High χ P2PFBEMA-b-P2VP Block Copolymers Forming 6-8 nm Domains for Semiconductor Lithography.

We leveraged the potential of high χ-low N block copolymer (BCP), namely, poly[2-(perfluorobutyl) ethyl methacrylate]-block-poly(2-vinylpyridine) (P2PFBEMA-b-P2VP), and demonstrated its utility in next-generation nanomanufacturing. By combining molecular dynamics simulations with experiments, the χ value was calculated to be as high as 0.4 (at 150 °C), surpassing similar structures. Highly ordered features suitable for application were observed, ranging in periods from 19.0 nm down to 12.1 nm, with feature sizes as small as 6 nm. Transmission electron microscopy images of the BCP solutions indicated that preformed micelles in the solution facilitated the self-assembly process of the thin film. In addition, the vertical or parallel orientation of the cylindrical structure was determined by manipulating the solvent, substrate, and annealing conditions. Finally, guided by a wide topographical template, nearly defect-free directed self-assembly (DSA) lines with a resolution of 8 nm were achieved, highlighting its potential practical application in DSA lithography technology.

Base-Promoted (5 + 2) Annulation between 2-(Alkynylaryl)acetonitriles and Arylalkynes for the Synthesis of Benzocycloheptene Derivatives.

Herein, we describe a novel approach to the synthesis of benzocycloheptene derivatives via base-promoted (5 + 2) annulation between 2-(alkynylaryl)acetonitriles and arylalkynes. In this chemistry, 2-(alkynylaryl)acetonitriles are employed as a new C5 synthon to construct various benzocycloheptene(s) derivatives by building two C-C bonds in one single step. This method features excellent regioselectivity, the use of readily available starting materials, and good functional group tolerance. The practicality of the strategy was further demonstrated by gram-scale synthesis, late-stage functionalizations, and the post-modification of natural products such as probenecid and tetrahydrofurfuryl alcohol.

Dimensional Reduction of Metal-Organic Frameworks for Photocatalytic Synthesis of Fused Tetracyclic Heterocycles.

Heterogeneous palladium catalysts with high efficiency, high Pd atom utilization, simplified separation, and recycle have attracted considerable attention in the field of synthetic chemistry. Herein, we reported a zirconium-based two-dimensional metal-organic framework (2D-MOF)-based Pd(II) photocatalyst (Zr-Ir-Pd) by merging the Ir photosensitizers and Pd(II) species into the skeletons of the 2D-MOF for the Pd(II)-catalyzed oxidation reaction. Morphological and structural characterization identified that Zr-Ir-Pd with a specific nanoflower-like structure consists of ultrathin 2D-MOF nanosheets (3.85 nm). Due to its excellent visible-light response and absorption capability, faster transfer and separation of photogenerated carriers, more accessible Pd active sites, and low mass transfer resistance, Zr-Ir-Pd exhibited boosted photocatalytic activity in catalyzing sterically hindered isocyanide insertion of diarylalkynes for the construction of fused tetracyclic heterocycles, with up to 12 times the Pd catalyst turnover number than the existing catalytic systems. In addition, Zr-Ir-Pd inhibited the competitive agglomeration of Pd(0) species and could be reused at least five times, owing to the stabilization of 2D-MOF on the single-site Pd and Ir sites. Finally, a possible mechanism of the photocatalytic synthesis of fused tetracyclic heterocycles catalyzed by Zr-Ir-Pd was proposed.

Palladium-Catalyzed Annulation of Tertiary Anilines with 3-Butenoic Acid via Dual C-H Bond Activation.

Catalytic cyclization via dual C-H bond activation has evolved as a powerful strategy for building bi- and polycyclic molecules. Herein, a palladium-catalyzed annulation of tertiary anilines with 3-butenoic acid via N-α-C(sp3)-H and ortho-C(sp2)-H activation is described. The remarkable characteristics of this reaction include excellent diastereoselectivity, broad substrate scope, and good tolerance for some highly sensitive groups. In addition, the KIE experiment suggested that the C-H bond abscission is not the turnover-limiting step.

Synthesis of Dienamides via Palladium-catalyzed Oxidative N-α,ß-Dehydrogenation of Amides.

