An Automotive LiDAR Performance Test Method in Dynamic Driving Conditions.

The Light Detection and Ranging (LiDAR) sensor has become essential to achieving a high level of autonomous driving functions, as well as a standard Advanced Driver Assistance System (ADAS). LiDAR capabilities and signal repeatabilities under extreme weather conditions are of utmost concern in terms of the redundancy design of automotive sensor systems. In this paper, we demonstrate a performance test method for automotive LiDAR sensors that can be utilized in dynamic test scenarios. In order to measure the performance of a LiDAR sensor in a dynamic test scenario, we propose a spatio-temporal point segmentation algorithm that can separate a LiDAR signal of moving reference targets (car, square target, etc.), using an unsupervised clustering method. An automotive-graded LiDAR sensor is evaluated in four harsh environmental simulations, based on time-series environmental data of real road fleets in the USA, and four vehicle-level tests with dynamic test cases are conducted. Our test results showed that the performance of LiDAR sensors may be degraded, due to several environmental factors, such as sunlight, reflectivity of an object, cover contamination, and so on.

Nonreciprocal infrared absorption via resonant magneto-optical coupling to InAs.

Nonreciprocal elements are a vital building block of electrical and optical systems. In the infrared regime, there is a particular interest in structures that break reciprocity because their thermal absorptive (and emissive) properties should not obey the Kirchhoff thermal radiation law. In this work, we break time-reversal symmetry and reciprocity in n-type-doped magneto-optic InAs with a static magnetic field where light coupling is mediated by a guided-mode resonator structure, whose resonant frequency coincides with the epsilon-near-zero resonance of the doped indium arsenide. Using this structure, we observe the nonreciprocal absorptive behavior as a function of magnetic field and scattering angle in the infrared. Accounting for resonant and nonresonant optical scattering, we reliably model experimental results that break reciprocal absorption relations in the infrared. The ability to design these nonreciprocal absorbers opens an avenue to explore devices with unequal absorptivity and emissivity in specific channels.

Nanoscale axial position and orientation measurement of hexagonal boron nitride quantum emitters using a tunable nanophotonic environment.

Color centers in hexagonal boron nitride (hBN) have emerged as promising candidates for single-photon emitters (SPEs) due to their bright emission characteristics at room temperature. In contrast to mono- and few-layeredhBN, color centers in multi-layered flakes show superior emission characteristics such as higher saturation counts and spectral stability. Here, we report a method for determining both the axial position and three-dimensional dipole orientation of SPEs in thickhBN flakes by tuning the photonic local density of states using vanadium dioxide (VO2), a phase change material. Quantum emitters under study exhibit a strong surface-normal dipole orientation, providing some insight on the atomic structure ofhBN SPEs, deeply embedded in thick crystals. Next, we optimized a hot pickup technique to reproducibly transfer thehBN flake from VO2/sapphire substrate onto SiO2/Si substrate and relocated the same emitters. Our approach serves as a practical method to systematically characterize SPEs inhBN prior to integration in quantum photonics systems.

Identification and composition of carbonate minerals of the calcite structure by Raman and infrared spectroscopies using portable devices.

A portable Raman device with a 532 nm excitation laser and a portable infrared spectrometer with ATR (Attenuated Total Reflection) mode were used to analyse the spectral features associated with the identification and compositional variation of Ca-Mg-Fe-Mn natural carbonate minerals with a calcite structure (calcite, ankerite, dolomite, siderite, rhodochrosite, and magnesite). A systematic study of the variations of the peak positions with various compositional ratios was carried out. Most of the band positions were shifted to lower wavenumbers with increasing ionic radius or atomic mass of the divalent cations but the band of the translational lattice (T) mode in Raman and the symmetric bending (ν4) band in the mid-infrared were the most sensitive. Therefore, the elemental variation of the Ca-Mg-Fe-Mn ratio in this carbonate series can be estimated from Raman and infrared band positions from spectra acquired with portable spectrometers.

Complete mitochondrial genome of the hybrid grouper Hyporthodus septemfasciatus (♀) × Epinephelus lanceolatus (♂).

The complete mitochondrial genome of the novel hybrid grouper (Hyporthodus septemfasciatus ♀ × Epinephelus lanceolatus ♂) includes 13 protein-coding genes, 2 ribosomal RNAs, 22 transfer RNA genes, and 1 control region (D-loop) for a total length of 16,559 bp. The overall nucleotide composition encoded on the heavy strand comprises 28.64% A, 28.26% C, 16.26% G, and 26.84% T.

