双分布聚乙二醇接枝纳米二氧化硅的高效可控制备

在混合溶剂中通过"grafting to"的方法将2种分子量不同的聚乙二醇单甲醚(MPEG M_w=750,4000)接枝到氨基修饰的St?ber法二氧化硅(SiO_2-NH_2)表面,制备双分布纳米接枝复合物.采用二步法,先将带环氧端基的低分子量聚乙二醇单甲醚(MPEG-EO)与SiO_2-NH_2在甲苯溶剂中充分反应后,与高分子量的MPEG-EO在甲苯和正癸烷的混合溶剂中使用相同的反应条件和后处理方法,能便捷制备出具有双分布接枝的纳米复合物.在接枝反应体系中,分子链的链段尺寸和接枝密度之间存在着密切关系.一定的范围内,接枝密度随链段尺寸减小而增大.通过改变混合溶剂比例来调控接枝链段的尺寸,可以很好控制聚合物的接枝密度.在双分布接枝的纳米复合物中,低分子量的接枝密度为0.85 chains/nm~2,高分子量的接枝密度能达到0.40 chains/nm~2,体现出了简单、高效、可控的特点,与聚环氧乙烷(PEO)共混后分散良好,对于制备出均匀分散的纳米复合材料起到了一定的指导作用.     

Periodic swelling and collapse of polyelectrolyte brushes driven by chemical oscillation

Poly(acrylic acid) (PAA) chains exhibit conformational change in response to pH, whereas bromate-sulfite-ferrocyanide (BSF) solution shows pH oscillation between 3.2 and 6.6. By use of quartz crystal microbalance with dissipation (QCM-D), we have investigated the pH induced conformational change of PAA brushes under a continuous flow of BSF solution in real time. The changes in frequency and dissipation clearly indicate the periodic swelling and collapse of brushes with pH oscillation. The changes in thickness, viscosity, and elastic modulus further indicate the oscillation of the interface.     

pH-responsive poly(methacrylic acid)-grafted hollow silica vesicles

Poly(methacrylic acid)-grafted hollow silica vesicles (PMAA-g-hollow silica vesicles) were obtained through a grafting-from approach. PMAA brushes were formed by performing atom-transfer radical polymerisation of sodium methacrylate with an initiator attached to the hollow silica spheres. PMAA-g-hollow silica vesicles were characterised by using TEM, thermogravimetric analysis (TGA) and FTIR spectroscopy. pH-dependent ξ potential and (1)H NMR spectra of PMAA-g-hollow silica vesicles were measured, and the results indicated that MAA brushes in PMAA-g-hollow silica vesicles had a lower ionisation degree and low solubility in acidic aqueous solution, for example, pH 3.4, but a higher ionisation degree and high solubility when the pH was higher than 7. Also it was demonstrated that calcein blue and fluorescein isothiocyanate (FITC) labelled dextran (M(n):10 kDa) could be encapsulated in the interiors of the PMAA-g-hollow silica vesicles with a negligible amount in PMAA brushes at pH 2, and pH-triggered release of calcein blue and FITC-labelled dextran from PMAA-g-hollow silica vesicles was observed at pH 7.4.     

Preparation and characterization of pure and mixed monolayers of poly(ethylene glycol) brushes chemically adsorbed to silica surfaces

We prepared pure and mixed monolayers of methoxy-terminated poly(ethylene glycol)s (m-PEG's) chemically attached to silica surfaces by using m-PEG silane coupling agents of three different molecular weights. These films were subsequently characterized in water by atomic force microscopy (AFM). Images of pure m-PEG monolayers showed the formation of polymer brushes on silica. Force curves between two modified surfaces suggested that an increase in the number of oxyethylene (OE) groups from 6 (PEG6 surface) to 43 (PEG43 surface) to 113 (PEG113 surface) decreased the flexibility of the m-PEG chains in the m-PEG brushes. Frictional force measurements also showed that the friction increased in the order PEG6 < PEG43 相似文献   

Single component and selective competitive protein adsorption in a patchy polymer brush: opposition between steric repulsions and electrostatic attractions

