双亲性光敏感遥爪聚合物C-PNIPAAm的合成与性能

以7-羟基-4-甲基香豆素为原料,依次与环氧氯丙烷、二硫化钠反应得一含香豆素基元的二硫化物(C-S-S-C),并以其与三丁基膦复合体系为链转移剂,偶氮二异丁腈(AIBN)为引发剂,N-异丙基丙烯酰胺(NIPAAm)为单体制备了末端为香豆素光响应基元的双亲性遥爪聚合物(C-PNIPAAm).用傅里叶变换红外(FT-IR)光谱、凝胶渗透色谱(GPC)、氢核磁共振(1H-NMR)等对该聚合物进行了结构表征.研究显示该双亲性遥爪聚合物可在水中直接形成胶束,并以荧光素为疏水性客体考察了聚合物胶束的光控释放行为.在波长大于310 nm的紫外光照射下,聚合物链末端的香豆素单元可进行光二聚,胶束结构随之改变,因而所负载的荧光素可得到逐步有效释放.动态激光光散射(DLS)检测显示,光二聚反应使聚合物胶束平均粒径从56.6 nm增大至101.0 nm.     

具有疏水核/亲水壳的双亲胶体粒子的制备

制备了具有疏水性聚苯乙烯核/亲水性聚丙烯酰胺壳的双亲粒子.疏水核通过超浓乳液聚合制备,亲水壳层通过过氧化羟基异丙苯和硫酸亚铁的界面引发制备.控制条件可得到网孔(半包覆)、褶皱(全包覆)两种形态的壳层.壳层孔的存在使得核层聚合物能够与外界接触.粒子的双亲性通过吸水吸油率进行表征.     

Fe_3O_4/PEI/GO复合材料的制备及其吸附效果研究

以氧化石墨烯(GO)和聚乙烯亚胺(PEI)为反应物,采用共混法制备PEI/GO,然后将Fe_3O_4纳米颗粒分散沉积到PEI/GO表面,得到了复合材料Fe_3O_4/PEI/GO。利用傅里叶红外光谱(FT-IR)、透射电子显微镜(TEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等方法对该材料进行表征,并研究了其对Cu~(2+)的吸附性能。结果表明,PEI与GO的羧基反应生成了酰胺键,Fe_3O_4成功沉积在GO表面,GO层状结构的规整性被破坏。Freundlich等温吸附模型和准二级动力学模型能更好地拟合Cu~(2+)在Fe_3O_4/PEI/GO表面的吸附过程,说明该吸附主要受化学作用控制,可能是Fe_3O_4/PEI/GO表面的胺基、羧基、羟基等活性基团与Cu~(2+)发生了离子交换或络合反应所致。     

高分子量立构复合结晶的三枝化PPO-PDLA-PLLA嵌段共聚物

以三枝化低不饱和度聚环氧丙烷(PPO)引发D-丙交酯(D-LA)逐步开环聚合, 合成了三枝化聚环氧丙烷-聚右旋乳酸(PPO-PDLA)共聚物. 用辛酸亚锡Sn(Oct)₂与PPO-PDLA端羟基反应进行Sn(Oct)封端, 制备了三枝化PPO-PDLA-Sn(Oct)预聚物. 再于130 ℃下, 以其作为大分子引发剂与L-丙交酯(L-LA)开环聚合, 合成了分子量>10⁵的三枝化PPO-PDLA-PLLA嵌段共聚物. 活性端基的引入, 降低了聚合反应温度, 从而降低了聚合中的酯交换或热降解反应发生的概率. 实现了高分子量PPO-PDLA-PLLA嵌段共聚物的合成. 结构测试结果表明, 合成的嵌段共聚物具有分子结构易控及立构规整度高等特点. 在结晶-熔融-再结晶重复热处理下, 三枝化PPO-PDLA-PLLA嵌段共聚物仅发生立构复合聚乳酸结晶, 且结晶能力稳定.     

