Near-Infrared Circularly Polarized Luminescent Physical Unclonable Functions.

Distinguished from traditional physical unclonable functions (PUFs), optical PUFs derive their encoded information from the optical properties of materials, offering distinct advantages, including solution processability, material versatility, and tunable luminescence performance. However, existing research on optical PUFs has predominantly centered on visible photoluminescence, while advanced optical PUFs based on higher-level covert light remain unexplored. In this study, we present optical PUFs based on the utilization of the covert light of near-infrared circularly polarized luminescence (NIR-CPL). This interesting property is achieved by incorporating Yb-doped metal halide perovskite nanocrystals (Yb-PeNCs) possessing NIR emission property into chiral imprinted photonic (CIP) films. By employing a solvent immersion method, we successfully integrated Yb-PeNCs into these CIP films, thereby creating an optically unclonable surface. The resulting NIR-CPL emission adds a layer of advanced security to the optical PUF systems. These findings underscore the potential of solution-processable chiral films to play a pivotal role in advancing the next generation of PUFs.

Screening of plant growth-promoting rhizobacteria helps alleviate the joint toxicity of PVC+Cd pollution in sorghum plants.

Combined microplastic and heavy metal pollution (CM-HP) has become a popular research topic due to the ability of these pollutants to have complex interactions. Plant growth-promoting rhizobacteria (PGPR) are widely used to alleviate stress from heavy metal pollution in plants. However, the effects and mechanisms by which these bacteria interact under CM-HP have not been extensively studied. In this study, we isolated and screened PGPR from CM-HP soils and analyzed the effects of these PGPR on sorghum growth and Cd accumulation under combined PVC+Cd pollution through pot experiments. The results showed that the length and biomass of sorghum plants grown in PVC+Cd contaminated soil were significantly lower than those grown in soils contaminated with Cd alone, revealing an enhancement in toxicity when the two contaminants were mixed. Seven isolated and screened PGPR strains effectively alleviated stress due to PVC+Cd contamination, which resulted in a significant enhancement in sorghum biomass. PGPR mitigated the decrease in soil available potassium, available phosphorus and alkali-hydrolyzable nitrogen content caused by combined PVC+Cd pollution and increased the contents of these soil nutrients. Soil treatment with combined PVC+Cd pollution and PGPR inoculation can affect rhizosphere bacterial communities and change the composition of dominant populations, such as Proteobacteria, Firmicutes, and Actinobacteria. PICRUSt2 functional profile prediction revealed that combined PVC+Cd pollution and PGPR inoculation affected nitrogen fixation, nitrification, denitrification, organic phosphorus mineralization, inorganic phosphorus solubilization and the composition and abundance of genes related the N and P cycles. The Mantel test showed that functional strain abundance, the diversity index and N and P cycling-related genes were affected by test strain inoculation and were significant factors affecting sorghum growth, Cd content and accumulation. This study revealed that soil inoculation with isolated and screened PGPR can affect the soil inorganic nutrient content and bacterial community composition, thereby alleviating the stress caused by CM-HP and providing a theoretical basis and data support for the remediation of CM-HP.

Photon Upconversion Cooperates with Downshifting in Chiral Systems: Modulation, Amplification, and Applications of Circularly Polarized Luminescence.

Circularly polarized luminescence (CPL)-active materials are increasingly recognized for their potential applications such as 3D imaging, data storage, and optoelectronic devices. Typically, CPL materials have required high-energy (HE) photons for excitation to emit low-energy (LE) circularly polarized light, a process known as downshifting CPL (DSCPL). However, the emergence of upconverted CPL (UCCPL), where the absorption of multi LE photons results in the emission of a single HE photon with circular polarization, has recently attracted considerable attention. This minireview highlights the intricate relationship between upconversion and CPL phenomena. During upconversion, the dissymmetry factor (glum) value can be improved in certain systems. Additionally, the integration of both LE and HE photons in upconversion-downshifting-synergistic systems offers avenues for dual-excitation or dual-emission CPL functionalities. More in detail, the emerging UCCPL based on various photon upconversion mechanisms and their synergy with DSCPL are introduced. Additionally, several examples that demonstrate the applications of UCCPL are presented to highlight the future opportunities.

