An Assembled Nanocomplex for Improving both Therapeutic Efficiency and Treatment Depth in Photodynamic Therapy

Photodynamic therapy (PDT) shows unique selectivity and irreversible destruction toward treated tissues or cells, but still has several problems in clinical practice. One is limited therapeutic efficiency, which is attributed to hypoxia in tumor sites. Another is the limited treatment depth because traditional photosensitizes are excited by short wavelength light (<700 nm). An assembled nano‐complex system composed of oxygen donor, two‐photon absorption (TPA) species, and photosensitizer (PS) was synthesized to address both problems. The photosensitizer is excited indirectly by two‐photon laser through intraparticle FRET mechanism for improving treatment depth. The oxygen donor, hemoglobin, can supply extra oxygen into tumor location through targeting effect for enhanced PDT efficiency. The mechanism and PDT effect were verified through both in vitro and in vivo experiments. The simple system is promising to promote two‐photon PDT for clinical applications.     

Valency‐Controlled Framework Nucleic Acid Signal Amplifiers

Weak ligand–receptor recognition events are often amplified by recruiting multiple regulatory biomolecules to the action site in biological systems. However, signal amplification in in vitro biomimetic systems generally lack the spatiotemporal regulation in vivo. Herein we report a framework nucleic acid (FNA)‐programmed strategy to develop valence‐controlled signal amplifiers with high modularity for ultrasensitive biosensing. We demonstrated that the FNA‐programmed signal amplifiers could recruit nucleic acids, proteins, and inorganic nanoparticles in a stoichiometric manner. The valence‐controlled signal amplifier enhanced the quantification ability of electrochemical biosensors, and enabled ultrasensitive detection of tumor‐relevant circulating free DNA (cfDNA) with sensitivity enhancement of 3–5 orders of magnitude and improved dynamic range.     

{Nb288O768(OH)48(CO3)12}: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms

A protein‐sized (ca. 4.2×4.2×3.6 nm³) non‐biologically derived molecule {Nb₂₈₈O₇₆₈(OH)₄₈(CO₃)₁₂} ( Nb₂₈₈ ) containing up to 288 niobium atoms has been obtained, which is by far the largest and the highest nuclearity polyoxoniobate (PONb). Particularly, in terms of metal nuclearity number, Nb₂₈₈ is the second largest cluster so far reported in classic polyoxometalate chemistry (V, Mo, W, Nb, and Ta). Nb₂₈₈ can be described as a giant windmill‐like cluster aggregate of six nanoscale high‐nuclearity PONb units {Nb₄₇O₁₂₈(OH)₆(CO₃)₂} ( Nb₄₇ ) joined together by six additional Nb ions. Interestingly, the 47‐nuclearity Nb₄₇ units generated in situ can be isolated and bridged by copper complexes to form an inorganic–organic hybrid three‐dimensional PONb framework, which exhibits effective catalytic activity for hydrolyzing nerve agent simulant of dimethyl methylphosphonate. The unique Nb₄₇ cluster also provides a new type of topology to very limited family of Nb‐O clusters.     

超声辐照引发MMA微乳液聚合

研究了超声波引发甲基丙烯酸甲酯(MMA)的微乳液聚合.辐照40min时单体转化率高达90%.透射电镜观察发现,PMMA微乳液平均粒径为36.5nm,粒径分布窄,表明超声波引发是制备PMMA微乳液的有效方法.采用分光光度计对微乳液聚合过程中乳胶粒的形成和大小进行了间接表征,研究了超声功率输出、乳化剂、助乳化剂、单体和引发剂对MMA微乳液聚合的影响.     

强聚电解质对离子型芘衍生物探针的键合

由于芘单线态寿命长 ,单体态发射光谱精细结构对微环境极性敏感 ,在特定的环境下能形成激基缔合物 ,而且可作为非辐射能量转移过程的受体 ,因而被广泛应用于水溶性聚合物的研究 [1～ 3] .芘微溶于水 ,可以作为自由“探针”加入体系探测环境极性的变化与疏水微区的形成 .而离子型的芘衍生物由于良好的水溶性 ,可以同相反电荷的聚电解质发生静电键合 ,最近已经被用来研究聚电解质多层膜的结构 [4 ] .但是芘的离子衍生物同聚电解质键合的规律还不是十分清楚 ,例如聚电解质的电荷密度和化学结构对键合的影响 ,尤其是键合的化学计量关系 ,这对芘…     

