Project description:We tested the performance of several (13)C homonuclear mixing sequences on perdeuterated microcrystalline ubiquitin. All sequences were applied without (1)H decoupling and at relatively low MAS frequencies. We found that RFDR gave the highest overall transfer efficiency and that DREAM performs surprisingly well under these conditions being twice as efficient in the aliphatic region of the spectrum than the other mixing sequences tested.
Project description:The small homonuclear coupling constant between H2 and H8 protons of adenine (0.5 +/- 0.2 Hz) was determined and exploited to assign the H2 proton of adenine residues in DNA oligonucleotides. The utility of this approach is demonstrated for two different DNA sequences in D(2)O, for which we show a rapid and unambiguous assignment of the A H2 resonances.
Project description:The typical linewidths of 1 H NMR spectra of powdered organic solids at 111 kHz magic-angle spinning (MAS) are of the order of a few hundred Hz. While this is remarkable in comparison to the tens of kHz observed in spectra of static samples, it is still the key limit to the use of 1 H in solid-state NMR, especially for complex systems. Here, we demonstrate a novel strategy to further improve the spectral resolution. We show that the anti-z-COSY experiment can be used to reduce the residual line broadening of 1 H NMR spectra of powdered organic solids. Results obtained with the anti-z-COSY sequence at 100 kHz MAS on thymol, β-AspAla, and strychnine show an improvement in resolution of up to a factor of two compared to conventional spectra acquired at the same spinning rate.
Project description:Plasmonic nanoclusters, an ordered assembly of coupled metallic nanoparticles, support unique spectral features known as Fano resonances due to the coupling between their subradiant and superradiant plasmon modes. Within the Fano resonance, absorption is significantly enhanced, giving rise to highly localized, intense near fields with the potential to enhance nonlinear optical processes. Here, we report a structure supporting the coherent oscillation of two distinct Fano resonances within an individual plasmonic nanocluster. We show how this coherence enhances the optical four-wave mixing process in comparison with other double-resonant plasmonic clusters that lack this property. A model that explains the observed four-wave mixing features is proposed, which is generally applicable to any third-order process in plasmonic nanostructures. With a larger effective susceptibility ?(3) relative to existing nonlinear optical materials, this coherent double-resonant nanocluster offers a strategy for designing high-performance third-order nonlinear optical media.
Project description:In this article, we investigate composite media which present both a local resonance and a periodic structure. We numerically and experimentally consider the case of a very academic and simplified system that is a quasi-one dimensional split ring resonator medium. We modify its periodicity to shift the position of the Bragg bandgap relative to the local resonance one. We observe that for a well-chosen lattice constant, the local resonance frequency matches the Bragg frequency thus opening a single bandgap which is at the same time very wide and strongly attenuating. We explain this interesting phenomenon by the dispersive nature of the unit cell of the medium, using an analogy with the concept of white light cavities. Our results provide new ways to design wide and efficient bandgap materials.
Project description:Excitons are fundamental quasiparticles that are ubiquitous in photoexcited semiconductors and insulators. Despite causing a sharp and strong photoabsorption near the interband absorption edge, charge-neutral excitons do not yield photocurrent in conventional photovoltaic processes unless dissociated into free charge carriers. Here, we experimentally demonstrate that excitons can directly contribute to photocurrent generation through a nonlinear light-matter interaction in a noncentrosymmetric semiconductor CuI. Epitaxial thin films of CuI exhibit a substantial enhancement of photocurrent at exciton resonance energies even below the bandgap. From the light polarization dependence, this photocurrent is identified to be shift current, a nonlinear photocurrent driven by the change in the geometric Berry phase of electron wave functions upon the optical transition. The shift current at the exciton resonance is much larger than that induced above the band gap by free electron-hole excitation, and their signs are opposite. First-principles calculations elucidate that the sign and magnitude of the exciton shift current are strongly dependent on the strain in the thin film. The present study reveals the crucial role of excitons in enhancing the shift current magnitude and its strain sensitivity, and will open an unprecedented route for efficient manipulation of nonlinear optical effects.
Project description:Magnetic resonances not only play crucial roles in artificial magnetic materials but also offer a promising way for light control and interaction with matter. Recently, magnetic resonance effects have attracted special attention in plasmonic systems for overcoming magnetic response saturation at high frequencies and realizing high-performance optical functionalities. As novel states of matter, topological insulators (TIs) present topologically protected conducting surfaces and insulating bulks in a broad optical range, providing new building blocks for plasmonics. However, until now, high-frequency (e.g. visible range) magnetic resonances and related applications have not been demonstrated in TI systems. Herein, we report for the first time, to our knowledge, a kind of visible range magnetic plasmon resonances (MPRs) in TI structures composed of nanofabricated Sb2Te3 nanogrooves. The experimental results show that the MPR response can be tailored by adjusting the nanogroove height, width, and pitch, which agrees well with the simulations and theoretical calculations. Moreover, we innovatively integrated monolayer MoS2 onto a TI nanostructure and observed strongly reinforced light-MoS2 interactions induced by a significant MPR-induced electric field enhancement, remarkable compared with TI-based electric plasmon resonances (EPRs). The MoS2 photoluminescence can be flexibly tuned by controlling the incident light polarization. These results enrich TI optical physics and applications in highly efficient optical functionalities as well as artificial magnetic materials at high frequencies.