This work explores the use of "patchy" polymer brushes to control protein adsorption rates on engineered surfaces and to bind targeted species from protein mixtures with high selectivity but without invoking molecular recognition. The brushes of interest contain embedded cationic "patches" composed of isolated adsorbed poly(l-lysine) coils (PLL) that are about 10 nm in diameter and are randomly arranged on a silica substrate. Around these patches is a protein-resistant poly(ethylene glycol) (PEG) brush that is formed from the adsorption of a PLL-g-PEG graft copolymer on the remaining silica surface. Electrostatic attractions between individual cationic patches and the negative regions of approaching proteins may be energetically insufficient to bind proteins. Furthermore, protein-patch attractions are reduced by steric repulsions between proteins and the PEG brush. We show that protein adsorption, gauged by ultimate short-term coverages and by the initial protein adsorption rate, exhibits an adhesion threshold: pure PEG brushes of the architectures employed here and brushes containing sparse loadings of PLL patches do not adsorb protein. Above a critical PLL patch loading or threshold, protein adsorption proceeds, often dramatically. The PLL patch thresholds are specific to the protein of interest, allowing surfaces to be engineered to adhesively discriminate different proteins within a mixture. The separation achieved is remarkably sharp: one protein adsorbs, but the second is completely rejected from the interface. The surfaces in this study, by virtue of their well-controlled and well-characterized patchy nature, distinguish themselves from multicomponent brushes or brushes used to end-tether peptide sequences and nucleotides.     

A Rocket‐Like Encapsulation and Delivery System with Two‐Stage Booster Layers: pH‐Responsive Poly(methacrylic acid)/Poly(ethylene glycol) Complex‐Coated Hollow Silica Vesicles

Rocket‐like vesicles formed are composed of poly(acrylic aicd) (PMAA )/poly(ethylene glycol) (PEG) complex coated hollow silica spheres, and the structure and composition of the vesicles are characterized using TGA, ¹H NMR, FTIR, and TEM. Although only one‐third of EG units of PEG brushes grafted to hollow silica spheres form the complex with PMAA via hydrogen bonding, the first “booster” layer composed of PMAA/PEG complex can provide secure encapsulation of model compound calcein blue under an acidic condition. The second “booster” layer composed of PEG brushes can be formed by changing acidic pH to 7.4 through the disassociation of the PMAA/PEG complex. A higher molecular weight PMAA exhibits a faster disassembly due to the formation of a looser PMAA/PEG complex on the surfaces of hollow silica spheres.

     

基于硅胶整体材料研磨颗粒的多功能聚乙二醇键合固定相的制备及其在高效液相色谱多模式分离中的应用

研究通过对溶胶-凝胶法制备的硅胶整体材料进行研磨、浮选、假晶相转换和水热处理，最终获得了粒径为2~5 μm、孔径为20~60 nm的硅胶颗粒。利用部分含氟的阴离子表面活性剂Capstone FS-66和常用的阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）组成的双胶束模板体系对硅胶基质进行假晶相转换处理；再采用碳酸钠溶液水热处理的方式，进一步扩大孔径。用扫描电镜（SEM）和N₂吸附-解吸等温线测量对扩孔处理前后的硅胶整体材料研磨颗粒进行表征，结果清楚地显示了处理前后的形貌变化和差异。随后将含有长链聚乙二醇（PEG）的硅烷键合到扩孔后的硅胶颗粒表面，分别利用元素分析、红外光谱以及热重分析对固定相进行表征，并对固定相进行色谱性能评价。对键合固定相的元素分析和热重分析数据进行分析表明，硅胶表面键合PEG的含量约为8%。研究揭示了利用假晶相转换法与碳酸钠溶液水热处理和长链PEG硅烷修饰的硅胶整体材料颗粒在尺寸排阻色谱分离蛋白质方面的良好分离效果。同时进一步的高效液相色谱评价结果表明，该键合固定相还可用于疏水作用色谱模式分离核糖核酸酶A和溶菌酶，以及可用于亲水作用色谱模式分离吡啶甲酸、左旋多巴、三聚氰胺和邻苯二酚等极性比较强的化合物。研究显示了PEG键合固定相具有多功能性，及其在多模式高效液相色谱分离中的应用潜力。     

