Carbohydrate-DNA Conjugation Enabled by Glycosyl Radicals Generated from Glycosyl Sulfinates.

Herein, we report a method that enables the synthesis of carbohydrate-DNA conjugates by radical addition. Key to the success is the use of readily available, bench-stable, and unprotected glycosyl sulfinates as precursors to glycosyl radicals. The redox neutral reaction proceeds under mild and simple conditions and tolerates a broad substrate scope. A small library of carbohydrate-DNA conjugates was prepared.

Hair Heavy Metals and Food Consumption in Residents of Chengdu: Factors, Food Contribution, and Health Risk Assessment.

Heavy metal pollution is one of the most pressing issues threatening food security and human health. This study assesses heavy metal (chromium, cadmium, copper, zinc, nickel, and lead) exposure via hair metal concentrations in Chengdu residents, reflecting metal intake from food consumption. From June 2020 to February 2021, a sampling survey was conducted on residents' hair (n=182) and food (n=301) in six main urban areas of Chengdu. The concentrations of heavy metals in hair and food were analyzed by inductively coupled plasma mass spectrometry, and the results showed that the residents of Chengdu City had high hair concentrations of Cd (0.17±0.03 mg kg-1) and Zn (293±21.3 mg kg-1). Gender significantly affected the hair Cr, Zn, and Ni concentrations. Based on the survey results obtained from Chengdu City residents, the habits and diet structure are assessed for the influence of six heavy metals in the hair of the residents. Adolescents' (13-18 years old) hair had significantly higher Pb concentrations than adults (19-59 years old). The concentration of Ni in hair was affected by perming and dyeing habits. For dietary exposure, cereals and meat were the main contributors to the residents' daily intake of heavy metals. The bioaccessibility of Cr, Cd, Cu, Zn, Ni, and Pb in food was 2.45-74.67%, 10.6-78.7%, 13.4-82.5%, 8.89-89.2%, 7.70-85.1%, and 15.4-86.2%, respectively. In health risk evaluation based on the bioaccessible fraction of six heavy metals, the hazard quotient of each heavy metal in food was less than 1, indicating no potential non-carcinogenic risk.

Real-time programmable metasurface for terahertz multifunctional wave front engineering.

Terahertz (THz) technologies have become a focus of research in recent years due to their prominent role in envisioned future communication and sensing systems. One of the key challenges facing the field is the need for tools to enable agile engineering of THz wave fronts. Here, we describe a reconfigurable metasurface based on GaN technology with an array-of-subarrays architecture. This subwavelength-spaced array, under the control of a 1-bit digital coding sequence, can switch between an enormous range of possible configurations, providing facile access to nearly arbitrary wave front control for signals near 0.34 THz. We demonstrate wide-angle beam scanning with 1° of angular precision over 70 GHz of bandwidth, as well as the generation of multi-beam and diffuse wave fronts, with a switching speed up to 100 MHz. This device, offering the ability to rapidly reconfigure a propagating wave front for beam-forming or diffusively scattered wide-angle coverage of a scene, will open new realms of possibilities in sensing, imaging, and networking.

Generation and Use of Glycosyl Radicals under Acidic Conditions: Glycosyl Sulfinates as Precursors.

We herein report a method that enables the generation of glycosyl radicals under highly acidic conditions. Key to the success is the design and use of glycosyl sulfinates as radical precursors, which are bench-stable solids and can be readily prepared from commercial starting materials. This development allows the installation of glycosyl units onto pyridine rings directly by the Minisci reaction. We further demonstrate the utility of this method in the late-stage modification of complex drug molecules, including the anticancer agent camptothecin. Experimental studies provide insight into the reaction mechanism.

Dynamic terahertz transmission based on coupling reconfiguration of spoof surface plasmon polaritons.

In this paper, we propose a dynamic transmission structure based on the coupling reconfiguration of spoof surface plasmon polaritons (SSPPs) in a 2D coplanar grating. By embedding a VO2 film into the signal line, the dynamic transmission is realized by reconfiguring the coupling of terahertz waves from quasi-TEM waves to SSPPs. The analysis shows that the transmission can be modulated in almost the entire band of the SSPPs, which further benefits a promising group delay due to the weak dispersion characteristic in the frequency region much lower than the cut-off frequency of SSPPs. In addition, for the dynamic modulation caused by the coupling reconfiguration, only rather a small area of VO2 film is needed to break the robustness of the 2D coplanar grating. Therefore, the coupling reconfiguration mechanism proposed in this paper facilitates the realization of an easily on-chip integrated dynamic SSPPs transmission structure with ultra-large bandwidth, and low group delay time difference. Accordingly, the presented mechanism will play a positive role in promoting the development of terahertz dynamic devices.

