Spatiotemporal imaging of charge transfer in photocatalyst particles.

The water-splitting reaction using photocatalyst particles is a promising route for solar fuel production1-4. Photo-induced charge transfer from a photocatalyst to catalytic surface sites is key in ensuring photocatalytic efficiency5; however, it is challenging to understand this process, which spans a wide spatiotemporal range from nanometres to micrometres and from femtoseconds to seconds6-8. Although the steady-state charge distribution on single photocatalyst particles has been mapped by microscopic techniques9-11, and the charge transfer dynamics in photocatalyst aggregations have been revealed by time-resolved spectroscopy12,13, spatiotemporally evolving charge transfer processes in single photocatalyst particles cannot be tracked, and their exact mechanism is unknown. Here we perform spatiotemporally resolved surface photovoltage measurements on cuprous oxide photocatalyst particles to map holistic charge transfer processes on the femtosecond to second timescale at the single-particle level. We find that photogenerated electrons are transferred to the catalytic surface quasi-ballistically through inter-facet hot electron transfer on a subpicosecond timescale, whereas photogenerated holes are transferred to a spatially separated surface and stabilized through selective trapping on a microsecond timescale. We demonstrate that these ultrafast-hot-electron-transfer and anisotropic-trapping regimes, which challenge the classical perception of a drift-diffusion model, contribute to the efficient charge separation in photocatalysis and improve photocatalytic performance. We anticipate that our findings will be used to illustrate the universality of other photoelectronic devices and facilitate the rational design of photocatalysts.

Experimental Quantum Non-Gaussian Coincidences of Entangled Photons.

Quantum non-Gaussianity, a more potent and highly useful form of nonclassicality, excludes all convex mixtures of Gaussian states and Gaussian parametric processes generating them. Here, for the first time, we conclusively test quantum non-Gaussian coincidences of entangled photon pairs with the Clauser-Horne-Shimony-Holt-Bell factor S=2.328±0.004 from a single quantum dot with a depth up to 0.94±0.02 dB. Such deterministically generated photon pairs fundamentally overcome parametric processes by reducing crucial multiphoton errors. For the quantum non-Gaussian depth of the unheralded (heralded) single-photon state, we achieve the value of 8.08±0.05 dB (19.06±0.29 dB). Our Letter experimentally certifies the exclusive quantum non-Gaussianity properties highly relevant for optical sensing, communication, and computation.

Experimental Generation of Spin-Photon Entanglement in Silicon Carbide.

A solid-state approach for quantum networks is advantageous, as it allows the integration of nanophotonics to enhance the photon emission and the utilization of weakly coupled nuclear spins for long-lived storage. Silicon carbide, specifically point defects within it, shows great promise in this regard due to the easy of availability and well-established nanofabrication techniques. Despite of remarkable progresses made, achieving spin-photon entanglement remains a crucial aspect to be realized. In this Letter, we experimentally generate entanglement between a silicon vacancy defect in silicon carbide and a scattered single photon in the zero-phonon line. The spin state is measured by detecting photons scattered in the phonon sideband. The photonic qubit is encoded in the time-bin degree of freedom and measured using an unbalanced Mach-Zehnder interferometer. Photonic correlations not only reveal the quality of the entanglement but also verify the deterministic nature of the entanglement creation process. By harnessing two pairs of such spin-photon entanglement, it becomes straightforward to entangle remote quantum nodes at long distance.

In vitro assessment of thyroid peroxidase inhibition by chemical exposure: comparison of cell models and detection methods.

