聚酰胺-胺树形分子的合成及其包覆的CdSe@CdS核壳结构量子点的性能研究

以乙二胺和丙烯酸甲酯为原料,采用扩散法合成了不同端基类型不同代数的聚酰胺-胺(PAMAM)树形高分子,并用红外光谱进行表征;以G5.0-NH2 PAMAM树形高分子为模板,以二甲基亚砜为溶剂,在常温下制备了稳定的PAMAM树形高分子包覆的CdSe@CdS核壳结构量子点,并用紫外-可见吸收光谱和荧光发射光谱进行表征。结果表明,适当厚度CdS的包覆修饰可以有效提高CdSe量子点的发光性能;与单一组分的CdSe量子点相比,CdSe@CdS核壳结构量子点的相对荧光强度最大提高约123 %。     

巯基乙胺为稳定剂制备水溶性荧光量子点的合成探究

本文用巯基乙胺作为稳定剂分别利用了水相加热回流法、水热法两种方法制备出CdTe水溶性荧光量子点。这种荧光量子点可溶于水,且根据其特性可调控发射波长,发光性能较好。同时本文亦研究了在合成CdTe荧光量子点的过程中其反应温度、反应时间,pH环境等对于CdTe量子点发光性能的影响,以此甄选出最优化的量子点合成条件。     

CdTe量子点与蛋白质相互作用的荧光猝灭效应

本文在水热法合成水溶性CdTe及核壳结构CdTe/CdS量子点的基础上,分别研究了细胞色素c对CdTe量子点及CdTe/CdS核壳量子点荧光的猝灭效应和CdTe量子点对牛血清白蛋白荧光的猝灭效应,并阐述了猝灭机理。结果显示,细胞色素c对CdTe量子点的荧光猝灭效应具有一定的粒径依赖性,粒径越小,猝灭效应越强;细胞色素c对CdTe/CdS核壳量子点的猝灭效应比对CdTe量子点的更强,揭示了受激电子的表面传递机理。CdTe量子点通过松散牛血清白蛋白的螺旋结构而猝灭其荧光。     

CdTe量子点的纯化以及作为pH探针的研究

以巯基乙酸为稳定剂在水相中合成了CdTe量子点,并将合成的CdTe量子点进行表征、纯化。通过用0.05 mol.L-1PBS缓冲溶液调节不同的pH来考察量子点的荧光强度和pH的关系。研究发现,水溶性的CdTe量子点是pH敏感的,随着pH值的降低,量子点荧光强度的下降规律与溶液pH值呈现良好的线性关系。结果表明,CdTe量子点是一个令人满意的pH敏感的探针,有潜在的化学和生物传感能力。     

PAMAM树状大分子模板法合成CdSe量子点及其发光性质的研究

以聚酰胺-胺(PAMAM)树状大分子为模板合成了CdSe量子点,X-射线粉末衍射(XRD)分析表明产品与闪锌矿结构的CdSe晶体的标准粉末衍射花样的3个强峰位置相同,透射电镜(TEM)分析显示CdSe量子点包裹在树状大分子孔隙中,分散良好.实验表明以2.5 G和3.5 G PAMAM为模板合成的产品没有检测到荧光发射,而以4.5 G PAMAM树状大分子为模板制备的产品在410～465 nm范围内有较强的荧光发射,其发光波长随反应温度改变.     

巯基丙酸还原TeO_2水相一步法合成CdTe/ZnTe核壳型量子点

以TeO2为碲源,巯基丙酸(MPA)为稳定剂和还原剂,采用微波辅助加热法一步合成水溶性CdTe/ZnTe核壳结构的半导体量子点。考察了Cd/Zn反应物配比及MPA用量对CdTe/ZnTe量子点性能的影响,并用紫外、荧光光谱、高分辨透射电子显微镜(HRTEM)、X射线粉末衍射(XRD)光谱和EDX电子能谱对CdTe/ZnTe进行了表征。结果表明,在不需要另加NaBH4的条件下,同样能合成水溶性的CdTe/ZnTe量子点,且该核壳结构的CdTe/ZnTe量子点比单一的CdTe量子点具有更高的荧光量子产率。     

