两亲性壳聚糖基聚合物碳点的合成及其在载药方面的应用

通过水热法合成了系列具有高荧光量子产率（42.9%）辛基化壳聚糖基两亲性聚合物碳点荧光材料。利用红外光谱、紫外吸收光谱、光电子能谱、透射电镜、X射线衍射及荧光光谱对聚合物碳点进行了表征。以阿霉素为模型药物,研究了聚合物碳点对阿霉素的载药性能。当辛基取代度为76.42%时,其最大载药量和包封率分别为49.6%与47.4%。在磷酸盐缓冲液中,载药纳米胶束呈前期快速释放,后期缓慢释放的双相特征。将载药纳米胶束与鼻咽癌细胞作用,发现其存活率随着载药纳米胶束加入量的增加而降低,说明该纳米胶束对鼻咽癌细胞有一定的抑制作用。总之,该聚合物碳点材料在药物载体与荧光示踪方面有潜在的应用价值。     

壳聚糖基聚合物碳点荧光材料合成及其自组装载药应用

荧光碳点具有化学稳定性好、毒性小、可表面功能化等优点,引起了人们极大的兴趣。近年来,由高分子多糖合成的聚合物碳点成为另一研究热点。本文通过水热法合成了一种壳聚糖基荧光聚合物碳点材料（P（CS-g-mPEG-CA）CDs）,并用于载药研究。基于壳聚糖和聚乙二醇既是碳点的碳源也是碳点的钝化试剂,本文选择壳聚糖接枝聚乙二醇单甲醚和柠檬酸衍生物作为聚合物碳点的碳源,以提高聚合碳点的量子产率。另外,聚合物碳点还可以保留聚乙二醇与壳聚糖分子结构,为其在载药方面的应用提供有利条件。采用红外光谱、紫外光谱、X射线衍射、光电子能谱、透射电子显微镜和光致发光光谱对P（CS-g-mPEG-CA）CDs进行了结构表征以及pH值稳定性的测试。结果表明,所合成的P（CS-g-mPEG-CA）CDs具有较高的荧光量子产率（66.81%）、较长的荧光寿命（15.247 ns）、良好的pH稳定性。以阿霉素为模型药物,利用该聚合物碳点进行了负载研究,结果表明,当聚乙二醇单甲醚取代度为11.9%时,聚合物碳点的载药量最高为51.3%,最大药物释放率为28.7%,此外,药物的装载和释放可以通过mPEG的接枝率进行控制。采用MTT法评价了聚合物的碳点对鼻咽癌细胞（CNE-2）的毒性作用。研究表明,空白聚合物碳点无明显细胞毒性,CNE-2细胞存活率随着载药胶束的增加而降低,说明载药胶束对CNE-2细胞有较强的抑制作用。可见该P（CS-g-mPEG-CA）CDs在荧光标记、药物递送、荧光示踪系统和控制释放方面,具有一定的应用前景。     

有序结构氟聚合物压电驻极体的制备和压电性研究

描述了一种有序微孔结构压电聚合物功能膜的制备方法,利用模板的高度有序实现薄膜微孔结构的精确控制.将此制备方法用于氟聚合物压电驻极体薄膜的制备,通过扫描电子显微镜(SEM)对其微观结构的观察表明薄膜具有理想的有序结构.对氟聚合物压电驻极体压电性的研究则是利用正压电效应测量准静态压电系数d₃₃,通过等温衰减和压强依赖性的测量考察其压电性能.结果表明:有序结构氟聚合物压电驻极体的准静态压电系数d₃₃可高达300 pC/N;与无序结构氟聚合物     

非晶态聚合物主转变弛豫峰与玻璃化转变过程的相关性研究

从弛豫理论出发,在不同的时效时间和不同降温速率下,测量了非晶聚合物PVC玻璃化转变过程中与时间参量密切相关的α峰峰温(T_α)的响应关系,得出以下结论:1)玻璃化转变温度(T_g)一般是指非晶态聚合物热平衡态与非平衡态的温度转变点(T_t),是温度变化造成的热弛豫过程的直接结果,而α内耗峰是在动态力学测量过程中得到的聚合物玻璃态与高弹态(橡胶态)的分界点处的力学弛豫过程,表现为动态模量锐变过程,是非晶态聚合物热平衡态下的特征内耗峰.两者都与非晶态     