Enamides and their derivatives are prominent bioactive pharmacophores found in various bioactive molecules. Herein we report a palladium-catalyzed oxidative N-α,ß-dehydrogenation of amides to produce a range of enamides with high yields and excellent tolerance toward different functional groups. Mechanistic studies indicate that the reaction involves allylic C(sp3)-H activation followed by ß-H elimination. The effectiveness of this approach is demonstrated through late-stage functionalization of bioactive molecules and the synthesis of valuable compounds through product elaboration.

Identification and validation of anti-protein arginine methyltransferase 5 (PRMT5) antibody as a novel biomarker for systemic sclerosis (SSc).

OBJECTIVES: In the complex panorama of autoimmune diseases, the characterisation of pivotal contributing autoantibodies that are involved in disease progression remains challenging. This study aimed to employ a global antibody profiling strategy to identify novel antibodies and investigate their association with systemic sclerosis (SSc). METHODS: We implemented this strategy by conducting immunoprecipitation (IP) following on-bead digestion with the sera of patients with SSc or healthy donors, using antigen pools derived from cell lysates. The enriched antigen-antibody complex was proceeded with mass spectrometry (MS)-based quantitative proteomics and over-represented by bioinformatics analysis. The candidate antibodies were then orthogonally validated in two independent groups of patients with SSc. Mice were immunised with the target antigen, which was subsequently evaluated by histological examination and RNA sequencing. RESULTS: The IP-MS analysis, followed by validation in patients with SSc, revealed a significant elevation in anti-PRMT5 antibodies among patients with SSc. These antibodies exhibited robust diagnostic accuracy in distinguishing SSc from healthy controls and other autoimmune conditions, including systemic lupus erythematosus and Sjögren's syndrome, with an area under the curve ranging from 0.900 to 0.988. The elevation of anti-PRMT5 antibodies was verified in a subsequent independent group with SSc using an additional method, microarray. Notably, 31.11% of patients with SSc exhibited seropositivity for anti-PRMT5 antibodies. Furthermore, the titres of anti-PRMT5 antibodies demonstrated a correlation with the progression or regression trajectory in SSc. PRMT5 immunisation displayed significant inflammation and fibrosis in both the skin and lungs of mice. This was concomitant with the upregulation of multiple proinflammatory and profibrotic pathways, thereby underscoring a potentially pivotal role of anti-PRMT5 antibodies in SSc. CONCLUSIONS: This study has identified anti-PRMT5 antibodies as a novel biomarker for SSc.

Palladium-Catalyzed Carbohalogenation of Olefins with Alkynyl Oxime Ethers: Rapid Access to Chlorine-Containing Isoxazoles.

A palladium-catalyzed carbohalogenation of olefins with alkynyl oxime ethers has been described, which provides efficient and practical access to various chlorine-containing isoxazoles. This method exhibits excellent regioselectivity, good functional group compatibility, and mild reaction conditions. The mechanistic studies suggest that the reaction proceeds via a stabilized π-benzyl palladium intermediate, which is essential for the formation of C(sp3)-Cl bonds.

Enhanced LRP8 expression induced by Helicobacter pylori drives gastric cancer progression by facilitating ß-Catenin nuclear translocation.

INTRODUCTION: Helicobacter pylori (H. pylori) infection has been associated with gastric carcinogenesis. However, the precise involvement of LRP8, the low-density lipoprotein receptor-related protein 8, in H. pylori pathogenesis and gastric cancer (GC) remains poorly understood. OBJECTIVES: To investigate the potential role of LRP8 in H. pylori infection and gastric carcinogenesis. METHODS: Three-dimensional human-derived gastric organoids (hGO) and gastric cancer organoids (hGCO) were synthesized from the tissues obtained from human donors. In this work, multi-omics combined with in vivo and in vitro studies were conducted to investigate the potential involvement of LRP8 in H. pylori-induced GC. RESULTS: We found that H. pylori infection significantly upregulated the expression of LRP8 in human GC tissues, cells, organoids, and mouse gastric mucous. In particular, LRP8 exhibited a distinct enrichment in cancer stem cells (CSC). Functionally, silencing of LRP8 affected the formation and proliferation of tumor spheroids, while increased expression of LRP8 was associated with increased proliferation and stemness of GC cells and organoids. Mechanistically, LRP8 promotes the binding of E-cadherin to ß-catenin, thereby promoting nuclear translocation and transcriptional activity of ß-catenin. Furthermore, LRP8 interacts with the cytotoxin-associated gene A (CagA) to form the CagA/LRP8/ß-catenin complex. This complex further amplifies H. pylori-induced ß-catenin nuclear translocation, leading to increased transcription of inflammatory factors and CSC markers. Clinical analysis demonstrated that abnormal overexpression of LRP8 is correlated with a poor prognosis and resistance to 5-Fluorouracil in patients with GC. CONCLUSION: Our findings provide valuable information on the molecular intricacies of H. pylori-induced gastric carcinogenesis, offering potential therapeutic targets and prognostic markers for GC.

