Chemoselectivity Strategy Based on B-Label Integrated with Tailored COF for Targeted Metabolomic Analysis of Short-Chain Fatty Acids by UHPLC-MS/MS.

Chemoselective extraction strategy is an emerging and powerful means for targeted metabolomics analysis, which allows for the selective identification of biomarkers. Short-chain fatty acids (SCFAs) as functional metabolites for many diseases pose challenges in qualitative and quantitative analyses due to their high polarity and uneven abundance. In our study, we proposed the B-labeled method for the derivatization of SCFAs using easily available 3-aminobenzeneboronic acid as the derivatization reagent, which enables the introduction of recognition unit (boric acid groups). To analyze the B-labeled targeted metabolites accurately, cis-diol-based covalent organic framework (COF) was designed to specifically capture and release target compounds by pH-response borate affinity principle. The COF synthesized by the one-step Schiff base reaction possessed a large surface area (215.77 m2/g), excellent adsorption capacity (774.9 µmol/g), good selectivity, and strong regeneration ability (20 times). Combined with ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) analysis, our results indicated that the detection sensitivities of SCFAs increased by 1.2-2500 folds compared with unlabeled method, and the retention time and isomer separation were improved. Using this strategy, we determined twenty-six SCFAs in the serum and urine of rats in four groups about osteoporosis and identified important biomarkers related to the tricarboxylic acid cycle and fatty acid metabolism pathways. In summary, UHPLC-MS/MS based on B-labeled derivatization with tailored COF strategy shows its high selectivity, excellent sensitivity, and good chromatographic behavior and has remarkable application prospect in targeted metabolomics study of biospecimens.

Comprehensive characterization of Epimedium-Rhizoma drynariae herb pair in rat plasma, urine, and feces metabolic profiles by UHPLC-Q-Orbitrap HRMS combined with diagnostic extraction strategy and multicomponent pharmacokinetic study by UHPLC-MS/MS.

Epimedium-Rhizoma drynariae (EP-RD) was a well-known herb commonly used to treat bone diseases in traditional Chinese medicine. Nevertheless, there was incomplete pharmacokinetic behavior, metabolic conversion and chemical characterization of EP-RD in vivo. Therefore, this study aimed to establish metabolic profiles combined with multicomponent pharmacokinetics to reveal the in vivo behavior of EP-RD. Firstly, the diagnostic product ions (DPIs) and neutral losses (NLs) filtering strategy combined with UHPLC-Q-Orbitrap HRMS for the in vitro chemical composition of EP-RD and metabolic profiles of plasma, urine, and feces after oral administration of EP-RD to rats were proposed to comprehensively characterize the 47 chemical compounds and the 97 exogenous in vivo (35 prototypes and 62 metabolites), and possible biotransformation pathways of EP-RD were proposed, which included phase I reactions such as hydrolysis, hydrogenation, dehydrogenation, hydroxylation, dehydroxylation, isomerization, and demethylation and phase II reactions such as glucuronidation, acetylation, methylation, and sulfation. Moreover, a UHPLC-MS/MS quantitative approach was established for the pharmacokinetic analysis of seven active components: magnoflorine, epimedin A, epimedin B, epimedin C, icariin, baohuoside II, and icariin II. Results indicated that the established method was reliably used for the quantitative study of plasma active ingredients after oral administration of EP-RD in rats. Compared to oral EP alone, the increase in area under curves and maximum plasma drug concentration (P < 0.05). This study increased the understanding of the material basis and biotransformation profiles of EP-RD in vivo, which was of great significance in exploring the pharmacological effects of EP-RD.

Integrated untargeted and targeted testicular metabolomics to reveal the regulated mechanism of Gushudan on the hypothalamic-pituitary-gonadal axis of kidney-yang-deficiency-syndrome rats.

Modern studies have shown that neuroendocrine disorders caused by the dysfunction of the hypothalamic-pituitary-gonadal (HPG) axis are one of the important pathogenetic mechanisms of kidney-yang-deficiency-syndrome (KYDS). The preventive effect of Gushudan on KYDS has been reported, but its regulatory mechanisms on the HPG axis have not been elucidated. In this study, we developed an integrated untargeted and targeted metabolomics analysis strategy to investigate the regulatory mechanism of Gushudan on the HPG axis in rats with KYDS. In untargeted metabolomics, we screened 14 potential biomarkers such as glycine, lysine, and glycerol that were significantly associated with the HPG axis. To explore the effect of changes in the levels of potential biomarkers on KYDS, all of them were quantified in targeted metabolomics. With the quantitative results, correlations between potential biomarkers and testosterone, a functional indicator of the HPG axis, were explored. The results showed that oxidative stress, inflammatory response, and energy depletion, induced by metabolic disorders in rats, were responsible for the decrease in testosterone levels. Gushudan improves metabolic disorders and restores testosterone levels, thus restoring HPG axis dysfunction. This finding elucidates the special metabolic characteristics of KYDS and the therapeutic mechanism of Gushudan from a new perspective.