Disruption of the thyroid hormone (TH) system is connected with diverse adverse health outcomes in wildlife and humans. It is crucial to develop and validate suitable in vitro assays capable of measuring the disruption of the thyroid hormone (TH) system. These assays are also essential to comply with the 3R principles, aiming to replace the ex vivo tests often utilised in the chemical assessment. We compared the two commonly used assays applicable for high throughput screening [Luminol and Amplex UltraRed (AUR)] for the assessment of inhibition of thyroid peroxidase (TPO, a crucial enzyme in TH synthesis) using several cell lines and 21 compounds from different use categories. As the investigated cell lines derived from human and rat thyroid showed low or undetectable TPO expression, we developed a series of novel cell lines overexpressing human TPO protein. The HEK-TPOA7 model was prioritised for further research based on the high and stable TPO gene and protein expression. Notably, the Luminol assay detected significant peroxidase activity and signal inhibition even in Nthy-ori 3-1 and HEK293T cell lines without TPO expression, revealing its lack of specificity. Conversely, the AUR assay was specific to TPO activity. Nevertheless, despite the different specificity, both assays identified similar peroxidation inhibitors. Over half of the tested chemicals with diverse structures and from different use groups caused TPO inhibition, including some widespread environmental contaminants suggesting a potential impact of environmental chemicals on TH synthesis. Furthermore, in silico SeqAPASS analysis confirmed the high similarity of human TPO across mammals and other vertebrate classes, suggesting the applicability of HEK-TPOA7 model findings to other vertebrates.

Comparative transcriptome analysis provides insights into the resistance regulation mechanism and inhibitory effect of fungicide phenamacril in Fusarium asiaticum.

Fusarium asiaticum is a destructive phytopathogenic fungus that causes Fusarium head blight of wheat (FHB), leading to serious yield and economic losses to cereal crops worldwide. Our previous studies indicated that target-site mutations (K216R/E, S217P/L, or E420K/G/D) of Type I myosin FaMyo5 conferred high resistance to phenamacril. Here, we first constructed one sensitive strain H1S and three point mutation resistant strains HA, HC and H1R. Then we conducted comparative transcriptome analysis of these F. asiaticum strains after 1 and 10 µg·mL-1 phenamacril treatment. Results indicated that 2135 genes were differentially expressed (DEGs) among the sensitive and resistant strains. The DEGs encoding ammonium transporter MEP1/MEP2, nitrate reductase, copper amine oxidase 1, 4-aminobutyrate aminotransferase, amino-acid permease inda1, succinate-semialdehyde dehydrogenase, 2, 3-dihydroxybenzoic acid decarboxylase, etc., were significantly up-regulated in all the phenamacril-resistant strains. Compared to the control group, a total of 1778 and 2097 DEGs were identified in these strains after 1 and 10 µg·mL-1 phenamacril treatment, respectively. These DEGs involved in 4-aminobutyrate aminotransferase, chitin synthase 1, multiprotein-bridging factor 1, transcriptional regulatory protein pro-1, amino-acid permease inda1, ATP-dependent RNA helicase DED1, acetyl-coenzyme A synthetase, sarcoplasmic/endoplasmic reticulum calcium ATPase 2, etc., showed significantly down-regulated expression in phenamacril-sensitive strain but not in resistant strains after phenamacril treatment. In addition, cyanide hydratase, mating-type protein MAT-1, putative purine nucleoside permease, plasma membrane protein yro2, etc., showed significantly co-down-regulated expression in all the strains after phenamacril treatment. Taken together, This study provides deep insights into the resistance regulation mechanism and the inhibitory effect of fungicide phenamacril and these new annotated proteins or enzymes are worth for the discovery of new fungicide targets.

Experimental and Computational Evaluation of Self-Assembled Morphologies in Diblock Janus Bottlebrush Copolymers.

Diblock Janus-type "A-branch-B" bottlebrush copolymers (di-JBBCPs) consist of a backbone with alternating A and B side chains, in contrast to the side chain arrangement of conventional bottlebrush copolymers. As a result, A and B blocks of di-JBBCPs can microphase-separate perpendicular to the backbone, which is located at the interface between the two blocks. A reparametrized dissipative particle dynamics (DPD) model is used to theoretically investigate the self-assembly of di-JBBCPs and to compare with the experimental results of a range of polystyrene-branch-polydimethylsiloxane di-JBBCPs. The experimentally formed cylinder, gyroid, and lamellar morphologies showed good correspondence with the model phase diagram, and the effect of changing volume fraction and backbone length is revealed. The DPD model predicts a bulk-stable perforated lamella morphology together with two unconventional spherical phases, the Frank-Kasper A15 spheres and the hexagonally close-packed spheres, indicating the diversity of morphologies available from complex BCP molecular architectures.

