Resonant Enhancement Research Articles

MATRESHCA: Microtesla Apparatus for Transfer of Resonance Enhancement of Spin Hyperpolarization via Chemical Exchange and Addition.

We present an integrated, open-source device for parahydrogen-based hyperpolarization processes in the microtesla field regime with a cost of components of less than $7000. The device is designed to produce a batch of 13C and 15N hyperpolarized (HP) compounds via hydrogenative or non-hydrogenative parahydrogen-induced polarization methods that employ microtesla magnetic fields for efficient polarization transfer of parahydrogen-derived spin order to X-nuclei (e.g., 13C and 15N). The apparatus employs a layered structure (reminiscent of a Russian doll "Matryoshka") that includes a nonmagnetic variable-temperature sample chamber, a microtesla magnetic field coil (operating in the range of 0.02-75 microtesla), a three-layered mu-metal shield (to attenuate the ambient magnetic field), and a magnetic shield degaussing coil placed in the overall device enclosure. The gas-handling manifold allows for parahydrogen-gas flow and pressure control (up to 9.2 bar of total parahydrogen pressure). The sample temperature can be varied either using a water bath or a PID-controlled heat exchanger in the range from -12 to 80 °C. This benchtop device measures 62 cm (length) × 47 cm (width) × 47 cm (height), weighs 30 kg, and requires only connections to a high-pressure parahydrogen gas supply and a single 110/220 VAC power source. The utility of the device has been demonstrated using an example of parahydrogen pairwise addition to form HP ethyl [1-13C]acetate (P13C = 7%, [c] = 1 M). Moreover, the Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei (SABRE-SHEATH) technique was employed to demonstrate efficient hyperpolarization of 13C and 15N spins in a wide range of biologically relevant molecules, including [1-13C]pyruvate (P13C = 14%, [c] = 27 mM), [1-13C]-α-ketoglutarate (P13C = 17%), [1-13C]ketoisocaproate (P13C = 18%), [15N3]metronidazole (P15N = 13%, [c] = 20 mM), and others. While the vast majority of the utility studies have been performed in standard 5 mm NMR tubes, the sample chamber of the device can accommodate a wide range of sample container sizes and geometries of up to 1 L sample volume. The device establishes an integrated, simple, inexpensive, and versatile equipment gateway needed to facilitate parahydrogen-based hyperpolarization experiments ranging from basic science to preclinical applications; indeed, detailed technical drawings and a bill of materials are provided to support the ready translation of this design to other laboratories.

20µm Micro-LEDs Mass Transfer via Laser-Induced In Situ Nanoparticles Resonance Enhancement.

Ultrafast laser is expected as a promising strategy for micro-LEDs (µ-LEDs) transfer due to its inherent property of suppressing thermal effects. However, its ultrahigh peak power and the unclear transfer mechanism make its transfer quality and efficiency unsatisfactory. Here, the study reports the high-precision mass transfer of 20µm fine-pitch µ-LEDs via in situ nanoparticles (NPs) resonance enhancement in burst mode ultraviolet picosecond laser irradiation. This technique suppresses the thermal melting effect and rapid cooling behavior of plasma by temporal modulation of the burst mode, generating NPs-induced resonance enhancement that accurately and controllable drives a single unit up to tens of thousands of µ-LEDs. The transfer of large µ-LED arrays with more than 180 000 chips is also demonstrated, showing a transfer yield close to 99.9%, a transfer speed of 700 pcs s-1, and a transfer error of <±1.2µm. The transferred µ-LEDs perform excellent optoelectronic properties and enable reliable device operation regardless of complex strain environments, providing a reliable strategy for preparing broader classes of 3D integrated photonics devices.

