PAMAM修饰的六苯并蔻衍生物的合成及其光物理研究

设计合成了外围以0.5、1.5、2.5代聚酰胺-胺(PAMAM)树枝形聚合物修饰的六苯并蔻衍生物HBC-C₆-PAMAM-D_m(m=0.5, 1.5, 2.5), 化合物结构通过了¹HNMR、¹³CNMR、IR和MS的表征.测定了HBC-C₆-PAMAM-D_m在四氢呋喃、乙腈和二氯甲烷中的吸收和荧光发射光谱, 三种溶剂中不同代数的HBC-C₆-PAMAM-D_m均以聚集态形式存在,外围树枝形聚合物骨架与核心HBC发色团的振动耦合作用随代数增加而增强,导致HBC振动能级不均化,引起吸收和荧光光谱发生变化.     

Colorimetric Determination of Polyamidoamine Dendrimers and their Derivates using a Simple and Rapid Ninhydrin Assay

Abstract

A simple, accurate and rapid colorimetric method using ninhydrin reagent was developed for the determination of polyamidoamine (PAMAM) dendrimers (G4, G5, and G6) and their derivates in aqueous medium. This method was based on the interaction of the primary amino group of PAMAM dendrimers with ninhydrin reagent to form a blue‐colored product with λ_max at 570 nm. Beer's law was obeyed in the concentration range of 25–200 µg/ml of all the three investigated PAMAM dendrimers. The effects of experimental parameters such as reagent concentration and reaction time were studied to optimize the colorimetric method. Accuracy and precision of the colorimetric method were assessed by statistical analysis. Acetylated G5 PAMAM dendrimers with various acetylated rates were simultaneously measured by the described ninhydrin assay and NMR studies and the data obtained by the two methods approximately accorded with each other. Results showed that the suggested procedures were suitable for the determination of PAMAM dendrimers and their derivates in aqueous solutions with satisfactory accuracy and precision.     

激发态分子内质子转移(ESIPT)发色团修饰的树枝形聚合物合成及光物理研究

设计合成了0～4代外围修饰激发态分子内质子转移(ESIPT)发色团的聚酰胺-胺树枝形聚合物G0～G4,化合物结构经过IR,1H NMR,13C NMR和MS表征.稳态光谱研究表明,树枝形聚合物在四氢呋喃溶液中形成了聚集体,发色团酮式发光随着化合物代数增大呈先增加后减小的变化.质子化树枝形聚合物G1-H～G4-H能溶于水,并在水中形成20 nm左右的聚集体,发色团在聚集体疏水区中构象受限,仅发射酮式发光,并且发光强度受树枝形聚合物分子大小的影响.     

用于生物探测的PAMAM树形高分子增强免疫磁性微球

采用悬浮聚合的方法制备羧基修饰的聚苯乙烯磁性微球(CMM)，研究了CMM和CMM-PAMAM(第5代)两者与牛血清蛋白(BSA)的结合状况。结果显示；CMM与BSA的结合量为22.2μg／mg。PAMAM偶联在磁性微球表面后，提高了磁性微球表面官能团的密度，因而CMM-PAMAM(第5代)与BSA的结合量可达54．4μg／mg。     

以乙二胺为核心的聚酰胺-胺树形高分子的合成及毛细管电泳分离研究

在-30℃下合成了1．0G～6.0G聚酰胺．胺(PAMAM)树形高分子,并采用核磁共振、元素分析对其进行了表征;采用毛细管电泳对1．0GPAMAM进行了分离。结果表明：在该温度下合成的PAMAM具有较好的结构完整性,而毛细管电泳是一种有效的分离提纯PAMAM树形高分子的方法。     

