Deep strong light-matter coupling in plasmonic nanoparticle crystals.

In the regime of deep strong light-matter coupling, the coupling strength exceeds the transition energies of the material1-3, fundamentally changing its properties4,5; for example, the ground state of the system contains virtual photons and the internal electromagnetic field gets redistributed by photon self-interaction1,6. So far, no electronic excitation of a material has shown such strong coupling to free-space photons. Here we show that three-dimensional crystals of plasmonic nanoparticles can realize deep strong coupling under ambient conditions, if the particles are ten times larger than the interparticle gaps. The experimental Rabi frequencies (1.9 to 3.3 electronvolts) of face-centred cubic crystals of gold nanoparticles with diameters between 25 and 60 nanometres exceed their plasmon energy by up to 180 per cent. We show that the continuum of photons and plasmons hybridizes into polaritons that violate the rotating-wave approximation. The coupling leads to a breakdown of the Purcell effect-the increase of radiative damping through light-matter coupling-and increases the radiative polariton lifetime. The results indicate that metallic and semiconducting nanoparticles can be used as building blocks for an entire class of materials with extreme light-matter interaction, which will find application in nonlinear optics, the search for cooperative effects and ground states, polariton chemistry and quantum technology4,5.

Direct optical excitation of dark plasmons for hot electron generation.

An ideal plasmonic system for hot-electron generation allows the optical excitation of plasmons, limits radiation losses, exhibits strong non-radiative electron damping, and is made from scalable and cost-effective materials. Here we demonstrate the optical excitation of dark interlayer plasmons in bilayers of colloidal gold nanoparticles. This excitation is created by an antiparallel orientation of the dipole moments in the nanoparticle layers; it is expected to exhibit strongly reduced radiative damping. Despite the vanishing dipole moment, an incoming electromagnetic wave that is propagating normal to the surface will excite the dark mode due to field retardation. We observe a strong peak in the absorption spectrum of a colloidal gold bilayer (nanoparticle diameter = 46 nm); this peak is absent for a nanoparticle monolayer. The full width at half maximum of the dark mode is 230 meV for an ideal nanoparticle crystal and 320 meV for the structure produced by self-assembly out of solution. The position and width of the dark plasmon are efficiently tailored by the interparticle distance within the layer, nanoparticle size and layer number. We present time-resolved pump and probe experiments of hot-electron generation by bright and dark bilayer nanoparticle modes.

Determination of High-Frequency Dielectric Constant and Surface Potential of Graphene Oxide and Influence of Humidity by Kelvin Probe Force Microscopy.

We use Kelvin probe force microscopy (KPFM) and capacitance coupling (dC/dz) to study the electrical properties of graphene oxide (GO). We propose using the dC/dz signal to probe the high frequency dielectric constant of mono- and few-layer GO. Our measurements suggest that the dynamic dielectric constant of GO is on the order of εGO ≅ 3.0 ε0, in the high frequency limit, and independent of the number of GO layers. The measurements are performed at a humidity controlled environment (5% of humidity). The effects of increasing humidity on both the dC/dz and KPFM measurements are analyzed.

Glutamine and alanyl-glutamine increase RhoA expression and reduce Clostridium difficile toxin-a-induced intestinal epithelial cell damage.

Clostridium difficile is a major cause of antibiotic-associated colitis and is associated with significant morbidity and mortality. Glutamine (Gln) is a major fuel for the intestinal cell population. Alanyl-glutamine (Ala-Gln) is a dipeptide that is highly soluble and well tolerated. IEC-6 cells were used in the in vitro experiments. Cell morphology was evaluated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Cell proliferation was assessed by WST-1 and Ki-67 and apoptosis was assessed by TUNEL. Cytoskeleton was evaluated by immunofluorescence for RhoA and F-actin. RhoA was quantified by immunoblotting. TcdA induced cell shrinkage as observed by AFM, SEM, and fluorescent microscopy. Additionally, collapse of the F-actin cytoskeleton was demonstrated by immunofluorescence. TcdA decreased cell volume and area and increased cell height by 79%, 66.2%, and 58.9%, respectively. Following TcdA treatment, Ala-Gln and Gln supplementation, significantly increased RhoA by 65.5% and 89.7%, respectively at 24 h. Ala-Gln supplementation increased cell proliferation by 137.5% at 24 h and decreased cell apoptosis by 61.4% at 24 h following TcdA treatment. In conclusion, TcdA altered intestinal cell morphology and cytoskeleton organization, decreased cell proliferation, and increased cell apoptosis. Ala-Gln and Gln supplementation reduced intestinal epithelial cell damage and increased RhoA expression.

Biochemical, physicochemical and molecular characterization of a genuine 2-Cys-peroxiredoxin purified from cowpea [Vigna unguiculata (L.) Walpers] leaves.