Beyond single-molecule chemistry for electrified interfaces using molecule polaritons

Abstract This review introduces the preparation, observation, and characterization of systems of molecule polaritons. We summarize recent progress by our group on the control of molecular properties in the spaces of various optical cavities, such as plasmonic metal nanostructures and Fabry–Perot mirrors. After stating our motivations, we introduce topics on single-molecule observations based on surface-enhanced Raman scattering (SERS) spectroscopy. Our original findings are not limited to the ultrasensitive detection of molecules/materials, but include unique resonant enhancements of SERS through exotic electronic excitation processes at electrified interfaces. Comprehensive analyses of SERS spectra provide novel routes to electronic excitation using plasmonic metal nanostructures. This behavior leads to the distinct photoenergy conversion based on excited electrons and holes with anomalous electrochemical potentials. Such unique resonant electronic excitation emerges as a large optical force that can be used to manipulate small single molecules on surfaces in solution, even at room temperature. We also introduce systems for examining unique interactions between molecules and the optical modes of cavities, from single molecules to molecular ensembles. Plasmonic surface lattices and Fabry–Perot mirrors allow the formation of electronic and vibrational strong coupling states, respectively, showing unique properties of molecule polaritons, even under dark conditions, i.e. without photoillumination.

Recent Studies on Metal-Embedded Silica Nanoparticles for Biological Applications

Recently, silica nanoparticles (NPs) have attracted considerable attention as biocompatible and stable templates for embedding noble metals. Noble-metal-embedded silica NPs utilize the exceptional optical properties of novel metals while overcoming the limitations of individual novel metal NPs. In addition, the structure of metal-embedded silica NPs decorated with small metal NPs around the silica core results in strong signal enhancement in localized surface plasmon resonance and surface-enhanced Raman scattering. This review summarizes recent studies on metal-embedded silica NPs, focusing on their unique designs and applications. The characteristics of the metal-embedded silica NPs depend on the type and structure of the embedded metals. Based on this progress, metal-embedded silica NPs are currently utilized in various spectroscopic applications, serving as nanozymes, detection and imaging probes, drug carriers, photothermal inducers, and bioactivation molecule screening identifiers. Owing to their versatile roles, metal-embedded silica NPs are expected to be applied in various fields, such as biology and medicine, in the future.

Enhanced photocatalytic degradation of Rhodamine B using gold nanoparticles decorated on BaTiO3 with surface plasmon resonance enhancement.

This study focused on synthesizing and applying gold nanoparticle (Au NP) decorated barium titanate (BaTiO3) nanoparticles for photocatalytic purposes. BaTiO3 NPs were synthesized using a facile hydrothermal method. Various techniques were employed to characterize the structure and morphological characteristics of the prepared materials. The photocatalytic degradation of Rhodamine B over the Au NPs-modified BaTiO3 photocatalysts was studied. Trapping experiments were conducted using different scavengers to elucidate the degradation mechanism and the involvement of photogenerated species. The incorporation of an appropriate amount of Au NPs into the composites resulted in a significant improvement in photocatalytic activity, attributed to the combined effect of Schottky junction at the interface and the surface plasmon resonance of Au NPs.

Organization of Carotenoid Aggregates in Membranes Studied Selectively using Resonance Raman Optical Activity.

In living organisms, carotenoids are incorporated in biomembranes, remarkably modulating their mechanical characteristics, fluidity, and permeability. Significant resonance enhancement of Raman optical activity (ROA) signals of carotenoid chiral aggregates makes resonance ROA (RROA), a highly selective tool to study exclusively carotenoid assemblies in model membranes. Hence, RROA is combined with electronic circular dichroism (ECD), dynamic light scattering (DLS), molecular dynamics, and quantum-chemical calculations to shed new light on the carotenoid aggregation in dipalmitoylphosphatidylcholine (DPPC) liposomes. Using representative members of the carotenoid family: apolar α-carotene and more polar fucoxanthin and zeaxanthin, the authors demonstrate that the stability of carotenoid aggregates is directly linked with their orientation in membranes and the monomer structures inside the assemblies. In particular, polyene chain distortion of α-carotene molecules is an important feature of J-aggregates that show increased orientational freedom and stability inside liposomes compared to H-assemblies of more polar xanthophylls. In light of these results, RROA emerges as a new tool to study active compounds and drugs embedded in membranes.

Green synthesis of ZnO nanoparticles from ball moss (Tillandsia recurvata) extracts: characterization and evaluation of their photocatalytic activity.

