Exciton binding energies in carbon nanotubes from two-photon photoluminescence

One- and two-photon luminescence excitation spectroscopy showed a series of distinct excitonic states in single-walled carbon nanotubes. The energy splitting between one- and two-photon-active exciton states of different wavefunction symmetry is the fingerprint of excitonic interactions in carbon nanotubes. We determine exciton binding energies of 0.3-0.4 eV for different nanotubes with diameters between 0.7 and 0.9 nm. Our results, which are supported by ab-initio calculations of the linear and non-linear optical spectra, prove that the elementary optical excitations of carbon nanotubes are strongly Coulomb-correlated, quasi-one dimensionally confined electron-hole pairs, stable even at room temperature. This alters our microscopic understanding of both the electronic structure and the Coulomb interactions in carbon nanotubes, and has direct impact on the optical and transport properties of novel nanotube devices.Comment: 5 pages, 4 figure

Optical properties and charge-transfer excitations in edge-functionalized all-graphene nanojunctions

We investigate the optical properties of edge-functionalized graphene nanosystems, focusing on the formation of junctions and charge transfer excitons. We consider a class of graphene structures which combine the main electronic features of graphene with the wide tunability of large polycyclic aromatic hydrocarbons. By investigating prototypical ribbon-like systems, we show that, upon convenient choice of functional groups, low energy excitations with remarkable charge transfer character and large oscillator strength are obtained. These properties can be further modulated through an appropriate width variation, thus spanning a wide range in the low-energy region of the UV-Vis spectra. Our results are relevant in view of designing all-graphene optoelectronic nanodevices, which take advantage of the versatility of molecular functionalization, together with the stability and the electronic properties of graphene nanostructures.Comment: J. Phys. Chem. Lett. (2011), in pres

Adaptive statistical iterative reconstruction improves image quality without affecting perfusion CT quantitation in primary colorectal cancer

Objectives: To determine the effect of Adaptive Statistical Iterative Reconstruction (ASIR) on perfusion CT (pCT) parameter quantitation and image quality in primary colorectal cancer. Methods: Prospective observational study. Following institutional review board approval and informed consent, 32 patients with colorectal adenocarcinoma underwent pCT (100 kV, 150 mA, 120 s acquisition, axial mode). Tumour regional blood flow (BF), blood volume (BV), mean transit time (MTT) and permeability surface area product (PS) were determined using identical regions-of-interests for ASIR percentages of 0%, 20%, 40%, 60%, 80% and 100%. Image noise, contrast-to-noise ratio (CNR) and pCT parameters were assessed across ASIR percentages. Coefficients of variation (CV), repeated measures analysis of variance (rANOVA) and Spearmanâ rank order correlation were performed with statistical significance at 5%. Results: With increasing ASIR percentages, image noise decreased by 33% while CNR increased by 61%; peak tumour CNR was greater than 1.5 with 60% ASIR and above. Mean BF, BV, MTT and PS differed by less than 1.8%, 2.9%, 2.5% and 2.6% across ASIR percentages. CV were 4.9%, 4.2%, 3.3% and 7.9%; rANOVA P values: 0.85, 0.62, 0.02 and 0.81 respectively. Conclusions: ASIR improves image noise and CNR without altering pCT parameters substantially. Keywords: Perfusion imaging, Multidetector computed tomography, Colorectal neoplasms, Computer-assisted image processing, Radiation dosag

Designing all-graphene nanojunctions by covalent functionalization

We investigated theoretically the effect of covalent edge functionalization, with organic functional groups, on the electronic properties of graphene nanostructures and nano-junctions. Our analysis shows that functionalization can be designed to tune electron affinities and ionization potentials of graphene flakes, and to control the energy alignment of frontier orbitals in nanometer-wide graphene junctions. The stability of the proposed mechanism is discussed with respect to the functional groups, their number as well as the width of graphene nanostructures. The results of our work indicate that different level alignments can be obtained and engineered in order to realize stable all-graphene nanodevices

Optical Excitations and Field Enhancement in Short Graphene Nanoribbons

The optical excitations of elongated graphene nanoflakes of finite length are investigated theoretically through quantum chemistry semi-empirical approaches. The spectra and the resulting dipole fields are analyzed, accounting in full atomistic details for quantum confinement effects, which are crucial in the nanoscale regime. We find that the optical spectra of these nanostructures are dominated at low energy by excitations with strong intensity, comprised of characteristic coherent combinations of a few single-particle transitions with comparable weight. They give rise to stationary collective oscillations of the photoexcited carrier density extending throughout the flake, and to a strong dipole and field enhancement. This behavior is robust with respect to width and length variations, thus ensuring tunability in a large frequency range. The implications for nanoantennas and other nanoplasmonic applications are discussed for realistic geometries

Raman Fingerprints of Atomically Precise Graphene Nanoribbons.

