Spontaneous-Spin-Polarized 2D π-d Conjugated Frameworks Towards Enhanced Oxygen Evolution Kinetics.

Alternative strategies to design sustainable-element-based electrocatalysts enhancing oxygen evolution reaction (OER) kinetics are demanded to develop affordable yet high-performance water-electrolyzers for green hydrogen production. Here, it is demonstrated that the spontaneous-spin-polarized 2D π-d conjugated framework comprising abundant elements of nickel and iron with a ratio of Ni:Fe = 1:4 with benzenehexathiol linker (BHT) can improve OER kinetics by its unique electronic property. Among the bimetallic NiFex:y-BHTs with various ratios with Ni:Fe = x:y, the NiFe1:4-BHT exhibits the highest OER activity. The NiFe1:4-BHT shows a specific current density of 140 A g-1 at the overpotential of 350 mV. This performance is one of the best activities among state-of-the-art non-precious OER electrocatalysts and even comparable to that of the platinum-group-metals of RuO2 and IrO2. The density functional theory calculations uncover that introducing Ni into the homometallic Fe-BHT (e.g., Ni:Fe = 0:1) can emerge a spontaneous-spin-polarized state. Thus, this material can achieve improved OER kinetics with spin-polarization which previously required external magnetic fields. This work shows that a rational design of 2D π-d conjugated frameworks can be a powerful strategy to synthesize promising electrocatalysts with abundant elements for a wide spectrum of next-generation energy devices.

Clinical significance and potential pathogenesis of VCAN in adult non-cystic fibrosis bronchiectasis: a retrospective study.

BACKGROUND: The pathogenesis of adult non-cystic fibrosis (CF) bronchiectasis is complex, and the relevant molecular mechanism remains ambiguous. Versican (VCAN) is a key factor in inflammation through interactions with adhesion molecules. This study constructs a stable panoramic map of mRNA, reveals the possible pathogenesis of bronchiectasis, and provides new ideas and methods for bronchiectasis. METHODS: Peripheral blood and tissue gene expression data from patients with bronchiectasis and normal control were selected by bioinformatics analysis. The expression of VCAN in peripheral blood and bronchial tissues of bronchiectasis were obtained by transcriptome sequencing. The protein expression levels of VCAN in serums were verified by the enzyme-linked immunosorbent assay (ELISA). The mRNA expression levels of VCAN in co-culture of Pseudomonas aeruginosa and bronchial epithelial cells were verified by real-time quantitative polymerase chain reaction (RT-qPCR). In addition, the biological function of VCAN was detected by the transwell assay. RESULTS: The expression of VCAN was upregulated in the bronchiectasis group by sequencing analysis (P < 0.001). The expression of VCAN in the bronchial epithelial cell line BEAS-2B was increased in P. aeruginosa (P.a), which was co-cultured with BEAS-2B cells (P < 0.05). The concentration of VCAN protein in the serum of patients with bronchiectasis was higher than that in the normal control group (P < 0.05). Transwell experiments showed that exogenous VCAN protein induced the migration of neutrophils (P < 0.0001). CONCLUSIONS: Our findings indicate that VCAN may be involved in the development of bronchiectasis by increasing the migration of neutrophils and play an important role in bronchial pathogenesis.

Confirmation of the structure of (±)-preisomide by total synthesis.

The structure of preisomide has been confirmed by total synthesis involving chemoselective oxazine formation and vinyl iodide carbonylation in six steps (longest linear sequence) and 23% overall yield.

Dopant-induced modulation of lithium-ion conductivity in cubic garnet solid electrolytes: a first-principles study.