Topological super-modes engineering with acoustic graphene plasmons.

Acoustic graphene plasmons (AGPs) in a graphene-dielectric-metal structure possess extreme field localization and low loss, which have promising applications in strong photon-matter interaction and integrated photonic devices. Here, we propose two kinds of one-dimensional crystals supporting propagating AGPs with different topological properties, which is confirmed by the Zak phase calculations and the electric field symmetry analysis. Moreover, by combining these two plasmonic crystals to form a superlattice system, the super-modes exist because of the coupling between isolated topological interface states. A flat-like dispersion of super-modes is observed by designing the superlattice. These results should find applications in optical sensing and integrating photonic devices with plasmonic crystals.

Giant Second Harmonic Generation from Membrane Metasurfaces.

Metasurfaces have emerged as a fascinating framework for nonlinear optics, which have advantages of a compact footprint and unprecedented flexibility in manipulating light. But their nonlinear responses are generally limited by the short interaction lengths with light. Therefore, further enhancement is highly desired for building high-efficiency nonlinear devices. Here, we experimentally demonstrate a record high second harmonic generation (SHG) efficiency of 2.0 × 10-4 using lithium niobate (LN) membrane metasurfaces. Benefiting from the large refractive index contrast in the vertical direction and high fabrication quality, distinct spectral resonances and tight field confinements in the LN layer were achieved. Strong SHG peaks resulting from pump resonances of the metasurfaces were observed. Our nonlinear efficiency is more than 2 orders of magnitude larger than previously reported LN metasurfaces. The results inspire a way to improve the efficiency of nonlinear metasurfaces for ultracompact nonlinear light sources in applications of nonlinear holography, Li-Fi, beam shaping, etc.

Metasurfaces with high-Q resonances governed by topological edge state.

Achieving high-quality (Q)-factor resonances in metasurfaces is essential for various applications, including nano-lasers, nonlinear optics, and quantum optics. In this work, we propose a high-Q metasurface using a topological strategy: constructing the metasurface by stacking two conjugated nanopillar arrays with different topological invariants. Our study shows that a topological edge state steadily appears at the interfaces of the nanopillars, and a sharp transmission resonance with a Q-factor of more than 1000 can be obtained. The sensing application of such high-Q topological metasurface is also demonstrated, whose figure of merit reaches approximately 145. The proposed strategy and underlying theory can open up new avenues to realize ultrasharp resonances, which can promote numerous potential applications, such as biosensing, optical modulation, and slow-light devices.

Error analysis of a rotating-metasurface polarimeter.

Polarimeters, which measure the polarization states of light directly, are essentially desired in many areas of science and technology. In our previous work, we have constructed a polarimeter based on a rotating-metasurface, and the polarization Stokes parameters of the light were measured with the known Mueller elements of the metasurface. Here, we further perform the error analysis of the metasurface polarimeter. The errors in the measured Stokes parameters have been formulated for the errors in Mueller elements of the metasurface. This analysis can be used to evaluate and minimize the errors of the metasurface polarimeter.

Nanoinfrared Characterization of Bilayer Graphene Conductivity under Dual-Gate Tuning.

Dual-gate tuning on two-dimensional (2D) heterostructures can provide independent control of the carrier concentration and interlayer electrostatic potential, yielding novel electronic and optical properties. In this paper, by utilizing monolayer graphene as both the top gate and a plasmon wavelength magnifier, the optical properties of bilayer graphene (BLG) under dual-gate are quantitatively investigated by nanoinfrared imaging. The hybrid optical modes in the vertically coupled two-layer system are imaged from scattering-type scanning near-field microscopy (s-SNOM). Moreover, plasmon dispersion behaviors under varied dual-gate tuning are explored and explained well with theoretical ones employing tight binding approximation, which reveals the flexibility in individually manipulating the Fermi energy and bandgap. Especially, electron-hole asymmetry in BLG is verified from experiments. Our studies pave route for quantitative near-field investigation of superlattice, topological boundaries, and other emergent phenomena in graphene-based 2D heterostructures.

Tunable terahertz topological edge and corner states in designer surface plasmon crystals.

In this work, we study topological edge and corner states in two-dimensional (2D) Su-Schrieffer-Heeger lattices from designer surface plasmon crystals (DSPCs), where the vertical confinement of the designer surface plasmons enables signal detection without the need of additional covers for the sample. In particular, the formation of higher-order topological insulator can be determined by the two-dimensional Zak phase, and the zero-dimensional subwavelength corner states are found in the designed DSPCs at the terahertz (THz) frequency band together with the edge states. Moreover, the corner state frequency can be tuned by modifying the defect strength, i.e., the location or diameter of the corner pillars. This work may provide a new approach for confining THz waves in DSPCs, which is promising for the development of THz topological photonic integrated devices with high compactness, robustness and tunability.

