A new amide from the fruiting bodies of Tricholoma bakamatsutake.

A new amide tricholomine C was isolated from the dried fruiting bodies of Tricholoma bakamatsutake. Its structure was identified by a combination of nuclear magnetic resonance spectroscopic analysis and electronic circular dichroism (ECD) calculations. The ethyl alcohol crude extract and tricholomines A-C from T. bakamatsutake were evaluated for neuroprotective activities. Of these substances, the crude extract showed weak neurite outgrowth-promoting activity in rat pheochromocytoma (PC12) cells, as well as weak inhibitory activities against acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE).

Genetic algorithm assisted bridge fiber design and fabrication for few-mode multi-core fiber Fan-in/Fan-out device.

We present a rapid and precise method to design the multiple step-index bridge fiber for ultra-low insertion loss few-mode multi-core fiber Fan-in/Fan-out device. The genetic algorithm is applied to optimize the structural parameters to support multi-mode operation. Based on the proposed intelligent iteration platform, core-based multiplex/demultiplex optimization can be achieved with less than 1.0 dB insertion loss for the first 6 LP modes in space division multiplexing system consisting of few-mode multi-core fibers. Besides, we have successfully drew the designed bridge fiber and fabricated the corresponding Fan-in/Fan-out device. When connecting it with the single-core 6-mode fiber and 7-core 6-mode fiber, the average insertion losses of mode LP01, LP11a, LP11b, LP21a, LP21b, and LP02 are 0.88 dB, 1.11 dB, 1.07 dB, 1.42 dB, 1.33 dB, and 1.04 dB, respectively.

Exploring the intercalation binding of tiamulin with DNA using multispectroscopy and a molecular modelling approach.

The binding of tiamulin with calf thymus DNA was systematically investigated using multispectroscopy and molecular modelling techniques. For DNA, once tiamulin was added, viscosity (η) and melting temperature (Tm ) both exhibited an uptrend. The fluorescence performance of the tiamulin-DNA complex did not change with the ionic strength changes. The binding constant (Ka ) of tiamulin for single-stranded DNA (ssDNA, 1.48 × 104 M-1 ) was obviously higher than that for double-stranded DNA (dsDNA, 9.51 × 103 M-1 ) at 291 K. The helix structure became looser and the base stack force became stronger for DNA due to the presence of tiamulin as seen from circular dichroic (CD) spectra. The intercalation binding mode of tiamulin with DNA was disclosed. Molecular modelling also revealed tiamulin inserting into the base pairs with the lowest binding free energy of -18.73 kJ mol-1 using van der Waals forces as well as hydrogen bonds.

Unsupervised Domain Adaptation with Shape Constraint and Triple Attention for Joint Optic Disc and Cup Segmentation.

Currently, glaucoma has become an important cause of blindness. At present, although glaucoma cannot be cured, early treatment can prevent it from getting worse. A reliable way to detect glaucoma is to segment the optic disc and cup and then measure the cup-to-disc ratio (CDR). Many deep neural network models have been developed to autonomously segment the optic disc and the optic cup to help in diagnosis. However, their performance degrades when subjected to domain shift. While many domain-adaptation methods have been exploited to address this problem, they are apt to produce malformed segmentation results. In this study, it is suggested that the segmentation network be adjusted using a constrained formulation that embeds prior knowledge about the shape of the segmentation areas that is domain-invariant. Based on IOSUDA (i.e., Input and Output Space Unsupervised Domain Adaptation), a novel unsupervised joint optic cup-to-disc segmentation framework with shape constraints is proposed, called SCUDA (short for Shape-Constrained Unsupervised Domain Adaptation). A shape constrained loss function is novelly proposed in this paper which utilizes domain-invariant prior knowledge concerning the segmentation region of the joint optic cup-optical disc of fundus images to constrain the segmentation result during network training. In addition, a convolutional triple attention module is designed to improve the segmentation network, which captures cross-dimensional interactions and provides a rich feature representation to improve the segmentation accuracy. Experiments on the RIM-ONE_r3 and Drishti-GS datasets demonstrate that the algorithm outperforms existing approaches for segmenting optic discs and cups.

