Photodynamic therapy based on organic small molecular fluorescent dyes

This review aims to provide a summary of the progress in organic small molecular fluorescent dyes for photodynamic therapy in recent years and it is classified according to the structures of dyes including cyanines, phthalocyanine, BODIPYs and other agents.     

C2H4-K体系中振动态至电子态传能的研究

用TEA CO_2激光将C_2H_4分子激发到高振动激发态，高振动激发态的C_2H_4分子与基态的K原子碰撞发生振动态→电子态（V→E）传能过程，根据提出的能级组模型，对测得的时间分辨原子荧光信号进行处理，获得温度在453－663 K范围内，C_2H_4-K体系中V→E传能速率的数量级为10~(-10)/cm~3·molecule~(－1)·s~(－1)，对应的碰撞传能截面约为0.30～0.80 nm．随着反应温度升高，V→E传能截面减小．上述实验结果表明碰撞体间吸引相互作用在这种非共振的V→E传能过程中起主要作用．利用多极相互作用势下的碰撞络合物模型对实验结果进行了讨论．     

Quinolone Antibiotic Photodynamic Production of 8-Oxo-7,8-dihydro-2'-deoxyguanosine in Cultured Liver Epithelial Cells

To study the basis for the phototoxicity of quinolones, a class of synthetic antibacterials, the photodynamic ability to mediate 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxo-dG) formation in cultured cells was measured for lome-floxacin (LMX), which is strongly associated with clinical phototoxicity in humans, and ciprofloxacin (CFX), which has few reports of phototoxicity. Adult rat liver (ARL-18) cells were exposed to the quinolones in the presence of UVA and DNA was extracted and analyzed by HPLC with electrochemical detection. Low levels of 8-oxo-dG were found in the DNA of nonirradiated ARL-18 cells and this was increased up to 6-fold in the presence of either LMX (50–400 uAf) or up to 3.6-fold in the presence of CFX (50–400 µM) and UVA (20 J/cm²) when compared to the UVA control. Comparing separate experiments with LMX and CFX, LMX produced greater levels of 8-oxo-dG either after dark exposure or after UVA exposure at 20 J/cm². Also, LMX and CFX were both shown to photodegrade in the presence of UVA, and it was determined that UVA photoinstability alone does not reflect phototoxic potential. These data suggest that the photodynamic potential of LMX and CFX to produce 8-oxo-dG may relate to their human clinical phototoxicity profile. We suggest that the observed clinical phototoxicity is mediated through a UVA photodynamic effect on the quinolone to form reactive oxygen species in the presence of molecular oxygen. The findings indicate that 8-oxo-dG formation can serve as a marker for the potential phototoxicity of new quinolones.     

Photochemical and Photophysical Studies of 3-Amino-6-lodoacridine and the Inactivation of λ Phage

Abstract— The photochemistry and photophysics of 3-amino-6-io-doacridine (Acr-I) was studied. Photolysis (350 nm) of Acr-I (free base) generates products consistent with a free radical intermediate in methanol, benzene and carbon tetrachloride. The Acr-I hydrochloride is shown to bind to calf thymus DNA and to the self-complementary dinucleotide cytidylyl-(3′-5′)-guanosine (CpG) minidu-plex in a manner similar to that of proflavine (Acr-NH₂), a known DNA intercalator. The Acr-I is shown to more efficiently nick supercoiled plasmid DNA pBR322 upon 350 nm or 420 nm photolysis than Acr-NH₂. The efficiency of Acr-I-sensitized DNA nicking is not oxygen dependent. Photolysis of the Acr-I/(CpG)₂ complex leads to cleavage of the dinucleotide and to cytidine base release by selective damage to a specific ribose moiety. Dinucleotide cleavage occurs equally well in the presence or absence of oxygen, thereby eliminating a singlet oxygen- or peroxyl radical-mediated process. Photolysis of Acr-I in the presence of a mononucleotide (GMP) or a non-self-complementary dinucleotide (uridylyl-[3′-5′]-cytidine– UpC) does not lead to fragmentation and base release. Similarly, photolysis of the Acr-NH₂/(CpG)₂ complex does not lead to fragmentation and base release. The data indicate that photolysis of an iodinated intercalator bound to CpG or plasmid DNA generates an intercalated aryl radical and that the reactive intermediate initiates a sequence of reactions that efficiently nick nucleic acids. The inactivation of Λ phage sensitized by Acr-I with UV (350 nm) light is oxygen independent but with visible (420 nm) light is strongly oxygen dependent. The Acr-I fluoresces more intensely when excited at 446 than at 376 nm. Thus, UV photolysis may lead to C-I bond homolysis and free radical formation, a process that is not energetically feasible with visible light. The results demonstrate the difficulty of extrapolating model studies involving simple molecules and DNA to understanding the mechanism of viral inactivation with a particular sensitizer.     