Palladium-Catalyzed 1,2-Alkynylarylation of Vinyl Arenes with Haloalkynes and Arylboronic Acids.

We herein disclose a novel palladium-catalyzed 1,2-alkynylarylation of vinyl arenes using haloalkynes and arylboronic acids as coupling partners. This reaction is characterized by broad substrate scope, controllable reaction sequence, and excellent chemo- and regioselectivities. Mechanistic investigations suggest that the reaction is initiated by regioselective insertion of vinyl arenes into the alkynyl-Pd(II) species, and the silver salt is crucial for this transformation, serving as both the Lewis acid and halide scavenger. This protocol provides efficient access to new carbon skeletons, which are embedded in the key biologically active motifs.

Palladium-catalyzed ligand-regulated divergent synthesis of pyrrole[2,3-b]indoles and ureas from 2-ethynylanilines and isocyanides.

Herein, a palladium-catalyzed and ligand-controlled protocol for the divergent synthesis of pyrrole[2,3-b]indole and urea derivatives has been described. Pyrrole[2,3-b]indoles ("cyclization on" products) via tandem cyclization of o-alkynylanilines with isocyanides in the absence of a ligand and ureas ("cyclization off" products) via oxidative amination of anilines with isocyanides in the presence of a ligand were obtained both in moderate to good yields with high selectivity. In this chemistry, cyclic and acyclic products were easily accessed with the same starting materials under the regulation of the ligand.

The impact of kidney function on plasma neurofilament light and phospho-tau 181 in a community-based cohort: the Shanghai Aging Study.

BACKGROUND: The blood-based biomarkers are approaching the clinical practice of Alzheimer's disease (AD). Chronic kidney disease (CKD) has a potential confounding effect on peripheral protein levels. It is essential to characterize the impact of renal function on AD markers. METHODS: Plasma phospho-tau181 (P-tau181), and neurofilament light (NfL) were assayed via the Simoa HD-X platform in 1189 dementia-free participants from the Shanghai Aging Study (SAS). The estimated glomerular filter rate (eGFR) was calculated. The association between renal function and blood NfL, P-tau181 was analyzed. An analysis of interactions between various demographic and comorbid factors and eGFR was conducted. RESULTS: The eGFR levels were negatively associated with plasma concentrations of NfL and P-tau181 (B = - 0.19, 95% CI - 0.224 to - 0.156, P < 0.001; B = - 0.009, 95% CI - 0.013 to -0.005, P < 0.001, respectively). After adjusting for demographic characteristics and comorbid diseases, eGFR remained significantly correlated with plasma NfL (B = - 0.010, 95% CI - 0.133 to - 0.068, P < 0.001), but not with P-tau181 (B = - 0.003, 95% CI - 0.007 to 0.001, P = 0.194). A significant interaction between age and eGFR was found for plasma NfL (Pinteraction < 0.001). In participants ≥ 70 years and with eGFR < 60 ml/min/1.73 m2, the correlation between eGFR and plasma NfL was significantly remarkable (B = - 0.790, 95% CI - 1.026 to - 0,554, P < 0.001). CONCLUSIONS: Considering renal function and age is crucial when interpreting AD biomarkers in the general aging population.

TDA/rGO@WS with Joule heat and photothermal synergistic effect: A promising adsorption material for all-weather recovery of viscous oil spills at sea.

