Ultralow-loss Optical Waveguides through Balancing Deep-Blue TADF and Orange Room Temperature Phosphorescence in Hybrid Antimony Halide Microstructures

Harnessing the potential of thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) is crucial for developing light-emitting diodes (LEDs), lasers, sensors, and many others. However, effective strategies in this domain are still relatively scarce. This study presents a new approach to achieving highly efficient deep-blue TADF (with a PLQY of 25 %) and low-energy orange RTP (with a PLQY of 90 %) through the fabrication of lead-free hybrid halides. This new class of monomeric and dimeric 0D antimony halides can be facilely synthesized using a bottom-up solution process, requiring only a few seconds to minutes, which offer exceptional stability and nontoxicity. By leveraging the highly adaptable molecular arrangement and crystal packing modes, the hybrid antimony halides demonstrate the ability to self-assemble into regular 1D microrod and 2D microplate morphologies. This self-assembly is facilitated by multiple non-covalent interactions between the inorganic cores and organic shells. Notably, these microstructures exhibit outstanding polarized luminescence and function as low-dimensional optical waveguides with remarkably low optical-loss coefficients. Therefore, this work not only presents a pioneering demonstration of deep-blue TADF in hybrid antimony halides, but also introduces 1D and 2D micro/nanostructures that hold promising potential for applications in white LEDs and low-dimensional photonic systems.     

A Polarized Gel Electrolyte for Wide-Temperature Flexible Zinc-Air Batteries

The development of flexible zinc-air batteries (FZABs) has attracted broad attention in the field of wearable electronic devices. Gel electrolyte is one of the most important components in FZABs, which is urgent to be optimized to match with Zn anode and adapt to severe climates. In this work, a polarized gel electrolyte of polyacrylamide-sodium citric (PAM-SC) is designed for FZABs, in which the SC molecules contain large amount of polarized −COO⁻ functional groups. The polarized −COO⁻ groups can form an electrical field between gel electrolyte and Zn anode to suppress Zn dendrite growth. Besides, the −COO⁻ groups in PAM-SC can fix H₂O molecules, which prevents water from freezing and evaporating. The polarized PAM-SC hydrogel delivers a high ionic conductivity of 324.68 mS cm⁻¹ and water retention of 96.85 % after being exposed for 96 h. FZABs with the PAM-SC gel electrolyte exhibit long cycling life of 700 cycles at −40 °C, showing the application prospect under extreme conditions.     

Diboraanthracene-Doped Polymer Systems for Colour-Tuneable Room-Temperature Organic Afterglow

Organic ultralong room temperature phosphorescence (RTP), or organic afterglow, is a unique phenomenon, gaining widespread attention due to its far-reaching application potential and fundamental interest. Here, two laterally expanded 9,10-dimesityl-dihydro-9,10-diboraanthracene (DBA) derivatives are demonstrated as excellent afterglow materials for red and blue-green light emission, which is traced back to persistent thermally activated delayed fluorescence and RTP. The lateral substitution of polycyclic DBA scaffold, together with weak transversal electron-donating mesityl groups, ensures the optimal molecular properties for (reverse) intersystem crossing and long-lived triplet states in a rigid poly(methyl methacrylate) matrix. The achieved afterglow emission quantum yields of up to 3 % and 15 %, afterglow lifetimes up to 0.8 s and 3.2 s and afterglow durations up to 5 s and 25 s (for red and blue-green emitters, respectively) are attributed to the properties of single molecules.     

Targeted Delivery of Anticancer Drug Loaded Charged PLGA Polymeric Nanoparticles Using Electrostatic Field

