Post-synthetic Rhodium (III) Complexes in Covalent Organic Frameworks for Photothermal Heterogeneous C-H Activation.

Although photocatalytic C-H activation has been realized by using heterogeneous catalysts, most of them require high-temperature conditions to provide the energy required for C-H bond breakage. The catalysts with photothermal conversion properties can catalyze this reaction efficiently at room temperature, but so far, these catalysts have been rarely developed. Here, we construct bifunctional catalysts Rh-COF-316 and -318 to combine photosensitive covalent organic frameworks (COFs) and transition-metal catalytic moiety using a post-synthetic approach. The Rh-COF enable the heterogeneous C-H activation reaction by photothermal conversion for the first time, and exhibit excellent yields (up to 98 %) and broad scope of substrates in [4+2] annulation at room temperature, while maintaining the high stability and recyclability. Significantly, this work is the highest yield reported so far in porous materials catalyzing C(sp2)-C(sp2) formation at room temperature. The excellent performances can be attributed to the COF-316, which enhances the photothermal effect (ΔT=50.9 °C), thus accelerating C-H bond activation and the exchange of catalyst with substrates.

Characterization of Compound-Specific Chlorine Isotopologue Distributions of Polychlorinated Organic Compounds by GC-HRMS for Source Identification.

Distributions of chlorine isotopologues are potentially a fingerprint feature of organochlorines. However, the exact distributions remain little known. This study measured compound-specific chlorine isotopologue distributions of six polychlorinated organic compounds (POCs) for source identification. Complete chlorine isotopologues of POCs were detected by gas chromatography coupled to high-resolution mass spectrometry. The measured relative abundances (Ameas), theoretical relative abundances (Atheo), and relative variations between Ameas and Atheo (ΔA) of chlorine isotopologues were determined. These ΔA values were applied to characterize differences in isotopologue distribution patterns, and the ΔA patterns directly illustrated the distribution characteristics. Perchloroethylene (PCE) and trichloroethylene (TCE) from two manufacturers were chosen as model analytes to develop and validate the analytical method, including precision, concentration dependency, and temporal drift. The ΔA values of isotopologues of the PCE and TCE chemicals were from -82.5 to 19.9‰ with standard deviations (SDs) of 0.3-16.9‰. In addition, the ΔA values of the first three isotopologues (with 0-2 37Cl atoms) were from -15.5 to 19.9‰ with SDs of 0.3-1.6‰, showing sufficient precisions. No concentration dependency and temporal drift of ΔA were observed. The method has been successfully applied to source identification for PCE and TCE in commercial chemicals and plastic materials, and four polychlorinated biphenyls in chemicals and sediments, demonstrating that the ΔA values and ΔA patterns were discernable for POCs from different sources. This study demonstrates that compound-specific chlorine isotopologue distributions of POCs are differentiable and measurable, proposing a novel approach to perform fingerprinting analysis for the distributions, which is anticipated to facilitate source identification for organochlorine pollutants.

Responses of microbial communities and their interactions to ibuprofen in a bio-electrochemical system.

Ibuprofen has caused great concerns due to their potential environmental risks. However, their removal efficiency and their effects on microbial interactions in bio-electrochemical system remain unclear. To address these issues, a lab-scale bio-electrochemical reactor integrated with sulfur/iron-mediated autotrophic denitrification (BER-S/IAD) system exposing to 1000 µg L-1 ibuprofen was operated for about two months. Results revealed that the BER-S/IAD system obtained efficient simultaneous denitrification (98.93%) and phosphorus (82.67%) removal, as well as an excellent ibuprofen removal performance (96.98%). Ibuprofen had no significant impacts on the nitrate (NO3--N) removal and the ammonia (NH4+-N) accumulation, but decreased the total nitrogen (TN) and total phosphorus (TP) removal efficiencies. MiSeq sequencing analysis revealed that ibuprofen significantly (P < 0.05) decreased the microbial community diversity and changed their overall structure. Some bacteria related to denitrification and phosphorus removal, such as Pseudomonas and Thiobacillus, decreased significantly (P < 0.05). Moreover, molecular ecological network (MEN) analysis revealed that ibuprofen decreased the network's size and complexity, and enhanced the negative correlations of Proteobacteria and Firmicutes. Besides, ibuprofen decreased the links of some keystone bacteria related to denitrification and phosphorus removal. This research could provide a new dimension for our comprehending of the responses of microbial communities and their interactions to ibuprofen in bio-electrochemical system.