Effects of Long-Term Cryopreservation on the Transcriptomes of Giant Grouper Sperm.

The giant grouper fish (Epinephelus lanceolatus), one of the largest and rarest groupers, is a fast-growing economic fish. Grouper sperm is often used for cross-breeding with other fish and therefore sperm cryopreservation is important. However, freezing damage cannot be avoided. Herein, we performed a transcriptome analysis to compare fresh and frozen sperm of the giant grouper with frozen storage times of 0, 23, 49, and 61 months. In total, 1911 differentially expressed genes (DEGs), including 91 in El-0-vs-El-23 (40 upregulated and 51 downregulated), 251 in El-0-vs-El-49 (152 upregulated and 69 downregulated), and 1569 in El-0-vs-El-61 (984 upregulated and 585 downregulated), were obtained in the giant grouper sperm. DEGs were significantly increased at 61 months of cryopreservation (p < 0.05). GO and KEGG enrichment analyses of the DEGs revealed significant enrichment in the pilus assembly, metabolic process, MAPK signaling pathway, apoptosis, and P53 signaling pathway. Time-series expression profiling of the DEGs showed that consistently upregulated modules were also significantly enriched in signaling pathways associated with apoptosis. Four genes, scarb1, odf3, exoc8, and atp5f1d, were associated with mitochondria and flagella in a weighted correlation network analysis. These genes may play an important role in the response to sperm freezing. The experimental results show that long-term cryopreservation results in freezing damage to the giant grouper sperm. This study provides rich data for studies of the mechanism underlying frozen fish sperm damage as well as a technical reference and evaluation index for the long-term cryopreservation of fish sperm.

Effects of combined microplastic and cadmium pollution on sorghum growth, Cd accumulation, and rhizosphere microbial functions.

The interaction between microplastics (MPs) and cadmium (Cd) poses a threat to agricultural soil environments, and their effects on plant growth and rhizosphere microbial community functions are not yet clear. In this study, energy sorghum was used as a test plant to investigate the effects of two types of MPs, polystyrene (PS) and polyethylene (PE), at different particle sizes (13 µm, 550 µm) and concentrations (0.1%, 1% w/w), and Cd, as well as their interactions, on the growth of sorghum in a soil-cultivation pot experiment. The results showed that the combined effects of MP and Cd pollution on the dry weight and Cd accumulation rate in sorghum varied depending on the type, concentration, and particle size of the MPs, with an overall trend of increasing stress from combined pollution with increasing Cd content and accumulation. High-throughput sequencing analysis revealed that combined MP and Cd pollution increased bacterial diversity, and the most significant increase was observed in the abundance-based coverage estimator (ACE), Shannon, and Sobs indices in the 13 µm 1% PS+Cd treatment group. Metagenomic analysis based on the Kyoto Encyclopedia of Genes and Genomes (KEGG) metabolic pathways revealed that 19 groups of metabolic pathways, including microbial metabolism and methane metabolism, differed significantly under combined MP and Cd pollution. Hierarchical clustering results indicated that Cd treatment and combined MP and Cd treatment affected the abundances of sorghum rhizosphere soil nitrogen (N) and phosphorus (P) cycling genes and that the type of MP present was an important factor affecting N and P cycling genes. The results of this study provide a basis for exploring the toxic effects of combined MP and Cd pollution and for conducting soil environmental risk assessments.

A chiral bipolar host for efficient solution-processed circularly polarized OLEDs via a chirality energy transfer process.

Chiral bipolar hosts of (R/S)-L-2mCPCN are synthesized, which show high singlet/triplet energy levels and clear circularly polarized luminescence. Employing racemic phosphorescent and TADF materials as emitting guest molecules, solution-processable CP-OLEDs based on such chiral hosts are obtained with an EQEmax of 10.7% and |gEL| values of 5.0 × 10-3.

Pan-cancer analysis reveals a regulatory pattern of anoikis in human cancers.

