Miniaturized electrochemical sensors and their point-of-care applications

Most of the current analytical methods depend largely on laboratory-based analytical techniques that require expensive and bullky equipment,potentially incur costly testing,and involve lengthy detection processes.With increasing requirements for point-of-care testing(POCT),more attention has been paid to miniaturized analytical devices.Miniaturized electrochemical(MEC)sensors,including different material-based MEC sensors(such as DNA-,paper-,and screen electrode-based),have been in strong demand in analytical science due to their easy operation,portability,high sensitivity,as well as their short analysis time.They have been applied for the detection of trace amounts of target through measuring changes in electrochemical signal,such as current,voltage,potential,or impedance,due to the oxidation/reduction of chemical/biological molecules with the help of electrodes and electrochemical units.MEC sensors present great potential for the detection of targets including small organic molecules,metal ions,and biomolecules.In recent years,MEC sensors have been broadly applied to POCT in various fields,including health care,food safety,and environmental monitoring,owing to the excellent advantages of electrochemical(EC)technologies.This review summarized the state-of-the-art advancements on various types of MEC sensors and their applications in POCT.Furthermore,the future perspectives,opportunities,and challenges in this field are also discussed.     

Machine Learning towards Screening Solid-state Lithium Ion Conductors

Machine learning is an emerging method to discover new materials with specific characteristics.An unsupervised machine learning research is highlighted to discover new potential lithium ionic conductors by screening and clustering lithium compounds,providing inspirations for the development of solid-state electrolytes and practical batteries.     

Vanadium-based polyanionic compounds as cathode materials for sodium-ion batteries:Toward high-energy and high-power applications

Sodium ion batteries(SIBs)have been regarded as one of the alternatives to lithium ion batteries owing to their wide availability and significantly low cost of sodium sources.However,they face serious challenges of low energy&power density and short cycling lifespan owing to the heavy mass and large radius of Na⁺.Vanadium-based polyanionic compounds have advantageous characteristic of high operating voltage,high ionic conductivity and robust structural framework,which is conducive to their high energy&power density and long lifespan for SIBs.In this review,we will overview the latest V-based polyanionic compounds,along with the respective characteristic from the intrinsic crystal structure to performance presentation and improvement for SIBs.One of the most important aspect is to discover the essential problems existed in the present V-based polyanionic compounds for high-energy&power applications,and point out most suitable solutions from the crystal structure modulation,interface tailoring and electrode configuration design.Moreover,some scientific issues of V-based polyanionic compounds shall be also proposed and related future direction shall be provided.We believe that this review can serve as a motivation for further development of novel V-based polyanionic compounds and drive them toward high energy&power applications in the near future.     

Surface defect-rich ceria quantum dots anchored on sulfur-doped carbon nitride nanotubes with enhanced charge separation for solar hydrogen production

Designing defect-engineered semiconductor heterojunctions can effectively promote the charge carrier separation.Herein,novel ceria(CeO2) quantum dots(QDs) decorated sulfur-doped carbon nitride nanotubes(SCN NTs) were synthesized via a thermal polycondensation coupled in situ depositionprecipitation method without use of template or surfactant.The structure and morphology studies indicate that ultrafine CeO2 QDs are well distributed inside and outside of SCN NTs offering highly dispersed active sites and a large contact interface between two components.This leads to the promoted formation of rich Ce³⁺ ion and oxygen vacancies as confirmed by XPS.The photocatalytic performance can be facilely modulated by the content of CeO2 QDs introduced in SCN matrix while bare CeO2 does not show activity of hydrogen production.The optimal catalyst with 10% of CeO2 loading yields a hydrogen evolution rate of 2923.8 μmol h-1 g-1 under visible light,remarkably higher than that of bare SCN and their physical mixtures.Further studies reveal that the abundant surface defects and the created 0 D/1 D junctions play a critical role in improving the separation and transfer of charge carriers,leading to superior solar hydrogen production and good stability.     

