Design, Synthesis, and Biological Activity of Novel Triketone-Containing Phenoxy Nicotinyl Inhibitors of HPPD.

4-Hydroxyphenylpyruvate dioxygenase (HPPD) is a crucial target enzyme in albino herbicides. The inhibition of HPPD activity interferes with the synthesis of carotenoids, blocking photosynthesis and resulting in bleaching and necrosis. To develop herbicides with excellent activity, a series of 3-hydroxy-2-(6-substituted phenoxynicotinoyl)-2-cyclohexen-1-one derivatives were designed via active substructure combination. The title compounds were characterized via infrared spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopies, and high-resolution mass spectrometry. The structure of compound III-17 was confirmed via single-crystal X-ray diffraction. Preliminary tests demonstrated that some compounds had good herbicidal activity. Crop safety tests revealed that compound III-29 was safer than the commercial herbicide mesotrione in wheat and peanuts. Moreover, the compound exhibited the highest inhibitory activity against Arabidopsis thaliana HPPD (AtHPPD), with a half-maximal inhibitory concentration of 0.19 µM, demonstrating superior activity compared with mesotrione (0.28 µM) in vitro. A three-dimensional quantitative structure-activity relationship study revealed that the introduction of smaller groups to the 5-position of cyclohexanedione and negative charges to the 3-position of the benzene ring enhanced the herbicidal activity. A molecular structure comparison demonstrated that compound III-29 was beneficial to plant absorption and conduction. Molecular docking and molecular dynamics simulations further verified the stability of the complex formed by compound III-29 and AtHPPD. Thus, this study may provide insights into the development of green and efficient herbicides.

A robust thin-film droplet-induced electricity generator.

The pursuit of cost-effective, high-voltage electricity generators activated by droplets represents a new frontier in hydropower technology. This study presents an economical method for crafting droplet generators using common materials such as solid polytetrafluoroethylene (PTFE) films and readily available tapes, eliminating the need for specialized cleanroom facilities. A thorough investigation into voltage-limiting factors, encompassing device capacitance and induced electrode charges, reveals specific areas with potential for optimization. A substantial enhancement in the open-circuit voltage (Voc) was achieved, reaching approximately 282.2 ± 27.9 V-an impressive increase of around 60 V compared to earlier benchmarks. One device showcased its capability to power 100 LEDs concurrently, underscoring its efficacy. Ten such devices created diverse luminous patterns with uniform light intensity for each LED, showcasing the practical potential of the approach. The methodology's cost-effectiveness results in a remarkable cost reduction compared to solution-based materials, paving the way for the widespread adoption of large-scale water droplet energy harvesting.

Imaging-based intelligent spectrometer on a plasmonic rainbow chip.

Compact, lightweight, and on-chip spectrometers are required to develop portable and handheld sensing and analysis applications. However, the performance of these miniaturized systems is usually much lower than their benchtop laboratory counterparts due to oversimplified optical architectures. Here, we develop a compact plasmonic "rainbow" chip for rapid, accurate dual-functional spectroscopic sensing that can surpass conventional portable spectrometers under selected conditions. The nanostructure consists of one-dimensional or two-dimensional graded metallic gratings. By using a single image obtained by an ordinary camera, this compact system can accurately and precisely determine the spectroscopic and polarimetric information of the illumination spectrum. Assisted by suitably trained deep learning algorithms, we demonstrate the characterization of optical rotatory dispersion of glucose solutions at two-peak and three-peak narrowband illumination across the visible spectrum using just a single image. This system holds the potential for integration with smartphones and lab-on-a-chip systems to develop applications for in situ analysis.

Superhydrophobic 3D-Assembled Metallic Nanoparticles for Trace Chemical Enrichment in SERS Sensing.