壳聚糖基聚合物碳点荧光材料合成及其自组装载药应用（英文）

荧光碳点具有化学稳定性好、毒性小、可表面功能化等优点,引起了人们极大的兴趣。近年来,由高分子多糖合成的聚合物碳点成为另一研究热点。本文通过水热法合成了一种壳聚糖基荧光聚合物碳点材料(P(CS-g-m PEG-CA)CDs),并用于载药研究。基于壳聚糖和聚乙二醇既是碳点的碳源也是碳点的钝化试剂,本文选择壳聚糖接枝聚乙二醇单甲醚和柠檬酸衍生物作为聚合物碳点的碳源,以提高聚合碳点的量子产率。另外,聚合物碳点还可以保留聚乙二醇与壳聚糖分子结构,为其在载药方面的应用提供有利条件。采用红外光谱、紫外光谱、X射线衍射、光电子能谱、透射电子显微镜和光致发光光谱对P(CS-g-m PEG-CA)CDs进行了结构表征以及p H值稳定性的测试。结果表明,所合成的P(CS-g-m PEG-CA)CDs具有较高的荧光量子产率(66.81%)、较长的荧光寿命(15.247 ns)、良好的p H稳定性。以阿霉素为模型药物,利用该聚合物碳点进行了负载研究,结果表明,当聚乙二醇单甲醚取代度为11.9%时,聚合物碳点的载药量最高为51.3%,最大药物释放率为28.7%,此外,药物的装载和释放可以通过m PEG的接枝率进行控制。采用MTT法评价了聚合物的碳点对鼻咽癌细胞(CNE-2)的毒性作用。研究表明,空白聚合物碳点无明显细胞毒性,CNE-2细胞存活率随着载药胶束的增加而降低,说明载药胶束对CNE-2细胞有较强的抑制作用。可见该P(CS-g-m PEG-CA)CDs在荧光标记、药物递送、荧光示踪系统和控制释放方面,具有一定的应用前景。     

窄带系聚合物APFO3的激发态光物理特性 (cited: 1)

化学计算证实了光致激发窄带系聚合物APFO3后,会发生链内电荷转移(ICT)过程,同时这一特性还影响了吸收光谱中的第一吸收带. 瞬态吸收结果再一次表明了当聚合物在单分散体系中确实存在ICT特性,而且这种特性会同振动弛豫竞争. 在聚集态中,受链间相互作用的影响,ICT特性会消失,而且激子弛豫过程将在光致激发后的弛豫过程中占据主导地位. 混有PC₆₁BM的APFO3薄膜的光致激发动力学显示,当PC₆₁BM 的含量超过50%时,激子解离已经达到饱和. 基于此异质节的光     

荧光标记的聚(N-异丙基丙烯酰胺)链在水溶液中的折叠动力学

使用1.54 μm的激光脉冲(脉宽约10 ns)诱导丹磺酰基标记的热敏性线性聚N-异丙基丙烯酰胺(PNIPAM)发生线团到小球的转变．当聚合物链中NIPAM单体与丹磺酰基基团的摩尔比由110增至300时,共价键合到聚合物主链上的丹磺酰基发色团对PNIPAM相转变行为的影响会随之减小．PNIPAM链塌缩经历成核过程(伴随着初始珍珠的形成,快弛豫时间τ_fast=0.1 ms)和珍珠的增长粗化阶段(慢弛豫时间τ_slow=0.5 ms),这与之前使用水溶性的1-苯胺-8-萘磺酸铵盐作为荧光探针研究PNIPAM在水溶液中的折叠动力学得到的结果类似．τ_fast在很宽的分子量范围内都与分子量无关,而τ_slow则随链长增加而略有增大．     

PT-PEK-c电光聚合物薄膜的厚度和介电性质

研制了新的PT-PEK-c电光聚合物薄膜材料,用准波导耦合m线方法测量了PT-PEK-c电光聚合物薄膜的厚度,并测量了该聚合物薄膜在1×10²Hz到1×10⁷Hz频率范围内的室温介电常数.测量结果为:厚度d=2.328±0.315μm,在10KHz下,介电常数ε_r＝4023±0.063,介电损耗tanδ＝0.003.     

海藻酸改性的空心Fe3O4纳米颗粒的制备与应用

不使用任何模板一步制得空心Fe₃O₄纳米颗粒,然后将海藻酸钠嫁接在氨基化的空心Fe₃O₄表面,再利用海藻酸盐与钙离子的作用,在空心Fe₃O₄表面形成一个凝胶化层,制得海藻酸盐凝胶化的空心Fe₃O₄纳米颗粒,粒径约为400～500 nm．采用TEM、XRD、XPS、VSM等手段对纳米微球进行表征．VSM表征结果表明在室温下样品磁性材料为超顺磁性．改性Fe₃O₄纳米颗粒成功地用于柔红霉素的载负和缓释,最大载负率和载药量分别为28.4%和14.2%．缓释结果表明,海藻酸盐凝胶化层的存在,能更有效控制柔红霉素缓慢地释放．     

