稀世之宝—铂*

铂是一种化学性质极其稳定的贵金属,铂、铂合金以及铂配合物在催化剂、医药、传感器等领域具有重要应用。简要介绍铂的发现史、自然分布与资源现状、铂的应用等3个方面,其中铂的应用,重点从铂基催化剂、铂合金纳米材料、发光铂配合物、铂类抗癌药物等4个方面展开介绍。     

弛豫对光磁共振实验的影响

研究了弛豫对光磁共振实验的影响,弛豫过程影响粒子的分布,进而影响光抽运信号以及光磁共振信号的观测,但是对g因子的测量几乎没有影响。本文的研究结果将会加深对光磁共振实验及仪器工作原理的认识。     

烟草热解残余物中自由基的分析

使用顺磁共振波谱技术研究了烟草热解残余物中自由基的形成及其在环境中的转化。研究结果表明:烟草热解时会在其残余物上形成大量自由基。热解温度较低时(400~500℃)主要形成以O原子为中心的自由基,而热解温度较高(600~700℃)时,主要形成以C原子为中心的自由基。烟草热解残余物与空气接触后,会生成新的以O原子为中心的自由基,从而使自由基数量在短时间(60~120 min)内增加,随后自由基数量和种类趋于稳定,并可长期存在于环境中。     

新型生物相容性大分子磁共振成像造影剂的性质研究

将天冬氨酸与亮氨酸反应,合成了天冬氨酸-亮氨酸共聚物(PL),通过乙二胺将钆-1,4,7,10-四氮杂环十二烷-1,4,7,10-四乙酸(Gd-DOTA)连接到PL上,制备了大分子磁共振成像造影剂PL-A2-DOTA-Gd,通过核磁碳谱、凝胶色谱等方法对其结构进行了表征,利用细胞毒性实验、溶血性实验、体外弛豫效率测定以及体内动物磁共振成像等方法对其性能进行了评估。研究表明,PL-A2-DOTA-Gd的细胞毒性远低于临床应用的造影剂Gd-DOTA,且其弛豫效率(15.3 L/(mmol·s))是Gd-DOTA(5.8 L/(mmol·s))的2.6倍。大分子磁共振成像造影剂PL-A2-DOTA-Gd具有良好的血液相容性,对昆明小鼠的肝脏信号的增强效果约为Gd-DOTA的3.1倍,且能在较长时间内保持良好稳定的增强效果。     

顺铂前药接枝修饰硫代DNA及其自组装靶向纳米药物研究

选用具有良好生物相容性的硫代修饰嵌段核酸为载体,将其非硫代修饰部分设计为靶向MUC-1蛋白的核酸适配体序列,同时在其硫代修饰部分通过硫代磷酸酯基团（Phosphorothioate,PS）接枝修饰四价顺铂前药,制备了两亲性核酸-顺铂前药缀合物MUC-1/^PODNA-b-（^PSDNA-g-Pt）,并进一步自组装成类似球形核酸（Spherical nucleic acid,SNA）的含铂靶向纳米药物（MUC-1/Pt-SNAs）.结果表明,该纳米药物递送体系载药率高、形貌稳定、分散性好,能够高效靶向MUC-1蛋白过表达的MCF-7乳腺癌细胞,并在体内外实验中表现出优异的抗肿瘤效果和极低的毒副作用.     