Oil spills are a global environmental protection challenge, and traditional adsorption materials have poor effect on low temperature and high viscosity marine oil spills. This article reports composite adsorption materials TDA/rGO@WS for viscous oil spills: loaded with rGO/TDA coating on a commercial biomass wood pulp sponge (WS), achieving Joule heating, photothermal effect and hydrophobic modification. The results showed that the TDA/rGO@WS has good photothermal conversion ability and Joule heating ability, and the temperature increased to 83.7 °C and 148 °C, respectively, under simulated solar irradiation and additional voltage at room temperature. The efficiency of adsorption at a low temperature of 5 °C increased by 22.41% at 1 sun and by 51.53% at 10 V. Temperature effectively reduced the viscosity of the offshore oil spill and ensures the efficient adsorption of oil spills at low temperatures promoted. The TDA/rGO@WS also showed good hydrophobicity (WCA=129°), excellent efficiency of water-oil separation (99.53%) and good adsorption capacity (9.4-13.68 g/g) for marine fuel oils. TDA/rGO@WS effectively solves the problem of cleaning up high-viscosity oil spills from ships in winter and polar waters, and proposes a new strategy for all-weather efficient treatment of oil spills at sea.

Wavelet transform and deep learning-based obstructive sleep apnea detection from single-lead ECG signals.

Sleep apnea is a common sleep disorder. Traditional testing and diagnosis heavily rely on the expertise of physicians, as well as analysis and statistical interpretation of extensive sleep testing data, resulting in time-consuming and labor-intensive processes. To address the problems of complex feature extraction, data imbalance, and low model capacity, we proposed an automatic sleep apnea classification model (CA-EfficientNet) based on the wavelet transform, a lightweight neural network, and a coordinated attention mechanism. The signal is converted into a time-frequency image by wavelet transform and put into the proposed model for classification. The effects of input time window, wavelet transform type and data balancing on the classification performance are considered, and a cost-sensitive algorithm is introduced to more accurately distinguish between normal and abnormal breathing events. PhysioNet apnea ECG database was used for training and evaluation. The 3-min Frequency B-Spline wavelets transform of ECG signal was carried out, and Dice Loss was used to train the classification model of sleep breathing. The classification accuracy was 93.44%, sensitivity was 88.9%, specificity was 96.2% and most indexes were better than other related work.

Constructing bodily emotion maps based on high-density body surface potentials for psychophysiological computing.

Emotion is a complex physiological and psychological activity, accompanied by subjective physiological sensations and objective physiological changes. The body sensation map describes the changes in body sensation associated with emotion in a topographic manner, but it relies on subjective evaluations from participants. Physiological signals are a more reliable measure of emotion, but most research focuses on the central nervous system, neglecting the importance of the peripheral nervous system. In this study, a body surface potential mapping (BSPM) system was constructed, and an experiment was designed to induce emotions and obtain high-density body surface potential information under negative and non-negative emotions. Then, by constructing and analyzing the functional connectivity network of BSPs, the high-density electrophysiological characteristics are obtained and visualized as bodily emotion maps. The results showed that the functional connectivity network of BSPs under negative emotions had denser connections, and emotion maps based on local clustering coefficient (LCC) are consistent with BSMs under negative emotions. in addition, our features can classify negative and non-negative emotions with the highest classification accuracy of 80.77%. In conclusion, this study constructs an emotion map based on high-density BSPs, which offers a novel approach to psychophysiological computing.

Plasma p-tau217, p-tau181, and NfL as early indicators of dementia risk in a community cohort: The Shanghai Aging Study.

INTRODUCTION: Blood biomarkers showed values for predicting future cognitive impairment. Evidence from the community-based cohort was limited only in high-income countries. METHODS: This study included 1857 dementia-free community residents recruited in 2009-2011 and followed up in waves 2014-2016 and 2019-2023 in the Shanghai Aging Study. We intended to explore the relationships of baseline plasma ALZpath phosphorylated tau 217 (p-tau217), p-tau181, neurofilament light chain (NfL) with follow-up incident dementia, Alzheimer's disease (AD), and amyloidosis. RESULTS: Higher concentrations of plasma p-tau217, p-tau181, and NfL were correlated to higher decline speed of Mini-Mental State Examination score, and higher risk of incident dementia and AD. The p-tau217 demonstrated a significant correlation with longitudinal neocortical amyloid-beta (Aß) deposition (r = 0.57 [0.30, 0.76]) and a high accuracy differentiating Aß+ from Aß- at follow-ups (area under the receiver operating characteristic curve = 0.821 [0.703, 0.940]). DISCUSSION: Plasma p-tau217 may be an early predictive marker of AD and Aß pathology in older community-dwelling individuals.Highlights: Plasma p-tau217, p-tau181, and NfL were positively associated with long-term cognitive decline and risk of incident dementia.Plasma p-tau217 showed a better performance distinguishing Aß+ individuals from Aß- individuals at follow-ups.Plasma NfL may be a suitable predictor of general cognitive decline in older community-dwelling individuals.

