Metal–organic supramolecular compounds self-assembled from [Mg(H2O)6]2+ clusters and ferrocene-containing carboxylic acids to inverse lipid-like layered structures with good pH response

Two metal–organic supramolecular compounds, [Mg(H₂O)₆]·2FcCO₂·2H₂O (1) and [Mg(H₂O)₆]·2FcCOC₆H₄CO₂·2H₂O (2), were prepared by solvothermal synthesis. The solids exhibit non-covalent self-assembly and layered structures with unprecedented inverse lipid-like bilayer arrangements. Further investigations revealed that the layered structures were sensitive to pH changes. The proposed synthesis method in this report would allow development of new types of pH-responsive materials.     

NIR-II Fluorescent Brightness Promoted by “Ring Fusion” for the Detection of Intestinal Inflammation

Fluorophores with emission in the second near-infrared window (NIR-II) have displayed salient advantages for biomedical applications. However, the common strategy of reducing the energy bandgap of fluorophores so as to achieve red-shifted wavelengths always leads to compromised fluorescent brightness. Herein, we propose a molecular design concept of “ring-fusion” to modify the acceptor of AIEgen that can extend the luminous wavelength from NIR-I to NIR-II. The fused-acceptor-containing fluorophore yielded, TTQP, has an enhanced absorption coefficient with a higher brightness in nanoparticle formation compared to its NIR-I emissive counterpart (TTQ-DP) with a non-fused acceptor. Theoretical calculation further confirms that the ring fusion can efficiently promote the rigidity and planarity of the electron-deficient core, leading to a lower reorganization energy and nonradiative decay. The TTQP NPs yielded thus allow sensitive NIR-II fluorescence imaging of vasculature and intestinal inflammation in mice models. Therefore, we anticipate that our work will provide a promising molecular-engineering strategy to enrich the library and broaden the application scope of NIR-II fluorophores.     

Metabonomic profiling of liver metabolites by gas chromatography–mass spectrometry and its application to characterizing hyperlipidemia

The measurement of metabolites in tissues is of great importance in metabonomic research in the biomedical sciences, providing more relevant information than is available from systemic biofluids. The liver is the most important organ/tissue for most biochemical reactions, and the metabolites in the liver are of great interest to scientists. To develop an optimized extraction method and comprehensive profiling technique for liver metabolites, organic solvents of various compositions were designed using design of experiments to extract metabolites from the liver, and the metabolites were profiled by gas chromatography/time‐of‐flight mass spectrometry (GC/TOF‐MS). The resolved peak areas were processed by principle components analysis, partial least‐squares projections to latent structures, and discriminant analysis. The results suggest the highest extraction efficiency was for methanol–water, which maximized the majority of GC/TOF‐MS responses. The optimal solvent was applied to extract metabolites in liver of hyperlipidemia hamster and the control. The GC/TOF‐MS profiles of liver metabolites showed obvious differences between hyperlipidemic hamsters and controls. A comparison of liver and serum data from the same animals identified common biomarkers and presented complementary information. Our results suggest that liver metabonomics is a valuable technique and that the combined analysis of systematic biofluids and local tissues is meaningful and complementary, recovering more comprehensive metabonomic data than either analysis alone. Copyright © 2009 John Wiley & Sons, Ltd.     

从纸上到躬行:基于有机化学理论和文献的实验设计及优化之低年级本科教学初探

国际公认化学类本科生的培养目标是能够胜任化学专业技术职务,或具备相关的科研能力,而核心考核因素之一被认为是能否以纸上所学理论和文献助力实验方案的设计,并躬行实现。我们在有机化学基础实验教学中融合以上理念,初步探索出适合低年级本科生的以理论知识和文献指导实验设计和优化的教学策略。以乙酰二茂铁的合成为例,以问题-讨论为主线,引导学生从文献、底物的电子结构、傅-克酰基化反应机理和重要的物理化学性质等进行综合分析,设计乙酰二茂铁的合成路线,鼓励学生对教材提出质疑并自主设计和开展验证实验,对教材中的经典方法持续优化。学生深度参与实验路线设计和关键参数设置,沉浸学术研究氛围,敢于质疑并验证,提升了将已学理论转化为解决实际问题的能力,一定程度上有利于其科学思维和科研执行力的培养,提高其从事化学专业技术职务或相关科研工作的核心竞争力。     