Superfast and solvent-free core-shell assembly of sulfur/carbon active particles by hail-inspired nanostorm technology for high-energy-density Li-S batteries

The demand on low-carbon emission fabrication technologies for energy storage materials is increasing dramatically with the global interest on carbon neutrality.As a promising active material for metal-sulfur batteries,sulfur is of great interest due to its high-energy-density and abundance.However,there is a lack of industry-friendly and low-carbon fabrication strategies for high-performance sulfur-based active particles,which,however,is in critical need by their practical success.Herein,based on a hail-inspired sulfur nano-storm(HSN)technology developed in our lab,we report an energy-saving,solvent-free strategy for producing core-shell sulfur/carbon electrode particles(CNT@AC-S)in minutes.The fabrication of the CNT@AC-S electrode particles only involves low-cost sulfur blocks,commercial carbon nanotubes(CNT)and activated carbon(AC)micro-particles with high specific surface area.Based on the above core-shell CNT@AC-S particles,sulfur cathode with a high sulfur-loading of 9.2 mg cm^-2 delivers a stable area capacity of 6.6 mAh cm^-2 over 100 cycles.Furthermore,even for sulfur cathode with a super-high sulfur content(72 wt%over the whole electrode),it still delivers a high area capacity of 9 mAh cm^-2 over50 cycles in a quasi-lean electrolyte condition.In a nutshell,this study brings a green and industryfriendly fabrication strategy for cost-effective production of rationally designed S-rich electrode particles.     

Total synthesis of TRADD death domain with arginine N-GlcNAcylation by hydrazide-based native chemical ligation

TNFR1-associated death domain protein(TRADD)with arginine N-GlcNAcylation is a novel and structurally unique posttranslational modification(PTM)glycoprotein that blocks the formation of death-inducing signaling complex(DISC),orchestrating host nuclear factorκB(NF-κB)signaling in entero-pathogenic Escherichia coli(EPEC)-infected cells.This particular glycosylated modification plays an extremely vital role for the effective colonization and pathogenesis of pathogens in the gut.Herein we describe the total synthesis of TRADD death domain(residues 195-312)with arginine235 NGlcNAcylation(Arg-GIcNAc TRADD(195-312)).Two longish peptidyl fragments of the wild-type primary sequence were obtained by robust,microwave-assisted,highly efficient,solid-phase peptide synthesis(SPPS),the N-GlcNAcylated sector was built by total synthesis and attached specifically to resinbound peptide with an unprotected ornithine residue via silver-promoted on-resin guanidinylation,ArgGlcNAc TRADD(195-312)was constructed by hydrazide-based native chemical ligation(NCL).The facile synthetic strategy is expected to be generally applicable for the rapid synthesis of other proteins with Arg-GIcNAc modification and to pave the way for the related chemically biological study.     

Steam activation of Fe-N-C catalyst for advanced power performance of alkaline hydrazine fuel cells

Alkaline hydrazine liquid fuel cells(AHFC) have been highlighted in terms of high power performance with non-precious metal catalysts.Although Fe-N-C is a promising non-Pt electrocatalyst for oxygen reduction reaction(ORR),the surface density of the active site is very low and the catalyst layer should be thick to acquire the necessary number of catalytic active sites.With this thick catalyst layer,it is important to have an optimum pore structure for effective reactant conveyance to active sites and an interface structure for faster charge transfer.Herein,we prepare a Fe-N-C catalyst with magnetite particles and hierarchical pore structure by steam activation.The steam activation process significantly improves the power performance of the AHFC as indicated by the lower IR and activation voltage losses.Based on a systematic characterization,we found that hierarchical pore structures improve the catalyst utilization efficiency of the AHFCs,and magnetite nanoparticles act as surface modifiers to reduce the interracial resistance between the electrode and the ion-exchange membrane.     