Cubic garnet Li7La3Zr2O12 (c-LLZO) is a promising solid electrolyte for all-solid-state batteries, often doped with Ga, Al, and Fe to stabilize the structure and enhance Li-ion conductivity. Despite introducing the same amount of Li vacancies, these dopants with +3 classical charge yield different Li-ion conductivities by around an order of magnitude. In this study, we used density functional theory (DFT) calculations to investigate the impact of Ga, Fe, and Al dopants on Li chemical potential and Li-ion conductivity variations. We identified the energetically favorable dopant location in c-LLZO and determined the optimal U value of 7.5 eV for DFT+U calculations for dopant Fe in c-LLZO. Our calculations showed that Ga or Fe doping enhances the Li chemical potential by 0.05-0.08 eV, reducing Li-ion transfer barriers and increasing Li-ion conductivity, while Al doping lowers the Li chemical potential by 0.08 eV, reducing Li-ion conductivity. To determine the cause of Li chemical potential variations, we performed a combined analysis of the projected density of states, charge density, and Bader charge. The distinct charge distribution from dopant atoms to neighboring O atoms is critical for determining the Li-ion chemical potential. Ga and Fe dopants retain more electrons, which consequently makes the adjacent O atoms acquire a more positive charge that destabilizes Li ions by reducing the restraining force acting on them, thereby enhancing Li-ion conductivity. In contrast, Al doping transfers more electrons to neighboring O atoms, resulting in greater attraction forces to Li ions and reducing Li-ion conductivity. Additionally, Fe-doped LLZO exhibits extra states in the bandgap, potentially causing Fe reduction, as observed in experiments. Our findings provide valuable insights into the design of solid electrolytes and highlight the importance of the local charge distribution around the dopant and Li atoms in determining Li-ion conductivity. This insight could serve as a guiding principle for future materials design and optimization in solid-state electrolyte systems.

Connection between BosonSampling with quantum and classical input states.

BosonSampling is a problem of sampling events according to the transition probabilities of indistinguishable photons in a linear optical network. Computational hardness of BosonSampling depends on photon-number statistics of the input light. BosonSampling with multi-photon Fock states at the input is believed to be classically intractable but there exists an efficient classical algorithm for classical input states. In this paper, we present a mathematical connection between BosonSampling with quantum and classical light inputs. Specifically, we show that the generating function of a transition probability for Fock-state BosonSampling (FBS) can be expressed as a transition probability of thermal-light inputs. The closed-form expression of a thermal-light transition probability allows all possible transition probabilities of FBS to be obtained by calculating a single matrix permanent. Moreover, the transition probability of FBS is shown to be expressed as an integral involving a Gaussian function multiplied by a Laguerre polynomial, resulting in a fast oscillating integrand. Our work sheds new light on computational hardness of FBS by identifying the mathematical connection between BosonSampling with quantum and classical light.

Denoising ghost imaging under a small sampling rate via deep learning for tracking and imaging moving objects.

Ghost imaging (GI) usually requires a large number of samplings, which limit the performance especially when dealing with moving objects. We investigated a deep learning method for GI, and the results show that it can enhance the quality of images with the sampling rate even down to 3.7%. With a convolutional denoising auto-encoder network trained with numerical data, blurry images from few samplings can be denoised. Then those outputs are used to reconstruct both the trajectory and clear image of the moving object via cross-correlation based GI, with the number of required samplings reduced by two-thirds.

Development of an After-School Day Treatment Program for Children with Severe Emotional/Behavioral Disturbances.

This article introduces Aizone, an after-school day treatment program for children with emotional/behavioral disturbances, and examines its effectiveness. Aizone targets children whose problems require intensive care, but are not severe enough to warrant hospitalization, and prioritizes those from low-income families. Based on the bio-psycho-social model, this program provides a variety of therapeutic interventions for both children and their parents, including individual and group therapy integrated under the concept of milieu therapy, as well as community linkage services. This study uses a prospective comparative method to examine the effectiveness of Aizone by comparing and validating the treatment outcomes of seven Aizone programs across Seoul. The Korean Child Behavior Checklist was administered by caregivers before and after intervention and the data was used in a repeated measures analysis. The effectiveness of the program in terms of reduction in emotional, behavioral symptoms, as well as the implications of the results are discussed.

Inhibition of HSP90α protects cultured neurons from oxygen-glucose deprivation induced necroptosis by decreasing RIP3 expression.