CD42b Immunostaining as a Marker for Placental Fibrinoid in Normal Pregnancy and Complications.

BACKGROUND: There are two types of fibrinoids within the placenta, fibrin-type and matrix-type. The clinical importance of these fibrinoids is poorly understood. Design: Fibrinoid deposits occurring in normal and complicated pregnancies were studies with H&E stain and CD42b as a marker for platelet aggregates. Results: Fibrin-like fibrinoid was associated with platelet aggregates positive by CD42b immunostaining in the subchorionic and basal plate areas, facing the maternal circulation and intervillous spaces. Matrix-type fibrinoid did not stain with CD42b, and it was found in the intervillous spaces, trophoblastic cysts, intravillous tissue areas, and vascular walls in decidual vasculopathy. Conclusion: Fibrin-type fibrinoid within the intervillous spaces are mostly from maternal circulation and these fibrinoids are likely the result of the laminar flow change at specific anatomic locations, leading to activation of coagulatory cascades. The pathogenesis of matrix-like fibrinoid is unclear. CD42b immunostaining is helpful in differentiation of the types of fibrinoid in difficult cases.

Phenotypic Switch of Endovascular Trophoblasts in Decidual Vasculopathy with Implication for Preeclampsia and Other Pregnancy Complications.

BackgroundThis study aims to investigate decidual vasculopathy in preeclampsia at term and its relationship to spiral artery remodeling at implantation sites. Study design: Implantations sites with endovascular trophoblasts were reviewed from abortions with immunostaining for CD56. Placentas from patients with preeclampsia were also reviewed in association with other pathological features using placentas with decidual vasculopathy but not preeclampsia as controls. Results: Endovascular trophoblasts were phenotypically switched to express CD56 upon entering the spiral artery at implantation. CD56 expression is identified in classic decidual vasculopathy at term with or without preeclampsia. CD56 expression in addition to cytokeratin in decidual vasculopathy demonstrated the fetal trophoblastic origin, establishing the presence of endovascular trophoblasts at implantation and the decidual vasculopathy at term. Conclusion: Decidual vasculopathy at term contains the same CD56 positive extravillous endovascular trophoblasts seen with spiral artery remodeling in early pregnancy. CD56 may serve as a possible marker for decidual vasculopathy in the later stages of pregnancy.

The role of interlayers in enlarging the flux of GO membranes.

A graphene oxide (GO) membrane can be easily made by filtering a GO solution onto a supporting layer, and such a membrane is effective at adsorbing ions. But low flux and a high work pressure become an obstacle for its application in wastewater treatment. In this study, a positively charged mixture of carbon nanotubes and chitosan (CNTS) served as an interlayer to improve the GO membrane's flux. The three-layer membrane is known as MCG, while one without an interlayer is known as MG. For MCG and MG with the same GO load, the water flux of MCG reaches 2-8 times larger than that of MG. A better water permeability is consistently detected for MCG, with a contact angle descent speed of 3.3°/s, which is significantly faster than that of MG (0.5°/s). The ion rejections of MCG and MG are mostly attributed to GO adsorption, which stay at the same level. The flux varies with GO load, CNTS load and membrane dryness, while the ion rejection is correlated with the GO load. Optimized membrane fabrication conditions are suggested as being a CNTS load of 0.72 g m-2 and a GO load of 0.4 g m-2. A 'gap' mechanism is suggested to explain the interlayer effects. The rougher interlayer surface produces gaps between the GO and CNTS layers, which results in the faster water permeation and higher flux of MCG. These results demonstrate that it is possible to fabricate high flux GO membranes by adding a controlled-roughness interlayer.

Psiguadiols A-J, Rearranged Meroterpenoids as Potent PTP1B Inhibitors from Psidium guajava.