部分还原二氧化钛的NMR和EPR研究

Partially reduced TiO₂ nanomaterials have attracted significant interest because of their visible-light activity for catalysis and photodegradation. Herein, we prepared a partially reduced anatase TiO₂ (Re-A-TiO₂) nanoparticle material using a fast combustion method, demonstrating good activity toward decomposing methyl orange under visible light irradiation. The surface structure of the prepared material, after being surface-selectively ¹⁷O-labeled with H₂¹⁷O (¹⁷O-enriched water), was studied via ¹⁷O and ¹H solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and electron paramagnetic resonance (EPR) spectroscopy, and the obtained results were compared to those of non-reduced anatase TiO₂ (A-TiO₂). The EPR results showed that the concentrations of paramagnetic species (i.e., oxygen vacancies (OV) and Ti³⁺) in Re-A-TiO₂ were much higher than that in A-TiO₂, while the former was associated with a higher OV/Ti³⁺ ratio. The intensities of the EPR signals were significantly affected by the adsorbed water, and this phenomenon was explored in combination with ¹H NMR spectroscopy. The ¹H species on Re-A-TiO₂ appeared at larger chemical shifts, denoting the increased acidity of the sample, and these ¹H species on Re-A-TiO₂ were more difficult to remove than those on A-TiO₂. On the other hand, different features were observed for the signals arising from the two-coordinated oxygen atoms (μ₂-O) in ¹⁷O NMR, suggesting a typical anatase TiO₂(101) surface on A-TiO₂, but a more complex surface environment for Re-A-TiO₂. Furthermore, a larger amount of hydroxyl groups (OH) were observed on Re-A-TiO₂ compared to that on A-TiO₂, indicating a larger proportion of exposed (001) facets on Re-A-TiO₂. However, the μ₂-O signals broadened and became similar when the drying temperature was increased to 100 ℃, indicating a non-faceted anatase TiO₂ surface in such conditions. Based on the EPR and NMR results, a significant fraction of the OH species is believed to be formed from the reaction of the paramagnetic centers and adsorbed water molecules. The ¹H→¹⁷O cross polarization (CP) MAS and two-dimensional heteronuclear correlation (2D HETCOR) NMR spectra were used to verify the spatial proximity of the hydrogen and oxygen species, confirming the spectral assignments of a strongly adsorbed water and one type of surface OH species. In particular, the ¹H NMR signals at approximately 11 ppm were ascribed to the hydrogen species in the intramolecular hydrogen bond. In summary, this study investigated the paramagnetic species and surface structure of anatase TiO₂ materials by combining EPR along with ¹H and ¹⁷O solid-state NMR spectroscopy. The differences in the surface structures of Re-A-TiO₂ and A-TiO₂ should be closely related to their different properties toward the photodegradation of methyl orange.     

抗癌药物的先驱——顺铂

顺铂在人类抗癌历程中发挥着里程碑式的作用,本文重点介绍顺铂的作用机理、致毒机理和细胞对其产生耐药性的机理,并由此指出铂类药物所存在的缺陷以及发展方向。     

CdTe/Mn3 O4/SiO2荧光/磁共振双模成像纳米球的制备与表征

成功地制备了CdTe/Mn_3O_4/SiO_2核壳结构的荧光/磁共振成像双功能纳米球,并用透射电镜(TEM)、能谱分析(EDXA)、磁共振成像(MRI)、红外、荧光光谱等对其结构、磁共振成像和发光性能进行了表征。TEM照片显示所合成的纳米球具有明显的球形核壳结构。EDXA分析显示所制备的CdTe/Mn_3O_4/SiO_2纳米球表面只检测到Si和O元素,证明CdTe量子点和Mn_3O_4纳米立方体被成功地包被于二氧化硅纳米球之内。荧光发射光谱显示相对于CdTe量子点,CdTe/Mn_3O_4/SiO_2纳米球荧光发射光谱虽然发生了一定的蓝移,但是仍具有良好的荧光性能。MRI分析可知CdTe/Mn_3O_4/SiO_2纳米球的弛豫参数(r_1)为3.88 s~(-1)(mg·L~(-1))~(-1),说明所合成的CdTe/Mn_3O_4/SiO_2纳米球可用于T_1-加权磁共振成像。细胞毒性实验表明,当CdTe/Mn_3O_4/SiO_2溶液浓度达到300μg·mL~(-1)时,细胞活力仍可达到90%以上,表明此浓度对细胞的毒性作用较弱。     

脯氨酸类N-酰胺衍生物的核磁共振研究

脯氨酸类衍生物结构独特,鲜有报道利用核磁共振（nuclear magnetic resonance,NMR）技术对氨基酸的手性进行鉴别.利用多种NMR技术:1H NMR、1H-1H同核位移相关谱（1H-1H COSY）、1H-1H质子全相关谱（1H-1H TOCSY）、1H-1H核Overhauser效应谱（1H-1H NOESY）、13C NMR、无畸变的极化转移增强法（DEPT135°）、1H-13C检出1H的异核单量子相干（1H-13C HSQC）和1H-13C检出1H的异核多键相关（1H-13C HMBC）,对脯氨酸类N-酰胺衍生物两种构象异构体的1H和13C NMR进行了全归属,确定了室温下在二甲基亚砜（DMSO）中L型和D型的顺反异构体以相同的比例同时存在.