有机-无机压电材料TMCM-MnCl3的研究

有机-无机压电材料是一种分子铁电体，具有柔性、结构灵活、易成膜、全液相合成及环保节能等优点，可满足新一代薄膜器件及可穿戴设备的需求。该文以三甲基卤代甲基铵(TMXM, X=F, Cl, Br)为有机部分，MnCl₂为无机部分，通过溶液蒸发法制备了具有钙钛矿分子结构的有机-无机压电材料三甲基氯三氯化锰(TMCM-MnCl₃)，并对其分子结构组成、压电、热学、声学及铁电性进行表征。结果表明，TMCM-MnCl₃的压电常数为106 pC/N，居里温度为130 ℃，声阻抗值约为16.5 MRayl，低于压电陶瓷PZT-4(大于33 MRayl)，具有广阔的应用前景。     

Strong tribocatalytic dye degradation by tungsten bronze Ba4Nd2Fe2Nb8O30

The triboelectric effect has recently demonstrated its great potential in environmental remediation and even new energy applications for triggering a number of catalytic reactions by utilizing trivial mechanical energy. In this study, Ba₄Nd₂Fe₂Nb₈O₃₀ (BNFN) submicron powders were used to degrade organic dyes via the tribocatalytic effect. Under the frictional excitation of three PTFE stirring rods in a 5 mg/L RhB dye solution, BNFN demonstrates a high tribocatalytic degradation efficiency of 97% in 2 h. Hydroxyl radicals (?OH) and superoxide radicals (?O₂－) were also detected during the catalysis process, which proves that triboelectric energy stimulates BNFN to generate electron-hole pairs. The tribocatalysis of tungsten bronze BNFN submicron powders provides a novel and efficient method for the degradation of wastewater dye by utilizing trivial mechanical energy.     

凌庄子水厂保水堰流量系数试验

凌庄子水厂蓄水池进水口处有一保水堰,为非标准薄壁堰,不能使用已有堰流公式对其过流量进行准确计算。为了得出较为精确的过流流量,按照重力相似准则制作几何比尺为1∶5的模型进行试验研究。在已有自由出流公式的基础上,对自由出流流量系数进行修正并对淹没情况下流量变化过程进行研究。对该非标准堰自由出流流量系数的实测值与经验值进行分析比较,发现堰板槽降低了实际自由出流过流能力。淹没出流的流量系数主要与下游尾水位有关,试验中形成的淹没式堰流受实际堰型尺寸影响,下游尾水位和堰上水位近似相等,不完全适用已有淹没出流流量公式,通过试验给出了修正淹没系数随h/p的变化关系。结果表明利用堰前、堰后水位初步计算过流流量是可行的,可为该工程提供参考,也可为实际工程中非标准矩形堰的流量计算提供思路。     

煤炭资源型城市转型模式研究：以徐州贾汪区为例

煤炭资源型城市为我国经济发展提供了重要的资源和能源支持,研究资源型城市转型的经验模式对调整区域经济结构、确保社会稳定和改善生态环境具有重要的实践意义。本文采用文献综述法和实证分析法,研究我国东部煤炭资源枯竭型城市转型所面临的共性难题,并以徐州贾汪区转型探索经历为例,总结城市转型的"徐州贾汪区模式",主要包括放大正向外部效应、长期坚持矿地融合、大力建设矿区社会生态系统恢复力三条路径。研究结果表明,煤炭城市转型发展的共性问题相互联系、相互影响,是一个系统性难题,必须引入系统性思维。我国东部矿区普遍人口密集,农业发达、沉陷积水是最主要的共性特征,煤炭开采产生的社会问题、经济问题、生态问题、环境问题基本相同,转型发展模式值得互鉴。     

Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Nanovaccine-Mediated Cell Selective Delivery of Neoantigens Potentiating Adoptive Dendritic Cell Transfer for Personalized Immunization

Neoantigen vaccines and adoptive dendritic cell (DC) transfer are major clinical approaches to initiate personalized immunity in cancer patients. However, the immunization efficacy is largely limited by the in vivo trajectory including neoantigens’ access to resident DCs and DCs’ access to lymph nodes (LNs). Herein, an innovative strategy is proposed to improve personalized immunization through neoantigen-loaded nanovaccines synergized with adoptive DC transfer. It is found that it enables selective delivery of neoantigens to resident DCs and macrophages by coating cancer cell membranes onto neoantigen-loaded nanoparticles. In addition, the nanovaccines promote the secretion of chemokine C-C motif ligand 2 (CCL2), CCL3, and C-X-C motif ligand 10 from macrophages, thus potentiating the access of transferred DCs to LNs. This immunization strategy enables coordinated delivery of identified neoantigens and autologous tumor lysate-derived undefined antigens, leading to initiation of antitumor T cell immunity in a personalized manner. It significantly inhibits tumor growth in prophylactic and established mouse tumor models. The findings provide a new vision for potentiating adoptive cell transfer by nanovaccines, which may open the door to a transformative possibility for improving personalized immunization.     