Heat shock protein 90α (HSP90α) maintains cell stabilization and regulates cell death, respectively. Recent studies have shown that HSP90α is involved in receptor interacting protein 3 (RIP3)-mediated necroptosis in HT29 cells. It is known that oxygen and glucose deprivation (OGD) can induce necroptosis, which is regulated by RIP3 in neurons. However, it is still unclear whether HSP90α participates in the process of OGD-induced necroptosis in cultured neurons via the regulation of RIP3. Our study found that necroptosis occurs in primary cultured cortical neurons and PC-12 cells following exposure to OGD insult. Additionally, the expression of RIP3/p-RIP3, MLKL/p-MLKL, and the RIP1/RIP3 complex (necrosome) significantly increased following OGD, as measured through immunofluorescence (IF) staining, Western blotting (WB), and immunoprecipitation (IP) assay. Additionally, data from computer simulations and IP assays showed that HSP90α interacts with RIP3. In addition, HSP90α was overexpressed following OGD in cultured neurons, as measured through WB and IF staining. Inhibition of HSP90α in cultured neurons, using the specific inhibitor, geldanamycin (GA), and siRNA/shRNA of HSP90α, protected cultured neurons from necrosis. Our study showed that the inhibitor of HSP90α, GA, rescued cultured neurons not only by decreasing the expression of total RIP3/MLKL, but also by decreasing the expression of p-RIP3/p-MLKL and the RIP1/RIP3 necrosome. In this study, we reveal that inhibition of HSP90α protects primary cultured cortical neurons and PC-12 cells from OGD-induced necroptosis through the modulation of RIP3 expression.

Limits on manipulating conditional photon statistics via interference of weak lasers.

Photon anti-bunching, measured via the Hanbury-Brown-Twiss experiment, is one of the key signatures of quantum light and is tied to sub-Poissonian photon number statistics. Recently, it has been reported that photon anti-bunching or conditional sub-Poissonian photon number statistics can be obtained via second-order interference of mutually incoherent weak lasers and heralding based on photon counting [Phys. Rev. A92, 033855 (2015)10.1103/PhysRevA.92.033855; Opt. Express24, 19574 (2016)10.1364/OE.24.019574; https://arxiv.org/abs/1601.08161]. Here, we report theoretical analysis on the limits of manipulating conditional photon statistics via interference of weak lasers. It is shown that conditional photon number statistics can become super-Poissonian in such a scheme. We, however, demonstrate explicitly that it cannot become sub-Poissonian, i.e., photon anti-bunching cannot be obtained in such a scheme. We point out that incorrect results can be obtained if one does not properly account for seemingly negligible higher-order photon number expansions of the coherent state.

Generation of a non-zero discord bipartite state with classical second-order interference.

We report an investigation on quantum discord in classical second-order interference. In particular, we theoretically show that a bipartite state with D = 0.311 of discord can be generated via classical second-order interference. We also experimentally verify the theory by obtaining D = 0.197 ± 0.060 of non-zero discord state. Together with the fact that the nonclassicalities originated from physical constraints and information theoretic perspectives are not equivalent, this result provides an insight to understand the nature of quantum discord.

Bright source of polarization-entangled photons using a PPKTP pumped by a broadband multi-mode diode laser.

We report a bright source of polarization-entangled photon pairs using spontaneous parametric down-conversion (SPDC) in a 10 mm long type-II PPKTP crystal pumped by a broadband multi-mode diode laser with the coherence length of 330 µm. Ordinarily, the huge mismatch between the pump coherence length and the PPKTP length would degrade the polarization entanglement completely. By employing the universal Bell-state synthesizer scheme, we remove the spectral/temporal distinguishability of the biphoton amplitudes entirely to recover high-visibility and high-fidelity two-photon polarization entanglement. The pair detection rates are 7,000 pairs/mW via single-mode fibers (with 99.2% fidelity) and 90,900 pairs/mW via multi-mode fibers (with 96.8% fidelity). We also analyze the scheme theoretically to show the effect of broadband multi-mode pumping on the phase matching condition of the type-II PPKTP.