利用差异衍生同步分析醛糖和酮糖

建立了一种可同时对醛、酮糖进行精确定性和定量分析的方法。以肌醇作为内标，用80％乙醇超声提取，利用醋酸酐和HMDS＋TMCS（1：3）进行差异衍生，在EI源下用SIM模式进行GC／MS分析。结果表明：11种标准单糖在1—4mg／L范围内线性良好；仪器检出限：醛糖在8．15—22．4μg／L之间；酮糖为2．32μg／L和3．47μg/L；高、中、低3个量的平均回收率在73．0％-95．7％，相对标准偏差在3．1％-10．0％。对枸杞游离单糖进行测定，各单糖含量分别在0．26—368．6mg／g。该方法弥补了以前单糖分析中的缺陷，对既含有醛糖又含有酮糖的样品可同时进行精确的定性定量分析。     

EFFECT OF La_2O_3 AND CeO_2 ON CH_4-CO_2 REFORMING NICKEL CATALYST

IntroductionConsiderableattelltionisno\vbeillgpaidtotheCO7refonningof.etha..llto]forseveralreasonst(l)withthedevelopmentofindustrics.moreandnlorcCOZIsabettedintotheatmosphere,leadingto"greenhouseeffect",whichhasbroughtaboutgreatilltcreslallovertheworld.Th…     

羧酸铜催化反应的研究——Ⅰ.羧酸铜催化醛肟转变为睛

本文报道了在多种羧酸铜催化下,醛肟在含有氰基的溶剂中(如CH_3CN、CH_3OCH_2CH_2CN等),均可脱水转变成相应的腈。反应条件温和,产率较高。具有不同空间和电性效应取代基的羧酸铜对反应的产率影响不大。实验中还发现溶剂乙腈参与了上述反应。     

磺酸型聚氨酯离聚物的离子导电性能

本文以多种聚醚为软段，二异氰酸酯（ＭＤＩ和ＴＤＩ）为硬段，合成了多嵌段聚醚聚氨酯，以此聚氨酯为基材，与ＮａＨ及１，３－丙碳酸内酯反应，进一步合成了一系列不同离子化程度的阴离子型碳化聚氨酯离聚物，用交流阻抗谱仪测定了样品的阻抗谱，由此计算出样品的离子电导率。研究结果表明其他条件相同时，以聚乙二醇（ＰＥＧ）为软段的样品具有较高的离子电导率；以聚环氧丙烷（ＰＰＯ）为软段的样品次之，以聚四氢呋喃（ＰＴＭＯ）为软段的样品最低，对于离子化程度不同的聚氨酯离聚物以金属离子和烷氧单元之比为０．０５时导电性能最好。阳离子为Ｌｉ＋和Ｎａ＋的样品具有相近的离子电导率。     

铁(III)卟啉催化β-胡萝卜素分解动力学研究

使用BeckmannDU-8B紫外可见分光光度计研究了以氯合四－间三甲苯基卟啉铁（Ⅲ）（FeTMPCl）为催化剂，间氯过氧化苯甲酸（mCPBA）为氧化剂，咪唑（I_m）、2－甲基咪唑（MeI_m）、2－乙基－4－甲基咪唑（EMI_m）为轴向配体，催化β-胡萝卜素（β－cte）氧化分解为维生素A的动力学规律，提出了反应机理，研究了温度、催化剂浓度、氧化剂浓度及轴向配体对反应速率的影响，应用Gauss－Newton－Marquardt方法求得各基元反应的有关动力学参数．     

CeO2—LnO1.5固溶体的表征及其甲烷催化燃烧性能

向CeO2中引入Ln3 离子后形成的CeO2－LnO1.5（Ln=La，Nd，Sm，Gd）固溶体（n（Ce）：n（Ln）=1：1）是一种无贵金属的新型高效甲烷燃烧催化剂．比表面、XRD、Raman、TEM等分析证实，这类固溶体具有部分畸变的萤石结构，Ln3 进入晶格后诱发的结构变化使得团溶体的表面和本体能同时参与氧化还原反应．实验表明，该固态溶液体系是甲烷催化燃烧的良好催化剂．