Heterotrimetallic Mixed-Valent Molecular Precursors Containing Periodic Table Neighbors: Assignment of Metal Positions and Oxidation States

A known trinuclear structure was used to design the heterobimetallic mixed-valent, mixed-ligand molecule [Co^II(hfac)₃−Na−Co^III(acac)₃] ( 1 ). This was used as a template structure to develop heterotrimetallic molecules [Co^II(hfac)₃−Na−Fe^III(acac)₃] ( 2 ) and [Ni^II(hfac)₃−Na−Co^III(acac)₃] ( 3 ) via isovalent site-specific substitution at either of the cobalt positions. Diffraction methods, synchrotron resonant diffraction, and multiple-wavelength anomalous diffraction were applied beyond simple structural investigation to provide an unambiguous assignment of the positions and oxidation states for the periodic table neighbors in the heterometallic assemblies. Molecules of 2 and 3 are true heterotrimetallic rather than a statistical mixture of two heterobimetallic counterparts. Trinuclear platform 1 exhibits flexibility in accommodating a variety of di- and trivalent metals, which can be further utilized in the design of molecular precursors for the NaMM′O₄ functional oxide materials.     

FeOOH@Metal–Organic Framework Core–Satellite Nanocomposites for the Serum Metabolic Fingerprinting of Gynecological Cancers

High-throughput metabolic analysis is of significance in diagnostics, while tedious sample pretreatment has largely hindered its clinic application. Herein, we designed FeOOH@ZIF-8 composites with enhanced ionization efficiency and size-exclusion effect for laser desorption/ionization mass spectrometry (LDI-MS)-based metabolic diagnosis of gynecological cancers. The FeOOH@ZIF-8-assisted LDI-MS achieved rapid, sensitive, and selective metabolic fingerprints of the native serum without any enrichment or purification. Further analysis of extracted serum metabolic fingerprints successfully discriminated patients with gynecological cancers (GCs) from healthy controls and also differentiated three major subtypes of GCs. Given the low cost, high-throughput, and easy operation, our approach brings a new dimension to disease analysis and classification.     

相对性区域创新指数与经济周期挖掘

提出了一类新的相对性区域创新指数,并采用世界专利申请数据对其进行了具体计算.基于区域创新同经济发展水平之间的超线性关系,该指数消除了经济发展水平对创新能力的影响,可以实现对不同发展水平的经济体之间进行有效的创新能力横纵对比.该创新指数尽管极其简单,却揭示出一系列迥异于传统认知的现象,例如中国大陆地区的技术创新能力在1980年代就已经位居世界前列.采用该指数,不但可以在较高水平上解释世界各国的经济增长,还发现它同经济增长率之间的相关性存在一个20年的经济周期.这些结果显示,该指数作为一个单一性指标,以极小的数据依赖就实现了较高程度的解释性,不但重新定位了世界各经济体的创新能力,对深入理解创新同经济发展之间的关系提供了新的角度,而且暗示着这类相对性经济指标的发展潜力与应用空间.     

贝叶斯优化卷积神经网络公共场所异常声识别*

针对公共场所异常声的感知和识别问题,提出一种基于贝叶斯优化卷积神经网络的识别方法。提取声信号的Gammatone倒谱系数、倍频程功率谱、短时能量和谱质心,组合成声信号的特征图。构建卷积神经网络作为分类器,利用递增的卷积核设置和池化操作处理不同尺度的特征。基于贝叶斯优化算法优化卷积神经网络的模型参数,对包括火苗噼啪声、婴儿啼哭声、烟花燃放声、玻璃破碎声和警报声的5种公共场所异常声进行识别。该方法的识别结果与基于不同的特征提取和分类器方案得到的识别结果进行比较,结果表明该方法的识别效果优于其他特征提取和分类器方案的识别效果。最后分析了该方法在不同信噪比噪声干扰下的识别结果,验证了该方法的有效性。     

Palladium‐Catalyzed Electrophilic Functionalization of Pyridine Derivatives through Phosphonium Salts

Herein, we report a highly efficient and practical method for pyridine‐derived heterobiaryl synthesis through palladium‐catalyzed electrophilic functionalization of easily available pyridine‐derived quaternary phosphonium salts. The nice generality of this reaction was goes beyond arylation, enabling facile incorporation of diverse carbon‐based fragments, including alkenyl, alkynyl, and also allyl fragments, onto the pyridine core. Notably, the silver salt additive is revealed to be of vital importance for the success of this transformation and its pivotal role as transmetallation mediator, which guarantees a smooth transfer of pyridyl group to palladium intermediate, is also described.     