Multifunctional and tunable trigate graphene metamaterial with "Lakes of Wada" topology.

Many plasmon-induced transparency (PIT) metamaterials previously reported had limited functions. Their tunabilities were realized by complex discrete structures, which greatly increased the difficulty and cost of device fabrication and adversely affected their resonance characteristics. It is an open question to adjust the Fermi levels of many graphene patterns with only a few in-plane electrodes. We propose and numerically study a novel electrically tunable and multifunctional trigate graphene metamaterial (TGGM) based on the concept of "Lakes of Wada". Benefiting from the trigate regulation, our proposed TGGM turns out to exhibit excellent characteristics, that can not only be used for terahertz band-stop filter, terahertz refractive index sensor, near-field optical switch, slow-light device, but also for double PIT window metamaterial with broad transparency windows and large tunable frequency range.

Phase-Transition Optical Activity in Chiral Metamaterials.

Optical activity from chiral metamaterials is both fundamental in electrodynamics and useful for polarization control applications. It is normally expected that due to infinitesimally small thickness, two-dimensional (2D) planar metamaterials cannot introduce large optical rotations. Here, we present a new mechanism to achieve strong optical rotation up to 90° by evoking phase transition in the 2D metamaterials through tuning coupling strength between meta-atoms. We analytically elucidate such phenomenon by developing a model of phase-transition coupled-oscillator array. And we further corroborate our ideas with both numerical simulations and experiments. Our findings would pave a new way for applying the concept of phase transition in photonics for designing novel optical devices for strong polarization controls and other novel applications.

Real-space mapping of mid-infrared near-field of Yagi-Uda antenna in the emission mode.

By using transmission-mode, scattering-type scanning near-field optical microscopy, we characterize the mid-infrared near-field properties of a Yagi-Uda antenna in the emission mode. The underlying near-field properties, including the near-field dipole-dipole coupling between antenna elements, are clearly observed. Moreover, even though most of the radiation energy is emitted into the substrate, by adopting two detector antennas, we managed to verify the unidirectionality and frequency-selectivity of the Yagi-Uda antenna in the air side. All the experimental results presented in this work are in good qualitative agreement with our numerical simulations. Our work on the Yagi-Uda antenna could help lead to novel methods for mid-infrared material analysis and bio-sensing. It should also be applicable in all-optical processing like radiation routers or a chromatic discriminator.

Experimental observed plasmon near-field response in isolated suspended graphene resonators.

Because of extreme three-dimensional field confinement and easy electrically tunability, plasmons in graphene nanostructures are promising candidates for many applications, such as biosensing, photodetectors and modulators. However, up to now, graphene plasmons have been explored mostly on substrates. Scatterers, corrugations and dopants induced by substrates not only add damping to plasmons but also obscure the intrinsic electronic properties of graphene. In this work, the near-field response of surface plasmons of suspended graphene circular resonators is studied with the scattering-type scanning near-field optical microscopy under different excitation wavelengths, λ = 10.653 and 10.22 µm, respectively. Fundamental and higher order breathing plasmon modes are revealed in real-space with the Fermi energy of graphene of only 0.132 eV. Moreover, the direct experimental evidence on near-field electric tuning in suspended graphene resonators is demonstrated by using back-gate tuning. Our work not only provides a foundation to truly understand the properties of electrons inside pure graphene, but shines light on the applications in optoelectronic devices with suspended two-dimensional materials.

Mechanism of Electric Power Generation from Ionic Droplet Motion on Polymer Supported Graphene.

Graphene-based electric power generation that converts mechanical energy of flow of ionic droplets over the device surface into electricity has emerged as a promising candidate for blue-energy network. Yet the lack of a microscopic understanding of the underlying mechanism has prevented ability to optimize and control the performance of such devices. This requires information on interfacial structure and charging behavior at the molecular level. Here, we use sum-frequency vibrational spectroscopy to study the roles of solvated ions, graphene, surface moiety on substrate and water molecules at the aqueous solution/graphene/polymer interface. We discover that the surface dipole layer of the neutral polymer is responsible for ion attraction toward and adsorption at the graphene surface that leads to electricity generation in graphene. Graphene itself does not attract ions and only acts as a conducting sheet for the induced carrier transport. Replacing the polymer by an organic ferroelectric substrate could allow switching of the electricity generation with long durability. Our microscopic understanding of the electricity generation process paves the way for the rational design of scalable and more efficient droplet-motion-based energy transducer devices.