The complete mitochondrial genome of the hybrid grouper Epinephelus fuscoguttatus (♀) × E. polyphekadion (♂).

This study determined the complete mitochondrial genome of the hybrid grouper Epinephelus fuscoguttatus ♀ × E. polyphekadion ♂. The complete mitochondrial genome is 16,648 bp and includes 13 protein-coding, 2 ribosomal RNA, 22 transfer RNA genes, and a control region (D-loop). The nucleotide composition of the L-strand was A 29.12%, C 28.33%, G 15.65%, and T 26.90%. All except the NADH dehydrogenase subunit (ND6) and eight tRNA genes are encoded on the H-strand.

Phase Modulation with Electrically Tunable Vanadium Dioxide Phase-Change Metasurfaces.

We report a dynamically tunable reflectarray metasurface that continuously modulates the phase of reflected light in the near-infrared wavelength range under active electrical control of the phase transition from semiconducting to semimetallic states. We integrate a vanadium dioxide (VO2) active layer into the dielectric gap of antenna elements in a reflectarray metasurface, which undergoes an insulator-to-metal transition upon resistive heating of the metallic patch antenna. The induced phase transition in the VO2 film strongly perturbs the magnetic dipole resonance supported by the metasurface. By carefully controlling the volume fractions of coexisting metallic and dielectric regions of the VO2 film, we observe a continuous shift of the phase of the reflected light, with a maximal achievable phase shift as high as 250°. We also observe a reflectance modulation of 23.5% as well as a spectral shift of the resonance position by 175 nm. The metasurface phase modulation is fairly broadband, yielding large phase shifts at multiple operation wavelengths.

Ethylene Epoxidation Catalyzed by Ag Nanoparticles on Ag-LSX Zeolites formed by Pressure- and Temperature-Induced Auto-Reduction.

Ag+ -Exchanged LSX (Ag-LSX: Ag96 Al96 Si96 O384 ⋅n H2 O), a large pore low silica analogue (Si/Al=1.0) of faujasite, was prepared and post-synthetically modified using pressure and temperature in the presence of various pore-penetrating fluids. Using high-resolution synchrotron X-ray powder and single crystal diffraction we derive structural models of the as-prepared and post-synthetically modified Ag-LSX materials. In the as-prepared Ag-LSX model, we located 96 silver cations and 245 H2 O molecules distributed over seven and five distinctive sites, respectively. At 1.4(1) GPa pressure and 150 °C in ethanol the number of silver cations within the pores of Ag-LSX is reduced by ca. 47.4 %, whereas the number of H2 O molecules is increased by ca. 40.8 %. The formation of zero-valent silver nanoparticles deposited on Ag-LSX crystallites depends on the fluid present during pressurization. Ag-nanoparticle-Ag-zeolite hybrid materials are recovered after pressure release and shown to have different chemical reactivity when used as catalysts for ethylene epoxidation.

Hollowing out MOFs: hierarchical micro- and mesoporous MOFs with tailorable porosity via selective acid etching.

We report a new strategy for the synthesis of robust hierarchical micro- and mesoporous MOFs from water stable MOFs via a selective acid etching process. The process is controlled by the size-selective diffusion of acid molecules through the MOF windows. This method enables the fine-tuning of the porosity of hierarchical MOFs, allowing for the generation of well-defined mesopores with high mesopore volume. Because of the size-selective diffusion of acid molecules, the inherent crystallinity and external morphology of the resulting MOFs are well-maintained after acid treatment. This novel strategy may provide an alternative route towards the synthesis of diverse hierarchical MOFs.

Triazenyl Radicals Stabilized by N-Heterocyclic Carbenes.

Notwithstanding the notable progress in the synthesis of N-heterocyclic carbene-stabilized radicals, aminyl radicals, supported by NHCs or otherwise, have been scarcely studied due to synthetic challenges. Triazenyl radical is a particular form of aminyl radical that contains three adjacent nitrogen atoms, and offers intriguing possibilities for unique reactivity and physical properties stemming from expected delocalization of the spin density over the NNN moiety and its conjugated substituents. Here, we report the synthesis and full characterization of the first NHC-stabilized triazenyl radicals, obtained by one-electron reduction of the corresponding triazenyl cations with potassium metal. These radicals reversibly oxidize back to the cations upon treatment with transition metal sources or electrophiles, and abstract H atom from xanthene to form a new N-H bond at the center nitrogen atom. Potential application of the redox couple between triazenyl cation and triazenyl radical was demonstrated as cathode active materials in lithium ion batteries.