Anoikis emerges when a cell finds itself extricated from the appropriate extracellular matrix, leading to an interruption in integrin ligation and thus triggering programmed cellular demise. The cardinal role of Anoikis in the realms of tumor invasion and metastasis is undeniable, although our grasp on its precise influence within the convoluted landscape of cancer biology remains somewhat circumscribed. Notably, both the immune milieu of the tumor and its inherent aggression are correlated with the fluctuating variables of Anoikis. We conducted a thorough evaluation of the genes associated with anoikis and studied the regulatory patterns of these genes as well as the prognostic impact of anoikis in 33 different types of tumors. We provided functional annotations for the regulatory patterns linked to Anoikis. Additionally, we described the associations between immunological factors and genes associated with Anoikis. By applying gene set variation analysis (GSVA), we utilized the inherent abilities of 34 basic genes to calculate the Anoikis index. The Anoikis index is closely related to prognosis, immune microenvironment, immunotherapy, and other aspects. Our functional research revealed a correlation between immune cell infiltration, EMT, and a regulatory gene that is synonymous with adverse survival outcomes. In addition, our observations revealed a direct relationship between the expression of CEACAM5 and CEACAM6,the amplification of epithelial mesenchymal transition (EMT) phenomenon, and a decrease in survival outcomes.The potential therapeutic utility of anoikis-related genes was highlighted by the possible links between TME, clinical samples, genetic mutations, drug resistance, and immunotherapy.

Dual Enhancement of Phosphorescence and Circularly Polarized Luminescence through Entropically Driven Self-Assembly of a Platinum(II) Complex.

Addressing the dual enhancement of circular polarization (glum) and luminescence quantum yield (QY) in circularly polarized luminescence (CPL) systems poses a significant challenge. In this study, we present an innovative strategy utilizing the entropically driven self-assembly of amphiphilic phosphorescent platinum(II) complexes (L-Pt) with tetraethylene glycol chains, resulting in unique temperature dependencies. The entropically driven self-assembly of L-Pt leads to a synergistic improvement in phosphorescence emission efficiency (QY was amplified from 15 % at 25 °C to 53 % at 60 °C) and chirality, both in the ground state and the excited state (glum value has been magnified from 0.04×10-2 to 0.06) with increasing temperature. Notably, we observed reversible modulation of phosphorescence and chirality observed over at least 10 cycles through successive heating and cooling, highlighting the intelligent control of luminescence and chiroptical properties by regulating intermolecular interactions among neighboring L-Pt molecules. Importantly, the QY and glum of the L-Pt assembly in solid state were measured as 69 % and 0.16 respectively, representing relatively high values compared to most self-assembled CPL systems. This study marks the pioneering demonstration of dual thermo-enhancement of phosphorescence and CPL and provides valuable insights into the thermal effects on high-temperature and switchable CPL materials.

Liquid-crystalline circularly polarised fluorescent emitters with a high luminescence dissymmetry factor.

Chiral liquid-crystalline emitters based on 9,9-dimethyl-10-(4-(phenylsulfonyl)phenyl)-9,10-dihydroacridine and a functionalised binaphthol show smectic liquid crystal phases and circularly polarised blue fluorescence with a high luminescence dissymmetry factor |glum| of 0.13. Solution-processable organic light-emitting diodes (OLEDs) based on the enantiomers were explored.

Liquid-crystalline circularly polarised TADF emitters for high-efficiency, solution-processable organic light-emitting diodes.

Achieving a high emission efficiency and a large luminescence asymmetry factor (glum) in a single molecule exhibiting circularly polarised thermally activated delayed fluorescence (CP-TADF) remains a formidable challenge. In this work, a proof-of-concept, liquid-crystalline CP-TADF molecule is proposed to realise high glum by taking advantage of the order inherent in liquid crystals. Employing a chiral dinaphthol-based CP-TADF molecule as the emissive unit, a pair of liquid-crystalline CP-TADF molecules (R/S-4) is synthesised via the introduction of six mesogenic moieties. The enantiomers show intense emission at about 520 nm which has clear TADF and liquid-crystalline characteristics. Both enantiomers display symmetrical electronic circular dichroism (CD) and circular polarisation luminescence (CPL) signals as thin films. Impressively, relatively large glum values of 0.11 are realised for the films. Solution-processed devices were fabricated using R/S-4 as the dopants, with the TADF molecule CzAcSF as the sensitiser. The OLEDs so prepared show a very high maximum external quantum efficiency of 21.2%, revealing a novel strategy for realising large glum values in CP-TADF.