Bottom-up approaches allow the production of ultranarrow and atomically precise graphene nanoribbons (GNRs) with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab initio simulations, we show that GNR width, edge geometry, and functional groups all influence their Raman spectra. The low-energy spectral region below 1000 cm(-1) is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs and differentiates them from other sp(2) carbon nanostructures.We acknowledge funding from: the Alexander von Humboldt Foundation in the framework of the Sofja Kovalevskaja Award, endowed by the Federal Ministry for Education and Research of Germany; the ESF project GOSPEL (Ref. No. 09-EuroGRAPHENE-FP-001); the European Research Council (grant NOC-2D, NANOGRAPH, and Hetero2D); the Italian Ministry of Research through the national projects PRIN-GRAF (Grant No. 20105ZZTSE) and FIRB-FLASHit (Grant No. RBFR12SWOJ); the DFG Priority Program SPP 1459; the Graphene Flagship (Ref. No. CNECT-ICT-604391); the EU project MoQuaS; EPSRC Grants (EP/K01711X/1, EP/K017144/1); the EU grant GENIUS; a Royal Society Wolfson Research Merit Award. Computer time was granted by PRACE at the CINECA Supercomputing Center (Grant No. PRA06 1348), and by the Center for Functional Nanomaterials at Brookhaven National Laboratory, supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under contract number DE-SC0012704.This is the author accepted manuscript. The final version is available from the American Chemical Society via http://dx.doi.org/10.1021/acs.nanolett.5b0418

A microRNA profile of human CD8(+) regulatory T cells and characterization of the effects of microRNAs on Treg cell-associated genes.

Recently, regulatory T (Treg) cells have gained interest in the fields of immunopathology, transplantation and oncoimmunology. Here, we investigated the microRNA expression profile of human natural CD8(+)CD25(+) Treg cells and the impact of microRNAs on molecules associated with immune regulation. We purified human natural CD8(+) Treg cells and assessed the expression of FOXP3 and CTLA-4 by flow cytometry. We have also tested the ex vivo suppressive capacity of these cells in mixed leukocyte reactions. Using TaqMan low-density arrays and microRNA qPCR for validation, we could identify a microRNA 'signature' for CD8(+)CD25(+)FOXP3(+)CTLA-4(+) natural Treg cells. We used the 'TargetScan' and 'miRBase' bioinformatics programs to identify potential target sites for these microRNAs in the 3'-UTR of important Treg cell-associated genes. The human CD8(+)CD25(+) natural Treg cell microRNA signature includes 10 differentially expressed microRNAs. We demonstrated an impact of this signature on Treg cell biology by showing specific regulation of FOXP3, CTLA-4 and GARP gene expression by microRNA using site-directed mutagenesis and a dual-luciferase reporter assay. Furthermore, we used microRNA transduction experiments to demonstrate that these microRNAs impacted their target genes in human primary Treg cells ex vivo. We are examining the biological relevance of this 'signature' by studying its impact on other important Treg cell-associated genes. These efforts could result in a better understanding of the regulation of Treg cell function and might reveal new targets for immunotherapy in immune disorders and cancer

Gap Opening in Double-Sided Highly Hydrogenated Free-Standing Graphene

Conversion of free-standing graphene into pure graphane-where each C atom is sp3bound to a hydrogen atom-has not been achieved so far, in spite of numerous experimental attempts. Here, we obtain an unprecedented level of hydrogenation (≈90% of sp3bonds) by exposing fully free-standing nanoporous samples-constituted by a single to a few veils of smoothly rippled graphene-to atomic hydrogen in ultrahigh vacuum. Such a controlled hydrogenation of high-quality and high-specific-area samples converts the original conductive graphene into a wide gap semiconductor, with the valence band maximum (VBM) ∼3.5 eV below the Fermi level, as monitored by photoemission spectromicroscopy and confirmed by theoretical predictions. In fact, the calculated band structure unequivocally identifies the achievement of a stable, double-sided fully hydrogenated configuration, with gap opening and no trace of πstates, in excellent agreement with the experimental results

Exciton-exciton annihilation and biexciton stimulated emission in graphene nanoribbons

Graphene nanoribbons display extraordinary optical properties due to one-dimensional quantum-confinement, such as width-dependent bandgap and strong electron-hole interactions, responsible for the formation of excitons with extremely high binding energies. Here we use femtosecond transient absorption spectroscopy to explore the ultrafast optical properties of ultranarrow, structurally well-defined graphene nanoribbons as a function of the excitation fluence, and the impact of enhanced Coulomb interaction on their excited states dynamics. We show that in the high-excitation regime biexcitons are formed by nonlinear exciton-exciton annihilation, and that they radiatively recombine via stimulated emission. We obtain a biexciton binding energy of \ue2 \u2030250 meV, in very good agreement with theoretical results from quantum Monte Carlo simulations. These observations pave the way for the application of graphene nanoribbons in photonics and optoelectronics