Polyvalent choline phosphate as a universal biomembrane adhesive

Phospholipids in the cell membranes of all eukaryotic cells contain phosphatidyl choline (PC) as the headgroup. Here we show that hyperbranched polyglycerols (HPGs) decorated with the 'PC-inverse' choline phosphate (CP) in a polyvalent fashion can electrostatically bind to a variety of cell membranes and to PC-containing liposomes, the binding strength depending on the number density of CP groups per macromolecule. We also show that HPG-CPs can cause cells to adhere with varying affinity to other cells, and that binding can be reversed by subsequent exposure to low molecular weight HPGs carrying small numbers of PCs. Moreover, PC-rich membranes adsorb and rapidly internalize fluorescent HPG-CP but not HPG-PC molecules, which suggests that HPG-CPs could be used as drug-delivery agents. CP-decorated polymers should find broad use, for instance as tissue sealants and in the self-assembly of lipid nanostructures.     

One-dimensional protein analysis of an HT29 human colon adenocarcinoma cell

A single HT29 human colon adenocarcinoma cell was introduced into a fused-silica capillary and lysed, and the protein content was fluorescently labeled with the fluorogenic reagent 3-(2-furoyl)quinoline-2-carboxaldehyde. The labeled proteins were separated by capillary electrophoresis in a submicellar buffer and detected by laser-induced fluorescence in a postcolumn sheath-flow cuvette. Several dozen components were resolved. A number of experiments were done to verify that these components were proteins. Most components of the single-cell electropherogram had the same mobility as components present in the 30-100 kDa fraction of a protein extract prepared from the cell culture. One component was identified as a approximately 100 kDa protein by co-injecting the sample with purified protein obtained from an SDS-PAGE gel. Protein expression varied significantly between cells, but the average expression was consistent with that observed from a protein extract prepared from 10(6) cells.     

Fluorometric detection of lectin with water-soluble hyperbranched conjugated polymer using mannose mediation

A water-soluble hyperbranched polymer containing boronic acid groups at the ends of the polymer, which are capable of binding to diol-containing mannose, was syntheized. The hyperbranched polymer was prepared by a palladium-catalyzed Suzuki cross-coupling reaction using the tribromo monomer for the hyperbranched type structure. The water-soluble hyperbranched polymer (HP) exhibited enhanced fluorescence intensity upon exposure to lectin in the presence of mannose compared to other proteins, such as lysozyme and cytochrome c, because mannose plays a key role in binding both lectin and HP resulting in selective sensing toward lectin.     

Mammalian cell cultures on micropatterned surfaces of weak-acid, polyelectrolyte hyperbranched thin films on gold

A four-step soft lithographic process based on micro-contact printing of organic monolayers, hyperbranched polymer grafting, and subsequent polymer functionalization results in polymer/n-alkanethiol patterns that direct the growth and migration of mammalian cells. The functional units on these surfaces are three-dimensional cell "corrals" that have walls 52+/-2 nm in height and lateral dimensions on the order of 60 microm. The corrals have hydrophobic, methyl-terminated n-alkanethiol bottoms, which promote cell adhesion, and walls consisting of hydrophilic poly(acrylic acid)/poly(ethylene glycol) layered nanocomposites that inhibit cell growth. Cell viability studies indicate that cells remain viable on the patterned surfaces for up to 21 days, and fluorescence microscopy studies of stained cells demonstrate that cell growth and spreading does not occur outside of the corral boundaries. This simple, chemically flexible micropatterning method provides spatial control over growth of IC-21 murine peritoneal macrophages, human umbilical vein endothelial cells, and murine hepatocytes.     

超支化聚对苯共聚物的合成及表征

利用Suzuki缩聚反应,合成了以1,3,6,8-(N-己基)咔唑为核的新型超支化聚对苯撑共聚物.用红外、核磁共振对聚合物的结构进行测定,表明咔唑以及吡啶单元成功引入聚合物中.聚合物可溶于四氢呋喃、氯仿和甲苯等有机溶剂.用凝胶渗透色谱法测得超支化聚合物的分子量在40000～110000之间,分子量随着1,3,6,8-(N-已基)咔唑含量的增加逐渐增加.超支化聚合物在溶液和薄膜状态下的吸收峰分别位于315～334nm和402～410nm之间.随着支化咔唑单元含量的增加,超支化聚合物的吸收峰均发生一定程度的蓝移.超支化聚合物在溶液和薄膜状态下的最大发射峰分别位于402～410nm和402～415nm之间,并且随着引入的支化咔唑单元含量的增加,分子内发生更加有效的分子内电荷转移,PL光谱发生略微的红移.     