The performance of surface-enhanced Raman spectroscopy (SERS) is determined by the interaction between highly diluted analytes and boosted localized electromagnetic fields in nanovolumes. Although superhydrophobic surfaces are developed for analyte enrichment, i.e., to concentrate and transfer analytes toward a specific position, it is still challenging to realize reproducible, uniform, and sensitive superhydrophobic SERS substrates over large scales, representing a major barrier for practical sensing applications. To overcome this challenge, a superhydrophobic SERS chip that combines 3D-assembled gold nanoparticles on nanoporous substrates is proposed, for a strong localized field, with superhydrophobic surface treatment for analyte enrichment. Intriguingly, by concentrating droplets in the volume of 40 µL, the sensitivity of 1 nm is demonstrated using 1,2-bis(4-pyridyl)-ethylene molecules. In addition, this unique chip demonstrates a relative standard deviation (RSD) of 2.2% in chip-to-chip reproducibility for detection of fentanyl at 1 µg mL-1 concentration, revealing its potential for quantitative sensing of chemicals and drugs. Furthermore, the trace analysis of fentanyl and fentanyl-heroin mixture in human saliva is realized after a simple pretreatment process. This superhydrophobic chip paves the way toward on-site and real-time drug sensing to tackle many societal issues like drug abuse and the opioid crisis.

Super-Resolution Displacement Spectroscopic Sensing over a Surface "Rainbow".

Subwavelength manipulation of light waves with high precision can enable new and exciting applications in spectroscopy, sensing, and medical imaging. For these applications, miniaturized spectrometers are desirable to enable the on-chip analysis of spectral information. In particular, for imaging-based spectroscopic sensing mechanisms, the key challenge is to determine the spatial-shift information accurately (i.e., the spatial displacement introduced by wavelength shift or biological or chemical surface binding), which is similar to the challenge presented by super-resolution imaging. Here, we report a unique "rainbow" trapping metasurface for on-chip spectrometers and sensors. Combined with super-resolution image processing, the low-setting 4× optical microscope system resolves a displacement of the resonant position within 35 nm on the plasmonic rainbow trapping metasurface with a tiny area as small as 0.002 mm2. This unique feature of the spatial manipulation of efficiently coupled rainbow plasmonic resonances reveals a new platform for miniaturized on-chip spectroscopic analysis with a spectral resolution of 0.032 nm in wavelength shift. Using this low-setting 4× microscope imaging system, we demonstrate a biosensing resolution of 1.92 × 109 exosomes per milliliter for A549-derived exosomes and distinguish between patient samples and healthy controls using exosomal epidermal growth factor receptor (EGFR) expression values, thereby demonstrating a new on-chip sensing system for personalized accurate bio/chemical sensing applications.

Design, Synthesis, Structure-Activity Relationship, Molecular Docking, and Herbicidal Evaluation of 2-Cinnamoyl-3-Hydroxycyclohex-2-en-1-one Derivatives as Novel 4-Hydroxyphenylpyruvate Dioxygenase Inhibitors.

Cinnamic acid, isolated from cinnamon bark, is a natural product with excellent bioactivity, and it effectively binds with cyclohexanedione to form novel 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors. According to the active sub-structure combination principle, a series of novel 3-hydroxy-2-cinnamoyl-2-en-1-one derivatives were designed and synthesized. The title compounds were characterized by infrared, 1H NMR, 13C NMR, and HRMS. The in vitro inhibitory activity of AtHPPD verified that compound II-13 showed the most activity with a half-maximal inhibitory concentration (IC50) value of 0.180 µM, which was superior to that of mesotrione (0.206 µM) in vitro. The preliminary herbicidal activity tests demonstrated that some compounds had good herbicidal activity especially compound II-13 at a concentration of 150 g ai/ha. The binding mode of AtHPPD through molecular docking indicated that two oxygens of compounds II-13 formed bidentate interactions with metal ions, and the benzene ring formed π-π accumulation effects with Phe-381 and Phe-424. The results of molecular dynamics simulations showed that compound II-13 exhibited a more stable binding ability with AtHPPD than mesotrione. This study provided insights into the development of natural and efficient herbicides in the future.

Sustainable and Inexpensive Polydimethylsiloxane Sponges for Daytime Radiative Cooling.

Radiative cooling is an emerging cooling technology that can passively release heat to the environment. To obtain a subambient cooling effect during the daytime, chemically engineered structural materials are widely explored to simultaneously reject sunlight and preserve strong thermal emission. However, many previously reported fabrication processes involve hazardous chemicals, which can hinder a material's ability to be mass produced. In order to eliminate the hazardous chemicals used in the fabrication of previous works, this article reports a white polydimethylsiloxane (PDMS) sponge fabricated by a sustainable process using microsugar templates. By substituting the chemicals for sugar, the manufacturing procedure produces zero toxic waste and can also be endlessly recycled via methods widely used in the sugar industry. The obtained porous PDMS exhibits strong visible scattering and thermal emission, resulting in an efficient temperature reduction of 4.6 °C and cooling power of 43 W m-2 under direct solar irradiation. In addition, due to the air-filled voids within the PDMS sponge, its thermal conductivity remains low at 0.06 W (m K)-1 . This unique combination of radiative cooling and thermal insulation properties can efficiently suppress the heat exchange with the solar-heated rooftop or the environment, representing a promising future for new energy-efficient building envelope material.

