A Novel d-f Heterometallic CdII-EuIII Metal-organic Framework as a Sensitive Luminescent Sensor for the Dual Detection of Ronidazole and 4-Nitrophenol

A novel three-dimensional (3D) d-f heterometallic metal-organic framework (MOF) formulated as [EuCd_1.5L₂(H₂O)₃] · 2H₂O ( 1 ) [H₃L = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid] was successfully synthesized and characterized. Structural analysis displays that 1 features a 3D (3, 12)-connected framework constructed by [Eu₂Cd₃(tetrazole)₄(COO)₈] units. The powder X-ray diffraction measurement of 1 immersed in different solvents reveals that 1 possess good solvent stability. It is worth noting that 1 displays highly selective detection for ronidazole (RDZ) and 4-nitrophenol (4-NP) through luminescence quenching. The possible mechanism of luminescent sensing is also well discussed.     

偶氮苯高分子的光致可逆固液转变

偶氮苯化合物是一种极具吸引力以及较为常用的光响应材料,本文主要介绍偶氮苯的光响应性质以及一些偶氮苯高分子的合成方法,解析光化学反应导致偶氮苯高分子固液转变的机理,并介绍其在粘结性材料、光致动器、光致热导开关器件及非热纳米压印中的应用。     

花青醛的合成工艺优化

以3-异丙基苯乙酮(1)为原料,经3步反应合成了花青醛[3-(3-异丙基苯基)丁醛(4)],并优化了反应条件。确定合成3-(3-异丙基苯基)-2-丁烯酸乙酯(2)的最优条件为：n(1)/n(磷酰基乙酸三乙酯)/n(氢化钠)=5/6/6,于室温反应12 h,收率84.5%;合成3-(3-异丙基苯基)-1-丁醇(3)的最佳条件为:n(2)/n(硼氢化钠)/n(六水合二氯化钴)/n(二异丙基胺)=10/20/1/2,于55 ℃反应24 h,收率87.8%;合成4的最优条件为: n(3)/n(乙酸酐)/n(亚硝酸钠)=5/4/15,投料顺序为:乙酸酐、3、亚硝酸钠,反应时间为2 min,收率91.0%。产物结构经¹H NMR, ¹³C NMR和MS(ESI)确证。     

C−C Bond Formation in Syngas Conversion over Zinc Sites Grafted on ZSM‐5 Zeolite

Despite significant progress achieved in Fischer–Tropsch synthesis (FTS) technology, control of product selectivity remains a challenge in syngas conversion. Herein, we demonstrate that Zn²⁺‐ion exchanged ZSM‐5 zeolite steers syngas conversion selectively to ethane with its selectivity reaching as high as 86 % among hydrocarbons (excluding CO₂) at 20 % CO conversion. NMR spectroscopy, X‐ray absorption spectroscopy, and X‐ray fluorescence indicate that this is likely attributed to the highly dispersed Zn sites grafted on ZSM‐5. Quasi‐in‐situ solid‐state NMR, obtained by quenching the reaction in liquid N₂, detects C₂ species such as acetyl (‐COCH₃) bonding with an oxygen, ethyl (‐CH₂CH₃) bonding with a Zn site, and epoxyethane molecules adsorbing on a Zn site and a Brønsted acid site of the catalyst, respectively. These species could provide insight into C?C bond formation during ethane formation. Interestingly, this selective reaction pathway toward ethane appears to be general because a series of other Zn²⁺‐ion exchanged aluminosilicate zeolites with different topologies (for example, SSZ‐13, MCM‐22, and ZSM‐12) all give ethane predominantly. By contrast, a physical mixture of ZnO‐ZSM‐5 favors formation of hydrocarbons beyond C₃₊. These results provide an important guide for tuning the product selectivity in syngas conversion.     