水溶性Cu∶CdTe/CdS核壳量子点的合成、表征及细胞毒性检测

采用水相法合成了Cu掺杂CdTe量子点,并用CdS壳层进行包覆,得到了Cu∶CdTe/CdS核壳结构量子点。采用荧光发射光谱(FL)、紫外可见吸收光谱(UV-Vis)、透射电镜(TEM)以及能谱仪(EDS)等手段对CdTe量子点和Cu∶CdTe/CdS核壳量子点进行了表征。研究了不同Cu掺杂浓度、CdS壳层生长时间以及Cd/硫脲物质的量比对Cu∶CdTe掺杂量子点光学性能的影响,并采用人成骨肉瘤细胞(MG-63细胞)对样品做了细胞毒性分析。研究结果表明:通过掺杂和包壳的步骤,合成的Cu∶CdTe/CdS核壳量子点在CdTe量子点的基础上实现了荧光发射红移,荧光强度提高,以及细胞毒性降低。     

化学亚胺化和热亚胺化合成超支化聚酰亚胺

以三(4-氨基苯基)胺(TAPA)为三胺单体、均苯四甲酸二酐(PMDA)为二酐单体,采用A2+B3的方式,分别通过化学亚胺化和热亚胺法化制得了氨基封端超支化聚酰亚胺(AM-HBPI)和酐基封端超支化聚酰亚胺(AD-HBPI),然后采用红外(FT-IR)、核磁共振(1H-NMR)、X射线衍射(XRD)、溶解性和热失重分析(TGA)等对合成的超支化聚酰亚胺(HBPI)进行了测试和表征,并将两种方法所得HBPI进行了对比。结果表明,化学亚胺化和热亚胺化均能制得AM-HBPI和AD-HBPI,它们结晶度低,分子链间距比线性聚酰亚胺小;化学亚胺化AM-HBPI和AD-HBPI的溶解性比对应的热亚胺化HBPI好;所得的AM-HBPI和AD-HBPI的10%的失重温度分别为580℃和550℃,800℃时的质量保持率分别为62%和45%。     

端丙烯酸酯基超支化聚氨酯丙烯酸酯的合成

通过异氟尔酮二异氰酸酯(IPDI)与二乙醇胺(DEOA)反应得到AB2中间体,AB2中间体进行自聚反应合成端羟基超支化聚氨酯(HPU)。并通过红外光谱仪(FT-IR)、核磁共振氢谱(1 H-NMR)对其结构进行分析表征,研究了自聚反应温度对合成HPU的影响。以HPU为核,将其与半封端IPDI-PPG-HEMA反应,引入端丙烯酸酯基团,得到最终产物超支化聚氨酯丙烯酸酯(HPUA)。对HPUA进行红外光谱(FT-IR)、核磁共振氢谱(1 H-NMR)、热重(TG)等分析表征。结果表明:AB2中间体进行自聚合成HPU的最佳反应条件为温度55℃、反应时间为20h,用化学分析法滴定得出HPU的NCO%含量达到0.13%,经计算分子量为17827,说明HPU是由质量含量较高的HPU-5代和含量较低的HPU-6代组成。     

超支化聚氨酯的合成与性能

以异佛尔酮二异氰酸酯(IPDI)和聚乙二醇2000(PEG2000)为单体,通过逐步聚合反应合成了-NCO封端的聚氨酯顸聚体(PPU);再通过接枝使PPU与端羟基超支化聚合物(HPAE)共聚得到一种新型超支化聚氨酯(HBPU).利用红外光谱仪(FT-IR)、核磁共振(1H-NMR)、热重分析仪(TGA)、X射线衍射(X...     

超支化水性聚氨酯的合成与表征

以异佛尔酮二异氰酸酯(IPDI)、二乙醇胺(DEOA)及二羟甲基丙酸(DMPA)为原料,合成超支化聚氨酯核HBPU-0;以IPDI、聚四氢呋喃(PTMEG)及DMPA等原料合成线性聚氨酯,然后,将线性聚氨酯接枝到HBPU-0上,制备了一种具有超支化结构的水性聚氨酯,产物具有良好的水分散性和耐水性,其中HBPU-6的24h吸水率为6%,48h吸水率为11%,72h吸水率为18%。通过红外光谱对产物结构进行了表征。采用电子万用试验机和热失重分析仪对产物的性能进行测试,结果表明,所制备的水性超支化聚氨酯具有良好的力学性能和热稳定性,HBPU-6的拉伸强度为16.8MPa,热分解温度达到238℃。     