基质隔离红外光谱结合理论计算研究第五族金属原子和硫化氢反应

利用基质隔离红外光谱结合理论计算,研究了激光溅射获得的第五族金属原子和硫化氢分子的反应. 结果表明金属原子插入H₂S的H-S化学键形成HMSH分子(M=V,Nb,Ta). 对Nb和Ta该HMSH分子重排为H₂MS分子. HMSH分子和H₂S进一步反应生成H₂M(SH)₂分子. 通过D₂S和H₂³⁴S同位素标定确定了产物的分子结构,同时我们用DFT(B3LYP和BPW91)理论计算预测了产物分子的能量、结构和振动频率. 通过DFT IRC计算研究了第五族金属原子和₂S分子的反应机理. HVSH分子通过光照解离为VS和H₂,然后通过退火可以发生VS和H₂复合反应. 计算表明HVSH释放H₂需要16.9 kcal/mol的活化能及吸热13.5 kcal/mol.     

Synthesis and Application for Porous Scaffold Materials of Mono-Methoxy Polyethylene Glycol/Polylactide Diblock Copolymer

An amphiphilic diblock copolymer, consisting of mono-methoxy polyethylene glycol (mPEG) and polylactide (PLA), was synthesized by ring-opening polymerization. The chemical structure of the diblock copolymer was verified by means of Fourier transform infrared spectroscopy (FT-IR) and ¹H-NMR, and the weight average molecular weight (M_w ) and polydispersity index (PDI) were measured by gel permeation chromatography (GPC). An mPEG/PLA (20/80) copolymer with a M_w of 4.6 × 10⁴ Da and PDI of 1.39 were obtained when polymerization was conducted at 130°C for 36 h using Sn(Oct)₂ as a catalyst. The compressive strength of an mPEG/PLA scaffold was lower than that of a PLA scaffold; however, the introduction of mPEG into the PLA matrix enhanced its hydrophilicity, and it still meets the requirement of cartilage tissue engineering.     

Preparation of poly (styrene)-b-poly (acrylic acid)/γ-Fe2O3 composites

The use of a block copolymer, poly (styrene)-b-poly (acrylic acid) (PS-b-PAA) to prepare a magnetic nanocomposite was investigated. Poly (styrene)-poly (t-butyl acrylate) block copolymer, being synthesized by atom transfer radical polymerization, was hydrolyzed with hydrochloric acid for obtaining PS-b-PAA. The obtained PS-b-PAA was then compounded with the modified γ-Fe₂O₃, and subsequently the magnetic nanocomposite was achieved. The products were characterized by ¹H NMR, FTIR, gel permeation chromatography, thermogravimetric analysis, transmission electron microscopy and vibrating sample magnetometer. The results showed that the nanocomposites exhibited soft magnetism, with the mean diameter of 100 nm approximately.     

单甲氧基聚乙二醇-聚(己内酯-co-丙交酯)嵌段共聚物的NMR表征

利用溶液¹³C NMR和HMBC实验对AB型两亲性嵌段共聚物单甲氧基聚乙二醇－聚（己内酯-co-丙交酯）[MeOPEG-P(Cap-co-LL)]的嵌段结构以及聚（己内酯-co-丙交酯）[P(Cap-co-LL)]嵌段中Cap和LL的无规结构进行了表征. 研究发现,P(Cap-co-LL)中Cap、LL的组成对P(Cap-co-LL)的无规度、Cap和LL的酯交换程度以及不同组分的平均链长均有影响. 对LL中立体结构不同所产生的酯交换也进行了表征.     

New approach in synthesis,characterization and release study of pH-sensitive polymeric micelles,based on PLA-Lys-<Emphasis Type="Italic">b</Emphasis>-PEGm,conjugated with doxorubicin

Amphiphilic block copolymers are well established as building blocks for the preparation of micellar drug carriers. The functional polymer micelles possess several advantages, such as high drug efficiency, targeted delivery, and minimized cytotoxicity. The synthesis of block copolymers using nano-structured templates has emerged as a useful and versatile approach for preparing drug carriers. Here, we report the synthesis of a smart polymeric compound of a diblock PLA-Lys-b-PEG copolymer containing doxorubicin. We have synthesized functionalized diblock copolymers, with lysinol, poly(lactide) and monomethoxy poly(ethylene glycol) via thermal ring-opening polymerization and a subsequent six-step substitution reaction. A variety of spectroscopic methods were employed here to verify the product of our synthesis. ¹H-Nuclear magnetic resonance and Fourier transform infrared studies validated the expected synthesis of copolymers. Doxorubicin is chemically loaded into micelles, and the ex vitro release can be evaluated either in weak acidic or in SBF solution by UV–vis spectroscopy. Dynamic light scattering, thermo gravimetric analysis, and size exclusion chromatography have also been used.     