Unveiling the Localized Exciton-Based Photoluminescence of Manganese Doped Cesium Zinc Halide Nanocrystals.

Lead-free metal halide nanocrystals (NCs) have aroused increasing attention due to their unique optoelectronic properties based on localized excitons (LEs). However, the vital influencing factors for the LEs based photoluminescence (PL) are still not well-understood due to the coupling of various intrinsic and extrinsic factors of the NCs. Herein, by engineering the phase, size, morphology, and chemical composition, we are able to decouple the intrinsic and extrinsic factors of manganese doped cesium zinc-halide NCs. We found both the intrinsic metal-halide coordination field and the extrinsic crystal defects have significant influences on the LEs' recombination and energy transfer processes, and hence determine the PL efficiency. Unlike for the free excitons (FEs) based PL, the phase as well as the crystal morphology do not play major roles for the LEs based PL. This work provides a new insight for the study of LE dynamics of metal halide NCs.

Blue Long Afterglow and Ultra Broadband Vis-NIR Emission from All-Inorganic Copper-Doped Silver Halide Single Crystals.

All-inorganic metal halides with afterglow emission have attracted increasing attention due to their significantly longer afterglow duration and higher stability compared to their organic-inorganic hybrid counterparts. However, their afterglow colors have not yet reached the blue spectral region. Here, we report all-inorganic copper-doped Rb2AgBr3 single crystals with ultralong blue afterglow (>300 s) by modulating defect states through doping engineering. The introduction of copper(I) ions into Rb2AgBr3 facilitates the formation of bromine vacancies, thus increasing the density of trap states available for charge storage and enabling bright, persistent emission after ceasing the excitation. Moreover, cascade energy transfer between distinct emissive centers in the crystals results in ultra-broadband photoluminescence, not only covering the whole white light with near-unity quantum yield but also extending into the near-infrared region. This 'cocktail' of exotic light-emission properties, in conjunction with the excellent stability of copper-doped Rb2AgBr3 crystals, allowed us to demonstrate their implementation to solid-state lighting, night vision, and intelligent anti-counterfeiting.

Comprehensive measurement of the near-infrared refractive index of GaAs at cryogenic temperatures.

The refractive index is a critical parameter in optical and photonic device design. However, due to the lack of available data, precise designs of devices working in low temperatures are still frequently limited. In this work, we have built a homemade spectroscopic ellipsometer (SE) and measured the refractive index of GaAs at a matrix of temperatures (4 K < T < 295 K) and photon wavelengths (700 nm < λ < 1000 nm) with a system error of ∼0.04. We verified the credibility of the SE results by comparing them with afore-reported data at room temperature and with higher precision values measured by vertical GaAs cavity at cryogenic temperatures. This work makes up for the lack of the near-infrared refractive index of GaAs at cryogenic temperatures and provides accurate reference data for semiconductor device design and fabrication.

Berry Curvature and Bulk-Boundary Correspondence from Transport Measurement for Photonic Chern Bands.

Berry curvature is a fundamental element to characterize topological quantum physics, while a full measurement of Berry curvature in momentum space was not reported for topological states. Here we achieve two-dimensional Berry curvature reconstruction in a photonic quantum anomalous Hall system via Hall transport measurement of a momentum-resolved wave packet. Integrating measured Berry curvature over the two-dimensional Brillouin zone, we obtain Chern numbers corresponding to -1 and 0. Further, we identify bulk-boundary correspondence by measuring topology-linked chiral edge states at the boundary. The full topological characterization of photonic Chern bands from Berry curvature, Chern number, and edge transport measurements enables our photonic system to serve as a versatile platform for further in-depth study of novel topological physics.

N-Protonation as a Switch of the Twisted Excited States with ππ* or nπ* Character and Correlation with the π-Electrons Characteristic of Rotatable Bonds.