Anti-tumor activity of phenoxybenzamine hydrochloride on malignant glioma cells.

Phenoxybenzamine hydrochloride (PHEN) is a selective antagonist of both α-adrenoceptor and calmodulin that exhibits anticancer properties. The aim of this study was to explore the anti-tumor function of PHEN in glioma. Cell proliferation assay was used to assess glioma cell growth. Migration and invasion capacity of glioma cells was monitored by wound-healing and transwell assay, respectively. Neurosphere formation test was adopted for the tumorigenesis of glioma cells, which was also confirmed by soft agar cloning formation test in vitro and a nude mouse model in vivo. Finally, we explored the potential pathway utilized by PHEN using Western blot and immunofluoresce staining. PHEN exhibited a significant inhibitory effect on the proliferation of both U251 and U87MG glioma cell lines in a positive dose-dependent manner. PHEN apparently attenuated the malignancy of glioma in terms of migration and invasion and also suppressed the tumorigenic capacity both in vitro and in vivo. Mechanism study showed that PHEN promoted tumor suppression by inhibiting the TrkB-Akt pathway. The results of the present study demonstrated that PHEN suppressed the proliferation, migration, invasion, and tumorigenesis of glioma cells, induced LINGO-1 expression, and inhibited the TrkB-Akt pathway, which may prove to be the mechanisms underlying the anti-tumor effect of PHEN on glioma cells.

Quantum discord protection from amplitude damping decoherence.

Entanglement is known to be an essential resource for many quantum information processes. However, it is now known that some quantum features may be acheived with quantum discord, a generalized measure of quantum correlation. In this paper, we study how quantum discord, or more specifically, the measures of entropic discord and geometric discord are affected by the influence of amplitude damping decoherence. We also show that a protocol deploying weak measurement and quantum measurement reversal can effectively protect quantum discord from amplitude damping decoherence, enabling to distribute quantum correlation between two remote parties in a noisy environment.

Avoiding entanglement sudden death using single-qubit quantum measurement reversal.

When two entangled qubits, each owned by Alice and Bob, undergo separate decoherence, the amount of entanglement is reduced, and often, weak decoherence causes complete loss of entanglement, known as entanglement sudden death. Here we show that it is possible to apply quantum measurement reversal on a single-qubit to avoid entanglement sudden death, rather than on both qubits. Our scheme has important applications in quantum information processing protocols based on distributed or stored entangled qubits as they are subject to decoherence.

Fundamental bounds in measurements for estimating quantum states.

Quantum measurement unavoidably disturbs the state of a quantum system if any information about the system is extracted. Recently, the concept of reversing quantum measurement has been introduced and has attracted much attention. Numerous efforts have thus been devoted to understanding the fundamental relation of the amount of information obtained by measurement to either state disturbance or reversibility. Here, we experimentally prove the trade-off relations in quantum measurement with respect to both state disturbance and reversibility. By demonstrating the quantitative bound of the trade-off relations, we realize an optimal measurement for estimating quantum systems with minimum disturbance and maximum reversibility. Our results offer fundamental insights on quantum measurement and practical guidelines for implementing various quantum information protocols.

Two-Dimensional Metal-Organic Frameworks/Epoxy Composite Coatings with Superior O2/H2O Resistance for Anticorrosion Applications.

