Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal-rich silicon phosphides RuSi₄P₄ and IrSi₃P₃ are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X-ray diffraction and ²⁹Si and ³¹P magic angle spinning NMR. In agreement with previous report RuSi₄P₄ crystallizes in NCS space group P1, while IrSi₃P₃ is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi₄P₄ and IrSi₃P₃ to be wide bandgap (E_g) semiconductors, E_g = 1.9 and 1.8 eV, respectively. RuSi₄P₄ and IrSi₃P₃ outperform the current state-of-the-art infrared SHG material, AgGaS₂, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi₄P₄ and IrSi₃P₃ are promising candidates for longer wavelength NLO materials.     

Organic Semiconducting Luminophores for Near-Infrared Afterglow,Chemiluminescence, and Bioluminescence Imaging

Optical imaging has played a pivotal role in deciphering in vivo bioinformatics but is limited by shallow penetration depth and poor imaging performance owing to interfering tissue autofluorescence induced by concurrent photoexcitation. The emergence of near-infrared (NIR) self-luminescence imaging independent of real-time irradiation has timely addressed these problems. There are two main kinds of self-luminescent agents, namely inorganic and organic luminophores. Inorganic luminophores usually suffer from long-term biotoxicity concerns resulting from potential heavy-metal ions leakage and nonbiodegradability, which hinders their further translational application. In contrast, organic luminophores, especially organic semiconducting luminophores (OSLs) with good biodegradable potential, tunable design, and outstanding optical properties, are preferred in biological applications. This review summarizes the recent progress of OSLs used in NIR afterglow, chemiluminescence, and bioluminescence imaging. Molecular manipulation and nanoengineering approaches of OSLs are discussed, with emphasis on strategies that can extend the emission wavelength from visible to NIR range and amplify luminescence signals. This review concludes with a discussion of current challenges and possible solutions of OSLs in the self-luminescence field.     

Designing Semipermeable Hydrogel Shells with Controlled Thickness through Internal Osmosis in Triple-Emulsion Droplets

Hydrogel shells that compartmentalize the water core from the aqueous surrounding provide molecular selectivity on size and charge in transmembrane transport. It is highly demanding to produce thin hydrogel shells to minimize diffusion length and maximize core volume. Here, internal osmosis in water-in-oil-in-water-in-oil (W/O/W/O) triple-emulsion droplets is used to produce thin hydrogel shells enclosing a large water core. The triple-emulsion droplets are prepared to have an ultrathin middle oil layer using a capillary microfluidic device. The innermost water droplet has a higher osmolarity than the outer water layer containing photopolymerizable hydrogel precursors, which pumps water from the outer layer to the core through the ultrathin oil layer by the osmosis. Therefore, the outer layer gets thinner and hydrogel precursors are enriched while the size of the triple-emulsion droplets remains unchanged. Through photopolymerization of precursors and phase transfer from oil to water, hydrogel shells enclosing water core are produced in the water environment; the oil layer is ruptured for molecular exchange through the shells. The thickness and composition of the hydrogel shells are precisely controllable by the osmotic conditions. The shells show a high permeation rate due to the thinness as well as controlled cut-off threshold of permeation for neutral and charged molecules.     

Progressive NO2 Sensors with Rapid Alarm and Persistent Memory-Type Responses for Wide-Range Sensing Using Antimony Triselenide Nanoflakes

Antimony triselenide (Sb₂Se₃) nanoflake-based nitrogen dioxide (NO₂) sensors exhibit a progressive bifunctional gas-sensing performance, with a rapid alarm for hazardous highly concentrated gases, and an advanced memory-type function for low-concentration (<1 ppm) monitoring repeated under potentially fatal exposure. Rectangular and cuboid shaped Sb₂Se₃ nanoflakes, comprising van der Waals planes with large surface areas and covalent bond planes with small areas, can rapidly detect a wide range of NO₂ gas concentrations from 0.1 to 100 ppm. These Sb₂Se₃ nanoflakes are found to be suitable for physisorption-based gas sensing owing to their anisotropic quasi-2D crystal structure with extremely enlarged van der Waals planes, where they are humidity-insensitive and consequently exhibit an extremely stable baseline current. The Sb₂Se₃ nanoflake sensor exhibits a room-temperature/low-voltage operation, which is noticeable owing to its low energy consumption and rapid response even under a NO₂ gas flow of only 1 ppm. As a result, the Sb₂Se₃ nanoflake sensor is suitable for the development of a rapid alarm system. Furthermore, the persistent gas-sensing conductivity of the sensor with a slow decaying current can enable the development of a progressive memory-type sensor that retains the previous signal under irregular gas injection at low concentrations.     