The effect of polystyrene-block-poly(4-vinylpyridine) prepared by a RAFT method in the dispersion polymerization of styrene

The dispersion polymerization of styrene has been carried out using polystyrene-block-poly(4-vinylpyridine) copolymer [P(S-b-4VP)], prepared by a reversible addition-fragmentation chain transfer (RAFT) method, as a steric stabilizer in alcohol media. These block copolymer contains a long poly(4-vinylpyridine) block and a short polystyrene block. The stable spherical particles were obtained when the block copolymer concentrations increased from 2 to 20 wt.% relative to the monomer and the average particle sizes decreased from 340 to 200 nm with increasing concentration of the block copolymer. Alcoholic solvents, from methanol to n-hexanol, are responsible for the particle size. These results indicate that the poly(S-b-4VP) block copolymer is effective for providing polystyrene nano-sized particles with a low content of it working as a good stabilizer in any kind of alcoholic medium.     

Dual Gas-responsive Fluorescent Diblock Copolymer Synthesized via RAFT Polymerization

Stimulus-responsive polymers with luminescence properties have a wide range of applications in the fields of controlled drug release, fluorescent probes, and biological stents. In this paper, carbon dioxide (CO₂)/oxygen (O₂) dual-responsive fluorescent diblock copolymers were synthesized by the reversible addition-fragmentation chain transfer (RAFT) polymerization method with two fluorescent monomers synthesized as its luminescence source, DEAEMA (CO₂ responsive monomer) and tFMA (O₂ responsive monomer). An experimental study demonstrated that the synthesized stimulus-responsive fluorescent polymer had a high sensitivity to CO₂; the double-responsive fluorescent diblock copolymer could form and achieve the reversal of polymer micelles in the aqueous solution when it was sequentially subjected to the introduction of CO₂ and O₂.

     

Self-assembled block polymer templates as high resolution lithographic masks

Diblock copolymer thin films have recently received more attention due to their ability to organize into nanometric structures under thermal annealing. This phenomenon was studied for an asymmetric poly(styrene-block-methyl methacrylate) (PS-b-PMMA) diblock copolymer with PMMA weight fraction of 0.3 and MW = 67,100 g mol⁻¹. First, the surface chemistry of the substrate was modified to favor the formation of vertical PMMA cylinders surrounded by a PS matrix. We have also found that the mean pore area of cylinders increases with their coordination number. Finally, these films were used as a deposition or etching mask to produce well-organized arrays of holes, dots and nanopillars.     

Ultrasound responsive block copolymer micelle of poly(ethylene glycol)–poly(propylene glycol) obtained through click reaction

The well-defined amphiphilic poly(ethylene glycol)-block-poly(propylene glycol) copolymer containing 1, 2, 3-triazole moiety and multiple ester bonds (PEG-click-PPG) was prepared by click reaction strategy. The PEG-click-PPG copolymer can self-assemble into spherical micelles in aqueous solution. It is found that high intensity focused ultrasound (HIFU) can open the copolymer PEG-click-PPG micelles and trigger the release of the payload in the micelle. The multiple ester bonds introduced in the junction point of the copolymer chain through click reactions were cleaved under HIFU, and leads to the disruption of the copolymer micelle and fast release of loaded cargo. The click reaction provides a convenient way to construct ultrasound responsive copolymer micelles with weak bonds.     

General approach for fabricating nanoparticle arrays via patterned block copolymer nanoreactors

A general approach to fabricate nanoparticle arrays of different kinds of materials is demonstrated in this paper. It was found that the center-to-center distance of the nanoparticles or the nanoclusters can be controlled using patterned block copolymer nanoreactors by adding polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer thin film. The number of the nanoparticles formed in the P4VP nanodomains can also be adjusted by addition of polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer. In fabrication of Au nanoparticle arrays, HAuCl₄ precursor was directly loaded into P4VP nanodomains of the diblock copolymer thin film by using a methanol solvent, which is a good solvent for P4VP but non-solvent for PS. The Au nanoparticle arrays were then obtained by reducing HAuCl₄ with sodium citrate dihydrate, and then in situ transferred to silicon substrate by a two-step calcination method. ZnO and Fe _x O _y nanoparticle arrays were also synthesized by this approach with thermal decomposition and double decomposition reactions, respectively. Additionally, the advantage of using two-step calcination method over the air plasma method was discussed.     

光电子成像研究AgOCH3-和Ag-(CH3OH)x (x=1, 2)

用光电子成像技术和从头算法研究Ag^-(CH₃OH)_x (x=1, 2)和AgOCH₃^-. 从AgOCH₃^-振动分辨的光电子谱得 到AgOCH₃^-的绝热和垂直电离能分别为1.29(2)和1.34(2) eV. Ag^-(CH₃OH)_{1,2相似文献}