The Value of Shear Wave Elastography in Predicting the Risk of Endometrial Cancer and Atypical Endometrial Hyperplasia.

OBJECTIVES: To evaluate shear wave elastography (SWE) technology diagnosis value of endometrial cancer (EC) and atypical endometrial hyperplasia (AEH), and to establish predictive logistic regression models for the diagnosis of EC and AEH. METHODS: Clinical information collection, transvaginal conventional ultrasonography, and SWE check were performed on 122 patients, who were perimenopausal or postmenopausal vaginal bleeding with ≥4.5 mm thick endometrium. The maximal (Emax) and mean (Emean) of Young's modulus for the endometrium were obtained. Using pathology as the gold standard, ROC curves were plotted to evaluate Young's modulus on the diagnostic effectiveness of EC and AEH. Single-factor analysis and bivariate logistic regression methods were applied to assess the clinical variables, transuaginal conventional ultrasonography variables, and Young's modulus on the identification of EC and AEH. RESULTS: Out of 122 cases of endometrial lesions, 85 cases were benign lesions, and the remaining 37 cases were EC and AEH. The Emax and Emean for the benign group were 29.80 ± 11.40 and 17.96 ± 8.05 kPa, respectively. The Emax and Emean values for EC and AEH group were 59.49 ± 16.95 and 38.46 ± 17.10 kPa, respectively. Emax and Emean for both groups were statistically significant, with p <.001. In the logistical regression analysis, endometrial thickness, Color score, and Young's modulus were identified as independent risk factors for EC and AEH. CONCLUSIONS: SWE technology plays an important role in the diagnosis of EC and AEH, and the diagnostic effectiveness would be higher when combined with conventional ultrasonography.

Tricholomines A and B, two new amides from the fruiting bodies of Tricholoma bakamatsutake.

Two new amides tricholomines A (1) and B (2), along with nine known compounds, were isolated from the dried fruiting bodies of Tricholoma bakamatsutake. Their structures were determined on the basis of extensive spectroscopic analysis or comparison with the data in the literatures. The absolute configuration of 1 was confirmed by single crystal X-ray diffraction analysis.

Continuous and Rapid Synthesis of UiO-67 by Electrochemical Methods for the Electrochemical Detection of Hydroquinone.

Continuous and rapid synthesis of UiO-67 under mild conditions has been achieved by electrochemical methods for the first time. In the reaction system, a zirconium sheet was utilized as electrodes and a metal source for the assembly of UiO-67. High-crystalline UiO-67 with a regular tetrahedral morphology of around 1 µm was obtained within 1.5 h under the optimized solvent composition, voltage, and temperature conditions. This electrochemical synthetic method of UiO-67 in our work overcomes the shortcomings of high temperature and pressure of a traditional solvothermal method, which proposes new ideas for the large-scale and rapid synthesis of UiO-67. The UiO-67 synthesized by an electrochemical method was prepared as a UiO-67-carbon paste electrode (CPE), which exhibited a linear response to hydroquinone (HQ) in the range of 5-300 µM with a detection limit of 3.6 × 10-9 M (S/N = 3), for the electrochemical detection of HQ. It was confirmed that UiO-67-CPE possessed excellent reusability and antiinterference ability for the detection of HQ, and its detection ability even did not change after standing for 3 months. We further tried to apply UiO-67-CPE to the practical determination of HQ in tap water and river water samples, and the results proved that the recovery rate is 97.9-104.7% in real samples.

Rapid and Low-Cost Electrochemical Synthesis of UiO-66-NH2 with Enhanced Fluorescence Detection Performance.