溶剂工程调控钙钛矿薄膜中PbI2和PbI2(DMSO)的形成

钙钛矿太阳能电池以其高效、低成本的特点备受关注。到目前为止,钙钛矿太阳能电池的最高光电转换效率已经超过25%,显示出良好的应用前景。钙钛矿薄膜的结晶性能是决定器件性能的关键,因此,调控钙钛矿薄膜的生长过程至关重要。本工作中,我们发现通过简单调节前驱体溶剂,即调节二甲基亚砜：1, 4-丁内酯: N, N-二甲基甲酰胺(DMSO : GBL : DMF)的三种混合溶剂的比例,可实现钙钛矿薄膜中PbI₂和PbI₂(DMSO)含量的调节,从而调节电池的器件性能。此外,本工作系统研究了PbI₂和PbI₂(DMSO)的含量对器件性能的影响。结果表明,PbI₂(DMSO)的形成会导致300–425 nm波长范围内电池的外量子效率(EQE)降低,从而导致器件性能下降。相反,通过在前驱体溶液中添加额外的碘化亚甲基铵(MAI),可以抑制PbI₂和PbI₂(DMSO)的形成。     

Controllable Photoelectric Properties of Carbon Dots and Their Application in Organic Solar Cells

Organic solar cells are a current research hotspot in the energy field because of their advantages of lightness,translucency,roll to roll printing and building integration.With the rapid development of small molecule acceptor materials with high-performance,the efficiency of organic solar cells has been greatly improved.Further improving the device efficiency and stability and reducing the cost of active layer materials will contribute to the industrial development of organic solar cells.As a novel type of carbon nanomaterials,carbon dots gradually show great application potential in the field of organic solar cells due to their advantages of low preparation cost,non-toxicity and excellent photoelectric performance.Firstly,the synthesis and classification of carbon dots are briefly introduced.Secondly,the photoelectric properties of carbon dots and their adjusting,including adjustable surface energy level structure,good film-forming performance and up/down conversion characteristics are summarized.Thirdly,based on these intrinsic properties,the feasibility and advantages of carbon dots used in organic solar cells are discussed.Fourthly,the application progress of carbon dots in the active layer,hole transport layer,electron transport layer,interface modification layer and down-conversion materials of organic solar cells is also reviewed.Finally,the application progress of carbon dots in organic solar cells is prospected.Several further research directions,including in-depth exploration of the controllable preparation of carbon dots and their application in the fields of interface layer and up/down conversion for improving efficiency and stability of device are pointed out.     

Synthesis and characterization of carbon-supported transition metal oxide nanoparticles — Cobalt porphyrin as catalysts for electroreduction of oxygen in acids

Unpyrolyzed, non noble metal catalysts for Oxygen Reduction Reaction (ORR), denoted MeOx–CoP/C, were obtained using a two-step procedure. The procedure consisted of a synthesis of carbon-supported transition metal (Me═Co, or Ni, or Fe) nanoparticles, followed by adsorption of cobalt porphyrin (CoP). TEM and XPS analyses confirm the formation of nanoparticles and the presence of transition metal oxides. Rotating disk electrode measurements showed that the as-synthesized materials exhibit catalytic ORR activity in acidic medium toward oxygen reduction, which is higher than that of cobalt porphyrin on carbon. This reveals that the metal oxide nanoparticles enhance the activity of the metalloporphyrin without being electroactive themselves. The catalytic activity follows the sequence: CoOx–CoP/C > NiOx–CoP/C > FeOx–CoP/C, showing the influence of nature of the transition metal on the enhancing effect. The presence of a cobalt center incorporated in the macrocycle was found to be essential to the oxygen reduction reaction, appearing thus to be the catalytic active site of the reaction. Our data suggest the ORR occurs at a single active site.