Project description:Fast magic angle spinning (MAS) NMR spectroscopy is emerging as an essential analytical and structural biology technique. Large resolution and sensitivity enhancements observed under fast MAS conditions enable structural and dynamics analysis of challenging systems, such as large macromolecular assemblies and isotopically dilute samples, using only a fraction of material required for conventional experiments. Homonuclear dipolar-based correlation spectroscopy constitutes a centerpiece in the MAS NMR methodological toolbox, and is used essentially in every biological and organic system for deriving resonance assignments and distance restraints information necessary for structural analysis. Under fast MAS conditions (rotation frequencies above 35-40 kHz), dipolar-based techniques that yield multi-bond correlations and non-trivial distance information are ineffective and suffer from low polarization transfer efficiency. To overcome this limitation, we have developed a family of experiments, CORD-RFDR. These experiments exploit the advantages of both zero-quantum RFDR and spin-diffusion based CORD methods, and exhibit highly efficient and broadband dipolar recoupling across the entire spectrum, for both short-range and long-range correlations. We have verified the performance of the CORD-RFDR sequences experimentally on a U-(13)C,(15)N-MLF tripeptide and by numerical simulations. We demonstrate applications of 2D CORD-RFDR correlation spectroscopy in dynein light chain LC8 and HIV-1 CA tubular assemblies. In the CORD-RFDR spectra of LC8 acquired at the MAS frequency of 40 kHz, many new intra- and inter-residue correlations are detected, which were not observed with conventional dipolar recoupling sequences. At a moderate MAS frequency of 14 kHz, the CORD-RFDR experiment exhibits excellent performance as well, as demonstrated in the HIV-1 CA tubular assemblies. Taken together, the results indicate that CORD-RFDR experiment is beneficial in a broad range of conditions, including both high and moderate MAS frequencies and magnetic fields.
Project description:Although gas breakdown phenomena have been intensively studied over 100 years, the breakdown mechanism in a strongly magnetized system, such as tokamak, has been still obscured due to complex electromagnetic topologies. There has been a widespread misconception that the conventional breakdown model of the unmagnetized system can be directly applied to the strongly magnetized system. However, we found clear evidence that existing theories cannot explain the experimental results. Here, we demonstrate the underlying mechanism of gas breakdown in tokamaks, a turbulent ExB mixing avalanche, which systematically considers multi-dimensional plasma dynamics in the complex electromagnetic topology. This mechanism clearly elucidates the experiments by identifying crucial roles of self-electric fields produced by space-charge that decrease the plasma density growth rate and cause a dominant transport via ExB drifts. A comprehensive understanding of plasma dynamics in complex electromagnetic topology provides general design strategy for robust breakdown scenarios in a tokamak fusion reactor.
Project description:In homonuclear 1H NMR (nuclear magnetic resonance) spectra such as [1H,1H]-NOESY (Nuclear Overhauser Enhancement spectroscopy), which is a historic cornerstone spectrum for biomolecular NMR structural biology, hundreds to thousands of cross peaks are present within a square of approximately 100 ppm2 leading to a lot of signal overlap. Spectral resolution is thus a limiting factor for unambiguous chemical shift assignment and data interpretation for dynamics and structure elucidation. Acquiring the spectra at higher magnetic fields such as at a 1.2 GHz 1H frequency helps to reduce spectral crowding, since resolution scales proportionally to the magnetic field strength. Here, we show that the linewidths of cross peaks in [1H,1H]-NOESY and [1H,1H]-TOCSY spectra can be further reduced by a factor of 2-3 in each dimension by super-resolution spectroscopy. In the indirect dimension a composite exponential-cosine weighted number of scans along the time increments are recorded and digitally smoothened by a window function, while in the direct dimension an exponential-cosine window function is applied. Furthermore, measurement time saving by reduced-acquisition super-resolution (RASR) is introduced. Application to the 20 kDa protein KRAS shows that highly resolved NMR spectra suitable for automated analysis can be acquired within less than 3 hours. The method opens an avenue towards automated chemical shift assignment, dynamics and structure determination of unlabeled small and medium size proteins within 24 hours.