铕(Ⅲ)荧光增敏体系在微乳液中的发光性质和荧光衰减动力学研究

利用稳态和瞬态光谱方法研究了不同铕离子发光体系中各种因素对铕离子发光性质的影响.通过吸收和激发光谱的变化分析了稀土离子Gd³⁺对Eu³⁺增敏机理,并从荧光衰减动力学角度证明了主配体噻吩甲酰三氟丙酮(TTA)、协配体邻啡咯啉(Phen)、稀土离子Gd³⁺和表面活性剂TX-100对铕离子发光的增敏作用.4种发光体系Eu³⁺/Gd³⁺/TTA/Phen/TX-100,Eu³⁺/TTA/Phen/TX-100,Eu³⁺/Gd³⁺/TTA/Phen和Eu³⁺/Gd³⁺/TTA/TX-100中铕离子⁵D₀态的发光寿命依次为980>670>400>260μs,而且存在铕离子⁵D₁到⁵D₀的传能过程.在发光越强的体系中,⁵D₁的衰减越慢,相应地⁵D₀的上升时间也就越长.研究结果表明,在最佳发光体系中既存在分子内的能量转移,又存在分子间的能量传递.     

抗癌药物柔红霉素的光谱电化学研究

采用现场光谱电化学技术,结合循环伏安和红外光谱等手段,研究了柔红霉素的电极过程,并提出了可能的还原机理.结果表明,柔红霉素的还原途径与其浓度存在一定的联系:稀溶液的还原经历一ECE过程--得到两个电子还原为柔红霉氢醌后,发生化学反应脱去7位上的糖基侧链,得到的7-去氧柔红霉醌继续被还原,生成的自由基中间体可发生歧化反应或通过分子间缔合而稳定;当溶液浓度较大时,柔红霉素分子在得到一电子生成半醌自由基中间体后,以其双分子缔合物的形式稳定存在.     

多单体接枝聚丙烯对PBT/PP共混体系的形态结构及力学性能影响研究

研究了甲基丙烯酸缩水甘油酯 (GMA)和苯乙烯 (St)多单体熔融接枝聚丙烯 (PP g (GMA co St) )对聚对苯二甲酸丁二酯 (PBT) 聚丙烯 (PP)共混物的形态结构和力学性能的影响 .利用双螺杆挤出机对PBT PP合金进行共混挤出 ,使用DSC、FT IR和SEM、TEM等手段对共混物进行了分析和相形态观察 ,并测试了力学性能 .实验证明 ,熔融共混过程中PP g (GMA co St)的环氧基团可以与PBT的端羧基发生化学反应 ,就地生成了PBT g PP共聚物 ,该共聚物可对PBT PP合金起到良好的增容剂作用 ,使共混物的相区尺寸显著减小 ,共混物的拉伸强度和冲击强度等力学性能同时得到明显改善 ,达到了弹性体系或小分子增容所难以达到的力学性能平衡的效果 .此外 ,TEM的研究还在PBT PP g (GMA co St)共混物中发现了特殊的微相分离结构     

两种含氟三氮烯显色剂FNDAA与FFDAA的合成及其与镉显色反应的研究

报道了两种新显色剂 4 氟 4′ 硝基苯基重氮氨基偶氮苯 (FNDAA)和 4 氟 4′ 氟苯基重氮氨基偶氮苯 (FFDAA)的合成、性质及其与Cd(Ⅱ )的显色反应。在弱碱性介质中 ,TritonX 10 0存在下两种试剂均与Cd(Ⅱ )形成络合比为 3∶1的橙红色络合物。对FNDAA ,ε4 92 =1.5 4× 10 5 L·mol- 1·cm- 1,对FFDAA ,ε4 90 =1.17× 10 5 L·mol- 1·cm- 1。镉量分别在 0 15和 0 2 5 μg/2 5ml范围内遵守比耳定律。FNDAA有较好的选择性 ,用于测定环境水标样中镉含量 ,结果满意。     

New diterpenoid glucosides from Siegesbeckia pubescens

Plants of the genus Siegesbeckia are annual herbs widely distributed in tropical and temperate zones and they are used as a traditional medicine to treat rheumatic arthritis, hypertension, malaria, neurasthenia and snake-bite in China. In previous papers, we reported on five new ent-kaurane and ent-pimarane diterpenoids, siegesbeckioside, siegesbeckiol and siegesbeckic acid1, orientalin A and B, and eight know compounds2,3. The present paper describes the isolation and structural elucidation …