在醛基化交联聚苯乙烯微球表面同步合成与固载卟啉及固载化金属卟啉的高效催化氧化性能

采用Kornblum氧化反应, 先将氯甲基交联聚苯乙烯(CMCPS)的氯甲基氧化为醛基, 制得醛基(AL)化改性微球ALCPS, 然后使改性微球ALCPS与溶液中的苯甲醛(或取代的苯甲醛)、吡咯之间发生固-液相之间的Adler反应, 成功地实现了卟啉在交联聚苯乙烯微球表面的同步合成与固载, 制得了固载有苯基卟啉(PP) 、对氯苯基卟啉(CPP)、对硝基苯基卟啉(NPP)的功能微球, 最后使功能微球与钴盐发生配合反应, 制备了固载有三种钴卟啉的固体催化剂. 研究重点有两方面: (1)考察主要因素对卟啉同步合成与固载过程的影响|(2)考察固载化钴卟啉在催化分子氧氧化环己烷羟基化过程中的催化特性. 实验结果表明, 以醛基化改性微球ALCPS与溶液中的吡咯及小分子苯甲醛(或取代的苯甲醛)为共反应物, 通过固-液之间的Adler反应, 可以顺利地实现卟啉在微球ALCPS表面的同步合成与固载, 这是制备固载化卟啉的新途径|苯甲醛的取代基结构、催化剂的酸性与溶剂的性质对卟啉的同步合成与固载都有较大的影响|所制备的固体催化剂对分子氧氧化环己烷羟基化的反应, 具有很高的催化活性(环己烷最高转化率约为40%)与选择性(环己醇的选择性在90%以上), 这是由固体催化剂特殊的化学结构所决定的.     

硒/氧化石墨烯/二氧化钛复合薄膜的制备及光电转换性质

将氧化石墨烯(GO)掺入钛酸溶胶中,以导电玻璃(ITO)为基底,经浸渍-涂覆-煅烧得到GO/TiO2复合薄膜;采用电沉积技术在GO/TiO2薄膜表面沉积Se纳米微粒,得到Se/GO/TiO2复合薄膜;利用扫描电子显微镜和X射线衍射仪分析了复合薄膜的形貌和晶体结构,采用紫外可见光谱仪测定了其光谱学性质,利用光电转换实验测定了其光电转换性质.结果表明,所制备的Se/GO/TiO2复合薄膜各组分分布均匀,具有锐钛矿相结构的TiO2颗粒粒径为20nm,与TiO2结合的GO具有分散片层结构,薄膜中的Se颗粒粒径为60～80nm.与此同时,在Se和GO的共同作用下,Se/GO/TiO2复合薄膜对可见光有很好的光电转换效应.     

甲基羟基铀酰离子与水的复分解反应

以醋酸铀酰为主要试剂, 在负离子检测模式下, 采用电喷雾串联质谱法制备了甲基羟基铀酰负离子. 实验发现, 气相中的甲基羟基铀酰离子与水分子发生分子离子复分解反应, 并用串联质谱法对反应产生的离子性产物进行了结构确认, 提出了反应的可能机理. 热力学计算结果表明, 该反应的ΔGReaction为-473.0 kJ/mol, ΔHReaction为-236.5 kJ/mol, ΔSSystem为0.792 kJ·mol-1·K-1. 该反应的速率常数为2.26 s-1.     

氧化石墨烯增强卡拉胶复合膜的制备与性能

在Hummers法基础上制得了氧化石墨烯(GO), 采用流延法制备了氧化石墨烯/κ-卡拉胶(GO/κ-Car)复合膜材料. 结合红外光谱、 扫描电子显微镜及热重分析对其结构进行表征. 探讨了不同条件所得膜的成膜性、 溶解性、 透气性和力学性能, 得到性质稳定GO/κ-Car复合膜的制备条件为15.0 g 3%的κ-Car溶液、0.040 g GO粉末及5.0 g 8%的PVA溶液于75 ℃搅拌混合5 h后, 流延铺平, 于30 ℃烘干6.5 h. GO质量分数为5%的GO/κ-Car复合膜的最大负荷、 拉伸强度及杨氏模量分别是对照组κ-Car膜的1.5倍、 1.5倍和1.6倍. 同时, GO/κ-Car复合膜具有较强的透气性能, 且保留了κ-Car清除羟基自由基的生物性能.     

新型环氧树脂基液晶光定向层材料的合成与性能研究

经双酚A型环氧树脂与苯胺缩聚反应,制备含有羟基的先驱聚合物EP-AN,通过EP-AN上羟基与肉桂酰氯的酯化反应,制备了侧链带有肉桂酸酯基团的光敏聚合物EP-AN-CI.用核磁共振(1HNMR)、傅里叶红外光谱(FTIR)和热分析等手段确定了上述聚合物的结构与性能.用FTIR等方法表征了EP-AN-CI的光交联反应.经线性偏振光聚合技术(LPP)处理聚合物EP-AN-CI膜制备成液晶定向层,通过装配液晶盒和偏光显微镜观察表明,所制备的定向层具有很好的定向能力,该聚合物是一类具有潜在应用价值的新型液晶光定向层材料.     