Nanosegregated polymeric domains on the surface of Fe3O4@SiO2 particles

Multifunctional, biocompatible, and brush‐grafted poly(ethylene glycol)/poly(ε‐caprolactone) (PEG/PCL) nanoparticles have been synthesized, characterized, and used as vehicles for transporting hydrophobic substances in water. For anchoring the polymer mixed brushes, we used magnetic‐silica particles of 40 nm diameter produced by the reverse microemulsion method. The surface of the silica particle was functionalized with biocompatible polymer brushes, which were synthesized by the combination of “grafting to” and “grafting from” techniques. PEG was immobilized on the particles surface, by “grafting to,” whereas PCL was growth by ROP using the “grafting from” approach. By varying the synthetic conditions, it was possible to control the amount of PCL anchored on the surface of the nanoparticles and consequently the PEG/PCL ratio, which is a vital parameter connected with the arrangement of the polymer brushes as well as the hydrophobic/hydrophilic balance of the particles. Thus, adjusting the PEG/PCL ratio, it was possible to obtain a system formed by PEG and PCL chains grafted on the particle's surface that collapsed in segregated domains depending on the solvent used. For instance, the nanoparticles are colloidally stable in water due to the PEG domains and at the same time are able to transport, entrapped within the PCL portion, highly water‐insoluble drugs. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2966–2975     

Study viscoelasticity of ultrathin poly(oligo(ethylene glycol) methacrylate) brushes by a quartz crystal microbalance with dissipation

Ultrathin polymer brushes play important roles in natural and artificial systems. To better understand and utilize their unique behaviors, characterization is a fundamental, but not trivial, task. In this paper, we demonstrated that the quartz crystal microbalance with dissipation (QCM-D) could be applied to study ultrathin poly(oligo(ethylene glycol) methacrylate) brushes. First, we identified four linear relations between dissipation/frequency changes and thickness changes, which were measured by QCM-D and ellipsometry, respectively. Next, we derived a set of equations starting from the Voigt model to further extract viscoelasticity of poly(OEGMA) brushes (相似文献   

表面接枝亲水性聚合物刷磁性微球的制备及其对蜂蜜中四环素类抗生素残留的磁分散固相萃取

采用电子转移活化再生催化剂原子转移自由基聚合法（ARGET-ATRP）在磁性微球（MMs）表面连续接枝了聚碱类聚合物和聚乙二醇刷。首先将MMs包覆硅胶,接枝氨基,然后在其表面接枝溴引发剂,最后在MMs表面进行聚合,制备了亲水性聚合物刷磁性微球（HMMs）。通过透射电镜、傅里叶变换红外光谱对HMMs进行表征,并研究了HMMs对蛋白质的吸附性能。结果表明,合成的HMMs粒径较为均一,分散性良好并且具有良好的抗蛋白质吸附性能。利用制备的HMMs,采用磁分散固相萃取（MDSPE）-高效液相色谱法（HPLC）测定了蜂蜜中四环素类抗生素（TCs）残留。TCs的平均回收率为85.8%~94.5%,方法的检出限和定量限分别为1.92~2.56 μg/kg和6.40~8.53 μg/kg。该方法成功地用于蜂蜜中TCs残留的快速分离富集。     

Collapse and swelling of thermally sensitive poly(N-isopropylacrylamide) brushes monitored with a quartz crystal microbalance

Thermally sensitive poly(N-isopropylacrylamide) (PNIPAM) brushes grafted on SiO2-coated quartz crystal surface were prepared with a surface-immobilized initiator. Using quartz crystal microbalance (QCM), we investigated the collapse and swelling of the brushes in water in real time. Both frequency and dissipation of PNIPAM brushes were found to gradually change throughout a temperature range 20-38 degrees C, indicating that PNIPAM brushes undergo a continuous collapse transition in contrast with PNIPAM chains free in dilute solution exhibiting a sharp coil-to-globule transition. This result is in accordance with the previous theoretical prediction. The nonuniformity and stretching of PNIPAM brushes as well as the cooperativity between collapse and dehydration transitions are thought to be responsible for the continuity. On the other hand, a hysteresis was also observed in the cooling process. This is not only due to the intrachain and interchain interactions formed in the collapsed state but also to the nonuniform structure and stretching of the high-density brushes.     