The Redox Coupling Effect in a Photocatalytic RuII‐PdII Cage with TTF Guest as Electron Relay Mediator for Visible‐Light Hydrogen‐Evolving Promotion

A nanocage coupling effect from a redox Ru^II‐Pd^II metal–organic cage (MOC‐16) is demonstrated for efficient photochemical H₂ production by virtue of redox–guest modulation of the photo‐induced electron transfer (PET) process. Through coupling with photoredox cycle of MOC‐16, tetrathiafulvalene (TTF) guests act as electron relay mediator to improve the overall electron transfer efficiency in the host–guest system in a long‐time scale, leading to significant promotion of visible‐light driven H₂ evolution. By contrast, the presence of larger TTF‐derivatives in bulk solution without host–guest interactions results in interference with PET process of MOC‐16, leading to inefficient H₂ evolution. Such interaction provides an example to understand the interplay between the redox‐active nanocage and guest for optimization of redox events and photocatalytic activities in a confined chemical nanoenvironment.     

Asymmetric Total Syntheses of Di‐ and Sesquiterpenoids by Catalytic C−C Activation of Cyclopentanones

To show the synthetic utility of the catalytic C?C activation of less strained substrates, described here are the collective and concise syntheses of the natural products (?)‐microthecaline A, (?)‐leubehanol, (+)‐pseudopteroxazole, (+)‐seco‐pseudopteroxazole, pseudopterosin A–F and G—J aglycones, and (+)‐heritonin. The key step in these syntheses involve a Rh‐catalyzed C?C/C?H activation cascade of 3‐arylcyclopentanones, which provides a rapid and enantioselective route to access the polysubstituted tetrahydronaphthalene cores presented in these natural products. Other important features include 1) the direct C?H amination of the tetralone substrate in the synthesis of (?)‐microthecaline A, 2) the use of phosphoric acid to enhance efficiency and regioselectivity for problematic cyclopentanone substrates in the C?C activation reactions, and 3) the direct conversion of serrulatane into amphilectane diterpenes by an allylic cyclodehydrogenation coupling.     

Online high‐pH reversed‐phase liquid chromatography × low‐pH reversed‐phase liquid chromatography tandem electrospray ionization mass spectrometry combined with pulse elution gradient in the first dimension for the analysis of alkaloids in Macleaya cordata (willd.) R. Br

An online high‐pH reversed‐phase liquid chromatography× low‐pH reversed‐phase liquid chromatography tandem electrospray ionization mass spectrometry combined with pulse elution gradient in the first dimension was constructed to separate and identify alkaloids from Macleaya cordata (willd.) R. Br. The modulation was performed by using a dual second dimensional columns interface combined with a make‐up dilution pump, which is responsible for dilution and neutralization of the first dimensional effluent, and the dual second dimensional columns integrated the trapping and the separation function to reduce the second dimension system dead volume. Taking advantage of the dissociable characteristics of alkaloids, mobile phases with different pH values were applied in the first dimension (pH 9.0) and the second dimension (pH 2.6) to improve the orthogonality of two‐dimension separation. Besides, the pulse elution gradient in first dimension and second dimensional gradient were carefully optimized and much better separation was achieved compared to the separation with the traditional two‐dimensional liquid chromatography approach. Finally, mass measurement was performed for alkaloids in M. cordata (willd.) R. Br. by coupling proposed two‐dimensional liquid chromatography system with triple quadrupole mass spectrometry, and 39 alkaloids were successfully identified by comparing the obtained result with the former reported results.     

Hierarchical diversity entropy for the early fault diagnosis of rolling bearing

Nonlinear Dynamics - Intelligent fault diagnosis provides great convenience for the prognostic and health management of the rotating machinery. Recently, the multiscale diversity entropy has been...     

基于音素相关后验概率变换的发音质量评价

帧规整对数后验概率是目前公认最有效的发音质量的度量。但该文证明了该度量还反映了当前发音对应的声学模型与概率空间中声学模型的混淆程度,使其在评分任务上存在着严重的缺陷。因此,该文提出了可训练的音素相关的后验概率变换;并研究了线性和非线性sigmoid变换,同时给出线性变换的显式全局最优解和非线性变换的梯度下降解法。在全国采集的普通话水平测试现场考试的篇章朗读题型上进行实验。实验结果表明:当概率空间包含所有音素时,该方法能使人机相关度从0.582提升至0.768;当采用优化的概率空间时,该方法能使人机相关度从0.696提升至0.773。