Tetrathiafulvalene esters with high redox potentials and improved solubilities for non-aqueous redox flow battery applications

The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.

Correction:Brillouin scattering spectrum for liquid detection and applications in oceanography

After publication of this article1,it was brought to our at-tention that the mathematical expressions‘‰’were mis-takenly replaced by‘%’for salinities.Details are listed below.1.In the last sentence in abstract,“approximately 0.1℃and 0.5%”should be“approximately 0.1℃and 0.5‰”.

Modified Z-Plasty for Reconstruction of Webbed Scar Contractures

Rationale: Webbed scar contractures deformity caused by burns and other factors will lead to joint disorders and affect the mental health of patients, resulting in a severe decline in quality of life. Rapid, effective and less complicated surgical methods can help patients with post-burn rehabilitation. Objective: This article argues that a modified Z-plasty can quickly improve the range of motion caused by webbed scar contractures in joint areas, including surgical methods, postoperative care and prognosis. Methods and Results: The study took place from 2018 to 2022. Thirty-two patients with joint scar contracture deformity, with a mean age of 32.5 years, were included in the study. All patients underwent contracture scar revision and modified Z-plasty repair under anesthesia. All the flaps survived and the joint function was improved. Compared with the traditional Z-plasty, the duration of the operative procedure of the modified Z-plasty was significantly shorter, more surrounding scar tissue was mobilized, and the effectiveness of postoperative scar contracture release was better. Discussions: The modified Z-plasty for scar contracture deformity in joint area is simple, rapid, effective and easy to manage.

Brillouin scattering spectrum for liquid detection and applications in oceanography

The Brillouin scattering spectrum has been used to investigate the properties of a liquid medium.Here,we propose an improved method based on the double-edge technique to obtain the Brillouin spectrum of a liquid.We calculated the transmission ratios and deduced the Brillouin shift and linewidth to construct the Brillouin spectrum by extracting the Brillouin edge signal through filtered double-edge data.We built a detection system to test the performance of this method and measured the Brillouin spectrum for distilled water at different temperatures and compared it with the theoretical prediction.The observed difference between the experimental and theoretical values for Brillouin shift and linewidth is less than 4.3 MHz and 3.2 MHz,respectively.Moreover,based on the double-edge technique,the accuracy of the extracted temperatures and salinity is approximately 0.1°C and 0.5‰,respectively,indicating significant potential for application in water detection and oceanography.

Radical Operation and Everolimus Therapy for Rectal Neuroendocrine Tumor with Liver Metastases: A Case Report with Review of the Literature

Neuroendocrine tumors (NETs) are often misdiagnosed because they can involve any part of the body and have non-specific symptoms. Here, we report a case of a 39-year-old man with rectal neuroendocrine tumor (RNET) and hepatic metastases treated with a combination of radical surgery and Everolimus therapy. The patient complained of abdominal distension, pain, and constipation of one month duration. Enhanced CT scan of the abdomen, colonoscopy and Biopsy findings confirmed the diagnosis of rectal neuroendocrine tumor. As the anatomical structures were clear and the masses seemed to be resectable, we decided to initiate treatment with radical operation and Everolimus therapy. The patient has responded well to the treatment with no evidence of recurrence after 4 years of follow-up. This case is interesting because of the rarity of this neoplasm and its initial misdiagnosis as a giant hepatic carcinoma (hepatoma). It also demonstrates that a combination of curative surgical resection and Everolimus is a good option in a patient with large colorectal neuroendocrine tumors and massive hepatic metastases.

Fuzzy Torque Control of the Bionic Flexible Manipulator Actuated by Pneumatic Muscle Actuators

A bionic flexible manipulator driven by pneumatic muscle actuator(PMA)can better reflect the flexibility of the mechanism.Current research on PMA mainly focuses on the modeling and control strategy of the pneumatic manipulator system.Compared with traditional electro-hydraulic actuators,the structure of PMA is simple but possesses strong nonlinearity and flexibility,which leads to the difficulty in improving the control accuracy.In this paper,the configuration design of a bionic flexible manipulator is performed by human physiological map,the kinematic model of the mechanism is established,and the dynamics is analyzed by Lagrange method.A fuzzy torque control algorithm is designed based on the computed torque method,where the fuzzy control theory is applied.The hardware experimental system is established.Through the co-simulation contrast test on MATLAB and ADAMS,it is found that the fuzzy torque control algorithm has better tracking performance and higher tracking accuracy than the computed torque method,and is applied to the entity control test.The experimental results show that the fuzzy torque algorithm can better control the trajectory tracking movement of the bionic flexible manipulator.This research proposes a fuzzy torque control algorithm which can compensate the error more effectively,and possesses the preferred trajectory tracking performance.