A Highly Sensitive,Reversible, and Bidirectional Humidity Actuator by Calcium Carbonate Ionic Oligomers Incorporated Poly(Vinylidene Fluoride)

Sensitivity and multi-directional motivation are major two factors for developing optimized humidity-response materials, which are promising for sensing, energy production, etc. Organic functional groups are commonly used as the water sensitive units through hydrogen bond interactions with water molecules in actuators. The multi-coordination ability of inorganic ions implies that the inorganic ionic compounds are potentially superior water sensitive units. However, the particle forms of inorganic ionic compounds produced by classical nucleation limit the number of exposed ions to interact with water. Recent progress on the inorganic ionic oligomers has broken through the limitation of classical nucleation, and realized the molecular-scaled incorporation of inorganic ionic compounds into an organic matrix. Here, the incorporation of hydrophilic calcium carbonate ionic oligomers into hydrophobic poly(vinylidene fluoride) (PVDF) is demonstrated. The ultra-small calcium carbonate oligomers within a PVDF film endow it with an ultra-sensitive, reversible, and bidirectional response. The motivation ability is superior to other bidirectional humidity-actuators at present, which realizes self-motivation on an ice surface, converting the chemical potential energy of the humidity gradient from ice to kinetic energy.     

4-Methyl-2,4-bis(4-hydroxyphenyl)pent-1-ene,a Major Active Metabolite of Bisphenol A,Triggers Pancreatic β-Cell Death via a JNK/AMPKα Activation-Regulated Endoplasmic Reticulum Stress-Mediated Apoptotic Pathway

4-methyl-2,4-bis(4-hydroxyphenyl)pent-1-ene (MBP), a major active metabolite of bisphenol A (BPA), is generated in the mammalian liver. Some studies have suggested that MBP exerts greater toxicity than BPA. However, the mechanism underlying MBP-induced pancreatic β-cell cytotoxicity remains largely unclear. This study demonstrated the cytotoxicity of MBP in pancreatic β-cells and elucidated the cellular mechanism involved in MBP-induced β-cell death. Our results showed that MBP exposure significantly reduced cell viability, caused insulin secretion dysfunction, and induced apoptotic events including increased caspase-3 activity and the expression of active forms of caspase-3/-7/-9 and PARP protein. In addition, MBP triggered endoplasmic reticulum (ER) stress, as indicated by the upregulation of GRP 78, CHOP, and cleaved caspase-12 proteins. Pretreatment with 4-phenylbutyric acid (4-PBA; a pharmacological inhibitor of ER stress) markedly reversed MBP-induced ER stress and apoptosis-related signals. Furthermore, exposure to MBP significantly induced the protein phosphorylation of JNK and AMP-activated protein kinase (AMPK)α. Pretreatment of β-cells with pharmacological inhibitors for JNK (SP600125) and AMPK (compound C), respectively, effectively abrogated the MBP-induced apoptosis-related signals. Both JNK and AMPK inhibitors also suppressed the MBP-induced activation of JNK and AMPKα and of each other. In conclusion, these findings suggest that MBP exposure exerts cytotoxicity on β-cells via the interdependent activation of JNK and AMPKα, which regulates the downstream apoptotic signaling pathway.     

一株产羧酸酯酶菌的鉴定及酯酶特征的研究

目的:鉴定中国白酒发酵过程中的微生物种类，研究关键酶的特征与作用机制有利于提高白酒的优质品率。方法:本研究用形态学和生理学、16S rRNA、gyr B基因和antiSMASH分析的方法对酒曲中的一株微生物进行了验证；对该菌株的特性进行了研究，采用分子建模的方法获得了羧酸酯酶的3D模型，用分子对接的方法探讨了该菌株的羧酸酯酶的机理。结果:该菌株为产羧酸酯酶的革兰氏阴性菌Pb1（MW580690）；该菌株呈现典型的S型生长曲线，产物曲线为S型，羧酸酯酶活化最优pH范围为5.0~9.0。分子对接结果显示Phe21A为该酶具有催化活性的主要氨基酸，水解三丁酸甘油酯为丁酸和甘油。分子对接结果显示三丁酸甘油酯经过构象变化被转移到催化中心后，进一步被加工；酶的亲水性和疏水性的相互作用表面有利于配体向下转移，进而从疏水性通道释放产物到的酶表面。结论:产羧酸酯酶的菌株为贝莱斯芽胞杆菌，并为羧酸酯酶水解三丁酸甘油酯类物质的底物识别、转移和催化机理提供了新的见解。