光敏性无规-类接枝双亲聚合物的合成与自组装行为的研究

通过ε 己内酯改性丙烯酸酯 (FAn ,n =1～ 4 )与肉桂酰氯反应合成了一系列光敏性大单体 (FAnC ,n =1～ 4 ) ,以FAnC与甲基丙烯酸 (MAA)进行自由基聚合 ,制备具有光敏性的双亲无规 类接枝共聚物 (PMFAnC) .用红外光谱、凝胶渗透色谱、核磁共振和差示扫描量热仪等对共聚产物进行了表征 .双亲性PMFAnC可以在选择性溶剂中进行自组装 ,形成以PMFAnC中PFAnC疏水链段为核 ,PMAA亲水链段为壳的高分子胶束 .核内的肉桂酰基由紫外光引发发生光交联反应 ,得到具有稳定壳 核结构的胶束 .动态激光光散射、透射电子显微镜结果表明 ,PMFAnC在水溶液中形成了一定结构的光敏性纳米胶束 ,在紫外光照射下PMFAnC胶束内核发生光聚合反应使胶束粒径减小     

A new poly(l-lactide)-grafted graphite oxide composite: Facile synthesis, electrical properties and crystallization behaviors

A simple method was adopted to prepare poly(l-lactide)-grafted graphite oxide (PLLA-g-GO) by ring opening polymerization of l-lactide in the presence of graphite oxide (GO) with hydroxyl groups. GO was firstly treated with tolylene-2,4-diisocyanate (TDI) to create an anchor site on GO, and then reacted with 1,4-butanediol (BD) to afford functional hydroxyl groups grafted onto the surface of GO. So that, the dispersity of GO in the organic solution was enhanced. According to the thermogravimetric analysis (TGA), the organic composition of GO treated with TDI and BD (GO-TDI-OH) was estimated to be about 13 wt%. Also, using TGA, the composition of GO in the PLLA-g-GOs could be estimated. The hydroxyl groups on the GO surface acted as initiators for the ROP of l-lactide. Further, they also played as a vital role in controlling the molecular weight of the PLLA. The synthesized PLLA-g-GOs were characterized by the FTIR, ¹HNMR and UV/Vis spectroscopies. The dispersion states of GO in the PLLA-g-GOs were investigated by wide angle x-ray diffraction patterns. According to differential scanning calorimeter study, it was found that GO platelets have nucleating effect on the crystallization of PLLA in the PLLA-g-GO. Additionally, the incorporation of GO improved the electrical conductivity of PLLA, indicating that GOs is a good conducting-modifiers for polymers.     

Alternating Magnetic Field Controlled Targeted Drug Delivery Based on Graphene Oxide-Grafted Nanosupramolecules

Graphene oxide (GO)-grafted nanosupramolecules have recently emerged as neoteric nano drug carriers in the therapy of refractory diseases. Herein, a multicomponent nanosupramolecular drug carrier based on a targeted peptide and magnetic GO is reported, the drug-release behavior of which can be regulated by an alternating magnetic field (AMF). This multicomponent nanosupramolecular carrier is composed of β-cyclodextrin (β-CD)/nickel nanoparticle-modified graphene oxide (GONiCD) and mitochondrial ion-targeting peptide (MitP)-grafted hyaluronic acid (HAMitP). Owing to the host–guest interaction between β-cyclodextrin and the cyclohexyl groups on MitP, GONiCD and HAMitP could form supramolecular assemblies during the doxorubicin (Dox) loading process, which not only remarkably enhances the drug-loading capacity, but also improves the drug-release efficiency under AMF stimulus. During co-incubation with tumor cells, the Dox-loaded assemblies could strongly target the tumor mitochondria and damage both the mitochondria and the nuclei, owing to Dox release from the assemblies induced by AMF. This study sheds light on the exploration of peptide caps for controlled drug loading/release of supramolecular nanocarriers for efficient drug delivery and anticancer therapy.     