Psiguadiols A-J (1-10), new meroterpenoids with rearranged skeletons, were isolated from the leaves of Psidium guajava. Compounds 1-3 represent the first examples of 6,8-diformyl-5,7-dihydroxy-4-phenylchromane-coupled sesquiterpenoids with an unprecedented C-8-spiro-fused 6/6/9/4 tetracyclic ring system. Compounds 4 and 5 represent two unusual scaffolds featuring 1ß,6ß- and 3α,5α-epoxy rings, respectively. The combination of spectroscopic data analyses, comparison of experimental and calculated ECD data, and single-crystal X-ray diffraction data of 1, 6, and 8 allowed for the assignment of the structures. A putative biosynthetic pathway for 1-10 is discussed. Compounds 1, 7, and 8 exhibited inhibitory activities against PTP1B with IC50 values of 4.7, 6.2, and 9.2 µM, respectively. In addition, molecular docking was performed to investigate the mechanism of action.

Phloroglucinols with Immunosuppressive Activities from the Fruits of Eucalyptus globulus.

Five new phloroglucinol derivatives, eucalyptins C-G (1-5), together with 13 known analogues (6-18) were isolated from the fruits of Eucalyptus globulus. The structures and absolute configurations of 1-5 were established by means of spectroscopic data analysis, computational calculation methods, and single-crystal X-ray diffraction. Compounds 1-18 were investigated for their immunosuppressive effects in vitro, and 1, 2, 6, and 7 displayed moderate inhibitory activities with IC50 values of 11.8, 10.2, 18.2, and 19.1 µM, respectively. The stimulation index (SI) of 1 was 64.2 and was compared to that of cyclosporine A (SI = 149.57). Further study demonstrated that 1 exhibited an immunosuppressive effect through inducing apoptosis and inhibiting cytokine secretion.

CONE: A Connected Dominating Set-Based Flooding Protocol for Wireless Sensor Networks.

Wireless sensor networks (WSNs) play a significant role in a large number of applications, e.g., healthcare and industry. A WSN typically consists of a large number of sensor nodes which rely on limited power sources in many applications. Therefore, improving the energy efficiency of WSNs becomes a crucial topic in the research community. As a fundamental service in WSNs, network flooding offers the advantages that information can be distributed fast and reliably throughout an entire network. However, network flooding suffers from low energy efficiency due to the large number of redundant transmissions in the network. In this work, we exploit connected dominating sets (CDS) to enhance the energy efficiency of network flooding by reducing the number of transmissions. For this purpose, we propose a connected dominating set-based flooding protocol (CONE). CONE inhibits nodes that are not in the CDS from rebroadcasting packets during the flooding process. Furthermore, we evaluate the performance of CONE in both simulations and a real-world testbed, and then we compare CONE to a baseline protocol. Experimental results show that CONE improves the end-to-end reliability and reduces the duty cycle of network flooding in the simulations. Additionally, CONE reduces the average energy consumption in the FlockLab testbed by 15%.

Atropisomeric meroterpenoids with rare triketone-phloroglucinol-terpene hybrids from Baeckea frutescens.

Baefrutones A-F (1-6), six new meroterpenoids with rare triketone-phloroglucinol-monoterpene/sesquiterpene frameworks, together with their biosynthetically related intermediate (±)-baeckenon B (7), were isolated from the aerial part of Baeckea frutescens under the guidance of HPLC-Q/TOF-MS2 investigation. Compounds 1-4 represent the first examples of natural meroterpenoids existing as four pairs of inseparable diastereomeric atropisomers (2 : 1, 1H NMR integration) caused by the restricted rotation around the C-6-C-7-C-1' bonds arising from the intramolecular hydrogen bond between C-1 carbonyl and 2'-OH. The discovery of these architectures not only largely enriched the chemodiversity of the meroterpenoid and atropisomer library, but also might be exciting and challenging for asymmetric organic synthesis. Their structures and absolute configurations were established by extensive spectroscopic analysis, X-ray diffraction, and ECD calculations. Compounds 5 and 6 were biomimetically synthesized from 7 and ß-caryophyllene via a regioselective oxidative hetero-Diels-Alder reaction, thus providing access to the construction of the 6/6/9/4 tetracyclic ring system. The anti-inflammatory activities of these meroterpenoids were also discussed.

An Improved BLE Indoor Localization with Kalman-Based Fusion: An Experimental Study.