Unraveling the stabilization mechanism of solid electrolyte interface on ZnSe by rGO in sodium ion battery

Transition metal selenides have been widely studied as anode materials of sodium ion batteries(SIBs),however,the investigation of solid-electrolyte-interface(SEI)on these materials,which is critical to the electrochemical performance of SIBs,remains at its infancy.Here in this paper,ZnSe@C nanoparticles were prepared from ZIF-8 and the SEI layers on these electrodes with and without reduced graphene oxide(rGO)layers were examined in details by X-ray photoelectron spectroscopies at varied charged/discharged states.It is observed that fast and complicated electrolyte decomposition reactions on ZnSe@C leads to quite thick SEI film and intercalation of solvated sodium ions through such thick SEI film results in slow ion diffusion kinetics and unstable electrode structure.However,the presence of rGO could efficiently suppress the decomposition of electrolyte,thus thin and stable SEI film was formed.ZnSe@C electrodes wrapped by rGO demonstrates enhanced interfacial charge transfer kinetics and high electrochemical performance,a capacity retention of 96.4%,after 1000 cycles at 5 A/g.This study might offer a simple avenue for the designing high performance anode materials through manipulation of SEI film.     

CXN天然沸石的研究2: 吸附性质

采用N~2,NH~3,CO~2,乙烯,丙烯,水,甲醇,乙醇,丙醇等作为吸附剂,研究了由我国CXN天然沸石改性制得的H-STI和Na-STI沸石的吸附性质,H-STI和Na-STI沸石的BET表面积及微孔孔体积约为420m^2/g和0.20m^3/g。根据NH~3和CO~2在H-STI沸石上的吸附等温线计算得到它们的吸附热分别为44.8和26.5kJ/mol。乙烯,丙烯,甲醇,乙醇,丙醇等在Na-STI沸石上的吸附等温线表明该沸石对有机分子的吸附具有链长选择性。在低分压下水相对于甲醇的吸附量表明沸石具有一定的疏水性质。     

常温常湿条件下Au/MeO~x催化剂上CO氧化性能

利用共沉淀法制备了Au/MeO~x催化剂(Me=Al,Co,Cr,Cu,Fe,Mn,Ni,Zn)。在常温常湿条件下,考察了不同氧化物负载的金基催化剂的CO氧化性能。结果表明,氧化物种类对催化剂的活性和稳定性均有较大的影响。Cu,Mn,Cr等氧化物负载的金基催化剂的活性较差,而Zn,Fe,Co,Ni,Al等金属氧化物负载的金基催化剂可将CO完全氧化,又具有一定的稳定性,在相同反应条件下,CO完全转化时的稳定性顺序为Au/ZnO>Au/α-Fe~2O~3>Au/Co~3O~4>Au/γ-Al~2O~3≈Au/NiO。还发现水对Au/MnO~x催化剂的活性和稳定性有负作用,而对180℃焙烧制备的Au/ZnO-180催化剂的活性和稳定性均有明显的湿度增强作用。     

一步法合成螺双芴及螺氧杂蒽衍生物及其在有机发光二极管中的应用：性能增强及相关的光学现象关

以芴为原料,以钯为催化剂一步合成了2-(9-苯基芴基)-9,9′螺二芴(PF-SBF)。以PF-SBF作为有机发光二极管的发光及主体材料(FIrpic为磷光客体)时,观察到了不同于PF-SBF及FIrpic发光的红光带。这分别源于PF-SBF分子间的聚集和发光层/传输层诱导的激基复合物。通过选择合适的空穴和电子传输层,有效抑制了激基复合物的发光。同时,PF-SBF和TAPC双主体的结构不仅实现了纯FIrpic和Ir(ppy)3蓝光和绿光,还大幅提升了器件性能。蓝光、绿光器件的最大电流效率和最大亮度分达到16.7、50.5 cd·A^-1和7857 cd·m^-2(11 V)、23390 cd·m^-2(8 V)。另外,除了PF-SBF,利用相似的合成方法,我们也合成了2-(9-苯基芴基)-9,9′螺芴氧杂蒽(PF-SFX),其较大的三线态能级(2.8 eV)较PF-SBF更适合做蓝光主体。以TAPC和PFSFX为双主体的器件最大电流效率提升到了22.6 cd·A^-1。所有实验结果均表明,PF-SBF和PF-SFX是构建高效绿光/蓝光磷光主体材料的有效结构单元。     

Unexpected one-pot method to synthesize spiro[fluorene-9,9'-xanthene] building blocks for blue-light-emitting materials

[reaction: see text] An unexpected one-pot synthetic approach toward spiro[fluorene-9,9'-xanthene] (SFX) under excessive MeSO(3)H conditions has been developed. The key step involves a thermodynamically controlled cyclization reaction. Blue-light-emitting materials based on SFX building blocks that exhibit high thermal stability have also been synthesized.     