How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity?

Cucurbit[7]uril (CB[7]) is known to bind strongly to hydrophilic amino saccharide guests with exceptional α-anomer selectivities under aqueous conditions. Single-crystal X-ray crystallography and computational methods were used to elucidate the reason behind this interesting phenomenon. The crystal structures of protonated galactosamine (GalN) and glucosamine (GluN) complexes confirm the inclusion of α anomers inside CB[7] and disclose the details of the host-guest binding. Whereas computed gas-phase structures agree with these crystal structures, gas-phase binding free energies show preferences for the ß-anomer complexes over their α counterparts, in striking contrast to the experimental results under aqueous conditions. However, when the solvation effect is considered, the binding structures drastically change and the preference for the α anomers is recovered. The α anomers also tend to bind more tightly and leave less space in the CB[7] cavity toward inclusion of only one water molecule, whereas loosely bound ß anomers leave more space toward accommodating two water molecules, with markedly different hydrogen-bonding natures. Surprisingly, entropy seems to contribute significantly to both anomeric discrimination and binding. This suggests that of all the driving factors for the strong complexation of the hydrophilic amino saccharide guests, water mediation plays a crucial role in the anomer discrimination.

Light-Induced Acid Generation on a Gatekeeper for Smart Nitric Oxide Delivery.

We report herein the design of a light-responsive gatekeeper for smart nitric oxide (NO) delivery. The gatekeeper is composed of a pH-jump reagent as an intermediary of stimulus and a calcium phosphate (CaP) coating as a shielding layer for NO release. The light irradiation and subsequent acid generation are used as triggers for uncapping the gatekeeper and releasing NO. The acids generated from a light-activated pH-jump agent loaded in the mesoporous nanoparticles accelerated the degradation of the CaP-coating layers on the nanoparticles, facilitating the light-responsive NO release from diazeniumdiolate by exposing a NO donor to physiological conditions. Using the combination of the pH-jump reagent and CaP coating, we successfully developed a light-responsive gatekeeper system for spatiotemporal-controlled NO delivery.

The guest-dependent thermal response of the flexible MOF Zn2(BDC)2(DABCO).

The guest-dependent thermal response of the flexible MOF Zn2(BDC)2(DABCO) (1) has been studied. A series of temperature-dependent single crystallographic analyses revealed inherent structural thermal responses of 1. The guest-free framework 1 exhibited interesting thermal responses including anisotropic thermal expansion (negative thermal expansion (NTE) along the a- and b-axes, positive thermal expansion (PTE) along the c-axis) and disorder-order phase transition. In addition, inclusion of guest molecules (DMF and benzene) brought distinct thermal responses to 1 from host-guest interactions. 1·4DMF showed altered thermal responses, presenting disorder-order phase transitions at a higher temperature and PTE along the a- and b-axes. Meanwhile, 1·3benzene displayed a quite different type of thermal response such as a hinge like motion (breathing) without a symmetry change.

Hydrolytic Transformation of Microporous Metal-Organic Frameworks to Hierarchical Micro- and Mesoporous MOFs.

A new approach to the synthesis of hierarchical micro- and mesoporous MOFs from microporous MOFs involves a simple hydrolytic post-synthetic procedure. As a proof of concept, a new microporous MOF, POST-66(Y), was synthesized and its transformation into a hierarchical micro- and mesoporous MOF by water treatment was studied. This method produced mesopores in the range of 3 to 20 nm in the MOF while maintaining the original microporous structure, at least in part. The degree of micro- and mesoporosity can be controlled by adjusting the time and temperature of hydrolysis. The resulting hierarchical porous MOF, POST-66(Y)-wt, can be utilized to encapsulate nanometer-sized guests such as proteins, and the enhanced stability and recyclability of an encapsulated enzyme is demonstrated.

Porphyrin Boxes: Rationally Designed Porous Organic Cages.