Rapid and low-cost synthesis of metal-organic frameworks (MOFs) are very meaningful for their future practical application. In the present study, a Zr-based ultrastable MOF, UiO-66-NH2, was successfully synthesized by electrochemical method using metal Zr as the metal source at room temperature and atmospheric pressure. The effects of the reaction conditions, including the ratio of solvent (electrolyte), the applied voltage and different reaction time, on the crystallinity, morphology, and synthesis rate of the product were fully investigated. The results confirm that electrochemically synthesized UiO-66-NH2 under the optimized condition possesses apparent merits such as high crystallinity, uniform morphology and high porosity. Moreover, the electrochemical synthesis method of UiO-66-NH2 is promising for the large-scale and economical synthesis of nanoscale product to gramme degree. Interestingly, the resulting UiO-66-NH2 synthesized by this electrochemical method exhibits more excellent performance for the fluorescence detection of Fe3+ ions in water (detection limit of 10-8 mol/L) than that of the material prepared by solvothermal method.

Folic Acid Functionalized Zirconium-Based Metal-Organic Frameworks as Drug Carriers for Active Tumor-Targeted Drug Delivery.

Nanoscale metal-organic frameworks (NMOFs) have proven to be a class of promising drug carriers as a result of their high porosity, crystalline nature with definite structure information, and potential for further functionality. However, MOF-based drug carriers with active tumor-targeting function have not been extensively researched until now. Here we show a strategy for constructing active tumor-targeted NMOF drug carriers by anchoring functional folic acid (FA) molecules onto the metal clusters of NMOFs. Two zirconium-based MOFs, MOF-808 and NH2 -UiO-66, were chosen as models to reduce to the nanoscale for application as drug carriers, and then the terminal carboxylates of FA molecules were coordinated to Zr6 clusters on the surfaces of the nanoparticles by substitution of the original formate or terminal -OH ligands. The successful modification with FA was confirmed by solid-state 13 C MAS NMR and UV/Vis spectroscopy and other characterization methods. Drug loading and controlled release behavior at different pH were determined by utilizing the anticancer drug 5-fluorouracil (5-FU) as the model drug. Confocal laser scanning microscopy measurements further demonstrated that 5-FU-loaded FA-NMOFs have excellent targeting ability through the efficient cellular uptake of FA-NMOFs. This work opens up a new avenue to the construction of active tumor-targeted NMOF-based drug carriers with potential for cancer therapies.

Rapid and Large-Scale Synthesis of IRMOF-3 by Electrochemistry Method with Enhanced Fluorescence Detection Performance for TNP.

Rapid and large-scale synthesis of metal-organic frameworks (MOFs) materials is of great significance for their practical applications. For the first time, we have electrochemically synthesized IRMOF-3 at room temperature by applying a voltage to a zinc electrode immersed in electrolyte containing 2-aminoterephthalic acid (NH2-H2BDC). The reaction conditions, including the ratio of solvent (electrolyte), the applied voltage, and different reaction times, were investigated and optimized. The degree of crystallinity and nanomorphology of the synthesized IRMOF-3 can be controlled by changing the reaction conditions. More importantly, we demonstrated that the electrochemical synthesis strategy can rapidly obtain nanoscale IRMOF-3 with high crystallinity on a gram scale. In addition, in comparison with the product of solvothermal synthesis, the electrochemically synthesized nanoscale IRMOF-3 exhibits improved fluorescent detection ability to 2,4,6-trinitrophenol (TNP) with a detection limit of about 0.1 ppm.

Rational Design of MOF/COF Hybrid Materials for Photocatalytic H2 Evolution in the Presence of Sacrificial Electron Donors.

Crystalline and porous covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H2 evolution due to their long-range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two-dimensional (2D) COF with stable MOF. By covalently anchoring NH2 -UiO-66 onto the surface of TpPa-1-COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H2 evolution under visible light irradiation. Especially, NH2 -UiO-66/TpPa-1-COF (4:6) exhibits the maximum photocatalytic H2 evolution rate of 23.41 mmol g-1 h-1 (with the TOF of 402.36 h-1 ), which is approximately 20 times higher than that of the parent TpPa-1-COF and the best performance photocatalyst for H2 evolution among various MOF- and COF-based photocatalysts.

Effect of Imidazole Arrangements on Proton-Conductivity in Metal-Organic Frameworks.

