treatment of graphite fluoride that allows the manipulation of a soluble form of graphene.

Fuel cell membrane electrode assemblies with Pt loading of 0.2 mg Pt/cm2 at the anode and ultralow Pt loadings of 6 μg Pt/cm2 and 12 μg Pt/cm2 at the cathode have been fabricated using thin films of multiwalled carbon nanotube supported Pt catalysts (Pt/MWNTs) at the cathode. The Pt/MWNTs have a Pt weight loading of 26.8 wt % and a uniform and small Pt particle size of 2.1 nm. The MWNTs used are 360 μm long. This thin film cathode catalyst layer with a loading of 6 μg Pt/cm2 is about 1.3 μm thick, contains no ionomer, and exhibits surprisingly high performance in a hydrogen proton exchange membrane fuel cell. The peak power density for a membrane electrode assembly with a cathode loading of 12 μg Pt/cm2 when tested at 70 °C with hydrogen and oxygen is 613 mW/cm2. A mass activity (ampere per milligram of Pt) based on the cathode Pt loading greater than 250 A/mg Pt is achieved with 6 μg Pt/cm2, and this is among the highest reported to date.

We report an investigation into the effect of oxygen and sulfur substitution on the dimerization of phenalenyl-based neutral radicals; these substituents are expected to electronically stabilize the free radical while sterically interfering with dimerization. The 1,3,4,9-tetramethoxyphenalenyl (7a) and 1-ethoxy-3,4,9-trimethoxyphenalenyl (7b) radicals are prepared by chemical reduction of the cation salts, but the crystals that are isolated from these solutions are shown to be composed of alkoxy-substituted peropyrenes by X-ray crystallography. Crystallization of 1,9-dithiophenalenyl (8) gives rise to a π-dimer, and this is the first example of a radical based on a single phenalenyl unit that has been stabilized against σ-dimerization in the solid state by electronic effects rather than by the presence of sterically bulky substituents.

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.

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.

Reaction of N-alkylated pyridine-bridged bisdithiazolylium cations [1]+ (R1 =Me, Et; R2 =Ph) with selenium dioxide in acetic acid provides a one-step high-yield synthetic route to bisthiaselenazolylium cations [2]+ (R1 = Me, Et; R2 = Ph). The corresponding radicals 1 and 2 can be prepared by chemical or electrochemical reduction of the cations. Structural analysis of the radicals has been achieved by a combination of single-crystal and powder X-ray diffraction methods. While the two sulfur radicals 1 adopt different space groups (P3(1)21 for R1 = Me and P(-)1 for R1 = Et), the two selenium radicals 2 (space groups P3(1)21 for R1 = Me and P3(2)21 for R1 =Et) are isostructural with each other and also with 1 (R1 = Me, R2 = Ph). Variable-temperature magnetic measurements on all four compounds confirm that they are undimerized S = 1/2 systems, with varying degrees of weak intermolecular antiferromagnetic coupling. Variable-temperature electrical conductivity measurements on the two selenium radicals provide conductivities sigma(300 K) = 7.4 x 10-6 (R1 = Et) and 3.3 x 10-5 S cm-1 (R1 = Me), with activation energies, E(act), of 0.32 (R1 = Et) and 0.29 eV (R1 = Me). The differences in conductivity within the isostructural series is interpreted in terms of their relative solid-state bandwidths, as estimated from Extended Hückel band-structure calculations.

Single-walled carbon nanotubes (SWNTs) were dispersed in the form of individual nanotubes and small bundles, and subsequently polymerized to prepare composite films. The nanotubes were first dispersed in dimethylacetamide in the presence of 1,3-bis(3-aminophenoxy)benzene (APB), which was then polymerized with 4,4′-hexafluoroisopropylidiene diphthalic anhydride (6-FDA). Optical microscopy, SEM and TEM studies of the composite show that the SWNTs are homogenously distributed in the polymer matrix, and AFM observations indicate that ∼80% of the dispersed SWNTs are stabilized as individual nanotubes. The freestanding composite films were found to have very good optical, thermal and mechanical properties as well as enhanced electrostatic charge dissipation properties.