Indoor positioning has grasped great attention in recent years. A number of efforts have been exerted to achieve high positioning accuracy. However, there exists no technology that proves its efficacy in various situations. In this paper, we propose a novel positioning method based on fusing trilateration and dead reckoning. We employ Kalman filtering as a position fusion algorithm. Moreover, we adopt an Android device with Bluetooth Low Energy modules as the communication platform to avoid excessive energy consumption and to improve the stability of the received signal strength. To further improve the positioning accuracy, we take the environmental context information into account while generating the position fixes. Extensive experiments in a testbed are conducted to examine the performance of three approaches: trilateration, dead reckoning and the fusion method. Additionally, the influence of the knowledge of the environmental context is also examined. Finally, our proposed fusion method outperforms both trilateration and dead reckoning in terms of accuracy: experimental results show that the Kalman-based fusion, for our settings, achieves a positioning accuracy of less than one meter.

Regulation of induced pluripotent stem (iPS) cell induction by Wnt/ß-catenin signaling.

Wnt signaling has been implicated in promoting somatic cell reprogramming. However, its molecular mechanisms remain unknown. Here we report that Wnt/ß-catenin enhances iPSCs induction at the early stage of reprogramming. The augmented reprogramming induced by ß-catenin is not due to increased total cell population or activation of c-Myc. In addition, ß-catenin interacts with reprogramming factors Klf4, Oct4, and Sox2, further enhancing expression of pluripotency circuitry genes. These studies reveal novel mechanisms underlying the regulation of reprogramming somatic cells to pluripotency by Wnt/ß-catenin signaling.

The functional genetic link of NLGN4X knockdown and neurodevelopment in neural stem cells.

Genetic mutations in NLGN4X (neuroligin 4), including point mutations and copy number variants (CNVs), have been associated with susceptibility to autism spectrum disorders (ASDs). However, it is unclear how mutations in NLGN4X result in neurodevelopmental defects. Here, we used neural stem cells (NSCs) as in vitro models to explore the impacts of NLGN4X knockdown on neurodevelopment. Using two shRNAmir-based vectors targeting NLGN4X and one control shRNAmir vector, we modulated NLGN4X expression and differentiated these NSCs into mature neurons. We monitored the neurodevelopmental process at Weeks 0, 0.5, 1, 2, 4 and 6, based on morphological analysis and whole-genome gene expression profiling. At the cellular level, in NSCs with NLGN4X knockdown, we observed increasingly delayed neuronal development and compromised neurite formation, starting from Week 2 through Week 6 post differentiation. At the molecular level, we identified multiple pathways, such as neurogenesis, neuron differentiation and muscle development, which are increasingly disturbed in cells with NLGN4X knockdown. Notably, several postsynaptic genes, including DLG4, NLGN1 and NLGN3, also have decreased expression. Based on in vitro models, NLGN4X knockdown directly impacts neurodevelopmental process during the formation of neurons and their connections. Our functional genomics study highlights the utility of NSCs models in understanding the functional roles of CNVs in affecting neurodevelopment and conferring susceptibility to neurodevelopmental diseases.

Antiadhesion Biomaterials in Tendon Repair: Application Status and Future Prospect.

The healing process after tendon injury is often accompanied by the formation of peritendinous adhesion, contributing to limb dysfunction and exerting detrimental effects on the individuals, as well as the development of society and economy. With the continuous development of material science, as well as the augmented understanding of tendon healing and the mechanism of peritendinous adhesion formation, materials used for the fabrication of barrier membranes against peritendinous adhesion emerge endlessly. In this article, based on the analysis of the mechanism of adhesion formation, we first review the commonly used natural and synthetic materials, along with their corresponding fabrication strategies, in order to furnish valuable insights for the future optimization and development of antiperitendinous adhesion barrier membranes. This article also discusses the interaction between antiadhesion materials and cells for ameliorating peritendinous adhesion.

Investigation of epidemiological and clinical characteristics of people infected with SARS-CoV-2 during the second pandemic of COVID-19 in Chengdu, China.

