异核双金属探针在活细胞细胞核和线粒体中选择性定位DNA

用于实时成像活细胞DNA的细胞核探针是非常罕见的。通过Ru(N^N)₃、Ir(C^N)₂(N^N)、Re(CO)₃Cl(N^N)和Pt(C^N)(N^N)的结合,生成了4种异核双金属配合物：2种不同的功能金属位点被锚定在线性双齿螯和配体(N^N)-(N^N)的尾端,形成不对称哑铃状的双金属分子M₁-M₂,即Ru-Re、Ru-Pt、Ir-Re和Ir-Pt。Ru-Re和Ru-Pt的红色发射探针具有较大的斯托克斯位移、优异的核膜穿透能力、良好光稳定性的DNA结合能力。此外,Ru-Re和Ru-Pt探针的DNA成像可与专门用于活细胞细胞核DNA染色的Hoechst 33342商用染料相媲美,而Ir-Re和Ir-Pt探针直接靶向线粒体。不同探针的发光特性和选择性胞内定位高度依赖于在异核双金属配合物中的金属物种。     

A Specific Interaction between Ionic Liquids’ Cations and Reichardt’s Dye

Solvatochromic probes are often used to understand solvation environments at the molecular scale. In the case of ionic liquids constituted by an anion and a cation, which are designed and paired in order to obtain a low melting point and other desirable physicochemical properties, these two indivisible components can interact in a very different way with the probe. This is the case with one of the most common probes: Reichardt’s Dye. In the cases where the positive charge of the cation is delocalized on an aromatic ring such as imidazolium, the antibonding orbitals of the positively charged aromatic system are very similar in nature and energy to the LUMO of Reichardt’s Dye. This leads to an interesting, specific cation-probe interaction that can be used to elucidate the nature of the ionic liquids’ cations. Parallel computational and experimental investigations have been conducted to elucidate the nature of this interaction with respect to the molecular structure of the cation.     

八甲基环四硅氧烷正离子细乳液开环聚合动力学

以十二烷基苯磺酸钠(SDBS)为乳化剂,硫酸或盐酸为催化剂,八甲基环四硅氧烷(D4)为单体,十六烷为共稳定剂,超声预乳化,制备了聚硅氧烷细乳液,研究了超声时间、催化剂用量、乳化剂用量和温度对聚合动力学的影响.结果表明,在一定酸度范围内,聚合速度与硫酸浓度0.81次方、与盐酸浓度1.02次方、与乳化剂浓度-0.66次方成正比,反应的表观活化能为40.56kJ/mol.     

Screening an In-House Isoquinoline Alkaloids Library for New Blockers of Voltage-Gated Na+ Channels Using Voltage Sensor Fluorescent Probes: Hits and Biases

Voltage-gated Na⁺ (Na_V) channels are significant therapeutic targets for the treatment of cardiac and neurological disorders, thus promoting the search for novel Na_V channel ligands. With the objective of discovering new blockers of Na_V channel ligands, we screened an In-House vegetal alkaloid library using fluorescence cell-based assays. We screened 62 isoquinoline alkaloids (IA) for their ability to decrease the FRET signal of voltage sensor probes (VSP), which were induced by the activation of Na_V channels with batrachotoxin (BTX) in GH3b6 cells. This led to the selection of five IA: liriodenine, oxostephanine, thalmiculine, protopine, and bebeerine, inhibiting the BTX-induced VSP signal with micromolar IC₅₀. These five alkaloids were then assayed using the Na⁺ fluorescent probe ANG-2 and the patch-clamp technique. Only oxostephanine and liriodenine were able to inhibit the BTX-induced ANG-2 signal in HEK293-hNa_V1.3 cells. Indeed, liriodenine and oxostephanine decreased the effects of BTX on Na⁺ currents elicited by the hNa_V1.3 channel, suggesting that conformation change induced by BTX binding could induce a bias in fluorescent assays. However, among the five IA selected in the VSP assay, only bebeerine exhibited strong inhibitory effects against Na⁺ currents elicited by the hNav1.2 and hNav1.6 channels, with IC₅₀ values below 10 µM. So far, bebeerine is the first BBIQ to have been reported to block Na_V channels, with promising therapeutical applications.     