Imidazole molecules were frequently incorporated into porous materials to improve their proton conductivity. To investigate how different arrangements of imidazoles in metal-organic frameworks (MOFs) affect the overall proton conduction, we designed and prepared a MOF-based model system. It includes an Fe-MOF as the blank, an imidazole@Fe-MOF (Im@Fe-MOF) with physically adsorbed imidazole, and an imidazole-Fe-MOF (Im-Fe-MOF), which contains chemically coordinated imidazole molecules. The parent Fe-MOF, synthesized from the exchange of carboxylates in the preformed [Fe3(µ3-O)](carboxylate)6 clusters and multitopic carboxylate ligands, serves as a control. The Im@Fe-MOF was prepared by encapsulating free imidazole molecules into the pores of the Fe-MOF, whereas the Im-Fe-MOF was obtained in situ, in which imidazole ligands coordinate to the metal nodes of the framework. Proton-conductivity analyses revealed that the proton conductivity of Im-Fe-MOF was approximately two orders of magnitude greater than those of Fe-MOF and Im@Fe-MOF at room temperature. The high proton conductivity of 1.21 × 10-2 S cm-1 at 60 °C for Im-Fe-MOF ranks among the highest performing MOFs ever reported. The results of the density functional theory calculations suggest that coordinated imidazole molecules in Im-Fe-MOF provide a greater concentration of protons for proton transportation than do coordinated water molecules in Fe-MOF alone. Besides, Im-Fe-MOF exhibits steadier performance than Im@Fe-MOF does after being washed with water. Our investigation using the above ideal crystalline model system demonstrates that compared to disorderly arranged imidazole molecules in pores, the immobilized imidazole molecules by coordination bonds in the framework are more prone to form proton-conduction pathways and thus perform better and steadier in water-mediated proton conduction.

T-type calcium channels, but not Cav3.2, in the peripheral sensory afferents are involved in acute itch in mice.

T-type calcium channels are prominently expressed in primary nociceptive fibers and well characterized in pain processes. Although itch and pain share many similarities including primary sensory fibers, the function of T-type calcium channels on acute itch has not been explored. We investigated whether T-type calcium channels expressed within primary sensory fibers of mouse skin, especially Cav3.2 subtype, involve in chloroquine-, endothelin-1- and histamine-evoked acute itch using pharmacological, neuronal imaging and behavioral analyses. We found that pre-locally blocking three subtypes of T-type calcium channels in the peripheral afferents of skins, yielded an inhibition in acute itch or pain behaviors, while selectively blocking the Cav3.2 channel in the skin peripheral afferents only inhibited acute pain but not acute itch. These results suggest that T-type Cav3.1 or Cav3.3, but not Cav3.2 channel, have an important role in acute itch processing, and their distinctive roles in modulating acute itch are worthy of further investigation.

A de novo silencer causes elimination of MITF-M expression and profound hearing loss in pigs.

BACKGROUND: Genesis of novel gene regulatory modules is largely responsible for morphological and functional evolution. De novo generation of novel cis-regulatory elements (CREs) is much rarer than genomic events that alter existing CREs such as transposition, promoter switching or co-option. Only one case of de novo generation has been reported to date, in fish and without involvement of phenotype alteration. Yet, this event likely occurs in other animals and helps drive genetic/phenotypic variation. RESULTS: Using a porcine model of spontaneous hearing loss not previously characterized we performed gene mapping and mutation screening to determine the genetic foundation of the phenotype. We identified a mutation in the non-regulatory region of the melanocyte-specific promoter of microphthalmia-associated transcription factor (MITF) gene that generated a novel silencer. The consequent elimination of expression of the MITF-M isoform led to early degeneration of the intermediate cells of the cochlear stria vascularis and profound hearing loss, as well as depigmentation, all of which resemble the typical phenotype of Waardenburg syndrome in humans. The mutation exclusively affected MITF-M and no other isoforms. The essential function of Mitf-m in hearing development was further validated using a knock-out mouse model. CONCLUSIONS: Elimination of the MITF-M isoform alone is sufficient to cause deafness and depigmentation. To our knowledge, this study provides the first evidence of a de novo CRE in mammals that produces a systemic functional effect.