N-protonation for numerous fluorophores is widely known as an efficient switch for the fluorescence turn-on/off in acidic conditions, which has been applied in various scenarios that involve pH monitoring. Yet the universal mechanism for fluorescence regulation through N-protonation is still elusive. Herein, the excited state deactivation processes are systematically investigated for a series of nitrogen-containing fluorescent probes through theoretical approaches. Two types of mechanisms for the complex fluorescent phenomena by N-protonation are concluded: one is through the regulation for the transition to a ππ* twisted intramolecular charge transfer (TICT) state; the other one applies for the case when nonradiative decay pathway is predominant by a dark nπ* state, which is also accompanied by an evident structural twisting and can be regarded as another kind of TICT state. More generally, the formation of the TICT state is closely related to the conjugated π-electrons on the single bond that links the acceptor and donor part of fluorophores, which provides a simple strategy for evaluating the occurrence of the TICT process. The current contributions can bring novel insights for the rational design of functional fluorophores that involve TICT process in the excited states.

Revealing the excited-state dynamics of cytidine and the role of excited-state proton transfer process.

The high photostability of DNAs and RNAs is inextricably related to the photochemical and photophysical properties of their building blocks, nucleobases and nucleosides, which can dissipate the absorbed UV light energy in a harmless manner. The deactivation mechanism of the nucleosides, especially the decay pathways of cytidine (Cyd), has been a matter of intense debate. In the current study, we employ high-level electronic structure calculations combined with excited state non-adiabatic dynamic simulations to provide a clear picture of the excited state deactivation of Cyd in both gas phase and aqueous solution. In both environments, a barrierless decay path driven by the ring-puckering motion and a relaxation channel with a small energy barrier driven by the elongation motion of CO bond are assigned to <200 fs and sub-picosecond decay time component, respectively. The presence of ribose group has a subtle effect on the dynamic behavior of Cyd in gas phase as the ribose-to-base hydrogen/proton transfer process is energetically inaccessible with a sizable energy barrier of about 1.4 eV. However, this energy barrier is significantly reduced in water, especially when an explicit water molecule is present. Therefore, we argue that the long-lived decay channel found in aqueous solution could be assigned to the Cyd-water intermolecular hydrogen/proton transfer process. The present study postulates a novel scenario toward deep understanding the intrinsic photostability of DNAs and RNAs and provides solid evidence to disclose the long history debate of cytidine excited-state decay mechanism, especially for the assignment of experimentally observed time components.

Generation of Polarization-Entangled Photons from Self-Assembled Quantum Dots in a Hybrid Quantum Photonic Chip.

Integration of entangled photon sources in a quantum photonic chip has enabled the most envisioned quantum photonic technologies to be performed in a compact platform with enhanced complexity and stability as compared to bulk optics. However, the technology to generate entangled photon states in a quantum photonic chip that are neither probabilistic nor restricted to low efficiency is still missing. Here, we introduce a hybrid quantum photonic chip where waveguide-coupled self-assembled quantum dots (QDs) are heterogeneously integrated onto a piezoelectric actuator. By exerting an anisotropic stress, we experimentally show that the fine structure splitting of waveguide-coupled quantum dots can be effectively eliminated. This allows for the demonstration of chip-integrated self-assembled QDs for generating and routing polarization-entangled photon pairs. Our results presented here would open up an avenue for implementing on-demand quantum information processing in a quantum photonic chip by employing all-solid-state self-assembled quantum dot emitters.

Bacterial Cytochrome P450 Catalyzed Post-translational Macrocyclization of Ribosomal Peptides.