Objective: This study investigated the epidemiological and clinical characteristics of Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) infected patients during the second pandemic of COVID-19 (coronavirus disease of 2019) in Chengdu, China. Furthermore, the differences between first infection and re-infection cases were also compared and analyzed to provide evidence for better prevention and control of SARS-CoV-2 re-infection. Methods: An anonymous questionnaire survey was conducted using an online platform (wjx.cn) between May 20, 2023 to September 12, 2023. Results: This investigation included 62.94% females and 32.97% of them were 18-30 years old. Furthermore, 7.19-17.18% of the participants either did not receive vaccination at all or only received full vaccination, respectively. Moreover, 577 (57.64%) participants were exposed to cluster infection. The clinical manifestations of these patients were mainly mild to moderate; 78.18% of participants had a fever for 1-3 days, while 37.84% indicated a full course of disease for 4-6 days. In addition, 40.66% of the participants had re-infection and 72.97% indicated their first infection approximately five months before. The clinical symptoms of the first SARS-CoV-2 infection were moderate to severe, while re-infection indicated mild to moderate symptoms (the severity of symptoms other than diarrhea and conjunctival congestion had statistically significant differences) (p < 0.05). Moreover, 70.53 and 59.21% of first and re-infection cases had fever durations of 3-5 and 0-2 days, respectively. Whereas 47.91 and 46.40% of first and re-infection cases had a disease course of 7-9 and 4-6 days. Conclusion: The SARS-CoV-2 infected individuals in Chengdu, China, during the second pandemic of COVID-19 had mild clinical symptoms and a short course of disease. Furthermore, compared with the first infection, re-infection cases had mild symptoms, low incidences of complications, short fever duration, and course of disease.

Knockdown of PIK3R6 impedes the onset and advancement of clear cell renal cell carcinoma.

In this research, we investigated the role of PIK3R6, a regulatory subunit of PI3Kγ, known for its tumor-promoting properties, in clear cell renal cell carcinoma (CCRCC). Utilizing the UALCAN website, we found PIK3R6 upregulated in CCRCC, correlating with lower survival rates. We compared PIK3R6 expression in CCRCC tumor tissues and adjacent normal tissues using immunohistochemistry. Post RNA interference-induced knockdown of PIK3R6 in 786-O and ACHN cell lines, we performed CCK-8, colony formation, Edu staining, flow cytometry, wound healing, and transwell assays. Results showed that PIK3R6 silencing reduced cell proliferation, migration, and invasion, and induced G0/G1 phase arrest and apoptosis. Molecular analysis revealed decreased CDK4, Cyclin D1, N-cadherin, Vimentin, Bcl-2, p-PI3K and p-AKT, with increased cleaved caspase-3, Bax, and E-cadherin levels in CCRCC cells. Moreover, inhibiting PIK3R6 hindered tumor growth. These findings suggest a significant role for PIK3R6 in CCRCC cell proliferation and metastasis, presenting it as a potential therapeutic target.

Effects of visual neuroplasticity training on visual perception, visual quality, and macular blood flow in patients with strabismus.

PURPOSE: To observe the effects of visual neuroplasticity training on visual perception, visual quality, and macular blood flow in patients with concomitant strabismus postoperatively. METHODS: In total, 108 patients underwent binocular strabismus correction operation, and some patients underwent neuroplasticity training. All patients underwent clinical ophthalmic examination, including measurement of best-corrected visual acuity, spherical equivalent, axis length, optical coherence tomography angiography, optical quality analysis system, and visual perception examinations. RESULTS: A total of 78 patients received neuroplasticity training for 1 month postoperatively, and 30 patients did not receive training. All patients underwent a visual perception examination preoperatively and at 1 day, 1 week, and 1 month postoperatively. Macular blood flow and visual quality were examined preoperatively and at 1 month postoperatively. Postoperative visual perception was better than preoperative visual perception (P < 0.05). After neuroplasticity training, the visual perception of the trained subjects was better than that of the untrained subjects (P < 0.05), and the blood flow in the macular area of the trained patients was lower than that of the untrained subjects (P < 0.05). The visual quality of the untrained subjects was lower than that of the trained patients (P < 0.05). CONCLUSIONS: Visual inspection system could accurately evaluate binocular visual perception in patients with concomitant strabismus. After surgical alignment of the strabismus patient, training can stimulate and integrate the formation of stereovision in a short period of time, maintain the visual quality of patients after surgery, and provide conditions for the formation of binocular visual signals and binocular stereovision, but in the short term, it will lead to the decrease of macular blood vessel density and perfusion density. However, the long-term effects of training have not been proven.