Efficient detection of aklomide/nitromide based on a sensor of MPA capped CdTe QDs using fluorescence quenching method.

Based on the fluorescence sensor of 3-Mercaptopropionic acid (MPA) capped CdTe quantum dots (QDs), two novel detection methods for aklomide and nitromide were developed. The MPA-CdTe QDs were synthesized and characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), ultraviolet visible (UV-vis) and fluorescence (FL). The quenchings were all static. The binding constants (Ka) at different temperatures were obtained. Electrostatic forces were the main forces for the two bindings. For the detection of aklomide and nitromide, under the optimal conditions, the effects of some metal ions, glucose, bovine serum albumin (BSA) and congeneric drug on the determination were explored. The standard equations were established and the limits of detection (LOD) were 0.0215 and 0.0388 µg mL-1 (3S0/S), repectively. The methods were applied to analyse the samples of chicken and duck, the recoveries were 99.41 % - 101.24 % with RSDs of 0.29 % - 1.19 % (n = 5).

Sensitive detection of dextromethorphan hydrobromide based on portable Raman spectrometer and CuO@AgNPs nano composite SERS substrate.

A highly sensitive surface-enhanced Raman spectroscopy approach was established for the detection of dextromethorphan hydrobromide (DXM) utilizing nano CuO modified silver nanoparticles (CuO@AgNPs) as substrate. Ultraviolet visible spectra (UV-vis), X-ray diffraction (XRD) and transmission electron microscopy (TEM) characterized the synthesized CuO@AgNPs. UV-vis and fourier transform infrared (FT-IR) were adopted to investigate the interaction between DXM and CuO@AgNPs. The optimal experimental conditions (the dosages of CuO@AgNPs and NaCl as well as mixing time) were explored. The enhancement factor (EF) was 1.71 × 106. The linear relationship between SERS intensity and the concentration of DXM in the range of 67 - 1000 nmol L-1 was obtained as ISERS = 25.81 c + 40398.77, and the limit of detection (LOD) was 2.12 nmol L-1 (S/N = 3). The interference of K+, Mg2+, Zn2+, Ca2+, Cu2+, Fe3+, glucose, HSA, L-tryptophan, soluble starch and ibuprofen were investigated. The method was successfully applied to test DXM in serum samples. The recovery was 99.06% - 101.51% with the relative standard deviation (RSD) of 0.74% - 3.87%.

Effect of postharvest grape dehydration on chemical composition, antioxidant activity and sensory characeteristics of Marselan wines.

To explore the effect of postharvest dehydration on grape berries and wine quality, we determined physicochemical properties, polyphenols, antioxidant activities, volatile compounds and sensory characteristics for wines brewed by 'Marselan' (Vitis vinifera L.) grapes with 0%, 10%, 15%, 20%, and 25% of water loss. The result showed that postharvest dehydration improved the alcohol content, residual sugar and titratable acidity of Marselan wine. Phenolic compounds and antioxidant activities in wines with a dehydration of 20% have significantly increased. Postharvest dehydration increased the contents of isobutanol, isoamyl alcohol, phenylethyl alcohol, ethyl acetate, isoamyl acetate and ethyl butyrate in Marselan wines, and enhanced the floral, fruity and sweet taste of wines. Marselan wine had the lowest acceptability score under the condition of severe dehydration (25% dehydration), which was related to the significant increase of tannins content. In summary, postharvest dehydration was beneficial in improving the quality of Marselan wine.

Controlled synthesis of 2D-2D conductive metal-organic framework/g-C3N4 heterojunctions for efficient photocatalytic hydrogen evolution.

