一例含阴离子水簇的钴配合物的合成、结构及理论研究

金属配合物中的水簇研究为研究宏观意义上的水以及与蛋白质分子有关的水分子提供了有效途径。本文合成了一个含有阴离子水簇的带状超分子配合物[Co(2,2-bipy)₂(N₃)₂](N₃)_0.5Cl_0.5·2H₂O(1,2, 2-bipy=2, 2-联吡啶)。单晶结构解析表明,配合物属于三斜晶系,P-1空间群,晶胞参数为:a=0.822 54(7) nm,b=1.175 58(9) nm,c=1.237 06(10) nm,α=91.379 0(10)°,β=92.151 0(10)°,γ=108.119 0(10)°,V=1.135 27(16) nm³,由一个单核[Co(2,2-bipy)₂(N₃)₂]⁺配合物阳离子、两个非配位水分子、0.5个游离的叠氮离子和0.5个氯离子组成,叠氮离子和氯离子位置无序,占有率各为50%。两个客体水分子通过强烈的分子间氢键作用形成了环状水四聚体,且与无序的N^-₃和Cl^-通过氢键作用形成了一个[(H₂O)₄(N₃)Cl]^2- 阴离子水簇。此外,本文基于密度泛函理论(DFT)对配合物[Co(2,2-bipy)₂(N₃)₂]⁺阳离子进行了量子化学计算,分析了其单点能和原子电荷,并计算了中心金属离子的氧化态,计算结果与实验相吻合。     

金催化乙炔氢氯化的密度泛函理论研究进展

乙炔氢氯化(AH)是生产氯乙烯的主要途径之一,传统上使用高毒性的汞催化剂,因此开发无汞催化剂迫在眉睫。金(Au)催化剂是最有潜力的替代催化剂之一,然而其活性Au物种、反应物的活化过程或反应过渡态结构等催化机理仍不够清晰。密度泛函理论（DFT）在研究由Au催化AH的反应机理中发挥了极其重要的作用。本文综述了DFT对金催化剂活性位点、反应物在催化剂上的吸附性质及反应机理的研究进展。重点讨论了DFT对阳离子金和金簇催化AH反应过程的模拟计算,包括Au电子状态、其它原子掺杂及金簇尺寸和形状对催化AH反应影响的模拟。结果表明DFT模拟计算在微观分子尺度上研究反应物的吸附、反应中间体及过渡态等方面发挥了关键作用,对理解Au催化AH反应机理做出了重要贡献。     

基于石墨烯Tamm等离子体激元的太赫兹强耦合效应

设计了一种全新的一维石墨烯-光子晶体(PhC)复合谐振结构,使用传输矩阵法(TMM)对其所支持的太赫兹Tamm等离子体激元(TPP)和腔体模式(CM)之间的强耦合效应进行理论研究。研究表明,用于表征耦合强度的Rabi分裂能随着光子晶体周期数的减小而增大;改变间隔层和腔体厚度以及石墨烯的费米能级时,也会影响Rabi分裂能。最后通过入射角度对耦合模式进行主动调控,当入射角处于0°~60°时,耦合模式的特性与偏振无关。本文的研究结果为太赫兹强耦合效应的研究和应用提供了新的思路。     

用化学溶液方法在Ni-5at%W基底上制备La2Zr2O7过渡层的研究

La2Zr2O7(LZO)过渡层以其独特的物理化学性质越来越受到人们的关注。本文以乙酰丙酮镧和乙酰丙酮锆为前驱盐,丙酸为溶剂配置前驱液,用化学溶液方法(CSD)在具有立方织构的Ni-5at%W基底上制备了LZO过渡层薄膜。研究了前驱液成分、性质以及退火温度对LZO成相以及取向的影响。用常规XRD和X射线四环衍射仪分析了LZO薄膜的相成分和织构。结果显示,在1050℃下退火可以获得强立方织构的LZO薄膜,其中(222)峰的Phi扫描半高宽值为8.95°;(400)峰的Chi扫描半高宽值为6.8°。用高分辨扫描电子显微镜(FE-SEM)观察到LZO薄膜表面均匀致密,没有裂纹和空洞。     

Mesoporous sodium four-coordinate aluminosilicate nanoparticles modulate dendritic cell pyroptosis and activate innate and adaptive immunity

Pyroptosis is a programmed cell death widely studied in cancer cells for tumour inhibition, but rarely in dendritic cell (DC) activation for vaccine development. Here, we report the synthesis of sodium stabilized mesoporous aluminosilicate nanoparticles as DC pyroptosis modulators and antigen carriers. By surface modification of sodium-stabilized four-coordinate aluminium species on dendritic mesoporous silica nanoparticles, the resultant Na-^IVAl-DMSN significantly activated DC through caspase-1 dependent pyroptosis via pH responsive intracellular ion exchange. The released proinflammatory cellular contents further mediated DC hyperactivation with prolonged cytokine release. In vivo studies showed that Na-^IVAl-DMSN induced enhanced cellular immunity mediated by natural killer (NK) cells, cytotoxic T cells, and memory T cells as well as humoral immune response. Our results provide a new principle for the design of next-generation nanoadjuvants for vaccine applications.