Covalent amphiphilic polymer networks

The recent literature on chemically cross-linked amphiphilic polymer networks is reviewed. The main subjects covered are network synthesis, characterization, modeling and applications. Special mention is made to more modern methods for amphiphilic network synthesis and in particular to those involving controlled polymerization techniques. A key question regarding synthesis is which method gives the most perfect networks. On the characterization side is the issue of microphase separation of amphiphilic networks in water and the morphologies obtained in these systems, in comparison with the morphologies of amphiphilic linear block copolymers in water. Major recent advances: The most important developments of the past year in the field of amphiphilic polymer networks involved mainly new syntheses: cross-linked stars of various star architectures, cross-linked linear chains of various architectures and compositions, poly(tetrahydrofuran)- and poly(propylene fumarate)-based networks, tricomponent networks containing silicon, and cross-linked poly(acrylic acid)-grafted Pluronics. A first crude model was also developed which shows that amphiphilic networks prefer to be mostly in the microphase separated state. Extensive and systematic experimental studies on network microphase separation are yet to be performed.     

Acetone‐Induced Graphene Oxide Film Formation at the Water–Air Interface

Graphene oxide (GO) is an amphiphilic soft material, which can accumulate at the water–air interface. However, GO sheets diffuse slowly in the aqueous phase because of their large size. It is still challenging to form high quality GO films in a controllable and simple way. In this study, we showed that GO sheets can quickly migrate to the water–air interface and form thin films when a suitable amount of acetone is directly mixed with a GO aqueous dispersion. The film formation rate and surface coverage of GO sheets depend on the volume of acetone added, GO dispersion concentration, and formation time. Among several organic solvents, acetone has its advantage for GO film formation owing to its three properties: a nonsolvent to GO aqueous dispersions, miscible with a GO aqueous dispersion, and fast evaporation. Furthermore, we have found that the film formation also is governed by the size of GO sheets and their oxygen content. Although smaller GO sheets could migrate to the water–air interface faster, the overlapping of small GO sheets and the increase in contact resistance is not desirable. A higher oxygen content in GO sheets could also result in smaller GO sheets. Multilayer GO films can be obtained through layer‐by‐layer dip‐coating. These findings open opportunities in developing simple scalable GO film fabrication processes.     

Facile fabrication of self-assembled PMMA/graphene oxide composite particles and their electroresponsive properties

Core–shell-structured poly(methyl methacrylate) (PMMA)/graphene oxide (GO) composite particles were prepared using a facile process, in which GO was adsorbed spontaneously onto a microspherical PMMA surface when hydrophobic microspheres were dispersed in deionized (DI) water stabilized by amphiphilic GO under ultrasonication. The fabricated composite was characterized by SEM, TEM, FT-IR, and thermogravimetric analysis. Results showed that the particle surface could be wrapped with GO without the need for surfactants. In addition, electrorheological behavior of the chain-forming process of the PMMA/GO composite particles was observed by optical microscopy under an applied electric field. Both shear stress and shear viscosity related to the strength of the applied electric field were measured using a rotational rheometer. The proposed Cho–Choi–Jhon model was used to describe their ER performances for the entire shear rate region. Moreover, the response of the shear stress to an imposed square voltage at a fixed shear rate was also examined.     

Protein determination using graphene oxide-aptamer modified gold nanoparticles in combination with Tween 80

Recently, graphene oxide (GO) has shown superiority for disease detection arising from its unique physical and chemical properties. However, proteins adsorbed on the surface of GO prevent sensitivity improvement in fluorescence-based detection methods. In this paper, a label-free method based on aptamer modified gold nanoparticles (GNPs) combined with Tween 80 was shown to solve this problem using the detection of thrombin as an example. An aptamer was designed and bound to thrombin by changing its conformation. Tween 80 was used for rapid and reproducible synthesis of stable DNA-functionalized GNPs and prevented the thrombin from nonspecific binding to GO. Thrombin was detected with a limit of 0.68 pM by taking advantage of the efficient cross-linking effect of aptamer-GNPs to GO. The sensor was validated by determining thrombin concentration in human blood serum samples. The results indicate that this method has promising analytical application in medical diagnostic.     