Nanopore sequencing demonstrates the roles of spermatozoal DNA N6-methyladenine in mediating transgenerational lipid metabolism disorder induced by excessive folate consumpton.

Increased consumption of folic acid is prevalent due to its beneficial effects, but growing evidence emphasizes the side effects pointing to excessive dietary folate intake. The effects of excessive paternal folic acid consumption on offspring and its transgenerational inheritance mechanism have not been elucidated. We hypothesize that excessive folic acid consumption will alter sperm DNA N6-methyladenine (6mA) and 5-methylcytosine (5mC) methylation and heritably influence offspring metabolic homeostasis. Here, we fed roosters either folic acid-control or folic acid-excess diet throughout life. Paternal chronic folic acid excessive supplementation increased hepatic lipogenesis and lipid accumulation but reduced lipolysis both in the roosters and their offspring, which was further confirmed to be induced by one-carbon metabolism inhibition and gene expression alteration associated with the Peroxisome proliferator-activated receptor pathway. Based on the spermatozoal genome-wide DNA methylome identified by Nanopore sequencing, multi-omics association analysis of spermatozoal and hepatic DNA methylome, transcriptome, and metabolome suggested that differential spermatozoal DNA 6mA and 5mC methylation could be involved in regulating lipid metabolism-related gene expression in offspring chickens. This model suggests that sperm DNA N6-methyladenine and 5-methylcytosine methylation were involved in epigenetic transmission and that paternal dietary excess folic acid leads to hepatic lipid accumulation in offspring.

No Racial Disparities Observed Using Point-of-Care Genetic Counseling and Testing for Endometrial and Ovarian Cancer in a Diverse Patient Population: A Retrospective Cohort Study.

We investigated genetic counseling and testing rates for patients with gynecologic malignancy at a tertiary care center with a large minority population. Our retrospective cohort included newly diagnosed epithelial ovarian, fallopian tube, peritoneal, or endometrial cancer patients between January 2014 and June 2022. For endometrial cancer, 373 patients were identified. A total of 207 (55%) patients were screened using mismatch repair immunohistochemistry (MMR IHC). A total of 82 (40%) had MMR deficiencies on IHC. Of these, 63 (77%) received genetic counseling. A total of 62 (98%) underwent genetic testing, and ultimately, 7 (11%) were diagnosed with Lynch syndrome (LS). The overall rate of LS was 1.9%. MMR IHC testing increased steadily, reaching 100% in 2022. For ovarian cancer, 144 patients were identified. A total of 104 (72%) patients received genetic counseling, and 99 (95%) underwent genetic testing. Rates were not influenced by race, ethnicity, insurance type, or family history of cancer. They were significantly different by cancer stage (p < 0.01). The proportion of patients who received genetic counseling increased from 47% in 2015 to 100% in 2022 (p < 0.01). Most counseling was performed by a gynecologic oncologist (93%) as opposed to a genetic counselor (6.7%). Overall, 12 (8.3%) patients were BRCA+. High rates of counseling and testing were observed with few disparities.

Recyclable fabrication of hollow N-doped amorphous carbon nanospindles with abundant short-range curved carbon fragments as bifunctional anode for lithium/sodium ion storage.

A recyclable hard-template method is proposed to exploit spindle-shaped hollow nitrogen-doped amorphous carbon (h-NAC) with a large number of short-range curved carbon fragments as anodes for lithium/sodium ion batteries (LIBs/SIBs). Besides providing adsorption sites due to the high existence of oxygen-containing functional groups (CO and COOH), the heavily exposed edge regions also provide a favorable storage environment with high adsorption energy for Li+/Na+ due to their short-range curved structure. Importantly, the etching solution of hard templates can be recycled to generate the FeOOH nanospindles as a precursor through a simple chemical titration, which supplies a new idea for the green preparation of hollow materials. The h-NAC electrode is proven to be bifunctional for storing lithium and sodium ions, displaying favorable rate capability (255 mAh g-1 and 106 mAh g-1 at 5 A g-1 for LIBs and SIBs, respectively). After 1000 cycles at 1 A g-1, the reproducible capacities of the LIBs and SIBs kept 496 mAh g-1 and 181 mAh g-1, respectively.