Green synthesis (GS), referred to the synthesis using bioactive agents such as plant materials, microorganisms, and various biowastes, prioritizing environmental sustainability, has become increasingly relevant in international scientific practice. The availability of plant resources expands the scope of new exploration opportunities, including the evaluation of new sources of organic extracts, for instance, to the best of our knowledge, no scientific articles have reported the synthesis of zinc oxide nanoparticles (ZnO NPs) from organic extracts of T. recurvata, a parasitic plant very common in semiarid regions of Mexico.This paper presents a greener and more efficient method for synthesizing ZnO NPs using T. recurvata extract as a reducing agent. The nanoparticles were examined by different techniques such as UV-vis spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and BET surface analysis. The photocatalytic and adsorptive effect of ZnO NPs was investigated against methylene blue (MB) dye in aqueous media under sunlight irradiation considering an equilibrium time under dark conditions. ZnO nanoparticles were highly effective in removing MB under sunlight irradiation conditions, showing low toxicity towards human epithelial cells, making them promising candidates for a variety of applications. This attribute fosters the use of green synthesis techniques for addressing environmental issues.This study also includes the estimation of the supported electric field distributions of ZnO NPs in their individual spherical or rounded shapes and their randomly oriented organization, considering different diameters, by simulating their behavior in the visible wavelength range, observing resonant enhancements due to the strong light-matter interaction around the ZnO NPs boundaries.

Advanced quasi-2D amorphous TiOx-Au photocatalyst: Harnessing defects and carriers transport to boost visible-light organic pollutants degradation

Amorphous materials have recently garnered significant interest due to their low-cost fabrication methods, extensive surface area and plentiful surface defects, which offer numerous active sites for catalytic reactions. However, carriers self-trapping and recombination caused by bulk defects limit the employment of amorphous materials as photocatalysts. As such, it is essential to adjust the structure and defects to improve carriers utilization for creating high-performance amorphous photocatalysts. In this study, we developed a novel and facile strategy to fabricate a quasi-2D amorphous crepe-like TiOx-Au (cTiOx-Au) photocatalyst, in which the cTiOx was synthesized simply through one-step hydrolysis method at room temperature by constructing discrete reaction system with mass-confinement of the precursor to guide the morphology of the cTiOx. The removal efficiencies of the cTiOx-Au to antibiotic tetracycline (TC) and gaseous pollutant formaldehyde (HCHO) under visible light were 84.43 % and 95.92 %, respectively, which greatly surpassed those of its counterparts, normal amorphous TiOx (amTiOx)-Au (54.32 % and 73.67 %) and crystalline catalyst TiO2-P25-Au (49.29 % and 54.03 %). The remarkable visible-light photocatalytic capacity of cTiOx-Au can be attributed to the unique quasi-2D morphology of cTiOx. The ultrathin nanostructure not only maximizes surface defects and minimizes bulk defects, but also effectively shortens the carriers transport time and reduces recombination probability, on the other hand, it provides ample adsorption sites and accessible binding sites for plasmonic Au nanoparticles to amplify the effect of surface plasmon resonance enhancement. The excellent photocatalytic performances of cTiOx-Au for removing both aqueous and atmospheric pollutants endow it great potential in real environmental remediation applications.

Plasmon resonance dynamics and enhancement effects in tris(2,2'-bipyridine)ruthenium(II) gold nanosphere oligomers.

Ruthenium-based metal complexes are one of the most widely studied dyes because of their rich photochemistry and light-harvesting properties. Significant attention has been paid to the energy and charge transfer dynamics of these dyes on semiconductor substrates. However, studies on photophysical and photochemical properties of these dyes in plasmonic environments are rare. In this study, we report a plasmon-mediated resonance energy transfer in an optimized oligomer system that enhances the photoexcited population of the well known dye, tris(2,2'-bipyridine)ruthenium(II), [Ru(BPY)3]2+ adsorbed on gold nanosphere surfaces with a defluorescenced Raman signal. Structural and chemical information is collected using a range of techniques that include in situ time-resolved UV/VIS, DLS, SERS, and TA. The findings have great potential to impact nanoscience broadly with special emphasis on surface photocatalysis, redox chemistry, and solar energy harvesting.