Application of coronarin enhances maize drought tolerance by affecting interactions between rhizosphere fungal community and metabolites.

Coronarin (COR), an analog of jasmonic acid, has been shown to enhance the tolerance of plants to drought. However, the effects of COR on the interactions among microorganisms associated with plant roots and their implications for enhancing the drought tolerance of plants remain unclear. Here, we studied the effects of applying COR on the microorganisms associated with plant roots and the rhizosphere metabolome. Treatment with COR affected the fungal community of the rhizosphere by inducing changes in the rhizosphere metabolome, which enhanced the drought tolerance of plants. However, treatment with COR had no significant effect on root microorganisms or rhizosphere bacteria. Specifically, the application of COR resulted in a significant reduction in the relative abundance of metabolites, such as mucic acid, 1,4-cyclohexanedione, 4-acetylbutyric acid, Ribonic acid, palmitic acid, and stearic acid, in maize roots under drought conditions; COR application also led to increases in the abundance of drought-resistant fungal microorganisms, including Rhizopus, and the assembly of a highly drought-resistant rhizosphere fungal network, which enhanced the drought tolerance of plants. Overall, the results of our study indicate that COR application positively regulates interactions between plants and microbes and increases the drought tolerance of plants.

A Single-Enantiomer Emitter Enabled Superstructural Helix Inversion for Upconverting and Downshifting Luminescence with Bidirectional Circular Polarization.

The helical twisting tendency of liquid crystals (LCs) is generally governed by the inherent configuration of the chiral emitter. Here, we introduce the multistage inversion of supramolecular chirality as well as circularly polarized luminescence (CPL) by manipulating the ratio of single enantiomeric emitters (R-PCP) to LC monomers (5CB). Increasing the content of R-PCP from 1 wt % to 3 wt % inverted the helix of LCs from left-handed to right-handed, accompanying a CPL sign changed from positive to negative. The biaxiality of chiral emitters, as well as the steric effect of chiral-chiral and chiral-achiral interaction, were identified as the reasons for helical sense inversion. Due to the strong helical twisting power, 4 wt % R-PCP drove the photonic band gap (PBG) of chiral LCs to match up with their emission range, leading to an inversion of the CPL again with a high dissymmetry factor (≈1.2). Directly adjusting the PBG using chiral emitters is seldom achieved in cholesteric LCs. On this basis, an achiral sensitizer PtTPBP was assembled into the helical superstructure. The generation of triplet-triplet annihilation-induced upconverted CPL from R-PCP and the downshifting CPL from PtTPBP with opposite rotation was achieved in a single chiral LC system by tuning the position of the PBG.

Recyclable soft photonic crystal film with overall improved circularly polarized luminescence.

Existing circularly polarized luminescence materials can hardly satisfy the requirements of both large luminescence dissymmetry factor and high luminescent quantum yield, which hinders their practical applications. Here, we present a soft photonic crystal film embedded with chiral nanopores that possesses excellent circularly polarized luminescence performance with a high luminescence dissymmetry factor as well as a large luminescent quantum yield when loaded with various luminescent dyes. Benefitting from the retention of chiral nanopores imprinted from a chiral liquid crystal arrangement, the chiral soft photonic crystal film can not only endow dyes with chiral properties, but also effectively avoid severe aggregation of guest dye molecules. More importantly, the soft photonic crystal film can be recycled many times by loading and eluting guest dye molecules while retaining good stability as well as circularly polarized luminescence performance, enabling various applications, including smart windows, multi-color circularly polarized luminescence and anticounterfeiting.

Double-pivot proper digital artery perforator flap for fingertip reconstruction.