New interaction solutions and nonlocal symmetry of an equation combining the modified Calogero–Bogoyavlenskii–Schiff equation with its negative-order form

The nonlocal symmetry is derived for an equation combining the modified Calogero–Bogoyavlenskii–Schiff equation with its negative-order form from the truncated Painlevéexpansion method. The nonlocal symmetries are localized to the Lie point symmetry by introducing new auxiliary dependent variables. The finite symmetry transformation and the Lie point symmetry for the prolonged system are solved directly. Many new interaction solutions among soliton and other types of interaction solutions for the modified Calogero–Bogoyavlenskii–Schiff equation with its negative-order form can be obtained from the consistent condition of the consistent tanh expansion method by selecting the proper arbitrary constants.     

第三族金属氧化物离子对二氧化碳转化的红外光谱研究

本文利用红外光解离光谱研究了第三族金属氧化物离子对二氧化碳分子的转化机制. 研究表明，对于[ScO(CO₂)_n]⁺体系，在n≤4时，形成了溶剂化结构；在n=5时，形成了碳酸盐结构，实现了二氧化碳的转化. 对于[YO(CO₂)_n]⁺体系，需要4个二氧化碳分子就可以实现二氧化碳的转化. 而在[YO(CO₂)_n]⁺体系中，只发现了溶剂化结构，没有观察到碳酸盐结构. 理论计算表明，[YO(CO₂)_n]⁺体系拥有最小的溶剂化结构向碳酸盐结构转化能垒，[LaO(CO₂)_n]⁺体系拥有最大的溶剂化结构向碳酸盐结构转化能垒. 本文从分子水平揭示了不同金属氧化物离子对二氧化碳分子转化的影响规律.     

阴离子-π复合物(I-·C6F6)的成键分析

最近Anst?ter, et al. 发表了对阴离子-π复合物(I^-·C₆F₆)的第一个定量谱学测量[J. Am. Chem. Soc. 141, 6132 (2019)]，认为成键作用中相关作用占41%，静电作用占23%，得出相关作用占主导的结论. 本研究表明，该文献的“静电作用”中混入了Pauli排斥作用，后者在数值上抵消了前者的作用. 在复合物I^-·C₆F₆中，发现静电作用是相关作用的两倍多，因而阴离子-π复合物中仍应是静电作用占主导.     

基于混合空穴注入层的湿法制备高效蓝光热激活延迟有机发光二极管

在溶液法制备有机电致发光器件(OLEDs)的研究中, PEDOT∶PSS由于具有较好的成膜性与高透光性而常被用作器件的空穴注入层。但相关研究表明, PEDOT∶PSS本身稳定性较差以及功函数较低,这使得溶液法制备OLEDs的性能差且不稳定。蓝色作为全彩色的三基色之一,制备高效的蓝光器件对于实现高质量显示器件和固态照明装置必不可少。而目前溶液法制备蓝光OLEDs的器件效率普遍较差,针对此问题,本文利用传统的蓝光热激活延迟荧光发光(TADF)材料DMAC-DPS作为发光层,用溶液法制备了蓝光TADF OLEDs,通过在PEDOT∶PSS中掺杂PSS-Na制备混合空穴注入层(mix-HIL)来提高空穴注入层的功函数,研究其对于蓝光TADF OLEDs器件性能的影响。首先在PEDOT∶PSS水溶液中掺入不同体积的PSS-Na溶液,在相同条件下旋涂制膜,进行器件制备。通过观测各个实验组器件的电致发光(EL)光谱,发现掺入PSS-Na后器件EL谱存在光谱蓝移的现象,这是由于掺入PSS-Na水溶液后, mix-HIL层的厚度有所降低,使得在微腔效应作用下, EL光谱发生蓝移。通过对比各组器件的电流密度-电压-亮度(J-V-L)曲线及其计算所得器件的电流效率,结果显示随着PSS-Na的掺入,器件的亮度和电流都有所增大,器件的电流效率也得到了提升,当掺杂比例为0.5∶0.5(PEDOT∶PSS/PSS-Na)时提升幅度最大(亮度提升86.7%,电流效率提升34.3%)。通过在瞬态电致发光测试过程中施加或撤去驱动电压观测了器件EL强度的变化,分析了在混合空穴注入层/发光层(mix-HIL/EML)界面处的电荷积累情况。实验证明,通过在PEDOT∶PSS中掺杂PSS-Na制备mix-HIL获得了蓝光TADF OLEDs器件性能的提升,这是一个获得高效率溶液法制备OLEDs的可行方法。     

Dynamic modeling,simulation and design of smart membrane systems driven by soft actuators of multilayer dielectric elastomers

Nonlinear Dynamics - A multilayer membrane element of absolute nodal coordinate formulation is proposed for dynamic modeling of multilayer dielectric elastomer actuators (DEAs). The coupled...