分子印迹聚合物功能化二氧化硅纳米颗粒的合成及其分离识别马兜铃酸

马兜铃酸是马兜铃科植物中含有硝基菲羧酸基团的一类物质,被广泛应用于各种疾病的治疗,研究表明含有马兜铃酸的植物或植物衍生产品对人体有害,需要监测药物中马兜铃酸的存在。分子印迹聚合物对目标物的高亲和力使其特别适合作为吸附剂从混合物中去除和识别目标物。以SiO₂胶体纳米颗粒为基底,利用表面分子印迹的方法合成了核-壳结构SiO₂表面印迹纳米颗粒(SiO₂@MIP NPs)。采用紫外可见光谱研究了模板分子马兜铃酸Ⅰ和功能单体丙烯酸、甲基丙烯酸、2-乙烯基吡啶、丙烯酰胺及甲基丙烯酰胺的作用,发现2-乙烯基吡啶与马兜铃酸Ⅰ的作用最强,被选为制备印迹聚合物的单体。采用傅立叶变换红外光谱仪(FT-IR)、透射电子显微镜(TEM)、热重分析仪、氮气吸附比表面分析仪对分子印迹聚合物进行了表征。TEM显示印迹纳米颗粒的粒径在270 nm左右,分子印迹层的厚度为35 nm,有利于模板分子的传输。TEM、FT-IR和热重分析仪的结果均证明实验成功合成了分子印迹聚合物。实验进一步研究了印迹聚合物SiO₂@MIP NPs和非印迹聚合物SiO₂@NIP NPs的吸附性能,并结合SiO₂@MIP NPs和SiO₂@NIP NPs的比表面积和孔径测定数据,发现SiO₂@MIP NPs表面的印迹位点是导致二者吸附差异的主要原因。SiO₂@MIP NPs和SiO₂@NIP NPs的动力学吸附表明SiO₂@MIP NPs具有快的吸附平衡时间(120 s),而且SiO₂@MIP NPs的吸附行为符合Langmuir单分子层吸附。SiO₂@MIP NPs的选择性通过印迹因子(IF)和选择性系数(SC)来评价。实验结果表明,SiO₂@MIP NPs具有高的印迹因子(4.9),对模板结构类似物有较好的选择性,选择系数为2.3~6.6。最后将制备的SiO₂@MIP NPs作为吸附剂用于加标中药样品川木通的预处理,用HPLC进行分析测定,方法的回收率为73%~83%,实验结果显示SiO₂@MIP NPs可作为高选择性材料用于中药中马兜铃酸的选择性分离分析。     

PLGA/O-CMC载药纳米粒子的体外释药行为研究

本文以聚乳酸-乙醇酸共聚物(PLGA)和自行制备的O-羧甲基壳聚糖(O-CMC)为原料,以5-氟尿嘧啶(5-FU)为抗癌药物模型,采用自身设计的改良复乳法制备了载药纳米微粒。微粒平均粒径为98.5nm,粒径分布指数为0.192,粒子表面∈电位为61．48eV,载药率高达18．9％,包封率为86％。然后用SEM动态监测载药纳米粒子降解过程中表面形貌的变化,并连续追踪粒子降解过程中的质量损失和降解介质的pH变化。载药纳米粒子在PBS中的释药行为研究表明：(1)前12h的释药动力学符合Huguchi方程,具有一级释放特性;(2)在20天内的释药动力学符合零级释放特性。     

Adsorption of polyelectrolyte multilayers and complexes on silica and cellulose surfaces studied by QCM-D