聚酰胺-胺型树形分子模板法制备Pt纳米簇

利用紫外-可见吸收光谱和红外光谱对Pt2＋与G5.5-COOCH3聚酰胺-胺型树形分子的络合机理进行了研究, 结果表明Pt2＋与G5.5-COOCH3 PAMAM的最外层叔胺基发生络合作用, 但两者之间达到络合平衡需要较长时间, 且平衡时间随Pt2＋与树形分子物质的量比增大而增长; Pt2＋与G5.5-COOCH3树形分子的最大络合数为50～55; 采用硼氢化钠还原法原位制备了G5.5-COOCH3 PAMAM包裹、平均粒径小于2 nm、多晶的球形Pt纳米簇, 并研究了Pt2＋与PAMAM物质的量比对Pt纳米簇形貌的影响, 实验结果表明, Pt2＋与PAMAM物质的量比为10时, 生成尺寸较小分布较窄的内型Pt纳米簇/树形分子复合材料, 而物质的量比为50时, 会生成部分尺寸较大、分布较宽的外型Pt纳米簇/树形分子纳米复合材料.     

以PAMAM树形分子为模板制备Pd纳米簇合物

以酯端基聚酰胺-胺树形分子(PAMAM)为模板在甲醇溶剂中制备了Pd纳米簇合物. 采用紫外-可见分光光度法和红外光谱法研究了Pd²⁺与树形分子的作用机理, 结果表明, Pd²⁺与树形分子内部胺基基团(主要为叔胺基)产生了络合作用. 采用硼氢化钠还原法制备了树形分子包裹的、粒径为2 nm的球形面心立方Pd纳米簇合物. 紫外-可见吸收光谱研究结果表明, Pd²⁺与树形分子的摩尔比越小, 生成的纳米簇合物尺寸越小; 由于高代数树形分子具有封闭结构, 且其内部配体数目较多, 采用较高代数的树形分子(5.5代)比低代数(3.5代)更有利于得到尺寸小、分散性较好的Pd纳米簇合物.     

PAMAM树形分子对CaCO3结晶影响的研究

研究了不同端基的聚酰胺胺(PAMAM)树形分子对CaCO₃在水溶液中结晶的影响。分别利用傅立叶变换红外光谱(FTIR)、X-射线衍射(XRD)、扫描电镜(SEM)等测试手段对样品进行了分析。结果表明:没有树形分子存在时CaCO₃是粒径为10μm的菱形方解石晶体;端基为-COONa的树形分子存在时CaCO₃则是粒径为1～2μm的球形球霰石晶体;-COOCH₃端基PAMAM树形分子存在时得到的CaCO_{3相似文献}   

聚酰胺-胺树形分子对胶带上油潜指纹的显现研究

研究了不同pH值和光源波长条件下,荧光性聚酰胺-胺树形分子(PAMAM)水溶液对胶带粘面上油潜指纹的显现效果.结果显示:PAMAM树形分子水溶液pH值大于7时,指纹残留物被不同程度地溶解,因此显现效果不佳;pH值为4—7时,显现效果较好,处理过的指纹发出明亮的蓝色荧光,指纹纹路完整、特征明显,且与基底的对比度较高;但由于用365 nm紫外光激发时,PAMAM树形分子的蓝色荧光容易受胶带中杂质蓝色荧光的影响,因此对比度仅为28.8%左右;采用其它波段的可见光或者复合白光作为光源后,有效规避了胶带中杂质的同色系荧光干扰,指纹对比度可提高至90%,并且避免了紫外光使用过程中对人体的伤害.PAMAM树形分子水溶液是一种环保的、具有潜在应用价值的识别胶带粘面上油潜指纹的优良显现材料.     

纳米CdS/PAMAM G5.0显现胶带粘面油潜指纹应用

利用傅立叶红外光谱检测了聚酰胺-胺(PAMAM)G5.0显现液与油酸反应机理,以相对峰高比来观察不同反应条件下的反应情况,确定在120 ℃下反应2～3 h较好。以这种复合纳米材料为显现液,对犯罪现场3种常见胶带粘面上的油潜指纹进行显现,透明胶带上油潜指纹在420 nm下拍照,黑色电工胶带上油潜指纹在365 nm下拍照可得到很好的图像效果。将该显现材料的显现效果与现在常用罗丹明6G显现液的显现效果进行横向比较,以考察CdS/PAMAM G5.0在显现胶带粘面上油潜指纹方面起到的作用。CdS/PAMAM G5.0显现法同现有方法相比,对于常见胶带粘面上的油潜指纹具有理想的显现效果,其荧光强度、选择性吸附性能非常优异;长时间浸显后背景吸附小,与指纹纹线的反差大;指纹纹线流畅,显现细节特征能力强,其中对陈旧油潜指纹也有比较理想的显现效果;可以通过室光反射和紫外可见荧光两种形式成像,适用范围更广。一系列实验证明,CdS/PAMAM G5.0可以有效显出常见胶带粘面上的油潜指纹。     