Vapor condensation with daytime radiative cooling.

A radiative vapor condenser sheds heat in the form of infrared radiation and cools itself to below the ambient air temperature to produce liquid water from vapor. This effect has been known for centuries, and is exploited by some insects to survive in dry deserts. Humans have also been using radiative condensation for dew collection. However, all existing radiative vapor condensers must operate during the nighttime. Here, we develop daytime radiative condensers that continue to operate 24 h a day. These daytime radiative condensers can produce water from vapor under direct sunlight, without active consumption of energy. Combined with traditional passive cooling via convection and conduction, radiative cooling can substantially increase the performance of passive vapor condensation, which can be used for passive water extraction and purification technologies.

Decomposition of dimethyl methylphosphonate vapor on ultrathin-film titania photocatalytic light absorber.

The decomposition of chemical warfare agent simulant, dimethyl methylphophonate (DMMP) vapor, was investigated on an ultrathin film titania (TiO2) photocatalytic light absorber. The light absorber contains an aluminum (Al) reflector and the TiO2 thin film with different thicknesses, sequentially deposited on a supportive glass substrate. The designed structure constructs a nanocavity that exhibits strong light absorption within the photocatalytic TiO2 ultrathin film. Thus, the intrinsic trade-off between optical absorption and charge carrier extraction efficiency, i.e., a light absorber should be thick enough to absorb the light allowable by its band gap but thin enough to allow charge carrier extraction for catalytic reactions, is conquered. The TiO2/Al light absorber significantly boosted TiO2 photocatalytic activity compared to the benchmark Aeroxide®P25 catalyst (i.e., up to 2013 times increase in reaction rate). The effects of reactant (i.e. DMMP, water and oxygen, respectively) partial pressure and reaction temperature on photocatalytic decomposition of DMMP by the ultrathin-film TiO2 photocatalytic light absorber were studied. Kinetic data of the DMMP decomposition can be described by the Langmuir-Hinshelwood model.

Iridescence-controlled and flexibly tunable retroreflective structural color film for smart displays.

Structural color materials, which use nano- or microstructures to reflect specific wavelengths of ambient white light, have drawn much attention owing to their wide applications ranging from optoelectronics, coatings, to energy-efficient reflective displays. Although various structural color materials based on specular or diffuse reflection have been demonstrated, neither efficient retroreflective structural colors nor iridescent and non-iridescent colors to different observers simultaneously were reported by existing artificial or natural structural color materials. Here, we show that by partially embedding a monolayer of polymer microspheres on the sticky side of a transparent tape, the spontaneously formed interferometric structure on the surface of air-cushioned microspheres can lead to unique structural colors that remain non-iridescent under coaxial illumination and viewing conditions, but appear iridescent under noncoaxial illumination and viewing conditions. Our findings demonstrate a smart, energy-efficient, and tunable retroreflective structural color material that is especially suitable for nighttime traffic safety and advertisement display applications.

Ultrathin-Film Titania Photocatalyst on Nanocavity for CO2 Reduction with Boosted Catalytic Efficiencies.

Photocatalytic CO2 reduction with water to hydrocarbons represents a viable and sustainable process toward greenhouse gas reduction and fuel/chemical production. Development of more efficient catalysts is the key to mitigate the limits in photocatalytic processes. Here, a novel ultrathin-film photocatalytic light absorber (UFPLA) with TiO2 films to design efficient photocatalytic CO2 conversion processes is created. The UFPLA structure conquers the intrinsic trade-off between optical absorption and charge carrier extraction efficiency, that is, a solar absorber should be thick enough to absorb majority of the light allowable by its bandgap but thin enough to allow charge carrier extraction for reactions. The as-obtained structures significantly improve TiO2 photocatalytic activity and selectivity to oxygenated hydrocarbons than the benchmark photocatalyst (Aeroxide P25). Remarkably, UFPLAs with 2-nm-thick TiO2 films result in hydrocarbon formation rates of 0.967 mmol g-1 h-1, corresponding to 1145 times higher activity than Aeroxide P25. This observation is confirmed by femtosecond transient absorption spectroscopic experiments where longer charge carrier lifetimes are recorded for the thinner films. The current work demonstrates a powerful strategy to control light absorption and catalysis in CO2 conversion and, therefore, creates new and transformative ways of converting solar energy and greenhouse gas to alcohol fuels/chemicals.