Close‐Packed Two‐Dimensional Silver Nanoparticle Arrays: Quadrupolar and Dipolar Surface Plasmon Resonance Coupling

Silver nanoparticles (NPs) ranging in size from 40 to 100 nm were prepared in high yield by using an improved seed‐mediated method. The homogeneous Ag NPs were used as building blocks for 2D assembled Ag NP arrays by using an oil/water interface. A close‐packed 2D array of Ag NPs was fabricated by using packing molecules (3‐mercaptopropyltrimethoxysilane) to control the interparticle spacing. The homogeneous 2D Ag NP array exhibited a strong quadrupolar cooperative plasmon mode resonance and a dipolar red‐shift relative to individual Ag NPs suspended in solution. A well‐arranged 2D Ag NP array was embedded in polydimethylsiloxane film and, with biaxial stretching to control the interparticle distance, concomitant variations of the quadrupolar and dipolar couplings were observed. As the interparticle distance increased, the intensity of the quadrupolar cooperative plasmon mode resonance decreased and dipolar coupling completely disappeared. The local electric field of the 2D Ag NP array was calculated by using finite difference time domain simulation and qualitatively showed agreement with the experimental measurements.     

Statistical Optimization of Flavonoid and Antioxidant Recovery from Macerated Chinese and Malaysian Lotus Root (Nelumbo nucifera) Using Response Surface Methodology

In this study, the combination of parameters required for optimal extraction of anti-oxidative components from the Chinese lotus (CLR) and Malaysian lotus (MLR) roots were carefully investigated. Box–Behnken design was employed to optimize the pH (X₁: 2–3), extraction time (X₂: 0.5–1.5 h) and solvent-to-sample ratio (X₃: 20–40 mL/g) to obtain a high flavonoid yield with high % DPPH_sc free radical scavenging and Ferric-reducing power assay (FRAP). The analysis of variance clearly showed the significant contribution of quadratic model for all responses. The optimal conditions for both Chinese lotus (CLR) and Malaysian lotus (MLR) roots were obtained as: CLR: X₁ = 2.5; X₂ = 0.5 h; X₃ = 40 mL/g; MLR: X₁ = 2.4; X₂ = 0.5 h; X₃ = 40 mL/g. These optimum conditions gave (a) Total flavonoid content (TFC) of 0.599 mg PCE/g sample and 0.549 mg PCE/g sample, respectively; (b) % DPPH_sc of 48.36% and 29.11%, respectively; (c) FRAP value of 2.07 mM FeSO₄ and 1.89 mM FeSO₄, respectively. A close agreement between predicted and experimental values was found. The result obtained succinctly revealed that the Chinese lotus exhibited higher antioxidant and total flavonoid content when compared with the Malaysia lotus root at optimum extraction condition.     

Association between the microbiomes of tonsil and saliva samples isolated from pediatric patients subjected to tonsillectomy for the treatment of tonsillar hyperplasia

Oral microbes have the capacity to spread throughout the gastrointestinal system and are strongly associated with multiple diseases. Given that tonsils are located between the oral cavity and the laryngopharynx at the gateway of the alimentary and respiratory tracts, tonsillar tissue may also be affected by microbiota from both the oral cavity (saliva) and the alimentary tract. Here, we analyzed the distribution and association of the microbial communities in the saliva and tonsils of Korean children subjected to tonsillectomy because of tonsil hyperplasia (n = 29). The microbiome profiles of saliva and tonsils were established via 16S rRNA gene sequencing. Based on the alpha diversity indices, the microbial communities of the two groups showed high similarities. According to Spearman’s ranking correlation analysis, the distribution of Treponema, the causative bacterium of periodontitis, in saliva and tonsils was found to have a significant positive correlation. Two representative microbes, Prevotella in saliva and Alloprevotella in tonsils, were negatively correlated, while Treponema 2 showed a strong positive correlation between saliva and tonsils. Taken together, strong similarities in the microbial communities of the tonsils and saliva are evident in terms of diversity and composition. The saliva microbiome is expected to significantly affect the tonsil microbiome. Furthermore, we suggest that our study creates an opportunity for tonsillar microbiome research to facilitate the development of novel microbiome-based therapeutic strategies.Subject terms: Comparative genomics, Metagenomics     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.