Corrosion protection technology plays a crucial role in preserving infrastructure, ensuring safety and reliability, and promoting long-term sustainability. In this study, we combined experiments and various analyses to investigate the mechanism of corrosion occurring on the epoxy-based anticorrosive coating containing the additive of two-dimensional (2D) and water-stable zirconium-based metal-organic frameworks (Zr-MOFs). By using benzoic acid as the modulator for the growth of the MOF, a 2D MOF constructed from hexazirconium clusters and BTB linkers (BTB = 1,3,5-tri(4-carboxyphenyl)benzene) with coordinated benzoate (BA-ZrBTB) can be synthesized. By coating the BA-ZrBTB/epoxy composite film (BA-ZrBTB/EP) on the surface of cold-rolled steel (CRS), we found the lowest coating roughness (RMS) of BA-ZrBTB/EP is 2.83 nm with the highest water contact angle as 99.8°, which represents the hydrophobic coating surface. Notably, the corrosion rate of the BA-ZrBTB/EP coating is 2.28 × 10-3 mpy, which is 4 orders of magnitude lower than that of the CRS substrate. Moreover, the energy barrier for oxygen diffusion through BA-ZrBTB/EP coating is larger than that for epoxy coating (EP), indicating improved oxygen resistance for adding 2D Zr-MOFs as the additive. These results underscore the high efficiency and potential of BA-ZrBTB as a highly promising agent for corrosion prevention in various commercial applications. Furthermore, this study represents the first instance of applying 2D Zr-MOF materials in anticorrosion applications, opening up new possibilities for advanced corrosion-resistant coatings.

In vitro and in vivo anti-inflammatory properties of an active fucoidan fraction from Sargassum fusiforme and a fraction-based hydrogel.

In a previous study, we separated an active fucoidan (JHCF4) from acid-processed Sargassum fusiforme, then analyzed and confirmed its structure. In the present study, we investigated the potential anti-inflammatory properties of JHCF4 and a JHCF4-based hydrogel in vitro and in vivo. JHCF4 reliably inhibited nitric oxide (NO) production in LPS-induced RAW 264.7 macrophages, with an IC50 of 22.35 µg/ml. Furthermore, JHCF4 attenuated the secretion of prostaglandin E2, tumor necrosis factor-α, interleukin (IL)-1ß, and IL-6, indicating that JHCF4 regulates inflammatory reactions. In addition, JHCF4 downregulated iNOS and COX-2 and inhibited the activation of the MAPK pathway. According to further in vivo analyses, JHCF4 significantly reduced the generation of reactive oxygen species (ROS), NO production, and cell death in an LPS-induced zebrafish model, suggesting that JHCF4 exhibits anti-inflammatory effects. Additionally, a JHCF4-based hydrogel was developed, and its properties were evaluated. The hydrogel significantly decreased inflammatory and nociceptive responses in carrageenan (carr)-induced mouse paws by reducing the increase in paw thickness and decreasing neutrophil infiltration in the basal and subcutaneous layers of the toe epidermis. These results indicate that JHCF4 exhibits potential anti-inflammatory activity in vitro and in vivo and that JHCF4-based hydrogels have application prospects in the cosmetic and pharmaceutical fields.

Dual-Vacancy-Engineered ZnIn2S4 Nanosheets for Harnessing Low-Frequency Vibration Induced Piezoelectric Polarization Coupled with Static Dipole Field to Enhance Photocatalytic H2 Evolution.

This study investigates the impact of In- and S-vacancy concentrations on the photocatalytic activity of non-centrosymmetric zinc indium sulfide (ZIS) nanosheets for the hydrogen evolution reaction (HER). A positive correlation between the concentrations of dual In and S vacancies and the photocatalytic HER rate over ZIS nanosheets is observed. The piezoelectric polarization, stimulated by low-frequency vortex vibration to ensure the well-dispersion of ZIS nanosheets in solution, plays a crucial role in enhancing photocatalytic HER over the dual-vacancy engineered ZIS nanosheets. The piezoelectric characteristic of the defective ZIS nanosheets is confirmed through the piezopotential response measured using piezoelectric force microscopy. Piezophotocatalytic H2 evolution over the ZIS nanosheets is boosted under accelerated vortex vibrations. The research explores how vacancies alter ZIS's dipole moment and piezoelectric properties, thereby increasing electric potential gradient and improving charge-separation efficiency, through multi-scale simulations, including Density Functional Theory and Finite Element Analysis, and a machine-learning interatomic potential for defect identification. Increased In and S vacancies lead to higher electric potential gradients in ZIS along [100] and [010] directions, attributing to dipole moment and the piezoelectric effect. This research provides a comprehensive exploration of vacancy engineering in ZIS nanosheets, leveraging the piezopotential and dipole field to enhance photocatalytic performances.

