TiO2纳米颗粒对钌(II)三联吡啶配合物光损伤小牛胸腺DNA能力的影响

由于极短的激发态寿命, 钌(II)三联吡啶配合物对脱氧核糖核酸(DNA)的光损伤能力低下. 设计合成了三个钌(II)三联吡啶配合物[Ru(ttp)(tpy)]^2＋ (1), [Ru(ttp-COOH)(tpy)]^2＋ (2)和[Ru(ttp-COOH)(tpy-pyr)]^2＋ (3), 其中tpy为2,2':6',2"-三联吡啶, ttp为4′-(4-甲苯基)-2,2':6',2"-三联吡啶, ttp-COOH为4′-(4-羧基苯基)-2,2':6',2"-三联吡啶, tpy-pyr为4'-(1-芘基)-2,2':6',2"-三联吡啶. 比较了TiO₂纳米颗粒对它们光损伤小牛胸腺DNA的影响. 发现TiO₂纳米颗粒在空气和氩气条件下均可显著提高配合物3光损伤DNA的能力. TiO₂纳米颗粒和配合物3间的光诱导电子转移作用及其该作用生成的钌(III)物种可能是促进配合物3对DNA光损伤的主要原因.     

竹红菌乙素镁、锌配位聚合物的光物理和光生物性质

竹红菌乙素(HB)能与Mg2+和Zn2+形成重复单元数为5-20的配位聚合物(Mg2+-HB,Zn2+-HB),利用紫外-可见(UV-Vis)吸收光谱,傅里叶变换红外(FTIR)光谱,核磁共振氢谱(1H NMR)对其进行了表征.Mg2+-HB和Zn2+-HB的单重态氧量子产率分别为HB的1.2倍和0.42倍.瞬态吸收实验表明:氧气能够猝灭Mg2+-HB和Zn2+-HB的三重态,其效率可超过96％.系间窜越效率(φT)和将能量传递给氧气并能产生单重态氧的三重态光敏剂的比例(fT△)对HB及其金属配合物的单重态氧量子产率有较大影响.电子自旋共振(EPR)实验结果表明:Mg2+-HB和Zn2+-HB产生半醌负离子自由基的能力较弱,进而降低了Mg2+-HB和Zn2+-HB光敏产生超氧负离子自由基的能力.紫外-可见吸收光谱与小牛胸腺脱氧核糖核酸(CT DNA)熔链温度实验表明:Mg2+-HB和Zn2+-HB可通过静电作用与DNA结合.有氧条件下,Mg2+-HB,HB和Zn2+-HB对小牛胸腺DNA的光敏损伤效率分别为32％,25％和22％.活性氧猝灭实验表明Mg2+-HB主要通过单重态氧光敏损伤DNA.     

Fluorescence Polarization as a Functional Parameter in Monitoring Living Cells: Theory and Practice

The use of fluorescence polarization as a functional parameter in monitoring cellular activation calls for the reliable and accurate measurement of the fluorescence intensity and polarization (FI and FP) of microscopic objects. The relevant experimental parameters that enter such measurements are thoroughly discussed. The possibility of executing FP measurements properly by flow-through systems is compared with that of static cytometry. Remarks on the effects of high-power excitation on markers and cells conclude the paper.     

In:Er:LiNbO3晶体生长及光损伤性能研究

在LiNbO3晶体中掺入In2O3和Er2O3,利用提拉法生长了In:Er:LiNbO3晶体,获得了In和Er在晶体中的分凝系数.通过测试晶体的吸收光谱和抗光损伤能力,确定In:Er:LiNbO3晶体中In的掺杂阈值浓度为～3mol;,In(3mol;):Er:LiNbO3晶体的抗光损伤能力比Er:LiNbO3提高3个数量级以上.研究了In的掺入使Er:LiNbO3晶体的吸收边移动和抗光损伤能力提高的机理.     

Mechanistic Insight into the Photoinduced Damage of an Unnatural Base Pair

Chemical- and photostability of unnatural base pairs (UBPs) are important to maintain the genetic code integrity, and critical for developing healthy semisynthetic organisms. As reported, dTPT3 was less stable upon irradiation, and thus might act as a pervasive photosensitizer to induce oxidative damage within DNA, causing harm to living semi-synthetic organisms when exposed to UVA radiation. However, there was no knowledge about molecular-level understanding of this damage process. In this paper, we not only identified four photoproducts of dTPT3, including desulfur-dTPT3 (dTPT3^H), TPT3 sulphinate (TPT3^SO2), TPT3 sulphonate (TPT3^SO3) and TPT3-thioTPT3 (TPT3^STPT3), but also established a Type II photosensitized oxidation mechanism. In addition, the antioxidant (sodium ascorbate) was able to effectively inhibit the photoproducts formation of dTPT3 and dTPT3 in DNA, suggesting that a reductive environment might protect DNA bearing dTPT3 against UVA oxidation and ameliorate its adverse biological effects. The comprehensive understanding of TPT3’ photochemical stability will give researchers helpful guidance to design more photostable UBPs and construct healthier semisynthetic organisms.     

竹红菌素及其衍生物敏化的生物膜和DNA结构的光损伤的Raman光谱研究

本文综述了具有抗癌和抗艾滋病毒活性的三种光敏剂—竹红菌素及其衍生物敏化的生物大分子—生物膜和ＤＮＡ结构的光损伤的Ｒａｍａｎ光谱特征；上述三种光敏剂对ＤＮＡ和生物膜损伤最强的均为５－Ｂｒ－ＨＢ，其次是ＨＢ，然后是ＨＡ，即５－Ｂｒ－ＨＢ＞ＨＢ＞ＨＡ。说明药物的结构与它的光敏活性密切相关，修饰结构是增进药效的重要途径。     

Synthesis of a Photostable Near‐Infrared‐Absorbing Photosensitizer for Selective Photodamage to Cancer Cells

A new class of near‐infrared (NIR)‐absorptive (>900 nm) photosensitizer based on a phenothiazinium scaffold is reported. The stable solid compound, o‐DAP, the oxidative form of 3,7‐bis(4‐methylaminophenyl)‐10H‐phenothiazine, can generate reactive oxygen species (ROS, singlet oxygen and superoxide) under appropriate irradiation conditions. After biologically evaluating the intracellular uptake, localization, and phototoxicity of this compound, it was concluded that o‐DAP is photostable and a potential selective photodynamic therapy (PDT) agent under either NIR or white light irradiation because its photodamage is more efficient in cancer cells than in normal cells and is without significant dark toxicity. This is very rare for photosensitizers in PDT applications.