BACKGROUND: Dorsal flap based on proper digital artery perforator has been commonly used in wound coverage of fingertip; yet a small diameter and short length poses a risk of pedicle kinking or occlusion. The present study aims to present our preliminary results of using a double-pivot perforator flap based on the end dorsal branch of proper digital artery to repair finger pulp defect. METHODS: We designed a double-pivot flap based on the end-dorsal perforator branch of proper digital artery, raised from the dorsal aspect of the middle phalanx, with inclusion of both the perforator and a section of the trunk of the artery. This modified procedure forms a pedicle with a larger diameter and length than traditional designs. Twelve patients (12 fingers) each with a soft-tissue defect of the fingertip were successfully treated and followed up in this retrospective study. RESULTS: All the flaps survived without showing any signs of necrosis; three cases presented with transient venous flow disorder, these self-resolving without requiring any additional treatment. At final follow-up (12-33 months, mean 20 months), mean static two-point discrimination on the flap was 7.0 mm (range, 6-9). CONCLUSION: The double-pivot proper digital artery flap serves as a reliable option in fingertip reconstruction offering added benefits of having greater rotation flexibility, a lower risk of vessel kinking or occlusion, and good recovery of cutaneous sensation.

Effect of non-permeable cryoprotectant sucrose on the development of spotted knifejaw (Oplegnathus punctatus) embryos.

In this study, the toxicity of sucrose to Oplegnathus punctatus embryos was evaluated. Embryos at the 4-6 somite, tail-bud, heart formation, and heart-beating stages were exposed to 0, 0.5, 1,1.5, 2, 2.5, or 3 M sucrose for 1 h. Survival rates of embryos at the tail-bud, heart formation, and heart-beating stages after rehydration for 1 h were not affected by treatment with 2 M sucrose (the maximum concentration). Embryos at the tail-bud, heart formation, and heart-beating stages were exposed to 2 M sucrose for 0, 30, 60, 90, 120, 150, or 180 min. Long-term developmental indicators, including rates of survival, hatching, swimming, and malformation, were evaluated for 4 days after rehydration. Based on the survival rates 10 min after rehydration, the longest tolerance time for embryos at the three stages was 120 min. Based on long-term developmental indicators, the longest tolerance times were 60 min at the tail-bud, 60 min at the heart formation stage and 30 min at the heart beating stage. The malformation rates increased as the treatment time increased. The malformation rates were 100% when embryos were exposed to sucrose for ≥120 min. Malformation was divided into larval and embryonic abnormality. As the exposure time increased for tail-bud stage embryos, the rate of larval malformation increased. Treatment at heart formation and heart-beating stages resulted in higher rates of failure to hatch at exposure time. Based on these results, toxicity tests of non-permeable cryoprotectant in embryos requires the observation of development for at least 2 days after rehydration. Based on long-term observation, it was concluded that dehydration before freezing was not the direct cause of larvae deformity that hatched from frozen-thawing embryo. These results provide a reference for the singly use of representative non-permeable cryoprotectant sucrose.

Cascade energy transfer boosted near-infrared circularly polarized luminescence of nanofibers from an exclusively achiral system.

We constructed chiral supramolecular nanofibers for light harvesting based on symmetry-breaking, and these can generate near-infrared circularly polarized luminescence (CPL) with high dissymmetry factor (glum) through a synergistic energy transfer and chirality transfer process. Firstly, the achiral molecule BTABA was assembled into a symmetry-breaking assembly using a seeded vortex strategy. Subsequently, the chiral assembly can endow the two achiral acceptors, Nile Red (NR) and Cyanine 7 (CY7), with supramolecular chirality, as well as chiroptical properties. CY7 can reach an excited state and emit near-infrared light through a cascade energy transfer process from BTABA to NR and then to CY7, but cannot directly acquire energy from the excited BTABA. Significantly, the near-infrared CPL of CY7 can be obtained with a boosted glum value of 0.03. This work will provide a deep insight into the preparation of materials with near-infrared CPL activity from an exclusively achiral system.

Enantioselective Effect of Chiral Small Molecules in SARS-CoV-2 Vaccine-Induced Immune Response.