Cold Vapor Generation beyond the Input Solar Energy Limit.

100% efficiency is the ultimate goal for all energy harvesting and conversion applications. However, no energy conversion process is reported to reach this ideal limit before. Here, an example with near perfect energy conversion efficiency in the process of solar vapor generation below room temperature is reported. Remarkably, when the operational temperature of the system is below that of the surroundings (i.e., under low density solar illumination), the total vapor generation rate is higher than the upper limit that can be produced by the input solar energy because of extra energy taken from the warmer environment. Experimental results are provided to validate this intriguing strategy under 1 sun illumination. The best measured rate is ≈2.20 kg m-2 h-1 under 1 sun illumination, well beyond its corresponding upper limit of 1.68 kg m-2 h-1 and is even faster than the one reported by other systems under 2 sun illumination.

Single-crystalline germanium nanomembrane photodetectors on foreign nanocavities.

Miniaturization of optoelectronic devices offers tremendous performance gain. As the volume of photoactive material decreases, optoelectronic performance improves, including the operation speed, the signal-to-noise ratio, and the internal quantum efficiency. Over the past decades, researchers have managed to reduce the volume of photoactive materials in solar cells and photodetectors by orders of magnitude. However, two issues arise when one continues to thin down the photoactive layers to the nanometer scale (for example, <50 nm). First, light-matter interaction becomes weak, resulting in incomplete photon absorption and low quantum efficiency. Second, it is difficult to obtain ultrathin materials with single-crystalline quality. We introduce a method to overcome these two challenges simultaneously. It uses conventional bulk semiconductor wafers, such as Si, Ge, and GaAs, to realize single-crystalline films on foreign substrates that are designed for enhanced light-matter interaction. We use a high-yield and high-throughput method to demonstrate nanometer-thin photodetectors with significantly enhanced light absorption based on nanocavity interference mechanism. These single-crystalline nanomembrane photodetectors also exhibit unique optoelectronic properties, such as the strong field effect and spectral selectivity.

Ultra-broadband enhancement of nonlinear optical processes from randomly patterned super absorbing metasurfaces.

Broadband light trapping and field localization is highly desired in enhanced light-matter interaction, especially in harmonic generations. However, due to the limited resonant bandwidth, most periodic plasmonic nanostructures cannot cover both fundamental excitation wavelength and harmonic generation wavelength simultaneously. Therefore, most previously reported plasmonic nonlinear optical processes are low in conversion efficiency. Here, we report a strong enhancement of second harmonic generation based on a three-layered super absorbing metasurface structure consisting of a dielectric spacer layer sandwiched by an array of random metallic nanoantennas and a metal ground plate. Intriguingly, the strong light trapping band (e.g. >80%) was realized throughout the entire visible to near-infrared spectral regime (i.e., from 435 nm to 1100 nm), enabling plasmonically enhanced surface harmonic generation and frequency mixing across a broad range of excitation wavelengths, which cannot be achieved with narrow band periodic plasmonic structures. By introducing hybrid random antenna arrays with small metallic nanoparticles and ultra-thin nonlinear optical films (e.g. TiO2) into the nanogaps, the nonlinear optical process can be further enhanced. This broadband light-trapping metastructure shows its potential as a building block for emerging nonlinear optical meta-atoms.

Extremely Cost-Effective and Efficient Solar Vapor Generation under Nonconcentrated Illumination Using Thermally Isolated Black Paper.