Palladium-Catalyzed Tandem Cyclization of Bromoalkynes, Anilines and CO: Access to 1,3-Substituted Maleimides.

A novel palladium-catalyzed three-component carbonylation reaction for the assembly of various 1,3-substituted maleimide derivatives from haloalkynes and simple anilines. The nucleophilic addition reaction of haloalkynes, anilines and CO, and insertion of carbonyl have been achieved sequentially in this reaction. The high chemo- and regioselectivities, as well as no need of expensive ligands or additives further illustrate the synthetic value of this approach.

Rapid assembly of structurally diverse cyanamides and disulfanes via base-mediated aminoalkylation of aryl thiourea.

A general method for the preparation of cyanamides and disulfanes from aryl thiourea and halide through a base-mediated strategy is described. Mercaptan and N-aryl cyanamide are the key intermediates in the reaction. The current method is convenient, eco-friendly, and has high yields for the synthesis of substituted cyanamide and functional disulfanes in a one-pot procedure from readily available starting materials.

Olfactory function, neurofilament light chain, and cognitive trajectory: A 12-year follow-up of the Shanghai Aging Study.

This study aimed to determine whether blood neurofilament light chain (NfL) modifies the association of olfactory dysfunction (OD) with long-term cognitive decline. A total of 1125 non-demented older adults in the Shanghai Aging Study were evaluated for baseline olfaction (12-item Sniffin' Sticks Smell Test) and cognitive trajectory by a 12-year follow-up. Baseline blood NfL was quantified using Single Molecular Array assay, and dichotomized into low and high levels based on the median value of concentration. The Mini-Mental State Examination (MMSE) and Telephone Interview for Cognitive Status-40 were used to assess participants' cognitive function. Cognitive decline was ascertained when dementia was diagnosed or documented in the medical record during follow-up, or the MMSE declining rate (slope) was 1.0 SD larger than the group mean. OD participants presented a steeper trajectory of MMSE score (p interaction = 0.004) and a high risk of cognitive decline (adjusted HR [95% CI], 1.82 [1.11, 2.98]) only in those with high NfL. Participants with combined OD and high NfL showed the highest risk of cognitive decline (adjusted HR, 2.43 [1.20, 4.92]). OD, especially in combination with high blood NfL concentration, may be able to identify individuals who later incur cognitive deterioration.

Multi-Party Quantum Private Comparison Based on Bell States.

Multi-party quantum private comparison (MQPC) assumes responsibility for overseeing the flow of data and communication among diverse entities, wherein it boasts powerful security capabilities that have garnered substantial attention. Most current MQPC protocols rely on difficult-to-prepare quantum states and are inefficient in their use of resources. In this paper, we propose a novel MQPC protocol without entanglement swapping, thereby building upon the assumption of an ideal channel. This protocol is based on Bell states, which simplifies implementation and addresses the challenges associated with using complex quantum states; it also enables the comparison of secret information by having a trusted party prepare and transmit encoded quantum sequences to participants, thereby facilitating efficient equality comparison among all parties. Our MQPC protocol showcased remarkable efficiency in comparison to existing protocols for quantum private comparison. Furthermore, the incorporation of decoy photon and shared key technologies made external and internal attacks ineffective, thereby ensuring the utmost security and integrity of the protocol.

Quantum Secure Multi-Party Summation Using Single Photons.

In this paper, we propose a secure multi-party summation based on single photons. With the help of a semi-honest third party, n participants can simultaneously obtain the summation result without revealing their secret inputs. Our protocol uses single photon states as the information carriers. In addition, each participant with secret input only performs simple single-particle operators rather than particle preparation and any complex quantum measurements. These features make our protocol more feasible to implement. We demonstrate the correctness and security of the proposed protocol, which is resistant to participant attack and outside attack. In the end, we compare in detail the performance of the quantum summation protocol in this paper with other schemes in terms of different indicators. By comparison, our protocol is efficient and easy to implement.