Na-^IVAl-DMSN acts as both antigen carriers and modulators to “hyperactivate” dendritic cells (DCs) via potassium (K⁺) efflux dependent pyroptosis, eventually leading to enhanced adaptive and innate immunity.     

基于金字塔模型的地形网格数据研究

地理空间情报在情报分析与作战指挥中发挥了越来越重要的作用,它包括一体化的影像、地理空间信息,而地形是地理空间信息中的重要因素。为了实时地绘制大规模地形数据,在继承传统算法基础上,借鉴遥感影像金字塔模型,将遥感影像和地理信息统一,提出了一种瓦片金字塔模型和线性四叉树索引相结合的地形数据结构,并采用一种新的基于瓦片四叉树的接边处理方法用于消除不同层次之间的裂缝,是对传统结构的优化。实验结果表明该方法在保持地形逼真的前提下,在PC机上运行时有很好的绘制网格帧率和实时动态交互效果。     

基于DSP的双频超声波流量计硬件电路设计

超声波流量测量技术是一种利用超声波信号在流体中传播时所载流体的流速信息来测量流体流量的新的测量技术,他具有非接触式测量、测量精度高、测量范围宽、安装维护方便等特点,特别适合用于临时管道流量、大口径管道流量以及危险性流体流量的测量。本文介绍了一种采用数字信号处理技术的双频超声波流量计的硬件电路设计方法。     

Multistimuli‐Responsive Display Materials to Encrypt Differentiated Information in Bright and Dark Fields

Visually readable codes play a crucial role in anticounterfeiting measures. However, current coding approaches do not enable time‐dependent codes to be visually read, adjusted, and differentiated in bright and dark fields. Here, using a combined strategy of piezoelectric lattice selection, oxygen vacancy engineering, and activator doping, a lanthanide ion‐doped titanate is developed that integrates mechano‐, thermo‐, and photo‐responsive color change (>18 h for bright field), persistent luminescence (>6 h for dark field), and stimulus‐triggered multimodal luminescence. The feasibility of optical encoding, visual displaying, and stimulus‐responsive encrypting of time‐dependent, dual‐field information by using the developed material is demonstrated. In particular, the differentiated display of dual‐field modes is achieved by combining mechanostimulated abolition of only the persistent luminescence and thermo‐ and photostimulated reversal of both the color change and persistent luminescence. The results provide new insights for designing advanced materials and encryption technologies for photonic displays, information security, and intelligent anticounterfeiting.     

Dynamic synovial fibroblasts are modulated by NBCn1 as a potential target in rheumatoid arthritis

Rheumatoid arthritis (RA) is an autoimmune disease characterized by aggressive fibroblast-like synoviocytes (FLSs) and pannus formation. Various therapeutic strategies have been developed against inflammatory cytokines in RA in recent decades. Based on the migratory features of FLSs, we examined whether modulation of the migratory module attenuates RA severity. In this study, inflamed synovial fluid-stimulated FLSs exhibited enhanced migration and migratory apparatus expression, and sodium bicarbonate cotransporter n1 (NBCn1) was identified in primary cultured RA-FLSs for the first time. The NBC inhibitor S0859 attenuated the migration of FLSs induced with synovial fluid from patients with RA or with TNF-α stimulation. Inhibition of NBCs with S0859 in a collagen-induced arthritis (CIA) mouse model reduced joint swelling and destruction without blood, hepatic, or renal toxicity. Primary FLSs isolated from the CIA-induced mouse model also showed reduced migration in the presence of S0859. Our results suggest that inflammatory mediators in synovial fluid, including TNF-α, recruit NBCn1 to the plasma membrane of FLSs to provide dynamic properties and that modulation of NBCn1 could be developed into a therapeutic strategy for RA.Subject terms: Chemotaxis, Bone, Ion channel signalling, Rheumatoid arthritis, Drug development