Adhesive peptides conjugated PAMAM dendrimer as a coating polymeric material enhancing cell responses

This present work aims to functionalize poly(amidoamine) (PAMAM) dendrimers with various reported adhesive peptides, including Arg-Gly-Asp (RGD), Tyr-Ile-Gly-Ser-Arg (YIGSR), and Ile-Lys-Val-Ala-Val (IKVAV) for enhancing cell responses. The RGD, YIGSR, or IKVAV functionalized PAMAM coated substrate could promote cell adhesion of bone marrow mesenchymal stem cells (BMSCs) within 1 h after incubation. The neurite differentiation and proliferation of pheochromocytoma (PC12) cells were also significantly enhanced after culturing on the peptide functionalized PAMAM dendrimers for two and four days. This peptide functionalized PAMAM dendrimers are considered as the potential candidates for various tissue engineering applications.     

Interaction of G-quadruplex Forming DNA Aptamers with PAMAM Dendrimers Studied by Dynamic Light Scattering and UV-VIS Spectrophotometry**

The complexes of G-quadruplex forming DNA thrombin binding aptamers (TBA) and polyamidoamine dendrimers (PAMAM) were studied with the aim to form a model targeted drug delivery system. Hydrodynamic diameter, zeta potential and melting temperature (T_m) were investigated by dynamic light scattering and UV-VIS spectrophotometry. Non-covalent adsorption by means of electrostatic interaction between positively charged amino groups of dendrimers (+) and negatively charged phosphate groups of aptamers (−) has driven the formation of aggregates. The size of complexes was in the range of 0.2–2 μm and depended on the type of dispersant, charge ratio (+/−) and temperature. Raising the temperature increased the polydispersity, new smaller size distributions were observed indicating the G-quadruplex unfolding. The melting transition temperature of TBA aptamer was affected by the presence of amino-terminated PAMAM rather than carboxylated succinic acid PAMAM−SAH dendrimer, thus supporting the electrostatic nature of interaction that disturbed denaturation of target-specific quadruplex aptamer structure.     

Poly (Ethylene Glycol)‐Based Hydrogels as Self‐Inflating Tissue Expanders with Tunable Mechanical and Swelling Properties

Tissue expansion is used by plastic/reconstructive surgeons to grow additional skin/tissue for replacing or repairing lost or damaged soft tissues. Recently, hydrogels have been widely used for tissue expansion applications. Herein, a self‐inflating tissue expander blend composition from three different molecular weights (2, 6, and 10 kDa) of poly (ethylene glycol) diacrylate (PEGDA) hydrogel with tunable mechanical and swelling properties is presented. The in vitro results demonstrate that, of the eight studied compositions, P6 (PEGDA 6 kDa:10 kDa (50:50)) and P8 (PEGDA 6 kDa:10 kDa (35:65)) formulations provide a balance of mechanical property and swelling capability suitable for tissue expansion. Furthermore, these expanders can be compressed up to 60% of their original height and can be loaded and unloaded cyclically at least ten times with no permanent deformation. The in vivo results indicate that these two engineered blend compositions are capable to generate a swelling pressure sufficient to dilate the surrounding tissue while retaining their original shape. The histological analyses reveal the formation of fibrous capsule at the interface between the implant and the subcutaneous tissue with no signs of inflammation. Ultimately, controlling the PEGDA chain length shows potential for the development of self‐inflating tissue expanders with tunable mechanical and swelling properties.