Enantioselective direct vinylogous Michael addition for constructing enantioenriched γ,γ-dialkyl substituted butyrolactams and octahydroindoles.

A nickel(II)-catalyzed asymmetric direct vinylogous Michael addition of γ-alkyl monosubstituted α,ß-unsaturated butyrolactams to α,ß-unsaturated carbonyl compounds has been disclosed, affording γ,γ-dialkyl substituted butyrolactams in good yields and satisfactory enantioselectivities. A tandem catalytic asymmetric vinylogous Michael addition/intramolecular Michael addition has also been developed based on this reaction, which enabled the construction of enantioenriched octahydroindoles with three consecutive stereogenic carbon centers.

Photo-induced enhanced negative absorption in the graphene-dielectric hybrid meta-structure.

Recently, the negative absorption in graphene-based metamaterials became a very attractive direction of THz electronic devices. Here we propose a graphene-dielectric hybrid meta-structure to realize photo-induced enhanced negative absorption in the THz regime, which results from strong graphene-light interaction. The negative absorption is derived from the degradation of the conductivity of graphene under optical pump. Meanwhile, the graphene-dielectric hybrid meta-structure introduces dispersion relation and resonance mode, which can couple with the incident wave to construct a strong resonance. In this case, both the dispersion of the propagating waves and resonance are contributed to the graphene-light interaction and enhance the negative absorption, in which the resonance coupling determines the distribution of negative absorption, and the maximum is dominated by dispersion. More importantly, compared with the previous work, the negative absorption is increased by nearly 100 times by adopting this meta-structure.

A fractional phase-coding strategy for terahertz beam patterning on digital metasurfaces.

Coding metasurfaces have drawn great attention for its digital wave manipulation in deep subwavelength-scale in the last decade, more sophisticated and flexible coding strategies suitable for terahertz wavefront manipulations are becoming more urgently demanded. Due to its rigidity in phase gradient division, both phase gradient metasurfaces and conventional phase coding technique lack the flexibility to expand applications in a large field of view and accurate targeting. This study presents a generalized coding method by precisely reconfiguring the array factor based on the phased array theory and metasurface concept, which can be applied for anomalous scattering and ultrafine radiation patterning. According to our quantitative analysis on the relationship between the deflected angles and the supercell spacing, a fractional coding method for arbitrary phase gradient distribution has been attained by logically discretizing the spacing scale of supercells. By switching on different coding sequences or incident frequencies, a single beam to multiple beam scanning in an expanded angular range with minimal step can be achieved on the fractional phase-coding metasurfaces. As a proof of concept, the 2-bit coding metasurfaces arranged by four fractional coding sequences have been fabricated and measured, demonstrating a consecutive single-beam steering pattern ranging from 22° to 74° in 0.34-0.5 THz. Crosswise verified by the good accordance among numerical prediction, simulation and experiment, the proposed coding strategy paves a path to delicate beam regulation for high-resolution imaging and detection.

Dual-band refractometric terahertz biosensing with intense wave-matter-overlap microfluidic channel.

We theoretically and experimentally demonstrate a label-free terahertz biosensor with ultrahigh sensitivity and distinctive discretion. By constructing a metal-air-metal (MAM) metamaterial perfect absorber (MPA) with a metallic paired-ring resonator array, a hollow microfluidic channel, and a backed reflector, a novel dual-band absorptive sensing platform is proposed in the THz range. The near field coupling by dipole-induced trapped modes and the magnetic momentum caused a vertical to transverse power flux that dramatically enhanced the electromagnetic field on top of the metasurface and in the microfluidic channel, respectively. Both the resonant modes exhibit perfect absorption and produce ultrahigh normalized sensitivities of 0.47/RIU (refractive index unit, RIU) and 0.51/RIU at 0.76 THz and 1.28 THz, respectively. Compared with conventional microfluidic sensors, the salient advantages of our design are the perfect spatial overlap for light-matter interaction and polarization insensitivity. Characterized by THz time domain spectroscopic absorption quantification measurements with different concentrations of bovine serum albumin (BSA), the proposed sensor exhibits promising applications in microfluidic biosensing.