Hyper-Raman spectroscopy of biomolecules.

The hyper-Raman scattering (HRS) spectra of biologically significant molecules (D-glucose, L-alanine, L-arabinose, L-tartaric acid) in aqueous solutions are reported. The HRS spectra were measured using a picosecond laser at 532 nm operating at a MHz repetition rate. High signal to noise spectra were collected with a commercial spectrometer and CCD without resonant, nanoparticle, or surface enhancement. The HRS peak frequencies, relative intensities, band assignments, and depolarization ratios are examined. By comparing HRS to Raman scattering (RS) and infrared absorption spectra we verify that the IR-active vibrational modes of the target molecules are observed in HRS spectra but come with substantially different peak intensities. The HRS of the biomolecules as well as water, dimethyl sulfoxide, methanol, and ethanol were deposited into a data repository to support the development of theoretical descriptions of HRS for these molecules. Depositing the spectra in a repository also supports future dual detection RS, HRS microscopes which permit simultaneous high-spatial-resolution vibrational spectroscopy of IR-active and Raman-active vibrational modes.

Relaxation enhancement by microwave irradiation may limit dynamic nuclear polarization.

Dynamic nuclear polarization enables the hyperpolarization of nuclear spins beyond the thermal-equilibrium Boltzmann distribution. However, it is often unclear why the experimentally measured hyperpolarization is below the theoretically achievable maximum polarization. We report a (near-) resonant relaxation enhancement by microwave (MW) irradiation, leading to a significant increase in the nuclear polarization decay compared to measurements without MW irradiation. For example, the increased nuclear relaxation limits the achievable polarization levels to around 35% instead of hypothetical 60%, measured in the DNP material TEMPO in 1H glassy matrices at 3.3 K and 7 T. Applying rate-equation models to published build-up and decay data indicates that such relaxation enhancement is a common issue in many samples when using different radicals at low sample temperatures and high Boltzmann polarizations of the electrons. Accordingly, quantification and a better understanding of the relaxation processes under MW irradiation might help to design samples and processes towards achieving higher nuclear hyperpolarization levels.

In-line Raman imaging of mixing by herringbone grooves in microfluidic channels.

The control over fluid flow achievable in microfluidic devices creates opportunities for applications in many fields. In simple microchannels, flow is purely laminar when one solvent is used, and hence, achieving reliable mixing is an important design consideration. Integration of structures, such as grooves, into the channels to act as static mixers is a commonly used approach. The mixing induced by these structures can be validated by determining concentration profiles in microfluidic channels following convergence of solvent streams from separate inlets. Spatially resolved characterisation is therefore necessary and requires in-line analysis methods. Here we report a line-focused illumination approach to provide operando, spatially resolved Raman spectra across the width of channels in the analysis of single- and multi-phase liquid systems and chemical reactions. A scientific complementary metal oxide semiconductor (sCMOS) sensor is used to overcome smearing encountered during spectral readout of images with CCD sensors. Isotopically labelled probes, in otherwise identical flow streams, show that z-confocality limits the spatial resolution and certainty as to the extent of mixing that can be achieved. These limitations are overcome using fast chemical reactions between reagents entering a microchannel in separate solvent streams. We show here that the progression of a chemical reaction, for which only the product is observable, is a powerful approach to determine the extent of mixing in a microchannel. Specifically resonance enhancement of Raman scattering from a product formed allows for determination of the true efficiency of mixing over the length and width of microchannels. Raman spectral images obtained by line-focused illumination show onset of mixing by observing the product of reagents entering from the separate inlets. Mixing is initially off-centre and immediately before the apex of the first groove of the static mixer, and then evolves along the entire width of the channel after a full cycle of grooves.