Pure positive electrostatic charges (PPECs) show suppressive effect on the proliferation and metabolism of invasive cancer cells without affecting normal tissues. PPECs are used for the delivery of drug-loaded polymeric nanoparticles (DLNs) capped with negatively charged poly(lactide-co-glycolide) (PLGA) and Poly(vinyl-alcohol) PVA into the tumor site of mouse models. The charged patch is installed on top of the skin in the mouse models' tumor region, and the controlled selective release of the drug is assayed by biochemical, radiological, and histological experiments on both tumorized models and normal rats' livers. It is found that DLNs synthesized by PLGA show great attraction to PPECs due to their stable negative charges, which would not degrade immediately in blood. The burst and drug release after less than 48h of this synthesized DLNs are 10% and 50%, respectively. These compounds can deliver the loaded-drug into the tumor site with the assistance of PPECs, and the targeted-retarded release will take place. Hence, local therapy can be achieved with much lower drug concentration (conventional chemotherapy [2 mg kg⁻¹] versus DLNs-based chemotherapy [0.75 mg kg⁻¹]) with negligible side effects in non-targeted organs. PPECs have many potential clinical applications for advanced-targeted chemotherapy with the lowest discernible side effects.     

Investigation of 500 keV Si ion induced surface structuring of Ni and Ti for enhancement of field emission properties

The present paper reports the investigation of surface morphology, elemental composition, phase changes and field emission properties of Si ion irradiated nickel (Ni) and titanium (Ti). The Ni and Ti targets have been irradiated with 500 keV Si ions generated by Pelletron accelerator at various fluences ranging from 6.9 × 10¹³ to 77.1 × 10¹³ ions/cm². Stopping range of ions in matter analysis revealed higher values of electronic stopping and sputtering yield for Ni as compared with Ti. For both irradiated metals, electronic energy loss dominant over the nuclear stopping. The growth of induced surface structures have been analysed by using field emission scanning electron microscopy (FESEM) analysis. In case of Ni, as the ion fluence increases from 6.9 × 10¹³ to 65.8 × 10¹³ ions/cm², the formation of spherical particulates, agglomers and sputtering is observed. Although in the case of Ti, with the increase of Si ion fluence from 11.6 × 10¹³ to 77.1 × 10¹³ ions/cm², the formation of irregular-shaped particulates along with crater and sputtered channels is observed. X-ray diffraction (XRD) analysis shows that no new phase is identified. However, a significant increase in peak intensity is observed with increasing ion fluence. The variation in crystallite size and dislocation line density is also observed as a function of Si ion fluence. Fourier transform infrared spectroscopy analysis shows that no bands are formed after the Si ion irradiation. Field emission properties of ion-structured Ni and Ti are well correlated with the growth of surface structures observed by SEM and dislocation line density evaluated by XRD analysis.     

Front Cover: Enhancement of dielectrophoresis-based particle collection from high conducting fluids due to partial electrode insulation

Dielectrophoresis (DEP) is a successful method to recover nanoparticles from different types of fluid. The DEP force acting on these particles is created by an electrode microarray that produces a nonuniform electric field. To apply DEP to a highly conducting biological fluid, a protective hydrogel coating over the metal electrodes is required to create a barrier between the electrode and the fluid. This protects the electrodes, reduces the electrolysis of water, and allows the electric field to penetrate into the fluid sample. We observed that the protective hydrogel layer can separate from the electrode and form a closed domed structure and that collection of 100 nm polystyrene beads increased when this occurred. To better understand this collection increase, we used COMSOL Multiphysics software to model the electric field in the presence of the dome filled with different materials ranging from low-conducting gas to high conducting phosphate-buffered saline fluids. The results suggest that as the electrical conductivity of the material inside the dome is reduced, the whole dome acts as an insulator which increases electric field intensity at the electrode edge. This increased intensity widens the high-intensity electric field factor zone resulting in increased collection. This informs how dome formation results in increased particle collection and provides insight into how the electric field can be intensified to the increase collection of particles. These results have important applications for increasing the recovery of biologically-derived nanoparticles from undiluted physiological fluids that have high conductance, including the collection of cancer-derived extracellular vesicles from plasma for liquid biopsy applications.     

电场下离子型聚合物复合囊泡结构变化的分子动力学模拟

利用粗粒化分子动力学模拟研究了电场作用下离子型聚合物复合囊泡形变与破裂的过程.定量分析了囊泡破裂过程中的结构变化,包括囊泡的形变程度、破裂速度、组分分布以及破裂后的结构.研究表明,电场强度较弱时,囊泡表面所吸附的聚电解质首先脱落,囊泡由球形结构转变为椭球结构.随着电场强度增大,离聚物的离子侧基发生重新排布,囊泡表面电荷的有序结构被破坏,导致囊泡的结构无法维持而破裂,囊泡塌缩,分裂形成离聚物团簇,并进一步破裂为小尺寸的离聚物聚集体,均匀分散于溶液中.本文利用分子动力学模拟明确了电场中离子型高分子复合囊泡破裂过程的分子机理,为药物释放技术的优化及发展提供了理论支持.     