Laser direct writing of graphene nanostructures beyond the diffraction limit by graphene oxidation.

The fabrication ability of graphene nanostructures is the cornerstone of graphene-based devices, which are of particular interest because of their broad optical response and gate-tunable properties. Here, via laser-induced redox reaction of graphene and silica, we fabricate nano-scale graphene structures by femtosecond laser direct writing. The resolution of destructed graphene lines is far beyond the diffraction limit up to 100 nm with a precision as small as ± 7 nm. Consequently, graphene nanostructures are fabricated precisely and excellent plasmon responses are detected. This novel fabrication method of graphene nanostructures has the advantages of low costs, high efficiency, maskless and especially high precision, which would pave the way for practical application of graphene-based optical and electronic devices.

Strain sensing based on a microbottle resonator with cleaned-up spectrum.

In this Letter, a microbottle-resonator-based strain sensor with individual mode distribution and recognizable resonance spectrum was proposed and demonstrated. A cleaned-up spectrum was achieved by inscribing horizontal microgroove scars close to the bottle center. The inscribing parameters of these grooves were designed according to the field distribution of the modes, and the obtained spectrum showed excellent consistency with theoretical analysis. The shift in the resonance peak with increasing stretching force was investigated, and the corresponding strain sensitivities were 0.085 pm/µÏµ for transverse electric polarization and 0.136 pm/µÏµ for transverse magnetic polarization, which could be further increased by using materials with smaller elastic moduli.

Nanoscale beam splitters based on gradient metasurfaces.

Beam splitters are essential components in various optical and photonic applications, for example, interferometers, multiplexers, and so on. Present beam splitters based on cubes or plates are normally bulky. Realizing beam splitters in nanoscales is useful to reduce the total size of photonic devices. We demonstrate here a beam splitter with nanoscale thickness based on a gradient metasurface comprising lithium niobate cylinder arrays. Since one unit cell of metasurface comprising two cylinder rows shows two opposite phase gradients, the incident light is split into different directions according to the generalized Snell's law. The split ratio is proven to be effectively tunable.

Near-field imaging of graphene triangles patterned by helium ion lithography.

Plasmon nanoresonators in graphene have many applications in biosensing, photodetectors and modulators. As a result, an efficient and precise patterning technique for graphene is required. Helium ion lithography (HIL) emerges as a promising tool for direct writing fabrication because it owns improved fabrication precision compared to electron beam lithography and conventional gallium focused ion beam technique. In this paper, utilizing HIL, a set of graphene triangles are patterned and excellent plasmon response is detected. Particularly, the evolution of breathing mode in these structures is unveiled by scattering-type scanning near-field optical microscopy. Besides, the plasmon response of graphene structures can be efficiently tuned by adjusting the irradiated ion dose during the etching process, which can be explained by the phenomenal simulation model. Our work demonstrates that HIL is a feasible way for precise plasmonic nanostructure fabrication, and can be applied to graphene plasmon control at the nanoscale as well.

Dynamic spontaneous emission control of an optical emitter coupled to plasmons in strained graphene.

Spontaneous emission control of an optical emitter is critical for many applications, such as in the fields of sensing, integrated photonics and quantum optics. Integrating optical emitters with a mechanical system can provide an avenue for strain sensors as well. Here, the dynamic spontaneous emission modification of an emitter coupled to graphene by uniaxial strain is demonstrated. Our results show that the emission rate can be controlled by tuning the strain of graphene, which depends on the polarized orientation of the emitter. More specifically, the decay rate can be enhanced for several times if the emitter is polarized perpendicular to graphene under strain. Azimuthal angle dependent oscillation of decay rate exists for the emitter polarized parallel to the graphene. Moreover, the controllable decay of the emitter comes from the anisotropic plasmons excitation in strained graphene, which is verified by the corresponding isofrequency contours of plasmons. The strain engineering provides a new platform for dynamic spontaneous emission modulation of emitters coupled with graphene, which opens up intriguing possibilities for the design of strain sensors and quantum devices.

Unidirectional excitation of graphene plasmons in Au-graphene composite structures by a linearly polarized light beam.

Controllable manipulation of propagating surface plasmon polaritons is critical in plasmonics and important for nanophotonic applications. Here, we demonstrate theoretically that graphene plasmons (GPs) can be unidirectionally excited in an Au-graphene composite structure by a linearly polarized optical wave at the wavelength of 10.2 µm. The unidirectional ratio can reach as large as 900 with the incidence angle at 37.7° off normal, which is obtained by the angular spectrum of GPs. Moreover, the physical mechanism behind the unidirectional excitation is revealed to be the interference between anti-symmetric and symmetric amplitude distributions of GPs, which are induced by the gold rod antenna under the normal and grazing illuminations, respectively.