The adsorption of polyelectrolyte (PE) multilayers and complexes, obtained from both high- and low-charge polyelectrolytes, was studied on silica and on cellulose model surfaces by quartz crystal microbalance with dissipation (QCM-D). The film properties acquired with the different strategies were compared. When polyelectrolytes were added on an oppositely charged surface in sequence to form multilayers both the change in frequency and dissipation increased. The changes in frequency and dissipation were clearly higher if low-charge PEs were used in the multilayer formation. The substrate, silica or cellulose, did not affect the adsorption behaviour of low-charge PEs and only minor differences were seen in the adsorbed amounts and changes in dissipation of high-charge PEs between SiO₂ and cellulose. The complexes formed by low-charge PEs had higher changes in frequency and dissipation at low ionic strength on both surfaces, while the complexes formed from high-charge polyelectrolytes adsorbed more at high salt concentration. The complexes of low-charge polyelectrolytes adsorbed more on silica, while the complexes formed by high-charge PEs formed thicker layers on cellulose. The charge ratio had a significant effect on the adsorption and the highest changes in frequency and dissipation were obtained in the anionic/cationic charge ratio of 0.5–0.6. Generally, the multilayers and complexes formed by low-charge polyacrylamides adsorbed highly and formed rather thick layers on both surfaces, unlike the high-charge PEs which formed thin layers using either one of the addition techniques.     

Target‐Specific Capture of Environmentally Relevant Gaseous Aldehydes and Carboxylic Acids with Functional Nanoparticles

Aldehyde and carboxylic acid volatile organic compounds (VOCs) present significant environmental concern due to their prevalence in the atmosphere. We developed biodegradable functional nanoparticles comprised of poly(d,l ‐lactic acid)‐poly(ethylene glycol)‐poly(ethyleneimine) (PDLLA‐PEG‐PEI) block co‐polymers that capture these VOCs by chemical reaction. Polymeric nanoparticles (NPs) preparation involved nanoprecipitation and surface functionalization with branched PEI. The PDLLA‐PEG‐PEI NPs were characterized by using TGA, IR, ¹H NMR, elemental analysis, and TEM. The materials feature 1°, 2°, and 3° amines on their surface, capable of capturing aldehydes and carboxylic acids from gaseous mixtures. Aldehydes were captured by a condensation reaction forming imines, whereas carboxylic acids were captured by acid/base reaction. These materials reacted selectively with target contaminants obviating off‐target binding when challenged by other VOCs with orthogonal reactivity. The NPs outperformed conventional activated carbon sorbents.     

Fabrication of Micropatterned Gold Nanoparticle Arrays as a Template for Surface‐Initiated Polymerization of Stimuli‐Responsive Polymers

Summary: This paper demonstrates a new, reliable, and simple method for fabricating micropatterned nanoparticle arrays that can serve as templates for the surface‐initiated polymerization of polymer brushes. As a proof of concept, we micropatterned gold nanoparticles (Au‐NPs, ≈10 nm) onto glass, silicon, polystyrene, and gold surfaces by a simple three‐step process: (1) microcontact printing of soluble polymer, (2) incubation with a solution of Au‐NPs, and (3) lift‐off of the template in a mixture of ethanol and deionized water. 40 µm wide features were successfully fabricated without any significant defects or nonspecific adsorption on the background. To demonstrate the utility of these Au‐NP templates, we subsequently polymerized N‐isopropylacrylamide by surface‐initiated polymerization, using a surface‐bound initiator.

Synthesis of PNIPAAm brushes from micropatterned Au‐NP.     

Dielectric properties of PANI-PEG nanocomposites filled with silica media for antistatic applications

The dielectric investigations of porous synthetic silica gel modified with polyaniline (PANI) and polyethylene glycol (PEG) polyblend at various concentrations are demonstrated in this paper. By using the chemical oxidative process to embed polyaniline (PANI) and polyethylene glycol (PEG) into a silica matrix, conducting gel nanocomposites were synthesized. For various dopant concentrations, the dielectric permittivity (ε′), D.C. conductivity (σ_dc), loss tangent (tanδ) and dielectric loss (ε″) were investigated. The samples were characterized using differential thermal analysis/thermogravimetric analysis, Fourier transform infrared spectroscopy and high-resolution transmission electron microscopy. Depending on the co-blend content, PANI-PEG modified silica structures produce nanoparticles ranging in size from 9.9 to 48.1 nm. The variation of DC conductivity (σ_dc) with PANI/PEG content shows Maxwell-Wagner Sillars (MWS) effect confirming the role of the conjugation and the structural order.     