Ribosomally synthesized and post-translationally modified peptides (RiPPs) are a fascinating group of natural products that exhibit diverse structural features and bioactivities. P450-catalyzed RiPPs stand out as a unique but underexplored family. Herein, we introduce a rule-based genome mining strategy that harnesses the intrinsic biosynthetic principles of RiPPs, including the co-occurrence and co-conservation of precursors and P450s and interactions between them, successfully facilitating the identification of diverse P450-catalyzed RiPPs. Intensive BGC characterization revealed four new P450s, KstB, ScnB, MciB, and SgrB, that can catalyze the formation of Trp-Trp-Tyr (one C-C and two C-N bonds), Tyr-Trp (C-C bond), Trp-Trp (C-N bond), and His-His (ether bond) crosslinks, respectively, within three or four residues. KstB, ScnB, and MciB could accept non-native precursors, suggesting they could be promising starting templates for bioengineering to construct macrocycles. Our study highlights the potential of P450s to expand the chemical diversity of strained macrocyclic peptides and the range of biocatalytic tools available for peptide macrocyclization.

Manipulating the Zinc Deposition Behavior in Hexagonal Patterns at the Preferential Zn (100) Crystal Plane to Construct Surficial Dendrite-Free Zinc Metal Anode.

Zinc metal has a severe dendrite issue caused by the uneven Zn plating/stripping during continual cycles, which hinders the practical application of ZIBs. The surficial atomic structure of zinc anode plays a decisive role in solving dendrites and improving the electrochemical performance. According to the density functional theory results, Zn (100) plane possesses a much stronger adsorption energy of zinc atom compared with the (002), thus zinc atom preferentially nucleates on the (100) surface. It subsequently continues to grow vertically on (100). Herein, the zinc anode is designed with hexagonal-hole patterns (h-Zn) through a phosphoric acid etching reaction. An abundance of Zn (100) crystal planes are exposed perpendicularly to the anode surface, while the (002) surfaces are at the bottom of these hexagonal holes. Zinc prefers to deposit in hexagonal holes at the (100) surfaces, favoring the restraining of the surficial dendrite growth and accelerating the Zn deposition kinetics. Thus, the symmetric cell using h-Zn exhibits a long cycling lifespan for over 1200 h and extremely low polarization voltage of ≈80 mV at 5 mA cm-2 and 1 mAh cm-2 . This work provides an insight into the surficial structure design and crystal plane regulation to fabricate brilliant zinc metal anodes.

Identification of PYGL as a key prognostic gene of glioma by integrated bioinformatics analysis.

Aim: PYGL has been reported to have carcinogenic effects in a variety of tumors. This study is the first to reveal the relationship between PYGL and the prognosis of glioma. Materials & methods: Analyzing the Chinese Glioma Genome Atlas database, the authors revealed the expression status and prognostic value of PYGL in gliomas and used quantitative real-time PCR to verify PYGL expression again. Subsequently, they used Gene Set Enrichment Analysis to explore the biological pathways that PYGL may participate in. The authors also used the tumor immune estimation resource database to explore the relationship between PYGL and tumor immune cells. Results: PYGL is involved in the malignant progression of glioma. Conclusions: PYGL can be used as a new biomarker and molecular target for evaluating the prognosis and immunotherapy of glioma.

Structurally Diverse Sesquiterpenoid Glycoside Esters from Pittosporum qinlingense with Anti-neuroinflammatory Activity.

Thirteen new sesquiterpenoid glycoside esters, including 11 aromadendrane-type compounds, pitqinlingosides A-K (1-11), one cadinane-type compound, pitqinlingoside L (12), and one eudesmane-type compound, pitqinlingoside M (13), together with seven known analogues (14-20) were isolated from the twigs, fruits, and leaves of Pittosporum qinlingense. Structures were elucidated by analysis of spectroscopic data, gas chromatography mass spectrometry (GC-MS), and chemical methods. The absolute configuration was confirmed by single-crystal X-ray crystallography analysis or electronic circular dichroism spectra. Unusual glycoside esters are characterized by the presence of polyacylated ß-d-fucopyranosyl, ß-d-glucopyranosyl, and ß-d-xylopyranosyl units. Pitqinlingosides A (1), B (2), D (4), and F (6), pittosporanoside A1 acetate (14), and pittosporanoside A1 (16) showed significant nitric oxide production inhibition in lipopolysaccharide (LPS)-induced BV-2 microglial cells with IC50 values ranging from 0.95 to 24.12 µM. Structure-activity relationships of the isolated compounds are discussed.