双光子荧光探针研究及其应用

双光子荧光显微成像兼具诸如近红外激发、暗场成像、避免荧光漂白和光致毒、定靶激发、高横向分辨率与纵向分辨率、降低生物组织吸光系数及降低组织自发荧光干扰等特点而显著地优于单光子荧光显微成像,为生命科学研究提供了更为锐利的工具。而用于像离子的含量及其对生理的影响、离子参与的生理活动机制、离子与分子的作用、特定分子的分布及其相互作用等方面研究的双光子荧光探针,是实现成像的关键。双光子荧光探针的研究旨在促进双光子荧光显微镜应用的发展,促进生命科学、医学科学的快速发展,同时也带动双光子荧光探针所隶属的化学这一学科的发展。因此对双光子荧光探针的研究具有重要的理论和实践意义。该文综述了双光子荧光显微成像的优点、双光子荧光探针设计的原理及双光子荧光探针在离子分析方面的应用,并展望了这类荧光探针的发展趋势与应用前景。     

Amphiphilic Graft Copolymers of Hydroxypropyl Cellulose Backbone with Nonpolar Polyisobutylene Branches

The novel amphiphilic graft copolymers with hydrophilic hard polar hydroxypropyl cellulose(HPC) backbone and hydrophobic soft nonpolar polyisobutylene(PIB) branches have been successfully synthesized through nucleophilic substitution reaction of living PIB chains carrying oxonium ions with the-OH groups along HPC backbone. The PIB branch length in the graft copolymers could be designed by living cationic polymerization and the grafting density could be adjusted by PIB~+/-OH molar ratio. The living PIB chains carrying oxonium ion were prepared by transformation of allyl bromide end groups in the presence of AgClO_4 and silver nanoparticles(3.2±0.3 nm, 0.7 wt%-1.8 wt%)generated in situ from AgBr. The phase-separation morphology was formed in the graft copolymers due to their incompatibility between backbone and branches. The hydrophilicity on the surface of graft copolymer films could be turned to hydrophobicity by increasing grafting density or/and length of PIB branches. The soft PIB segments in graft copolymers provided an unique surface via self-assembly for anti-protein adsorption against bovine serum albumin. A small amount of Ag nanoparticles in the copolymers contributed to good antibacterial activities against Staphylococcus aureus or Escherichia coli.     

Comparison of the effectiveness of epoxy cure accelerators using a fluorescent molecular probe

A simple optical method for quantitative comparison of the effectiveness of epoxy cure accelerators, used for speeding up the crosslinking process of epoxy resins with cyclic anhydrides, is described. Fluorescent molecular probes and a miniature fiber optic spectrometer have been applied for measurement of the cure kinetics of a model epoxy resin/anhydride composition in the presence of various cure accelerators. A quantitative index of accelerator performance has been determined for several of the most common accelerators.     

A Conductometric Sensor Specific for Cationic Surfactants

In this work, a fast, sensitive and miniaturised conductometric sensor based on interdigitated electrodes, working in differential mode, was developed for the determination of cationic surfactants. The membrane was composed of a polymer (PVC), a plasticizer (dinonylphtalate (DNP)) and a carrier (sodium tetraphenylborate (NaBΦ₄)). The sensor response was linear from at least 10^?9 M to 10^?2 M for dodecyltrimethylammonium (DTA⁺). No significant loss of sensor response was observed after 8 weeks. The sensor exhibited a lower sensitivity and a narrower dynamic range for tetrabutylammonium, decyltrimethylammonium and cetyltrimethylammonium cationic surfactants. A ten times lower sensitivity was observed for laurylsulfate anionic surfactant, (LS^?).