Effects of Grafting Density and Film Thickness on the Adhesion of Staphylococcus epidermidis to Poly(2‐hydroxy ethyl methacrylate) and Poly(poly(ethylene glycol)methacrylate) Brushes

Thin polymer films that prevent the adhesion of bacteria are of interest as coatings for the development of infection‐resistant biomaterials. This study investigates the influence of grafting density and film thickness on the adhesion of Staphylococcus epidermidis to poly(poly(ethylene glycol)methacrylate) (PPEGMA) and poly(2‐hydroxyethyl methacrylate) (PHEMA) brushes prepared via surface‐initiated atom transfer radical polymerization (SI‐ATRP). These brushes are compared with poly(ethylene glycol) (PEG) brushes, which are obtained by grafting PEG onto an epoxide‐modified substrate. Except for very low grafting densities (ρ = 1%), crystal violet staining experiments show that the PHEMA and PPEGMA brushes are equally effective as the PEG‐modified surfaces in preventing S. epidermis adhesion and do not reveal any significant variations as a function of film thickness or grafting density. These results indicate that brushes generated by SI‐ATRP are an attractive alternative to grafted‐onto PEG films for the preparation of surface coatings that resist bacterial adhesion.

     

Bacterial adhesion on hybrid cationic nanoparticle-polymer brush surfaces: ionic strength tunes capture from monovalent to multivalent binding

This paper describes the creation of hybrid surfaces containing cationic nanoparticles and biocompatible PEG (polyethylene glycol) brushes that manipulate bacterial adhesion for potential diagnostic and implant applications. Here, ～10 nm cationically functionalized gold nanoparticles are immobilized randomly on negative silica surfaces at tightly controlled surface loadings, and the remaining areas are functionalized with a hydrated PEG brush, using a graft copolymer of poly-l-lysine and PEG (PLL-PEG), containing 2000 molecular weight PEG chains and roughly 30% functionalization of the PLL. The cationic nanoparticles attract the negative surfaces of suspended Staphylococcus aureus bacteria while the PEG brush exerts a steric repulsion. With the nanoparticle and PEG brush heights on the same lengthscale, variations in ionic strength are demonstrated to profoundly influence the capture of S. aureus on these surfaces. For bacteria captured from gentle flow, a crossover from multivalent to univalent binding is demonstrated as the Debye length is increased from 1 to 4 nm. In the univalent regime, 1 um diameter spherical bacteria are captured and held by single nanoparticles. In the multivalent regime, there is an adhesion threshold in the surface density of nanoparticles needed for bacterial capture. The paper also documents an interesting effect concerning the relaxations in the PLL-PEG brush itself. For brushy surfaces containing no nanoparticles, bacterial adhesion persists on newly formed brushes, but is nearly eliminated after these brushes relax, at constant mass in buffer for 12h. Thus brushy relaxations increase biocompatibility.     

纳米SiO_2/含氟丙烯酸酯共聚物复合乳液的制备与性能及聚合动力学研究

采用原位聚合法制备纳米SiO2/含氟丙烯酸酯共聚物复合乳液,研究了其聚合反应动力学,并通过红外光谱(IR)、透射电子显微镜(TEM)、热失重(TGA)等方法表征所得产物的结构及形态、乳胶膜的耐热性能和表面性能.研究结果显示,聚合反应的表观活化能为83.15 kJ/mol,纳米SiO2/含氟丙烯酸酯共聚物复合粒子呈现出明显的核壳结构,纳米SiO2粒子的引入不仅改善了聚合物的耐热性能,也在一定程度上提高了乳胶膜的抗水性.对膜表面自由能的组成分析表明,与一般含氟乳胶膜的表面自由能的情况相反,该乳胶膜的表面能是由较大的极性部分和较小的色散部分组成.