含酰胺结构超低膨胀聚酰亚胺薄膜的热膨胀行为

采用联苯二酐与3种含酰胺结构二胺制备了具有不同取代基团的聚酰胺-酰亚胺薄膜, 考察了酰胺结构对薄膜力学、 耐热及尺寸稳定性的影响, 研究了聚集态结构与薄膜热膨胀行为的关系和规律. 该系列薄膜具有超高强度和优异的耐热性能, 拉伸强度高达280.5 MPa, 玻璃化转变温度在389~409 ℃, 并在30~300 ℃温度范围内表现出超低负膨胀, 热膨胀系数(CTE, ppm/℃, 即10 ⁶ cm·cm ^-1·℃ ^-1)在-3.05~-1.74 ppm/℃之间. 聚集态分析结果表明, 酰胺结构使分子链间形成了强氢键相互作用, 分子链在薄膜面内方向高度有序取向, 并在膜厚方向堆积更为紧密, 使薄膜表现出热收缩现象. 通过不同体积大小的取代基团进一步调控分子链间相互作用及排列堆积, 可实现薄膜在高温下近乎零尺寸形变, 为设计制备超低膨胀聚合物基板材料提供了新思路.     

Design of activatable red-emissive assay for cysteine detection in aqueous medium with aggregation induced emission characteristics

A novel water-soluble red-emissive AIE fluorescence probe for cysteine (Cys) in situ was prepared and the performance of selectivity and sensitivity has been carefully investigated in this study. The probe was established on the electrostatic interaction of sulfonate functionalized tetraphenylethene (TPE) and polycation generated by the reaction between a polymer bearing dinitrobenzenesulfonate groups and Cys. From the experimental results, it was easy to distinguish Cys from glutathione (GSH) and homocysteine (Hcy) with a detection limit of 73 nmol/L. The assay system also possessed strong anti-interference ability against multitudinous amino acids. The Stokes shift was 142 nm and the emission ranged from 550 nm to 850 nm. In addition, double responses in fluorescence and ultraviolet-visible spectra also make the red-emissive assay ideal for sensitive detection and quantification of Cys for most purposes, especially in-situ monitoring of Cys in aqueous medium.     

Synthesis of aggregation pheromone components of cerambycid species through α-hydroxylation of alkylketones

The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media.     

γ辐照引发[Cnmim][NTf2]离子液体变色研究

1-烷基-3-甲基咪唑双三氟甲基磺酰胺型离子液体(C_nmim][NTf₂])被认为是最有希望用于核燃料循环中的分离试剂之一, 虽然其化学结构在辐照过程中变化不大, 但在受到γ辐照后会发生明显的变色, 因此有必要研究该类离子液体的变色原因. 本文以⁶⁰Co为辐照源, 系统研究了辐照后不同C(1)－烷基链长和咪唑环上C(2)位上的H被甲基取代后离子液体的紫外-可见(UV-Vis)吸收光谱行为, 并结合辐照后离子液体荧光光谱和质谱的变化, 分析了导致该类离子液体辐照后颜色加深的原因. 结果表明, 随着咪唑环上C(1)―烷基链长度和剂量增大, 离子液体颜色加深; 而C(2)位上的H被甲基取代后颜色明显变浅. 辐照后咪唑型离子液体的变色主要来自于辐照后产生的烷基侧链含双键的咪唑阳离子, 咪唑阳离子二聚体和含氟咪唑化合物. 此外, γ辐照引起咪唑阳离子易发生π-π堆积, 而聚集态含量增加也会引起颜色加深.     

Metallo Phthalocyanines bearing 2‐Isopropyl‐6‐methylpyrimidin‐4‐yloxy Substituents: Synthesis,Characterization, Aggregation Behavior,Antioxidant and Antibacterial Activity,and Electronic Properties

A novel phthalonitrile derivative bearing 2‐isopropyl‐6‐methylpyrimidin‐4‐yloxy substituents at peripheral positions was synthesized by a nucleophilic substitution reaction. Metallophthalocyanines were obtained from the reaction of the novel phthalonitrile with metal Zn, Cu, Co, and Ni salts. The characterization of the compounds was performed using elemental analysis as well as UV/Vis, FT‐IR, and ¹H‐NMR spectroscopy. The aggregation behaviors of phthalocyanine complexes were also investigated. These metallophthalocyanines do not show any aggregation behavior between 10^–4–10^–6 M concentration range in THF. The antioxidant activities of the synthesized compounds were evaluated using three different tests: 2, 2‐diphenyl‐1‐picrylhydrazyl (DPPH) radical scavenging, metal chelating activity, and reducing power assays. All the compounds exhibited various antioxidant activities. In addition, antimicrobial activity of the compounds was tested over four gram positive and two gram negative bacteria. Moreover, the ground‐state geometries of the complexes were optimized using density functional theory (DFT) methods at B3LYP/6‐31G(d, p) level in order to obtain information about the 3D arrangements and electronic structure.     