大学基础化学教学中的知其所以然*

针对大学本科一年级基础化学如“化学概论”等课程教学中,学生对于不断出现的专业名词及物理化学含义的理解问题,以“焓”“熵”等外来词汇以及角动量l、能级分裂单位“Dq”等缩写为例,从专业名词来源开始讲解,使学生在学习过程中既知其然又知其所以然,更好地理解化学专业词汇,尤其是外来词汇的内涵与物理化学意义。     

ZIF-8衍生的具有可控氧空位的ZnO对光催化去除NO的增强及毒性NO2形成的抑制

氧化锌作为一种半导体材料,具有合适的能带结构位置,高催化效率,低成本和环境可持续性,因而广泛用于光催化领域.然而,由于氧化锌的宽带隙,可见光吸收能力差以及光生电子-空穴对的快速复合,极大地影响了其光催化效率.通过引入氧空位调控光催化剂的结构被证明是一种可以改善光生载流子的分离,从而提高光催化性能的有效方法.本文以ZIF-8为前驱体,采用两步煅烧法合成了具有不同浓度氧空位分布的ZnO纳米光催化剂,通过X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、紫外-可见漫反射光谱(UV-Vis DRS)、X射线光电子能谱(XPS)、电子顺磁共振(EPR)、荧光光谱仪(PL)等手段系统地分析了合成的光催化剂的理化性质,并评价了它们在可见光下光催化氧化去除NO反应性能.EPR结果表明,样品中氧空位的浓度取决于温度处理的过程.通过两步煅烧法得到氧化锌中氧空位的含量高于一步直接煅烧法所得的样品.此外,随着煅烧温度升高,合成的氧化锌晶格越完好,其氧空位含量越少.UV-Vis DRS结果表明,两步煅烧法合成的ZnO与商业的ZnO及一步法直接煅烧合成的ZnO相比,其吸光范围从紫外光拓展到了可见光,表现出了更加优异的吸光性能.光催化反应结果表明,与商业氧化锌和一步直接煅烧法所得样品相比,两步煅烧法合成的样品表现出了更优异的光催化去除NO性能,并抑制了中间产物毒性NO2的产生,促进了NO的深度氧化.具体反应路径为:在光照过程中,光生电子很容易被氧空位俘获,与O2反应产生更多的超氧自由基(·O2^-),从而将NO氧化成最终的产物硝酸盐.尤其有趣的是,先在350 ℃煅烧2小时再400℃煅烧1小时的两步法样品Z 350-400的NO去除效率分别比一步法样品Z 400(400℃煅烧)和商用ZnO高出1.5和4.6倍.这表明以MOF材料衍生的具有适当量氧空位的金属氧化物为一种高效去除NO的光催化剂具有很好的应用前景.     

理论研究晶体场效应和电荷转移效应对Co2+的2p电子X射线L2,3吸收边光谱的影响

运用多重态计算方法研究了在正八面体对称性的晶体场中Co²⁺离子的2p电子X射线L_2,3吸收边光谱, 研究了Co²⁺离子和周围的配位离子之间的正八面体(O_h)晶体场效应和相应的电荷转移效应对于吸收光谱的影响. 系统讨论了在多重态计算中起作用的所有物理参数对CoO和CoCl₂的X射线吸收光谱特性的特定影响及其物理机制. 将计算得出的光谱数据和同样具有O_h对称性结构Co²⁺离子的CoO和CoCl₂实验光谱数据进行了对比, 在实验光谱数据中发现的特征被确定为来自不同自旋态, 并且光谱强度的变化与晶体场的强度相关, 揭示了其中包含的电荷转移效应. 本文为低对称性复杂系统的多重态计算提供了一个基础的参考标准, 可以适用于含有钴元素或其它过渡金属的复杂体系的X射线吸收光谱的理论计算.