Tetra-alkylsulfonate functionalized poly(aryl ether) membranes with nanosized hydrophilic channels for efficient proton conduction

The microstructure of polymer electrolyte membranes plays a key role in ion conductivity and water transport.Herein,fluorinated poly(aryl ether)s with tetra-alkylsulfonate side chains(SFPAEs)have been successfully synthesized from the copolymerization of a newly developed tetra-allyl-containing bisphenol(TABP)monomer,followed by the thiol-ene addition with sodium 3-mercapto-1-propanesulfonate to attach the ionic groups at the end of the flexible chains.Being the first of its kind,the densely distributed and lengthy alkylsulfonate group possesses the benefit of ease to self-assemble into hydrophilic domains during membrane preparation via solution casting.Indeed,the TEM characterizations revealed that distinct hydrophilic channels of 1-2 nm width had been formed,much larger than those of a home-made control sample where only di-alkylsulfonate side chains were attached.The SFPAE-4-45 with an IECw of 2.0 mmol g^-1 exhibited an enhanced proton conductivity of 143.7 m S cm^-1 at room temperature,which was superior to that of Nafion 212(91.0 m S cm^-1).Furthermore,the oxidative stabilities of SFPAEs were significantly higher than those of non-fluorinated analogs in literature.This study offered a new route to engineering the pendent structure of ionomers for well-defined microscopic morphologies.

同轴静电喷涂法制备核壳靶向示踪重组人白细胞介素Ⅱ微球

重组人白细胞介素-2(rh IL-2)具有促进免疫细胞增殖和分化的潜能,可用于治疗肺癌。然而,rh IL-2半衰期短,生物活性不稳定,需要将其载入微球中进行缓释给药。本研究采用同轴静电喷涂技术制备了载rh IL-2的核壳微球。以量子点为示踪材料,核层用壳聚糖做载体包裹rh IL-2和量子点偶联物,壳层采用透明质酸做载体制备核壳复合微球。采用单因素法对载体浓度、电压、针孔内径、喷雾流量等因素进行了研究。优化了同轴静电喷雾法制备核壳微球的工艺参数。结果表明,制备的核壳微球粒径在1.2–2.0μm,包封率和载药量分别为78.39%±1.96%和19.58±2.76μg/mg。体外释放实验显示微球释放效果较好,无突释现象。该制剂的生物学活性实验表明,核壳微球中的rh IL-2与游离蛋白药物具有相同的作用。体内成像分析也显示微球具有主动靶向性。本研究为rh IL-2靶向缓释微球的研制提供了理论依据。

A novel approach for assessing color harmony of historical buildings via street view image

While new buildings continue to emerge in the process of urbanization,historical buildings,as valuable legacies carrying national historical memory,play an important role in the urban landscape.Previous studies have shown that color harmony is a crucial factor in coordinating urban landscapes.However,the evaluation of color harmony in historic areas and buildings lacks effective quantitative standards,often overlooking factors such as complementary color harmony and the compatibility of analogous colors.This study aims to build a new method to evaluate the color harmony of historical buildings through street view technology,semantic segmentation algorithms,quantification of color harmony methods based on image property detection and classification,questionnaire verification,and takes Shanghai’s historical buildings as an example to explore.Our study categorizes six types of color harmony indexes for Shanghai street-facing historic buildings into three levels,with the top tier serving as a benchmark for excellence and the lowest tier highlighting areas in need of urban environmental improvement.This study uniquely considers color compatibility within hue ranges and expanded relationship types like complementary harmony.This approach,applicable to cities globally,offers practical tools for urban planners and conservators in managing and preserving historic areas and buildings.