螺[二苯并[a,j]氧杂蒽-14,9’-芴]的合成及性质简

芴酮与2-萘酚在硫酸和3-巯基丙酸的作用下反应得到化合物螺[二苯并[a,j]氧杂蒽-14,9’-芴]. 采用核磁共振、质谱、红外光谱和元素分析等对该化合物进行了表征,并通过X射线衍射法测得了其晶体结构,确定该化合物是通过二苯并[a,j]氧杂蒽中的含氧六元杂环和芴中的五元环共用一个碳原子形成一个螺环. 利用荧光光谱和热分析等手段对该化合物的性质进行了研究,结果表明其最大荧光发射峰为366 nm,熔点为297 ℃,热分解温度为329 ℃,具有较高的热稳定性.     

螺[二苯并[a,j]氧杂蒽-14,9'-芴]的合成及性质

芴酮与2-萘酚在硫酸和3-巯基丙酸的作用下反应得到化合物螺[二苯并[a,j]氧杂蒽-14,9'-芴]. 采用核磁共振、 质谱、 红外光谱和元素分析等对该化合物进行了表征, 并通过X射线衍射法测得了其晶体结构, 确定该化合物是通过二苯并[a,j]氧杂蒽中的含氧六元杂环和芴中的五元环共用一个碳原子形成一个螺环. 利用荧光光谱和热分析等手段对该化合物的性质进行了研究, 结果表明其最大荧光发射峰为366 nm, 熔点为297 ℃, 热分解温度为329 ℃, 具有较高的热稳定性.     

Selective Introduction of Carbazole and Diphenylamine into Spirofluorenexanthene Core for Different Phosphorescent Hosts

Built on the spiro[fluorene‐9,9′‐xanthene] (SFX) core and two frequently‐used hole‐transporting groups such as carbazole and diphenylamine, two SFX derivatives, namely SFXCz and SFXDPA, have been synthesized by one‐step reaction for red, green and blue phosphorescent organic light‐emitting devices (PHOLEDs). Though the properties of these two groups are very similar, the devices based on SFXCz and SFXDPA exhibit distinct performances. In blue PHOLEDs, the device based on SFXCz exhibited much better performances than that based on SFXDPA. However, the latter was superior to the former in green and red PHOLEDs. And the red PHOLED based on SFXDPA exhibited maximum current efficiency (CE) of 27.1 cd·A^?1, power efficiency (PE) of 25.0 lm·W^?1, and external quantum efficiency (EQE) of 15.0%. The results show that the introduction of diphenylamine group is suitable for constructing green and red host materials, whereas the introduction of carbazole group is suitable for constructing blue host materials.     

基于三苯胺和螺(芴-9,9'-氧杂蒽)的星射形蓝光寡聚材料的合成与光电性质

通过Sonogashira 反应合成了基于三苯胺、螺(芴-9,9'-氧杂蒽)及芴的星射形寡聚物. 三种寡聚物(TPA-F、TPA-SFX和TPA-SFXCz)都具有很高的热分解温度, 分别为417、439和425 °C. 差示扫描量热(DSC)分析研究表明, 它们也具有高的玻璃化转变温度(T_g), 都在100 °C以上, 其中两种螺芴取代的寡聚物(TPA-SFX和TPA-SFXCz)的T_g分别达到141和127 °C. 光物理的研究发现, 在薄膜中, TPA-F具有很宽的双发射峰, 峰值为424 和455 nm; 而TPA-SFX 和TPA-SFXCz 仍保持单一蓝光发射, 发射峰分别为434 和442 nm. 这表明将三苯胺非平面结构和螺形取代基团相结合, 能有效抑制在薄膜中聚集和激基缔合物的产生. 电化学的研究表明, 由于引入富电子的三苯胺核心结构, 三者都具有-5.4 eV左右的较高的HOMO能级. 通过旋涂法制备了结构为ITO(氧化铟锡)/PEDOT:PSS(聚3,4-乙撑二氧噻吩:聚苯乙烯磺酸盐)/寡聚物/TPBI(1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯)/LiF/Al 电致发光器件. 器件测试结果表明, TPA-SFX的器件具有最好的光电性能. 以它为发光层, 获得最大亮度为2680 cd·m^-2、最大电流效率为0.35 cd·A^-1、色坐标为(0.17, 0.13)的蓝光器件.     