Combined LIBS and Raman spectroscopy: an approach for salinity detection in the field of seawater investigation.

As salinity is an important indicator in marine geology, ecology, breeding, and other fields, accurate, rapid, and continuous measurement of salinity is of great significance in marine investigations. At present, the seawater salinity detection methods used in practice are mainly based on the principle that the conductivity and refractive index parameters of the water change with the concentration of elements, which are composed of salinity change. However, these methods quantitatively analyze salinity values by measuring other parameters (electrical or optical parameters) that may change depending on the salinity of the water, rather than the mass fraction of the components that make up the salinity. Moreover, when the salinity value of seawater water changes substantially or the proportion of various common components composing salinity changes significantly, the detection accuracy of the above methods is difficult to guarantee. Therefore, a spectral approach, LIBS, and the Raman spectroscopy combination method for salinity analyzation, LRSS, were proposed to provide a new option. The main idea of this approach is to use the two spectral detection methods, LIBS and Raman, to determine the mole values of cations and non-monatomic anions in per unit quality (1 kg) of water, respectively. Then the mole value of the chloride ion, which is the main monatomic anion in seawater, can be determined according to the electrically neutral principle. Based on all the obtained molar values and the molar mass of each ion, the salinity of the water sample can be determined. To demonstrate the performance of this new method, we compared it with LIBS under laboratory conditions and found that, when non-monatomic anions are present in the water, the accuracy of LRSS is significantly improved compared to using the LIBS method alone. Moreover, we also compared the LRSS with the other two traditional methods through the 11 water samples configured and found that the absolute value relative error of the LRSS is only 2.63% when the salinity and components concentration change is in the possible range, which is better than the conductivity method 0.53 times and better than the refractive index method 1.52 times.

The Inhibitory Effect of Phycocyanin Peptide on Pulmonary Fibrosis In Vitro.

Phycocyanin is an excellent antioxidant with anti-inflammatory effects on which recent studies are growing; however, its specific target remains unclear. Linear tetrapyrrole compounds such as bilirubin have been shown to lead to the induction of heme oxygenase 1 expression in vivo, thus achieving antioxidant and anti-inflammatory effects. Phycocyanin is bound internally with linear tetrapyrrole phycocyanobilin in a similar structure to bilirubin. We speculate that there is probably a way of inducing the expression of heme oxygenase 1, with which tissue oxidative stress and inflammation can be inhibited, thus inhibiting pulmonary fibrosis caused by oxidative damage and inflammation of lung. By optimizing the enzymatic hydrolysis process, phycocyanobilin-bound phycocyanin peptide were obtained, and its in vitro antioxidant, anti-inflammatory, and anti-pulmonary fibrosis activities were investigated. The results show that the phycocyanobilin peptide was able to alleviate oxidative and inflammatory damage in cells through the Keap1-Nrf2-HO-1 pathway, which in turn relieved pulmonary fibrosis symptoms.

EN1 Regulates Cell Growth and Proliferation in Human Glioma Cells via Hedgehog Signaling.

Glioblastoma is an aggressive cancer of the nervous system that accounts for the majority of brain cancer-related deaths. Through cross-species transcriptome studies, we found that Engrailed 1 (EN1) is highly expressed in serum-free cultured glioma cells as well as glioma tissues, and increased expression level predicts a worse prognosis. EN1 controls glioma cell proliferation, colony formation, migration, and tumorigenic capacity in vivo. It also influences sensitivity of glioma cells to γ-ray irradiation by regulating intracellular ROS levels. Mechanistically, EN1 influences Hedgehog signaling by regulating the level of Gli1 as well as primary cilia length and the primary cilia transport-related protein TULP3. In conclusion, we demonstrate that EN1 acts as an oncogenic regulator that contributes to glioblastoma pathogenesis and could serve as a diagnostic/prognostic marker and therapeutic target for glioblastoma.