A Terahertz Metamaterial Sensor Based on Dual Resonant Mode and Enhancement of Sensing Performance

A Terahertz Metamaterial Sensor Based on Dual Resonant Mode and Enhancement of Sensing Performance

Prominently enhanced luminescence from a continuous monolayer of transition metal dichalcogenide on all-dielectric metasurfaces

Abstract 2D materials such as transition metal dichalcogenides (TMDCs) are a new class of atomic-layer materials possessing optical and electric properties that significantly depend on the number of layers. Electronic transitions can be manipulated in artificial resonant electromagnetic (EM) fields using metasurfaces and other designed nanostructures. Here, we demonstrate prominently resonant enhancement in the photoluminescence (PL) of atomic monolayer, WS2, doped with a small quantity of Mo. The excitonic PL showed a strong enhancement effect on a higher-order magnetic resonance of all-dielectric metasurfaces consisting of periodic arrays of Si nanopellets. The PL intensity witnessed a 300-fold enhancement compared to the reference PL intensity on a flat silicon dioxide (SiO2) layer, which suggests a drastic change in the dynamics of photoexcited states. Confocal PL microscopy and the analysis revealed that the single photons were coherently emitted from the TMDC monolayer on the metasurface. Furthermore, examining the PL lifetime in the ps and ns timescales clarified two exponential components at the prominent exciton PL: a short-time component decaying in 22 ps and a long-time component lasting over 10 ns. Therefore, we can infer that the radiative components were significantly activated in the TMDC monolayer on the metasurfaces in comparison to the reference monolayer on a flat SiO2 layer.

High-power intracavity single-cycle THz pulse generation using thin lithium niobate

Ultrafast laser driven, single-cycle THz pulsed sources hold immense potential for scientific and industrial applications; however, their limited average power hinders their widespread application. In particular, applications where high repetition rates in the multi-MHz region and beyond are required are more severely affected, due to the lower pulse energies available for frequency conversion. In this respect, resonant enhancement both in passive and active resonators is a well-known technique for boosting the efficiency of nonlinear frequency conversion; however, this route has remained poorly explored for the generation of broadband THz pulses due to the inadequacy of typically employed nonlinear crystals. Here, we demonstrate that using thin lithium niobate crystals inside multimode diode-pumped mode-locked thin-disk lasers is a promising platform to circumvent these difficulties. Using a 50 µm thin lithium niobate plate intracavity of a compact high-power mode-locked thin-disk laser, we generate milliwatt-level broadband THz pulses with a spectrum extending up to 3 THz at 44.8 MHz repetition rate, driven by 264 W of intracavity average power. This approach opens the door to efficient high-power single-cycle THz generation using affordable nonlinear crystals at very high repetition rates, scalable to kilowatt-level driving power with low cost and complexity.

PDSFit: PDS data analysis in the presence of orientation selectivity, g-anisotropy, and exchange coupling.

Pulsed dipolar electron paramagnetic resonance spectroscopy (PDS), encompassing techniques such as pulsed electron-electron double resonance (PELDOR or DEER) and relaxation-induced dipolar modulation enhancement (RIDME), is a valuable method in structural biology and materials science for obtaining nanometer-scale distance distributions between electron spin centers. An important aspect of PDS is the extraction of distance distributions from the measured time traces. Most software used for this PDS data analysis relies on simplifying assumptions, such as assuming isotropic g-factors of ~2 and neglecting orientation selectivity and exchange coupling. Here, the program PDSFit is introduced, which enables the analysis of PELDOR and RIDME time traces with or without orientation selectivity. It can be applied to spin systems consisting of up to two spin centers with anisotropic g-factors and to spin systems with exchange coupling. It employs a model-based fitting of the time traces using parametrized distance and angular distributions, and parametrized PDS background functions. The fitting procedure is followed by an error analysis for the optimized parameters of the distributions and backgrounds. Using five different experimental data sets published previously, the performance of PDSFit is tested and found to provide reliable solutions.