We report the electropolymerization and characterization of polypyrrole films doped with poly(m-aminobenzene sulfonic acid (PABS) functionalized single-walled nanotubes (SWNT) (PPy/SWNT-PABS). The negatively charged water-soluble SWNT-PABS served as anionic dopant during the electropolymerization to synthesize PPy/SWNTPABS composite films. The synthetic, morphological and electrical properties of PPy/SWNT-PABS films and chloride doped polypyrrole (PPy/Cl) films were compared. Characterization was performed by cyclic voltammetry, atomic force microscopy (AFM), scanning electron microscopy (SEM) and Raman spectroscopy. SEM and AFM images revealed that the incorporation of SWNT-PABS significantly altered the morphology of the PPy. Cyclic voltammetry showed improved electrochemical properties of PPy/SWNT-PABS films as compared to PPy/Cl films. Raman Spectroscopy confirmed the presence of SWNT-PABS within composite films. Field effect transistor (FET) and electrical characterization studies show that the incorporation of the SWNT-PABS increased the electronic performance of PPy/SWNT-PABS films when compared to PPy/Cl films. Finally, we fabricated PPy/SWNT-PABS nanotubes which may lead to potential applications to sensors and other electronic devices.

Low-temperature (LT) buffer-layer techniques were employed to improve the crystalline quality of ZnO films grown by molecular-beam epitaxy (MBE). Photoluminescence (PL) spectra show that CdO, as a hetero-buffer layer with a rock-salt structure, does not improve the quality of ZnO film grown on top. However, by using ZnO as a homo-buffer layer, the crystalline quality can be greatly enhanced, as indicated by PL, atomic force microscopy (AFM), x-ray diffraction (XRD), and Raman scattering. Moreover, the buffer layer grown at 450°C is found to be the best template to further improve the quality of top ZnO film. The mechanisms behind this result are the strong interactions between point defects and threading dislocations in the ZnO buffer layer.

High-quality ZnO films were grown on Si(1 0 0) substrates with low-temperature (LT) ZnO buffer layers by an electron cyclotron resonance (ECR)-assisted molecular-beam epitaxy (MBE). In order to investigate the optimized buffer layer temperature, ZnO buffer layers of about 1.1 μm were grown at different growth temperatures of 350, 450 and 550 °C, followed by identical high-temperature (HT) ZnO films with the thickness of 0.7 μm at 550 °C. A ZnO buffer layer with a growth temperature of 450 °C (450 °C-buffer sample) was found to greatly enhance the crystalline quality of the top ZnO film compared to others. The root mean square (RMS) roughness (3.3 nm) of its surface is the smallest, compared to the 350 °C-buffer sample (6.7 nm), the 550 °C-buffer sample (7.4 nm), and the sample without a buffer layer (6.8 nm). X-ray diffraction (XRD), photoluminescence (PL) and Raman scattering measurements were carried out on these samples at room temperature (RT) in order to characterize the crystalline quality of ZnO films. The preferential c -axis orientations of (0 0 2) ZnO were observed in the XRD spectra. The full-width at half-maximum (FWHM) value of the 450 °C-buffer sample was the narrowest as 0.209°, which indicated that the ZnO film with a buffer layer grown at this temperature was better for the subsequent ZnO growth at elevated temperature of 550 °C. Consistent with these results, the 450 °C-buffer sample exhibits the highest intensity and the smallest FWHM (130 meV) of the ultraviolet (UV) emission at 375 nm in the PL spectrum. The ZnO characteristic peak at 438.6 cm −1 was found in Raman scattering spectra for all films with buffers, which is corresponding to the E 2 mode.

The germanium (IV) and silicon (IV) complexes, tris-(9-oxophenalenone)-germanium (IV) tetrakis[3,5-bis(trifluoromethyl) phenyl] borate (7+TFPB−) and tris-(9-oxophenalenone)-silicon (IV) tetrakis[3,5-bis(trifluoromethyl) phenyl] borate (8+TFPB−), derived from 9-hydroxyphenalenone have been synthesized and characterized by elemental analyses, infrared spectra and as well as by single crystal X-ray study. The crystal structure of 7+TFPB− and 8+TFPB− shows a one-dimensional chain like structure and π-overlap between the neighbouring phenalenyl planes. The cyclic voltammograms of 7+TFPB− and 8+TFPB− show three reversible one-electron reduction steps due to the formation of the radical, anion and dianion as each phenalenyl moiety accepts an electron.

We report the preparation and solid state characterization of a silicon (IV) salt based on a new redox active tripodal hexadentate ligand [H3L = l,l,l-Tris(l′-oxophenalenyl-9′-N-methyl) ethane]. X-ray analysis of the complex reveals a short Si-N bond distance (av 1.878(16)). The compound is shown to undergo three reversible one-electron reduction steps (without decomposition) due to the formation of radical, anion and dianion of the phenalenyl moiety.