芳香族超支化聚酯型环氧树脂的合成及表征

以三羟甲基丙烷为中心核,与偏苯三酸酐和环氧氯丙烷开环聚合反应合成芳香族超支化聚酯,在碳酸钾水溶液作用下对其进行了闭环反应合成了超支化聚酯型环氧树脂。分别用红外光谱、核磁氢谱、凝胶色谱仪、热重分析表征了超支化聚酯型环氧树脂的结构。结果表明,合成产物具有芳香族超支化聚酯型环氧分子结构,合成的芳香族超支化聚酯型环氧树脂具有较好的热稳定性。     

超支化糖苷聚合物的合成及生物基质共混膜性能

单糖分子为原料,Koenigs-Knorr法合成一种带羧基和多羟基的糖苷衍生物,以此糖苷衍生物为单体制备超支化聚酯。用傅里叶变换红外光谱、核磁共振波谱、凝胶渗透色谱、差示扫描量热分析和热重分析表征中间产物和超支化聚酯结构。超支化聚酯与聚乳酸共混制备复合膜,扫描电镜观测复合膜的相容性,拉力试验测试复合膜的力学性能,差示扫描量热分析复合膜的热性能,接触角测量仪测试复合膜的润湿性。结果表明,成功合成了超支化聚酯目标产物,超支化聚酯的相对分子质量随代数的增加而上升,支化度较高,热稳定性较好。超支化聚酯与聚乳酸相容性良好,共混之后聚乳酸的力学性能、热性能及润湿性均有提高。     

Self-assembly of CdTe nanocrystals at the water/oil interface by amphiphilic hyperbranched polymers

A general strategy for realizing the self-assembly of aqueous CdTe nanocrystals (NCs) at the water/oil interface by means of an amphiphilic core-shell hyperbranched polymer has been proposed. Aqueous CdTe NCs were firstly transferred into the chloroform phase in the presence of palmityl chloride functionalized hyperbranched poly(amidoamine) (HPAMAM-PC), and then self-assembled at the water/chloroform interface by decreasing the pH value of the aqueous phase or introducing α-CDs to the aqueous phase. The resulting CdTe/HPAMAM-PC self-assembly film was characterized by fluorescence microscopy, UV-vis, PL, TEM, EDS, FT-IR, DSC and TGA.     

一种超支化聚酯的合成及反应动力学

以等物质的量比的间苯二甲酸（A2型单体）和三羟甲基丙烷（B3型单体）为原料,采用熔融聚合工艺制备了一种具有芳香-脂肪骨架的新型超支化聚酯（HBPE）。利用红外光谱、核磁共振、凝胶渗透色谱和热分析等手段对HBPE进行了表征。同时对合成HBPE的反应动力学进行了研究,建立了适合该体系的反应动力学方程,实验结果与理论研究符合...     

负载轴向取代硅(IV)酞菁配合物的聚合物纳米粒子的合成与表征

以二氯硅(IV)酞菁(SiPcCl2)为原料,与2-异丙基-6-甲基-4-嘧啶醇(PyO)反应合成轴向取代二-(2-异丙基-6-甲基-4-嘧啶氧基)硅(IV)酞菁配合物SiPc(PyO)2,并采用元素分析、红外光谱(IR)、核磁共振(1H-NMR)和质谱(MS)对其结构进行了表征。以两亲性嵌段共聚物聚赖氨酸-聚乙二醇-聚赖氨酸(PLL-PEG-PLL)为载体,透析法制备负载SiPc(PyO)2的聚合物纳米粒子SiPc(PyO)2/m。SiPc(PyO)2/m呈球形,直径约35 nm。SiPc(PyO)2包裹入聚合物胶束后,SiPc(PyO)2/m的Q带最大吸收峰强度降低,位置蓝移,荧光强度增加,荧光寿命增长。不同孵育时间HUVEC细胞的SiPc(PyO)2和SiPc(PyO)2/m的药代动力学表明,与自由酞菁3相比,SiPc(PyO)2/m摄取率增加,而且提前1 h达到最大浓度。     

One-pot synthesis of near-infrared fluorescent gold clusters for cellular fluorescence lifetime imaging

A facile strategy to synthesize water-soluble fluorescent gold nanoclusters (Au NCs) stabilized with the bidentate ligand dihydrolipoic acid (DHLA) is reported. The DHLA-capped Au NCs are characterized by UV-vis absorption spectroscopy, fluorescence spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The Au NCs possess many attractive features including ultrasmall size, bright near-infrared luminescence, high colloidal stability, and good biocompatibility, making them promising imaging agents for biomedical and cellular imaging applications. Moreover, their long fluorescence lifetime (>100 ns) makes them attractive as labels in fluorescence lifetime imaging (FLIM) applications. As an example, the internalization of Au NCs by live HeLa cells is visualized using the FLIM technique.     