A chip-scale second-harmonic source via self-injection-locked all-optical poling

Second-harmonic generation allows for coherently bridging distant regions of the optical spectrum, with applications ranging from laser technology to self-referencing of frequency combs. However, accessing the nonlinear response of a medium typically requires high-power bulk sources, specific nonlinear crystals, and complex optical setups, hindering the path toward large-scale integration. Here we address all of these issues by engineering a chip-scale second-harmonic (SH) source based on the frequency doubling of a semiconductor laser self-injection-locked to a silicon nitride microresonator. The injection-locking mechanism, combined with a high-Q microresonator, results in an ultra-narrow intrinsic linewidth at the fundamental harmonic frequency as small as 41 Hz. Owing to the extreme resonant field enhancement, quasi-phase-matched second-order nonlinearity is photoinduced through the coherent photogalvanic effect and the high coherence is mapped on the generated SH field. We show how such optical poling technique can be engineered to provide efficient SH generation across the whole C and L telecom bands, in a reconfigurable fashion, overcoming the need for poling electrodes. Our device operates with milliwatt-level pumping and outputs SH power exceeding 2 mW, for an efficiency as high as 280%/W under electrical driving. Our findings suggest that standalone, highly-coherent, and efficient SH sources can be integrated in current silicon nitride photonics, unlocking the potential of χ(2) processes in the next generation of integrated photonic devices.

Resonance Enhancement of Vibrational Polariton Chemistry Obtained from the Mixed Quantum-Classical Dynamics Simulations.

We applied a variety of mixed quantum-classical (MQC) approaches to simulate the VSC-influenced reaction rate constant. All of these MQC simulations treat the key vibrational levels associated with the reaction coordinate in the quantum subsystem (as quantum states), whereas all other degrees of freedom (DOFs) are treated inside the classical subsystem. We find that, as long as we have the quantum state descriptions for the vibrational DOFs, one can correctly describe the VSC resonance condition when the cavity frequency matches the bond vibrational frequency. This correct resonance behavior can be obtained regardless of the detailed MQC methods that one uses. The results suggest that the MQC approaches can generate semiquantitative agreement with the exact results for rate constant changes when changing the cavity frequency, the light-matter coupling strength, or the cavity lifetime. The finding of this work suggests that one can use computationally economic MQC approaches to explore the collective coupling scenario when many molecules are collectively coupled to many cavity modes in the future.

Microfiber knot resonator augmented quartz-enhanced photoacoustic spectroscopy

In this work, a microfiber knot resonator augmented quartz-enhanced photoacoustic spectroscopy (MKR-QEPAS) was developed for the analysis of trace gases. In the proof-of-concept experiment, a 1.39 μm laser diode was utilized for the detection of H2O molecules. Based on the H2O absorption line, the optical fiber-based MKR was meticulously designed to modulate the transmission spectrum, thereby inducing constructive interference with the excitation laser wavelength. The MKR was integrated with a clamp-type tuning fork, leading to a pronounced evanescent resonance enhancement. Consequently, the detection sensitivity of the MKR-QEPAS was improved by approximately one order of magnitude. The micro ring resonator is posited to hold significant promise for hybrid integration in QEPAS on-chip sensors.

Low terahertz frequency on-chip multi-functional modulator with amplitude and phase modulation

Terahertz amplitude and phase modulation technologies are crucial for terahertz communication, radar, and imaging. However, most current approaches can only achieve either amplitude or phase modulation. In this paper, we present a low terahertz frequency on-chip multi-functional modulator that consists of a hybrid coupler and reflection meta-structure. High-performance amplitude modulation is achieved by combining series resonant absorption of series coupling branch with resonance enhancement of parallel coupling branch in the reflection meta-structure. Meanwhile, the enhanced resonance provides a larger range of phase shifts, enabling effective amplitude and phase modulation in two different frequency regions. Therefore, we realize an amplitude modulation in the range of 115–135 GHz with a minimum transmission loss of 4 dB and a modulation depth of over 10 dB. At the same time, we achieved a continuous phase shift in the 103–113 GHz region, as well as a 180° two-bit phase shift in the 107–109 GHz range with only 5.7 dB transmission loss. Our simple method for terahertz amplitude and phase multi-functional modulation offers the potential to construe terahertz multifunctional integrated systems.