A pathological joint-liver axis mediated by matrikine-activated CD4^(+)T cells

The knee joint has long been considered a closed system.The pathological effects of joint diseases on distant organs have not been investigated.Herein,our clinical data showed that post-traumatic joint damage,combined with joint bleeding(hemarthrosis),exhibits a worse liver function compared with healthy control.With mouse model,hemarthrosis induces both cartilage degeneration and remote liver damage.Next,we found that hemarthrosis induces the upregulation in ratio and differentiation towards Th17 cells of CD4^(+)T cells in peripheral blood and spleen.Deletion of CD4^(+)T cells reverses hemarthrosis-induced liver damage.Degeneration of cartilage matrix induced by hemarthrosis upregulates serological type Ⅱ collagen(COL Ⅱ),which activates CD4^(+)T cells.Systemic application of a COL Ⅱ antibody blocks the activation.Furthermore,bulk RNAseq and single-cell qPCR analysis revealed that the cartilage Akt pathway is inhibited by blood treatment.Intra-articular application of Akt activator blocks the cartilage degeneration and thus protects against the liver impairment in mouse and pig models.Taken together,our study revealed a pathological joint-liver axis mediated by matrikine-activated CD4^(+)T cells,which refreshes the organ-crosstalk axis and provides a new treatment target for hemarthrosis-related disease.

Thiol-Disulfide Exchange Coordinates the Release of Nitric Oxide and Dexamethasone for Synergistic Regulation of Intestinal Microenvironment in Colitis

The cell-specific functions of nitric oxide(NO)in the intestinal microenvironment orchestrate its therapeutic effects in ulcerative colitis.While most biomaterials show promise by eliciting the characteristics of NO,the insufficient storage,burst release,and pro-inflammatory side effects of NO remain as challenges.Herein,we report the development of thiol-disulfide hybrid mesoporous organosilica nanoparticles(MONs)that improve the storage and sustained release of NO,broadening the therapeutic window of NO-based therapy against colitis.The tailored NO-storing nanomaterials coordinated the release of NO and the immunoregulator dexamethasone(Dex)in the intestinal microenvironment,specifically integrating the alleviation of oxidative stress in enterocytes and the reversal of NO-exacerbated macrophage activation.Mechanistically,such a synchronous operation was achieved by a self-motivated process wherein the thiyl radicals produced by NO release cleaved the disulfide bonds to degrade the matrix and release Dex via thiol-disulfide exchange.Specifically,the MON-mediated combination of NO and Dex greatly ameliorated intractable colitis compared with 5-aminosalicylic acid,even after delayed treatment.Together,our results reveal a key contribution of synergistic modulation of the intestinal microenvironment in NO-based colitis therapy and introduce thiol-disulfide hybrid nanotherapeutics for the management of inflammatory diseases and cancer.

Engineering vascularised organoid-on-a-chip:strategies,advances and future perspectives

In recent years,advances in microfabrication technology and tissue engineering have propelled the development of a novel drug screening and disease modelling platform known as organoid-on-a-chip.This platform integrates organoids and organ-on-a-chip technologies,emerging as a promising approach for in vitro modelling of human organ physiology.Organoid-on-a-chip devices leverage microfluidic systems to simulate the physiological microenvironment of specific organs,offering a more dynamic and flexible setting that can mimic a more comprehensive human biological context.However,the lack of functional vasculature has remained a significant challenge in this technology.Vascularisation is crucial for the long-term culture and in vitro modelling of organoids,holding important implications for drug development and personalised medical approaches.This review provides an overview of research progress in developing vascularised organoid-on-a-chip models,addressing methods for in vitro vascularisation and advancements in vascularised organoids.The aim is to serve as a reference for future endeavors in constructing fully functional vascularised organoid-on-a-chip platforms.

人工智能赋能高校韧性教学生态的路径研究

新冠疫情的反复使得师生频繁切换不同的混合式教学模式,这对教育韧性生态系统提出更高要求,依靠人工智能赋能韧性教学生态成为当前重要的研究课题。然而,现有研究缺少从系统性的视角综合分析韧性教学生态的构建路径。针对此问题,本研究以Z大学为案例,一方面探讨人工智能赋能韧性教学生态的框架和表现形态,另一方面对人工智能赋能下韧性教学生态的实践经验和教学效果进行分析。研究发现:Z大学以中台架构为技术底座丰富教学平台的功能应用,并贯穿导学、讲授、协作、评价四个阶段,有效地保障了疫情反复过程中师生对环境异化的适应性和教学效果的有效性。最后展望未来人工智能赋能韧性教学生态的发展重点,并对潜在的挑战进行反思。