A Clean synthesis of spiro[indoline-3,9'-xanthene]trione derivatives

A simple, clean and efficient method for the synthesis of spiro[indoline-3,9'-xanthene]trione derivatives and spiro[acenaphthene-1,9'-xanthene]-1',2,8'(2'H,5'H)-trione by condensation reaction of dimedone and isatins or acenaphthene in aqueous media is reported.     

基于激子和电致激基复合物双重发光的白光OLED

基于四苯基乙烯衍生物设计合成了两种蓝光材料TPE-4Br和TPE-3Br,并将其作为有机发光二极管(OLED)器件的发光层,研究发现其可与合适的邻层(空穴传输层/电子传输层)形成电致激基复合物。利用材料的本征激子发光及其电致激基复合物发光,可以得到理想的白光电致发光。将TPE-4Br和TPE-3Br掺杂于mCP中作为发光层,以TAPC和TmPyPB分别作为空穴传输层和电子传输层分别制备器件A和器件B,所得器件在操作电压为9 V时的色坐标分别为(0.32,0.33)和(0.31,0.34)。其中器件B的最大亮度和最大电流效率分别为364.66 cd?m~(-2)与0.79 cd?A~(-1)。     

基于联咔唑为骨架的双极主体材料的合成及其在有机电致发光器件中的应用

咔唑类衍生物具有良好的空穴传输性能和较高的三重态能级,在有机电致发光器件中一般用来构建空穴传输材料和主体材料。本文通过在联咔唑的3和6位引入具有电子传输能力的氰基,设计合成了一种以双咔唑二聚体为分子骨架的新型双极性有机电致发光主体材料6,6’-双氰基-9,9’-二苯基-3,3’-联咔唑（BCzDCN）,研究了其发光性能、热稳定性和电化学性质。低温磷光发射光谱测试表明BCzDCN的三重态能级高于传统的天蓝色磷光掺杂材料双（4,6-二氟苯基吡啶-N,C²’）吡啶甲酰合铱（FIrpic）。以BCzDCN为主体材料,FIrpic和双（4-苯并噻吩）[3,2-C]吡啶-N,C²’）乙酰丙酮合铱（PO-01）分别为蓝色和黄色磷光掺杂材料,制备了蓝色和白色有机磷光发光二极管器件。器件的最大电流效率分别达到34.6 cd/A和59.0 cd/A。并且在1000 cd/m²亮度下的效率滚降仅有4.1%和5.1%。     

A Silane-Based Bipolar Host with High Triplet Energy for High Efficiency Deep-Blue Phosphorescent OLEDs with Improved Device Lifetime

A high triplet energy host is developed using a silane moiety, 9-(4-(triphenylsilyl)dibenzo[b,d]furan-2-yl)-9H-carbazole (SiDBFCz), is designed through extensive density functional theory (DFT) calculations to obtain appropriate hole and electron injection barriers. The chemical hardness and the charge transport characteristics are comprehensively investigated to realize a bipolar host with high triplet energy over 2.9 eV for deep blue phosphorescent organic light-emitting diodes (PHOLEDs). The synthesized SiDBFCz clearly exhibits the bipolar characteristics especially with emitter molecules doped. An external quantum efficiency over 19 % without any microcavity optimization is achieved thanks to the good charge balance in the SiDBFCz PHOLED. The device lifetime of the SiDBFCz PHOLED is improved more than 1000 %, compared to the unipolar control devices at an initial luminance of 500 cd m⁻². The dramatic enhancement of the operational stability of the deep blue PHOLED is also thoroughly investigated in terms of electrochemical stability of host molecules in charged or excited states. The results clearly indicate that the device lifetime is strongly correlated with the bond dissociation energy and the activation energy for the bond dissociation reaction in triplet excited state.