水溶性CdTe量子点的制备和表面修饰及表征

近年来,半导体纳米晶CdTe引起人们越来越多的关注。它具有吸收光谱宽,发射光谱窄而对称,发光颜色可调,荧光强度和光稳定性高等特点,已经广泛用于生物标记,生物传感及生物检测领域。尤其在基于荧光共振能量转移原理的生物传感领域,量子点有望取代有机荧光发色基团作为能量供体。在文章实验中,以巯基丙酸(MPA)作为稳定剂,在水相中合成了CdTe量子点,并考察了回流时间,反应温度,溶液pH对CdTe光学性质的影响。利用透射电子显微镜(TEM),荧光分光光度计(FS)等手段对产物进行分析和表征。结果表明:在pH为9.1,反应温度为30℃,回流5 h,可以实现CdTe的优化合成。在紫外灯(254 nm)照射下,回流时间从1 h到7 h所得到的CdTe量子点,颜色由绿色变到黄色,对应的荧光光谱图的吸收峰位从515 nm(回流1 h)红移到573 nm(回流7 h),证实了CdTe量子点的尺寸随着回流时间的增长而增加。由TEM结果,所合成的CdTe量子点分散性好,且粒径大约在5 nm左右。该本实验制备的CdTe量子点具有较高的荧光强度和量子效率,将在生物标记,生物传感,生物成像等领域有重要作用。     

CdTe/CdS核壳型量子点的水相合成与荧光性质研究

在水相中制备了不同壳层厚度的核壳型半导体CdTe/CdS量子点,通过荧光光谱(PL)分析、原子力显微镜(AFM)和X-射线粉末衍射 (XRD)光谱分析对产物进行了表征.实验结果表明:反应时间、温度、硫化钠浓度和NaOH的量对CdTe/CdS量子点的壳层厚度和荧光强度都有很大影响.     

巯基丙酸还原TeO2水相一步法合成CdTe/ZnTe核壳型量子点

以TeO2为碲源,巯基丙酸（MPA）为稳定剂和还原剂,采用微波辅助加热法一步合成水溶性CdTe/ZnTe核壳结构的半导体量子点.考察了Cd/Zn反应物配比及MPA用量对CdTe/ZnTe量子点性能的影响,并用紫外、荧光光谱、高分辨透射电子显微镜（HRTEM）、X射线粉末衍射（XRD）光谱和EDX电子能谱对CdTe/ZnTe进行了表征.结果表明,在不需要另加NaBH4的条件下,同样能合成水溶性的CdTe/ZnTe量子点,且该核壳结构的CdTe/ZnTe量子点比单一的CdTe量子点具有更高的荧光量子产率.     

以谷胱甘肽修饰的CdTe量子点为荧光探针测量超痕量As(Ⅲ)

以谷胱甘肽(GSH)为稳定剂,在水相中制备了CdTe量子点,基于As3+离子对量子点荧光的淬灭作用,建立了定量测定As3+离子的方法。CdTe量子点对As3+离子呈现出高选择性,其它常见金属离子的存在对铜的测定几乎不产生干扰。考察了不同反应时间和不同价态砷等因素对CdTe量子点的影响,量子点的相对荧光强度与As3+离子的浓度呈很好的线性关系,该方法的线性范围为0.2~2·2μM,检出限为20 nM。本方法简单、快速,与文献报道的其它基于量子点荧光探针As3+离子分析方法相比,此法对As3+离子呈现出更高的选择性。将此法用于实际废水中As3+离子含量的测定,结果令人满意。     

以石墨烯为核树状大分子包覆Co纳米复合材料制备及其吸附性能研究

通过化学还原法制备了以石墨烯为核树状大分子包覆Co纳米复合材料。利用FTIR、TG、XRD和TEM对所制备产物进行了结构表征。考察了不同p H、吸附时间和温度条件下,制备的以石墨烯为核第三代数树状大分子纳米复合材料(G3.0-PAMAM/Co)对刚果红吸附效果的影响。结果表明,G3.0-PAMAM/Co对刚果红是强有力的磁性吸附剂;对刚果红的吸附动力学能符合Lagergren准二级吸附模型,主要为化学吸附;吸附热力学能符合Langmuir等温吸附模型,最大吸附量可达161.49 mg/g。     

端氨基树枝状大分子/环氧树脂体系固化动力学的FTIR研究

用傅立叶变换红外光谱(FTIR)法研究了双酚A二缩水甘油醚环氧树脂(GEBA)用低代端氨基聚(酯-胺)树枝状大分子G1.0(NH2)3、G1.5(NH2)8和聚(胺-酰胺)树枝状大分子PAMAM1.0(NH2)4作为固化剂的等温固化动力学,得到了不同温度下转化率与固化时间及反应速率与固化时间的关系.与小分子固化剂相比,端氨基树枝状大分子作固化剂时环氧基转化率在反应开始时增长得更快,较高代树枝状大分子在高温下固化环氧树脂时尤其如此.在相同温度和时间下,PAMAM1.0(NH2)4/DGEBA、G1.0(NH2)3/DGEBA、G1.5(NH2)8/DGEBA体系的转化率依次增大.进一步估算了3个体系在一定转化率下的固化反应表观活化能.在相同转化率时,用G1.5(NH2)8、PAMAM1.0(NH2)4、G1.0(NH2)3作固化剂的体系表观活化能依次减小.     