The porphyrin boxes (PB-1 and PB-2), which are rationally designed porous organic cages with a large cavity using well-defined and rigid 3-connected triangular and 4-connected square shaped building units are reported. PB-1 has a cavity as large as 1.95 nm in diameter and shows high chemical stability in a broad pH range (4.8 to 13) in aqueous media. The crystalline nature as well as cavity structure of the shape-persistent organic cage crystals were intact even after complete removal of guest molecules, leading to one of the highest surface areas (1370 m(2) g(-1)) among the known porous organic molecular solids. The size of the cavities and windows of the porous organic cages can be modulated using different sized building units while maintaining the topology of the cages, as illustrated with PB-2. Interestingly, PB-2 crystals showed unusual N2 sorption isotherms as well as high selectivity for CO2 over N2 and CH4 (201 and 47.9, respectively at 273 K at 1 bar).

N-heterocyclic carbene nitric oxide radicals.

N-Heterocyclic carbene-stabilized nitric oxide radicals were prepared by direct addition of nitric oxide to two N-heterocyclic carbenes in solution phase. The compounds were fully characterized by X-ray crystallography and EPR. The nitric oxide moiety in the solid compounds obtained can be thermally transferred to another N-heterocyclic carbene, suggesting potential applications to NO delivery.

Systematic study on the sensitivity enhancement in graphene plasmonic sensors based on layer-by-layer self-assembled graphene oxide multilayers and their reduced analogues.

The use of graphene in conventional plasmonic devices was suggested by several theoretic research studies. However, the existing theoretic studies are not consistent with one another and the experimental studies are still at the initial stage. To reveal the role of graphenes on the plasmonic sensors, we deposited graphene oxide (GO) and reduced graphene oxide (rGO) thin films on Au films and their refractive index (RI) sensitivity was compared for the first time in SPR-based sensors. The deposition of GO bilayers with number of deposition L from 1 to 5 was carried out by alternative dipping of Au substrate in positively- and negatively charged GO solutions. The fabrication of layer-by-layer self-assembly of the graphene films was monitored in terms of the SPR angle shift. GO-deposited Au film was treated with hydrazine to reduce the GO. For the rGO-Au sample, 1 bilayer sample showed a higher RI sensitivity than bare Au film, whereas increasing the rGO film from 2 to 5 layers reduced the RI sensitivity. In the case of GO-deposited Au film, the 3 bilayer sample showed the highest sensitivity. The biomolecular sensing was also performed for the graphene multilayer systems using BSA and anti-BSA antibody.

Effect of coupled graphene oxide on the sensitivity of surface plasmon resonance detection.

We investigated graphene-oxide-(GO-) coupled surface plasmon resonance (SPR) detection sensitivity for sandwiched antigen-antibody interaction between human and antihuman immunoglobulin G molecules. GO was prepared in a Langmuir-Blodgett solution on gold and dielectric surfaces. Theoretical and experimental data suggest that an increased dielectric spacer thickness reduces resonance shifts for GO-coupled SPR detection as dielectric properties of GO appear to prevail. In general, a metal-enhanced structure was shown to provide a larger resonance shift by plasmonic field enhancement. The far-field properties were described in terms of near-field overlap. The peak resonance shift that was obtained with GO-coupled SPR detection was enhanced to 113% of the resonance shift obtained by conventional thin-film-based SPR detection and may further be improved by GO stacking.

Self-aligned colocalization of 3D plasmonic nanogap arrays for ultra-sensitive surface plasmon resonance detection.

We report extremely sensitive plasmonic detection that was performed label-free based on the colocalization of target DNA molecules and electromagnetic hot spots excited at 3D nanogap arrays. The colocalization was self-aligned by oblique evaporation of a dielectric mask over the 3D nanopatterns, which creates nanogaps for spatially selective target binding. The feasibility was experimentally confirmed by measuring hybridization of 24-mer single-stranded DNA oligonucleotides on triangular and circular 3D nanogap arrays. We were able to achieve significantly amplified optical signatures that lead to sensitivity enhancement in terms of detectable binding capacity in reference to conventional thin film-based surface plasmon resonance detection on the order of 1 fg/mm(2).

Metal-ion metathesis in metal-organic frameworks: a synthetic route to new metal-organic frameworks.

A porous metal-organic framework, Mn(H(3)O)[(Mn(4)Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl(2) under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasma-atomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and Brunauer-Emmett-Teller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.