High current CO_(2)reduction realized by edge/defect-rich bismuth nanosheets

CO_(2)electroreduction has been regarded as an appealing strategy for renewable energy storage.Recently,bismuth(Bi)electrocatalysts have attracted much attention due to their excellent formate selectivity.However,many reported Bi electrocatalysts suffer from low current densities,which are insufficient for industrial applications.To reach the goal of high current CO_(2)reduction to formate,we fabricate Bi nanosheets(NS)with high activity through edge/terrace control and defect engineering strategy.Bi NS with preferential exposure sites are obtained by topotactic transformation,and the processes are clearly monitored by in-situ Raman and ex-situ X-ray diffraction(XRD).Bi NS-1 with a high fraction of edge sites and defect sites exhibits excellent performance,and the current density is up to ca.870 mA·cm^(−2)in the flow cell,far above the industrially applicable level(100 mA·cm^(−2)),with a formate Faradaic efficiency greater than 90%.In-situ Fourier transform infrared(FT-IR)spectra detect*OCHO,and theoretical calculations reveal that the formation energy of*OCHO on edges is lower than that on terraces,while the defects on edges further reduce the free energy changes(ΔG).The differential charge density spatial distributions reveal that the presence of defects on edges causes charge enrichment around the C–H bond,benefiting the stabilization of the*OCHO intermediate,thus remarkably lowering theΔG.

General synthesis of Pt and Ni co-doped porous carbon nanofibers to boost HER performance in both acidic and alkaline solutions

It is essential to develop efficient electrocatalysts to generate hydrogen from water electrolysis for hydrogen economy. In this work, platinum(Pt) and nickel(Ni) co-doped porous carbon nanofibers(Pt/NiPCNFs) with low Pt content were prepared via an electrospinning, carbonization and galvanic replacement reaction. Because of the high electrical conductivity, abundant electrochemical active sites and synergistic effect between Pt and Ni nanoparticles, the optimized Pt/Ni-PCNFs catalyst shows an excellent HER activity with overpotentials of 20 m V in 0.5 mol/L H_(2)SO_(4) and 46 m V in 1 mol/L KOH at a current density of10 m A/cm^(2). Furthermore, over 35-h long-term stability has been achieved without significant attenuation.This work provides a simple route to prepare highly efficient electrocatalysts for water splitting and has great prospects in the field of renewable energy.

Simultaneously transmitting and reflecting(STAR)RISs for 6G:fundamentals,recent advances,and future directions

Simultaneously transmitting and reflecting reconfigurable intelligent surfaces(STAR-RISs)have been attracting significant attention in both academia and industry for their advantages of achieving 360°coverage and enhanced degrees-of-freedom.This article first identifies the fundamentals of STAR-RIS,by discussing the hardware models,channel models,and signal models.Then,three representative categorizing approaches for STAR-RISs are introduced from the phase-shift,directional,and energy consumption perspectives.Furthermore,the beamforming design of STAR-RISs is investigated for both independent and coupled phase-shift cases.As a recent advance,a general optimization framework,which has high compatibility and provable optimality regardless of the application scenarios,is proposed.As a further advance,several promising applications are discussed to demonstrate the potential benefits of applying STAR-RISs in sixth-generation wireless communication.Lastly,a few future directions and research opportunities are highlighted.