Synthesis and characterization of poly(vinyl amine)‐based amphiphilic comb‐like dextran glycopolymers by a two‐step method

Poly(vinyl amine) (PVAm)‐based amphiphilic glycopolymers were synthesized by a two‐step method, that is dextran molecules (Dex, M_w = 1500) were attached to the PVAm backbone by reacting amine groups with dextran lactone, and then, hexanoyl groups (Hex) were attached by reacting the PVAm free amine groups with N‐(hexanoyloxy)succinimide. By adjustment of the feed ratios of Dex/Hex, amphiphilic comb‐like glycopolymers with various hydrophilic and hydrophobic balances were prepared, and their structures were characterized by ¹H NMR. Surface activity of the amphiphilic glycopolymers at the air/water interface was demonstrated by reduction in water surface tension. Adsorption of the amphiphilic glycopolymers at the solid/water interface was examined on octadecyltrichlorosilane (OTS)‐coated coverslips by water contact angle measurements. The results show that the amphiphilic glycopolymers need about 20 mol % of dextran attachment to make an effective hydrophilic coating. In comparison with the one‐step reaction by addition of dextran lactone and alkyl succinimide simultaneously, the two‐step approach can attach Dex on PVAm as high as possible in the first step, and offers quantitative advantages in controlling the ratio of hydrophilic and hydrophobic chains along the PVAm backbone, resulting in increased water solubility for the final amphiphilic glycopolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 192–199, 2006     

A facile graphene oxide-based DNA polymerase assay

The DNA polymerase assay is fundamental for related molecular biology investigations and drug screenings, however, the commonly used radioactive method is laborious and restricted. Herein, we report a novel, simple and cost-effective fluorometric DNA polymerase detection method by utilizing graphene oxide (GO) as a signal switch. In this strategy, in the absence of DNA polymerase, the fluorophore-labeled template ssDNA could be strongly adsorbed and almost entirely quenched by GO. However, as DNA polymerase exists, the polymerized dsDNA product might lead to a much lower quenching efficiency after addition of GO due to the much weaker interaction of dsDNA with GO than ssDNA, thus resulting in a much higher fluorescence signal detected. As proof of concept, the quantitative DNA polymerase activity assay was performed using the Klenow fragment exo(-) (KF(-)) as a model. It was confirmed that, after optimization of detection conditions, KF(-) activity could be sensitively detected through facile fluorescence measurements, with a detection limit of 0.05 U mL(-1) and a good linear correlation between 0.05-2.5 U mL(-1) (R(2) = 0.9928). In addition, this GO-based method was further inspected to evaluate the inhibitive behaviors of several drugs toward KF(-) activity, the result of which firmly demonstrated its potential application in polymerization-targeted drug screening.     

Processing micrometer-sized particles in crumpled graphene network for freestanding membrane enabled by freeze casting

Graphene oxide(GO)is widely used in the construction and application of various 2 D membrane-based materials due to its unique colloidal structure.Herein,we demonstrate that micrometer-sized particles can make up freestanding membranes enabled by the extraordinary amphiphilic and polymer-like properties of graphene oxide through freeze casting.The 2 D macromolecule,GO could well wrap the particles for better uniformity and stability in either dispersion or membrane.Importantly,freeze casting plays an important role in avoiding the severe aggregation of micrometer-sized particles in the solventremoving process.After reduction,the membrane exhibits good electrical conductivity while maintaining its integral structure,which can be directly used as a freestanding binder-free electrode.This work provides a universal approach to fabricate freestanding membranes with various micrometersized materials for energy storage.     

Preparation of Biocompatible Graphene Oxide Composite Hydrogel to Deliver Ophthalmic Drugs

Considering that conventional hydrogels showed limited capabilities of controlling hydrophobic drug loading and releasing and graphene materials had interactions with hydrophobic drugs, we designed a graphene oxide (GO) composite hydrogel for drug delivery. But GO could not disperse well in monomer solution and agglomerated badly. Thus, water-soluble GO (GO-tripolymer) was first prepared under the stabilization of amphiphilic polymer, Pluronic F-127. The GO-tripolymer showed good solubility in PBS with the increase of polymer concentration. All GO-tripolymer solutions had the same UV absorption peaks as GO. Then, GO composite hydrogels (HNG hydrogels) were formed by the polymerization of hydroxyethyl methacrylate (HEMA), N-Vinyl pyrrolidone (NVP) and GO-tripolymer mixture. The introduction of GO-tripolymer had little effect on the gelation time and equilibrium swelling ratio of hydrogel. The freeze-drying hydrogel showed porous structure. The pore size decreased and the rough surface was detected with the increase of GO concentration. HNG hydrogel could load more puerarin and norfloxacin than conventional hydrogel (HN hydrogel). Moreover, HNG hydrogel could control puerarin and norfloxacin release more steadily than HN hydrogel. HNG exhibited low cytotoxicity.