Designing photocatalysts with efficient charge separation and electron transport capabilities to achieve efficient visible-driven hydrogen production remains a challenge. Herein, 2D-2D conductive metal-organic framework/g-C3N4 heterojunctions were successfully prepared by an in situ assembly. Compared to pristine g-C3N4, the ratio-optimized Ni-CAT-1/g-C3N4 exhibits approximately 3.6 times higher visible-light H2 production activity, reaching 14 mmol g-1. Through investigations using time-resolved photoluminescence, surface photovoltage, and wavelength-dependent photocurrent action spectroscopies, it is determined that the improved photocatalytic performance is attributed to enhanced charge transfer and separation, specifically the efficient transfer of excited high-energy-level electrons from g-C3N4 to Ni-CAT in the heterojunctions. Furthermore, the high electrical conductivity of Ni-CAT enables rapid electron transport, contributing to the overall enhanced performance. This work provides a feasible strategy to construct efficient dimension-matched g-C3N4-based heterojunction photocatalysts with high-efficiency charge separation for solar-driven H2 production.

Construct ceRNA Network and Risk Model of Breast Cancer Using Machine Learning Methods under the Mechanism of Cuproptosis.

Breast cancer (BRCA) has an undesirable prognosis and is the second most common cancer among women after lung cancer. A novel mechanism of programmed cell death called cuproptosis is linked to the development and spread of tumor cells. However, the function of cuproptosis in BRCA remains unknown. To this date, no studies have used machine learning methods to screen for characteristic genes to explore the role of cuproptosis-related genes (CRGs) in breast cancer. Therefore, 14 cuproptosis-related characteristic genes (CRCGs) were discovered by the feature selection of 39 differentially expressed CRGs using the three machine learning methods LASSO, SVM-RFE, and random forest. Through the PPI network and immune infiltration analysis, we found that PRNP was the key CRCG. The miRTarBase, TargetScan, and miRDB databases were then used to identify hsa-miR-192-5p and hsa-miR-215-5p as the upstream miRNA of PRNP, and the upstream lncRNA, CARMN, was identified by the StarBase database. Thus, the mRNA PRNP/miRNA hsa-miR-192-5p and hsa-miR-215-5p/lncRNA CARMN ceRNA network was constructed. This ceRNA network, which has not been studied before, is extremely innovative. Furthermore, four cuproptosis-related lncRNAs (CRLs) were screened in TCGA-BRCA by univariate Cox, LASSO, and multivariate Cox regression analysis. The risk model was constructed by using these four CRLs, and the risk score = C9orf163 * (1.8365) + PHC2-AS1 * (-2.2985) + AC087741.1 * (-0.9504) + AL109824.1 * (0.6016). The ROC curve and C-index demonstrated the superior predictive capacity of the risk model, and the ROC curve demonstrated that the AUC of 1-, 3-, and 5-year OS in all samples was 0.721, 0.695, and 0.633, respectively. Finally, 50 prospective sensitive medicines were screened with the pRRophetic R package, among which 17-AAG may be a therapeutic agent for high-risk patients, while the other 49 medicines may be suitable for the treatment of low-risk patients. In conclusion, our study constructs a new ceRNA network and a novel risk model, which offer a theoretical foundation for the treatment of BRCA and will aid in improving the prognosis of BRCA.

Understanding Photocatalytic Overall Water Splitting of ß-Ketoamine COFs through the N-C Site Synergistic Mechanism.

Overcoming the sluggish reaction kinetics of the oxygen evolution reaction (OER) is a determining factor for the practical application of photocatalysts for overall water splitting. Two-dimensional covalent organic frameworks (2D-COFs) offer an ideal platform for catalyst design in the field of overall water splitting for their exceptional chemical tunability and high efficiency of light capture. In this work, four ß-ketoamine 2D-COFs, consisting of 1,3,5-triformylphloroglucinol (Tp) groups and different linkers with pyridine segments, were constructed and optimized. By means of first-principles calculations, the band structures, free energy changes of photocatalytic hydrogen evolution reaction (HER) and OER, and charge density distributions were calculated and investigated systemically to discuss the visible-light response, overall water splitting activities on active sites, and the characteristic of charge transfer and separation. The protonated pyridine N derived from the double-H2O closed-ring H-bond adsorption model could efficiently induce N-C sites' synergistic effect between pyridine N and its ortho-position C to minimize the OER energy barrier and to enhance the charge transfer and separation. A N-C site synergistic mechanism has been proposed to provide a comprehensive explanation for the experimental results and a new strategy to design novel 2D-COF photocatalysts for overall water splitting.