Passive solar vapor generation represents a promising and environmentally benign method of water purification/desalination. However, conventional solar steam generation techniques usually rely on costly and cumbersome optical concentration systems and have relatively low efficiency due to bulk heating of the entire liquid volume. Here, an efficient strategy using extremely low-cost materials, i.e., carbon black (powder), hydrophilic porous paper, and expanded polystyrene foam is reported. Due to the excellent thermal insulation between the surface liquid and the bulk volume of the water and the suppressed radiative and convective losses from the absorber surface to the adjacent heated vapor, a record thermal efficiency of ≈88% is obtained under 1 sun without concentration, corresponding to the evaporation rate of 1.28 kg (m2 h)-1. When scaled up to a 100 cm2 array in a portable solar water still system and placed in an outdoor environment, the freshwater generation rate is 2.4 times of that of a leading commercial product. By simultaneously addressing both the need for high-efficiency operation as well as production cost limitations, this system can provide an approach for individuals to purify water for personal needs, which is particularly suitable for undeveloped regions with limited/no access to electricity.

Frozen "Tofu" Effect: Engineered Pores of Hydrophilic Nanoporous Materials.

Frozen tofu is a famous Asian food made by freezing soft bean curds, which are naturally porous to store flavor and nutrients. When the narrow pores of the soft bean curd are saturated with water and then frozen, pore widths expand to generate a completely new porous structure-frozen tofu has visibly wider pores than the initial bean curd. Intriguingly, this principle can be generalized and applied to manipulate micro/nanopores of functional porous materials. In this work, we will manipulate the pore size of nanoporous polymeric photonic crystals based on the phase change between water and ice. Wet-drying and freeze-drying methods were applied to shrink or expand the pore size intentionally. This principle is validated by directly observing the optical reflection peak shift of the material. Owing to the change in pore size, the reflection peak of the polymeric photonic crystal structure can be permanently, and intentionally, tuned. This simple but elegant mechanism is promising for the development of smart materials/devices for applications ranging from oil/water membrane separations, health monitoring, and medical diagnostics to environmental monitoring, anticounterfeiting, and smart windows.

Flat metallic surface gratings with sub-10 nm gaps controlled by atomic-layer deposition.

Atomic layer lithography is a recently reported new technology to fabricate deep-subwavelength features down to 1-2 nm, based on combinations of electron beam lithography (EBL) and atomic layer deposition (ALD). However, the patterning area is relatively small as limited by EBL, and the fabrication yield is not very high due to technical challenges. Here we report an improved procedure to fabricate flat metallic surfaces with sub-10 nm features based on ALD processes. To demonstrate the scalability of the new manufacturing method, we combine the ALD process with large area optical interference patterning, which is particularly promising for the development of practical applications for nanoelectronics and nanophotonics with extremely strong confinement of electromagnetic fields.

Phase change dispersion of plasmonic nano-objects.

Phase is an inherent and important feature for coherent processes, which, unfortunately, has not been completely understood for surface plasmon polariton (SPP) and matter interactions. Here we propose a practical approach to extract the phase change dispersion during the interaction between free-space light, SPPs and nanogroove/slit based on far-field information only. Numerical simulation and experimental validation were both presented using nanoslit-groove plasmonic interferometers, agreeing well with theoretical near-field analysis. This approach is generally feasible to extract the intrinsic phase dispersion of other plasmonic nanostructures and can reveal more fundamental features of SPP-matter interactions.

Nanocavity absorption enhancement for two-dimensional material monolayer systems.

Here we propose a strategy to enhance the light-matter interaction of two-dimensional (2D) material monolayers based on strong interference effect in planar nanocavities, and overcome the limitation between optical absorption and the atomically-thin thickness of 2D materials. By exploring the role of spacer layers with different thicknesses and refractive indices, we demonstrate that a nanocavity with an air spacer layer placed between a graphene monolayer and an aluminum reflector layer will enhance the exclusive absorption in the graphene monolayer effectively, which is particularly useful for the development of atomically-thin energy harvesting/conversion devices.

A large-scale lithography-free metasurface with spectrally tunable super absorption.

Recently, periodically patterned metasurfaces have been employed to realize on-chip super/near-perfect optical absorption. However, most reported meta-absorbers rely on top-down micro/nano-lithography, which imposed a serious cost barrier on the development of practical applications, especially in the visible-infrared (IR) domain and at very large scales. Here we report a simple method to manufacture super absorptive metasurfaces using direct sputtering deposition. By controlling the deposition and post thermal treatment conditions, random metallic nanoparticles (NPs) can be formed easily on rigid and flexible substrates to function as the nanoantennas of spectrally tunable meta-absorbers. This low-cost and highly scalable approach would release the manufacturing barrier for previously reported meta-absorbers and therefore enable the development of affordable and large-scale thin-film metamaterial structures and devices.