Head group specificity of novel functionalized surfactants: synthesis,self-assembly and calcium tolerance

The present work describes the synthesis, characterization and application of functionalized surfactants derived through simple organic reaction steps. These surfactants have been particularly tailor made to resist hardness due to calcium ions in water. It is unique of its kind because here the surfactants have an analogous hydrophobic chain but differ structurally in the composition of the head groups in terms of the position of attachment of the chain. The effect of this small variability in the head group on the surfactant property, adsorption, self assembly and calcium tolerance behaviour has been studied in detail. This kind of phenol–keto surfactants has not been reported before. It was also found that one of the surfactants was more tolerant towards Ca²⁺ ion than the other. The individual packing behaviour of the surfactants at the air–water interface has been projected to cause this difference which is very interesting.     

Bioelectrochemistry for various facets of tau protein biochemistry

Tau protein undergoes complex biochemical processes involved in normal and diseased cellular functions; specifically, tau pathology has been linked to neurodegeneration. At the heart of tau biochemistry are three pillars: microtubules, phosphorylation, and aggregation. However, these three processes are also regulated through other biomolecules in the biological setting, such as metal ions and small and larger ligands, including proteins and nucleic acids. This review describes the latest electrochemical approaches toward greater understanding of tau biochemistry, early disease diagnosis, and drug inhibitor screening.     

Organic Nanocrystals Based on a Solid-emission-tunable AIEgen for Cell Imaging

The development of fluorescent nanocrystals based on organic small molecules is of great importance in bioimaging due to the merits of easy modification,high brightness and excellent photostability,however suffering from the emission-detrimental aggregation-caused quenching(ACQ)effect.Herein,we successfully designed and synthesized an AIE-active di(N,N-dimethylaniline)-dibenzofulvene(named as NFTPE),which exhibits the crystallization-induced emission enhancement(CIEE)effect.Interestingly,two types of yellow-and orange-emissive crystals for NFTPE were obtained,exhibiting aggregation microenvironment-dependent emission tuning in the solid state.Single-crystal analysis and density functional theory(DFT)calculations reveal that different aggregation microenvironments result in the distinct molecular conformation for various emission.Excitingly,the crystallization of NFTPE in an aqueous solution under the assistance of amphiphilic PEG polymer matrices could be monitored in situ by the fluorescence changes,facilitating the preparation of NFTPE nanocrystals(NFTPE-NCs)by adjusting the aggregation microenvironment.The obtained NFTPE-NCs exhibit the superior performance in cell imaging in respect to high brightness,photostability,and biocompatibility,thus demonstrating the potential in bioimaging applications.     

Recent Development of DNA-modified AIEgen Probes for Biomedical Application

A variety of DNA-based probes are utilized for the detections of multiple analytes and DNA nanotechnology has been thriving for recent decades and achieving numerous nanostructures,mainly focusing on DNA morphology modulation and multifunctional systems engineered into to the complicated works.Among the numerous detections,fluorescence method is a non-invasive,highly selective and sensitive means for varieties of applications,but their emissions are often compromised by the aggregation-caused quenching(ACQ)effect,which weakens their applications.The aggregation induced emission luminogens(AIEgens)are created with non emissive or weakly emissive in a low concentration but emit strong fluorescence in a high concentration with aggregated states.Herein,numerous functionalized AIEgens have been emerged and used for detection and imaging and DNA-modified AIEgen probes are introduced.In this vein,here we report the progress on DNA-modified AIEgen probes in recent years and highlight their conjugation strategies including covalent bonding,electrostatic interaction and their applications of biosensing.Moreover,multiple DNA strands are needed to introduce into the DNA-modified AIEgen probes for more purposes.At the end,some challenges are mentioned to discuss the new trend of DNA-modified AIEgen probes.