聚氧乙烯链封端的聚酰胺-胺树状聚合物的合成与表征

采用酰氯法,用丙烯酰氯和不同相对分子质量的聚乙二醇为原料,制备出一系列具有丙烯酰端基的聚氧乙烯大单体(PEO-A)。实验证明,较佳的原料摩尔比n(PEG)∶n(CH2CHCOCl)∶n〔(CH3CH2)3N〕=2∶1∶1。然后以聚氧乙烯大单体为端基改性剂,在氮气保护下50℃四氢呋喃溶液中分别与G1.0～G4.0聚酰胺-胺树状聚合物进行Michael加成反应96h,合成出了聚氧乙烯(PEO)链封端的非离子型聚酰胺-胺树状聚合物,并用傅立叶变换红外光谱(FTIR)、核磁共振波谱(1HNMR,13CNMR)对其组成和结构进行了表征。     

Polyamidoamine dendrimers as curing agents: The optimum polyamidoamine concentration selected by dynamic torsional vibration method and thermogravimetric analyses

Polyamidoamine (PAMAM) dendrimers were investigated as curing agents in bisphenol A epoxy resin systems. The cure behavior of epoxy resin/PAMAM at varying components was investigated by a dynamic torsional vibration method (DTVM); the thermal behavior of the materials was characterized by means of thermogravimetric (TGA) analyses. The DTVM results show that 10/100 parts of the resin (phr) PAMAM was the optimum concentration for 1.0, 3.0, and 5.0 G PAMAM dendrimers/resin systems in our experiment. Also, the TGA results agreed with the conclusions made by the DTVM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1430–1434, 2007     

PAMAM树状大分子负载和释放阿霉素的耗散粒子动力学模拟

采用耗散粒子动力学模拟方法研究了药物输送载体聚酰胺-胺（PAMAM）树状大分子对抗癌药物阿霉素（DOX）的负载和释放行为。构建了PAMAM树状大分子的粗粒化模型,该模型能准确地重现树状大分子的构象性质。考察了PAMAM树状大分子代数（G）对DOX负载以及pH环境对DOX释放的影响。模拟结果表明,PAMAM树状大分子主要通过疏水作用将DOX包封于内部空腔,G6和G7 PAMAM树状大分子的负载能力较强,因为其孔隙率较高,内部有更多的疏水空腔。在低pH环境下,PAMAM树状大分子结构发生变化,DOX分子能快速地从其中释放,主要原因是PAMAM的伯胺、叔胺和DOX伯胺发生质子化,质子化基团间的静电排斥作用使得PAMAM树状大分子发生溶胀,导致其内部空腔暴露,促进了DOX的释放。本工作可以为基于树状大分子的药物输送体系的设计和优化提供参考。     

A study of antimicrobial property of textile fabric treated with modified dendrimers

Dendrimers have been used as a vehicle to develop the antimicrobial properties of textile fabrics. We have taken advantage of the large number of functional groups present in the regular and highly branched three‐dimensional architecture of dendrimers. In this study, the poly(amidoamine) (PAMAM) G‐3 dendrimer was modified to provide antimicrobial properties. Following a procedure similar to what is suggested in the literature, PAMAM (G3) with primary amine end groups was converted into ammonium functionalities. The modification was then confirmed by FTIR and ¹³C‐NMR analysis. Dendrimers have unique properties owing to their globular shape and tunable cavities, this allows them to form complexes with a variety of ions and compounds; and also act as a template to fabricate metal nanoparticles. AgNO₃–PAMAM (G3) complex as well as a MesoSilver–PAMAM (G3) complex were formed and these modified dendrimers were characterized by a UV–Visible spectrophotometer to study the complex formation. Modified dendrimers were applied to the Cotton/Nylon blend fabric. SEM and EDX analysis were performed to study the dispersion of silver nanoparticles onto the fabric. An antimicrobial test of the treated‐fabric against Staphylococcus aureus exhibited significant biocidal activities for each type of modified‐dendrimer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Studies on the complexation between generation‐4.5 methyl ester‐terminated poly(amidoamine) dendrimer and Pd2+ ions in methanol