Construction of a panoramic mRNA map of adult noncystic fibrosis bronchiectasis and a preliminary study of the underlying molecular mechanisms.

BACKGROUND: The pathogenesis of noncystic fibrosis bronchiectasis in adults is complex, and the relevant molecular mechanisms remain unclear. In this study, we constructed a panoramic map of bronchiectasis mRNA, explored the potential molecular mechanisms, and identified potential therapeutic targets, thus providing a new clinical perspective for the preventive management of bronchiectasis and its acute exacerbation. METHODS: The mRNA profiles of peripheral blood and bronchiectasis tissues were obtained through transcriptome sequencing and public databases, and bioinformatics methods were used to screen for differentially expressed genes (DEGs). The DEGs were then subjected to biological function and pathway analyses. Some DEGs were validated using a real-time quantitative polymerase chain reaction (RT-qPCR) in peripheral blood. Spearman's correlation analysis was used to analyse the correlation between DEGs and clinical indicators. RESULTS: Based on transcriptome sequencing and public databases, the mRNA profile of bronchiectasis was determined. DEGs were obtained from the peripheral blood sequencing dataset (985 DEGs), tissue sequencing dataset (2919 DEGs), and GSE97258 dataset (1083 DEGs). Bioinformatics analysis showed that upregulated DEGs had enriched neutrophil-related pathways, and downregulated DEGs had enriched ribosome-related pathways. RT-qPCR testing confirmed the upregulated expression of VCAN, SESTD1, SLC12A1, CD177, IFI44L, SIGLEC1, and RSAD2 in bronchiectasis. These genes were related to many clinical parameters, such as neutrophils, C-reactive protein, and procalcitonin (P < 0.05). CONCLUSIONS: Transcriptomic methods were used to construct a panoramic map of bronchiectasis mRNA expression. The findings showed that neutrophil activation, chronic inflammation, immune regulation, impaired ribosomal function, oxidative phosphorylation, and energy metabolism disorders are important factors in the development of bronchiectasis. VCAN, SESTD1, SLC12A1, CD177, IFI44L, SIGLEC1, and RSAD2 may play important roles in the pathogenesis of bronchiectasis and are potential therapeutic targets.

Boosting Upconversion Efficiency in Optically Inert Shelled Structures with Electroactive Membrane through Electron Donation.

This study innovatively addresses challenges in enhancing upconversion efficiency in lanthanide-based nanoparticles (UCNPs) by exploiting Shewanella oneidensis MR-1, a microorganism capable of extracellular electron transfer. Electroactive membranes, rich in c-type cytochromes, are extracted from bacteria and integrated into membrane-integrated liposomes (MILs), encapsulating core-shelled UCNPs with an optically inactive shell, forming UCNP@MIL constructs. The electroactive membrane, tailored to donate electrons through the inert shell, independently boosts upconversion emission under near-infrared excitation (980 or 1550 nm), bypassing ligand-sensitized UCNPs. The optically inactive shell restricts energy migration, emphasizing electroactive membrane electron donation. Density functional theory calculations elucidate efficient electron transfer due to the electroactive membrane hemes' highest occupied molecular orbital being higher than the valence band maximum of the optically inactive shell, crucial for enhancing energy transfer to emitter ions. The introduction of a SiO2 insulator coating diminishes light enhancement, underscoring the importance of unimpeded electron transfer. Luminescence enhancement remains resilient to variations in emitter or sensitizing ions, highlighting the robustness of the electron transfer-induced phenomenon. However, altering the inert shell material diminishes enhancement, emphasizing the role of electron transfer. This methodology holds significant promise for diverse biological applications. UCNP@MIL offers an advantage in cellular uptake, which proves beneficial for cell imaging.