非等温DSC研究超支化聚醚/PEG/IPDI体系的固化反应动力学

采用非等温差示扫描量热法(DSC)研究了超支化聚醚对聚乙二醇/异佛尔酮二异氰酸酯体系(PEG/IPDI)固化反应动力学的影响。结果表明,PEG/IPDI体系的固化反应表观活化能约为53.278 kJ/mol,反应级数为0.914,指前因子为1.500×105min-1;加入6%的超支化聚醚后,体系的固化峰温升高,表观活化能、反应级数和指前因子分别提高至87.577 kJ/mol、0.960、1.201×1010min-1,机理函数仍遵循Avrami-Erofeev方程G(α)=[-ln(1-α)]n,只是方程中的指数n有所变化。超支化聚醚对PEG/IPDI体系的固化反应有一定的延缓作用,但不改变固化机理。浅析了超支化聚醚影响PEG/IPDI体系固化的原因。     

超支化聚酯的非等温热分解动力学

利用热重(TG)分析技术研究了端羟基超支化聚酯(HBP)以及十八酸改性的超支化聚酯(MHBP)的热失重行为,运用Flynn-Wal-l Ozawa法和Coats-Redfern法对非等温热分解动力学数据进行了分析。结果表明,HBP的分解过程分为三个阶段,三个阶段的表观活化能分别为120.238 kJ/mol、149.775 kJ/mol、173.540 kJ/mol,指前因子分别为1.386×109min-1、1.341×109min-1、4.569×1012min-1;MHBP的分解过程仅有一个阶段,表观活化能和指前因子分别为204.275kJ/mol和2.417×1014min-1。超支化聚酯的热稳定性与其端基有关,十八酸改性的超支化聚酯由于长链烷烃具有结晶性,因而热稳定性优于端羟基超支化聚酯。     

Magnetite/CdTe magnetic-fluorescent composite nanosystem for magnetic separation and bio-imaging

A new synthesis protocol is described to obtain a CdTe decorated magnetite bifunctional nanosystem via dodecylamine (DDA) as cross linker. High resolution transmission electron microscopy (HRTEM), energy-dispersive x-ray spectroscopy (EDAX), vibrating sample magnetometry (VSM), Fourier transform infrared spectroscopy (FTIR), diffuse reflectance spectroscopy (DRS) and fluorescence microscopy are used to characterize the constitution, size, composition and physical properties of these superparamagnetic-fluorescent nanoparticles. These CdTe decorated magnetite nanoparticles were then functionalized with anti-epidermal growth factor receptor (EGFR) antibody to specifically target cells expressing this receptor. The EGFR is a transmembrane glycoprotein and is expressed on tumor cells from different tissue origins including human leukemic cell line Molt-4 cells. The magnetite-CdTe composite nanosystem is shown to perform excellently for specific selection, magnetic separation and fluorescent detection of EGFR positive Molt-4 cells from a mixed population. Flow cytometry and confocal laser scanning microscopy results show that this composite nanosystem has great potential in antibody functionalized magnetic separation and imaging of cells using cell surface receptor antibody.     

末端含苯乙烯结构的超支化荧光聚合物的合成及性能

以季戊四醇、1,2,4-偏苯三甲酸酐和环氧氯丙烷为原料,合成超支化聚合物,利用合成聚合物分子外围的羧基与亚硫酰氯反应使其分子外围的羧基酰氯化,通过傅-克酰化反应将苯乙烯引入到超支化聚合物分子末端,得到末端含苯乙烯结构的超支化荧光聚合物。采用红外光谱、热分析及荧光光谱等手段表征了聚合物的结构,研究了其热稳定性及荧光性能与结构的关系。将苯乙烯接到超支化聚合物分子外围得到的聚合物具有较好的热稳定性,其荧光特性表现为:激发波长为254nm时,其发射光谱的峰值为500nm～506nm;激发波长为365nm时,其发射光谱峰值在361nm～365nm。