BACKGROUND: Peroxiredoxins have diverse functions in cellular defense-signaling pathways. 2-Cys-peroxiredoxins (2-Cys-Prx) reduce H2O2 and alkyl-hydroperoxide. This study describes the purification and characterization of a genuine 2-Cys-Prx from Vigna unguiculata (Vu-2-Cys-Prx). METHODS: Vu-2-Cys-Prx was purified from leaves by ammonium sulfate fractionation, chitin affinity and ion exchange chromatography. RESULTS: Vu-2-Cys-Prx reduces H2O2 using NADPH and DTT. Vu-2-Cys-Prx is a 44 kDa (SDS-PAGE)/46 kDa (exclusion chromatography) protein that appears as a 22 kDa molecule under reducing conditions, indicating that it is a homodimer linked intermolecularly by disulfide bonds and has a pI range of 4.56­4.72; its NH2-terminal sequence was similar to 2-Cys-Prx from Phaseolus vulgaris (96%) and Populus tricocarpa (96%). Analysis by ESI-Q-TOF MS/MS showed a molecular mass/pI of 28.622 kDa/5.18. Vu-2-Cys-Prx has 8% α-helix, 39% ß-sheet, 22% of turns and 31% of unordered forms. Vu-2-Cys-Prx was heat stable, has optimal activity at pH 7.0, and prevented plasmid DNA degradation. Atomic force microscopy shows that Vu-2-Cys-Prx oligomerized in decamers which might be associated with its molecular chaperone activity that prevented denaturation of insulin and citrate synthase. Its cDNA analysis showed that the redox-active Cys52 residue and the amino acids Pro45, Thr49 and Arg128 are conserved as in other 2-Cys-Prx. GENERAL SIGNIFICANCE: The biochemical and molecular features of Vu-2-Cys-Prx are similar to other members of 2-Cys-Prx family. To date, only one publication reported on the purification of native 2-Cys-Prx from leaves and the subsequent analysis by N-terminal Edman sequencing, which is crucial for construction of stromal recombinant 2-Cys-Prx proteins.

The effect of diode laser irradiation on dentin as a preventive measure against dental erosion: an in vitro study.

Increasing rates of non-carious cervical lesions due to dental erosion, exposure of dentinal tubules, and hypersensitivity to environmental stimuli have led to the development of new prevention strategies. This study evaluated the effects of a low-intensity diode laser (λ = 808 nm) on the dentinal chemical composition and prevention of demineralization. In addition, the study monitored temperature changes during the course of irradiation. Forty dentin specimens were randomly allocated into four groups (n = 10): G1 - No treatment (control), G2 - irradiated with 15 J/cm(2), G3 - irradiated with 30 J/cm(2), and G4 - irradiated with 60 J/cm(2). Each specimen was partially covered with nail varnish, treated according to the group irradiation levels, and exposed to an erosive challenge (1.0 M hydrochloric acid) for 5 min. Afterwards, dentin loss was profilometrically analyzed and examined by scanning electron microscopy (SEM) combined with energy dispersive X-ray (EDX). Intrapulpal temperatures were measured during the dentin irradiation. One-way ANOVA and Tukey tests (p < 0.05) were performed to assess differences. For all irradiated groups, intrapulpal temperature changes were less than 3°C. The G2 group showed statistically significant differences when compared to the other groups, representing the lowest temperature increase. A quantitative element analysis via EDX did not significantly differ (p < 0.05) for Ca, P, F, O, or C between the four groups when measured after irradiation/erosion. The mean wear rates (± SD, µm) were 35.66 ± 7.28; 40.70 ± 5.03; 38.17 ± 10.81 and 25.25 ± 6.87 for G1-G4, respectively. The G4 group statistically differed from all other groups representing the lowest wear rate. These results suggest that dentin irradiation, using a diode laser with levels set at 60 J/cm(2), may induce inhibitory effects on root dentin demineralization without causing any harmful thermal effects. However, the exact mechanism of the action of the laser remains unclear.

Functionalization of single-wall carbon nanotubes through chloroform adsorption: theory and experiment.

The interaction of chloroform (CHCl(3)) with single-wall carbon nanotubes (SWCNT) is investigated using both first principles calculations based on Density Functional Theory and vibrational spectroscopy experiments. CHCl(3) adsorption on pristine, defective, and carboxylated SWCNTs is simulated, thereby gaining a good understanding of the adsorption process of this molecule on SWCNT surfaces. The results predict a physisorption regime in all cases. These calculations point out that SWCNTs are promising materials for extracting trihalomethanes from the environment. Theoretical predictions on the stability of the systems SWCNT-CCl(2) and SWCNT-COCCl(3) are confirmed by experimental TGA data and Fourier Transform Infrared Spectroscopy (FT-IR) experiments. Results from resonance Raman scattering experiments indicate that electrons are transferred from the SWCNTs to the attached groups and these results are in agreement with the predictions made by ab initio calculations.

Selective tuning of the electronic properties of coaxial nanocables through exohedral doping.

The electronic properties of exohedrally doped double-walled carbon nanotubes (DWNTs) have been investigated using density functional theory and resonance Raman spectroscopy (RRS) measurements. First-principles calculations elucidate the effects of exohedral doping on the M@S and S@M systems, where a metallic (M) tube is either inside or outside a semiconducting (S) one. The results demonstrate that metallic nanotubes are extremely sensitive to doping even when they are inner tubes, in sharp contrast to semiconducting nanotubes, which are not affected by doping when the outer shell is a metallic nanotube (screening effects). The theoretical predictions are in agreement with RRS data on Br2- and H2SO4-doped DWNTs. These results pave the way to novel nanoscale electronics via exohedral doping.