首次抗VEGF早期应答对视网膜分支静脉阻塞继发黄斑水肿治疗的预测作用

目的:明确视网膜分支静脉阻塞(BRVO)导致黄斑水肿的患者首次抗血管内皮生长因子(VEGF)治疗24h后黄斑区视网膜厚度的变化是否与治疗应答相关,并分析可以预测患者长期治疗效果的阈值。方法:回顾性系列病例研究。收集2014年12月至2016年12月于哈尔滨医科大学附属第二医院眼科门诊明确诊断为BRVO且采用0.5mg雷珠单抗玻璃体腔首次注射+PRN治疗方案的患者276例。记录注射前,注射后24h、4~48周(每4周1次)视网膜水肿情况(光学相干断层扫描),各观察时间点最佳矫正视力(BCVA,ETDRS视力表),通过受试者工作特征(ROC)曲线确定预测48周能否治愈的阈值,采用Pearson相关性分析及多因素Logistic回归分析确定影响治疗效果的因素。结果:所有符合条件的60例BRVO患者(60眼)在注射后各时间点中央黄斑厚度(CMT)均有显著下降,BCVA明显提高。首次注射后24hCMT下降值与48周CMT下降值显著相关(r=0.664,P<0.001),与48周时视力变化显著相关(r=0.642,P<0.001)。ROC曲线分析显示,24hCMT下降达18%对预后判断最具敏感性及特异性,按此阈值将入组患者分为2组:A组为CMT在24h下降小于18%(24例);B组为下降超过18%(36例)。Logistic回归分析分组(<18%)是治愈的预测因子(OR:19.549,95%CI:4.324~88.378,P<0.01),48周内视力提高分别为(13±11)字母、(19±14)字母,2组差异有统计学意义(t=-1.375,P<0.001)。结论:BRVO导致黄斑水肿患者的抗VEGF长期治疗效果与早期视网膜厚度变化相关,首次治疗后24hCMT下降幅度超过18%者长期治疗效果好。

基于金属有机骨架材料的电化学生物传感器在癌症检测中的应用

金属有机骨架(metal-organic frameworks,MOFs)材料因具有稳定的骨架结构、可调的孔尺度和大的比表面积等优良特性,被作为固定生物探针的基体,用于构建电化学生物传感器.电化学生物传感器是一种以电极为信号转换器,通过敏感元件,将肿瘤标志物的高特异性与电化学传感器的高灵敏度相结合的检测装置,在临床癌症筛查方面具有重大应用.本文概述了金属有机骨架复合材料的分类,总结了过去五年基于有机金属骨架材料的电化学生物传感器在检测作为癌症早期诊断指标的各种标志物(如癌症标志物、microRNA和DNA)方面的进展,并对其未来发展进行了展望.

Ni-doped ZnCo2O4 atomic layers to boost the selectivity in solar-driven reduction of CO2

Regulating the selectivity of CO2 photoreduction is particularly challenging. Herein, we propose ideal models of atomic layers with/without element doping to investigate the effect of doping engineering to tune the selectivity of CO2 photoreduction. Prototypical ZnCo2O4 atomic layers with/without Ni-doping were first synthesized. Density functional theory calculations reveal that introducing Ni atoms creates several new energy levels and increases the density-of-states at the conduction band minimum. Synchrotron radiation photoemission spectroscopy demonstrates that the band structures are suitable for CO2 photoreduction, while the surface photovoltage spectra demonstrate that Ni doping increases the carrier separation efficiency. In situ diffuse reflectance Fourier transform infrared spectra disclose that the CO2^- radical is the main intermediate, while temperature-programed desorption curves reveal that the ZnCo2O4 atomic layers with/without Ni doping favor the respective CO and CH4 desorption. The Ni-doped ZnCo2O4 atomic layers exhibit a 3.5-time higher CO selectivity than the ZnCo2O4 atomic layers. This work establishes a clear correlation between elemental doping and selectivity regulation for CO2 photoreduction, opening new possibilities for tailoring solar-driven photocatalytic behaviors.

Personalized cancer vaccines from bacteria-derived outer membrane vesicles with antibody-mediated persistent uptake by dendritic cells

Nanocarriers with intrinsic immune adjuvant properties can activate the innate immune system while delivering tumor antigen,thus efficiently facilitating antitumor adaptive immunity.Bacteria-derived outer membrane vesicles(OMVs)are an excellent candidate due to their abundance of pathogen associated molecular patterns.However,during the uptake of OMVs by dendritic cells(DCs),the interaction between lipopolysaccharide and toll-like receptor 4 induces rapid DC maturation and uptake blockage,a phenomenon we refer to as“maturation-induced uptake obstruction"(MUO).Herein we decorated OMV with the DC-targeting aDEC205 antibody(OMV-DEC),which endowed the nanovaccine with an uptake mechanism termed as 4<not restricted to maturation via antibody modifying”(Normandy),thereby overcoming the MUO phenomenon.We also proved the applicability of this nanovaccine in identifying the human tumor neoantigens through rapid antigen display.In summary,this engineered OMV represents a powerful nanocarrier for personalized cancer vaccines,and this antibody modification strategy provides a reference to remodel the DC uptake pattern in nanocarrier design.