Poly(amidoamine) (PAMAM) dendrimers have attracted attention because of their well‐defined molecule structures and chemical versatility, which also complicate the mechanism of interactions between metal ions and PAMAM dendrimers. To further understand the complexation of dendrimers with metal ions, the interactions between Pd²⁺ ions and G4.5‐COOCH₃ PAMAM dendrimers were investigated by UV‐vis and FTIR spectrophotometric method. The results show that the addition of K₂PdCl₄ results in covalent attachment of the PdCl alcoholysis product of this complex to tertiary amines within the dendrimers under the appropriate conditions. This process was also supported by X‐ray photoelectron spectroscopy data of the new complex which indicated a 1 : 3 Pd/Cl ratio. The maximum loading of 80 Pd²⁺ ions within the G4.5‐COOCH₃ dendrimers and the best pH value of 8.3 for complexation system are also obtained. Details regarding the Pd species present in solution of different chemical environments are reported. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

星型聚合物破乳剂的合成与性能研究

采用“发散法”合成了以乙二胺为核心 1 0～ 3 0代的系列星型聚合物—聚酰胺 -胺(PAMAM)。采用IR、NMR和端基分析等手段对PAMAM的结构进行了表征并考察了这类聚合物对O/W型模拟原油乳液的破乳性能。结果表明 :随着支化代的增加 ,破乳性能提高。在 4 5℃、添加量为 15 0mg/L、90min的条件下 ,3 0代产品的破乳率达到 98 5 %。     

聚酰胺-胺／硫化铋复合纳米粒子的制备及其生物相容性研究

以聚酰胺-胺（PAMAM）为模板制备了粒度可控的聚酰胺-胺／硫化铋（PAMAM／Bi2S3）复合纳米粒子,所得复合纳米粒子用紫外可见吸收光谱（UV-Vis）和高分辨透射电镜（HRTEM）等手段进行表征。结果表明,以酯基为端基的半代树形聚合物（Gn.5）制备的PAMAM／BizSa复合纳米粒子分散比较均匀,粒度很小,并且粒径可通过调节实验条件（如铋源种类、PAMAM的端基性质、硫化钠浓度、反应温度、反应物配比、PAMAM的代数等）进行调控。细胞培养实验表明,G5．5PAMAM／Bi2S3复合纳米粒子无细胞毒性,可以应用于CT造影荆等生物领域。     

Novel Poly(EThyleneAmidoAmine) (PETAA) dendrimers produced through a unique and highly efficient synthesis

Polyamidoamine (PAMAM) dendrimers have unique attributes that have led to their use in a wide variety of biomedical applications. However, the complex synthesis of this polymer leads to variations in the structure and consistency of the final product, and makes scale-up of manufacturing difficult. This has limited the clinical translation of PAMAM-based materials. Here we describe a rapid and highly efficient two-step method for the synthesis of novel Poly(EThyleneAmidoAmine) (PETAA) dendrimers that have many of the favorable characteristics of PAMAM dendrimers. Generation 0 (G0) to 5 (G5) PETAA dendrimers were synthesized using a 3-(bis(2-(2,2,2,-trifluoroacetamido)ethyl)amino)propanoic acid AB₂ (compound 1) building block via a divergent approach. An ethylenediamine core was coupled with the AB₂ building block via O-(7-Azabenzotriazol-1-yl)N,N,N’,N’-tetramethyluronium hexafluorophosphate (HATU) in the presence of diisopropylethyl amine to give a G0 trifluoroacetamide surface dendrimer. The G0 amine surface dendrimer was then obtained by treating the G0 trifluoroacetamide surface dendrimer with potassium carbonate. Repetitions of these two coupling/deprotection reactions were then used to build the dendrimer by coupling the surface amino groups to the carboxyl moiety of the AB₂ building block, followed by the deprotection step with potassium carbonate. The resulting PETAA dendrimers have the same number of surface primary amino groups, the same number of chemical bonds between the dendrimer core and the surface, and the same number of tertiary amino groups throughout the structures as similar generations of PAMAM dendrimers. In contrast, the structure of the PETAA dendrimers is more complete and more uniform than PAMAM dendrimers, especially at higher generations. This unique synthetic process for PETAA dendrimers also offers the potential for large-scale production, therefore providing inherently more uniform and complete structures for exacting biomedical applications.