Although numerous chiral small molecules have been discovered and synthesized, the investigation on their enantioselective immunological effects remains limited. In this study, we designed and synthesized a pair of small molecule enantiomers (R/S-ResP) by covalently bonding two immunostimulators (resiquimod/Res) onto a planar chiral framework (paracyclophane/P). Notably, we found that S-ResP exhibits a 4.05-fold higher affinity for toll-like receptor 7 (TLR7) than R-ResP, thereby more effectively enhancing the functions of dendritic cells and macrophages in cytokine secretion and antigen internalization. Furthermore, we observed that S-ResP significantly enhances RBD antigen-induced cross-neutralization against various SARS-CoV-2 strains compared to R-ResP. These findings demonstrate the enantioselective effects of small molecules on regulating vaccine-induced immune responses and emphasize the significance of chirality in designing small molecular adjuvants.

Air-tolerant upconverted circularly polarized luminescence enabled by confined space of chiral micelle.

Circularly polarized luminescence (CPL) has been widely demonstrated that the circular polarization in excited state can be significantly amplified through the triplet-triplet annihilation-based upconversion (TTA-UC) luminescence process in various chiral nano-assemblies. However, constructing such an upconverted circularly polarized luminescence (UC-CPL) system in the aqueous phase remains a challenge. In this work, a kind of amphiphilic chiral cationic gemini surfactant is utilized to construct chiral spherical micelle in the aqueous phase, whose internal chiral cavity can provide a hydrophobic and deoxygenated environment for air-sensitive TTA-UC system. In addition, due to the co-assembly process between the emitters and chiral micelles, achiral emitters of upconversion pairs exhibit induced chiroptical properties. More importantly, the luminescence dissymmetry factor (glum ) can be amplified by one order of magnitude through TTA-UC process. This work provides an effective and useful strategy for realizing UC-CPL in aqueous phase.

Dual Band-Edge Enhancing Overall Performance of Upconverted Near-Infrared Circularly Polarized Luminescence for Anticounterfeiting.

Circularly polarized luminescence (CPL) is one of the critical chiroptical properties for chiral nanomaterials, which exhibit wide potential applications in many research fields. However, it remains a big challenge for real application, limited by their small luminescence dissymmetry factor or low emission intensity. Here, an upconverted near-infrared circularly polarized luminescence (UC-NIR-CPL) system is constructed based on the chiroptical property of chiral liquid crystals, embedding with the lanthanide-doped upconversion nanoparticles. More importantly, a strategy for improving the overall performance of UC-NIR-CPL was proposed and realized by taking advantage of the "dual-band-edge enhancement effect", wherein the glum value was amplified, while the NIR emission intensity showed dual enhancement and the threshold of excitation was decreased. Based on the improved overall performance of the UC-NIR-CPL, which can be used as a distinctive covert light, a kind of photonic barcode with multiple encryptions was realized. These findings will upgrade the level of information encryption through improving the overall performance of CPL-active materials.

Enhanced chiroptic properties of nanocomposites of achiral plasmonic nanoparticles decorated with chiral dye-loaded micelles.

The development of circularly polarized luminescence (CPL)-active materials with both large luminescence dissymmetry factor (glum) and high emission efficiency continues to be a major challenge. Here, we present an approach to improve the overall CPL performance by integrating triplet-triplet annihilation-based photon upconversion (TTA-UC) with localized surface plasmon resonance. Dye-loaded chiral micelles possessing TTA-UC ability are designed and attached on the surface of achiral gold nanorods (AuNRs). The longitudinal and transversal resonance peaks of AuNRs overlap with the absorption and emission of dye-loaded chiral micelles, respectively. Typically, 43-fold amplification of glum value accompanied by 3-fold enhancement of upconversion are obtained simultaneously when Au@Ag nanorods are employed in the composites. More importantly, transient absorption spectra reveal a fast accumulation of spin-polarized triplet excitons in the composites. Therefore, the enhancement of chirality-induced spin polarization should be in charge of the amplification of glum value. Our design strategy suggests that combining plasmonic nanomaterials with chiral organic materials could aid in the development of chiroptical nanomaterials.