Molecular‐level structures at poly(4‐vinyl pyridine)/acid interfaces probed by nonlinear vibrational spectroscopy

The molecular structures of the interfaces between a solid poly(4‐vinyl pyridine) (P4VP) surface and poly(acrylic acid) (PAA) as well as hydrochloric acid (HCl) solutions were probed using sum frequency generation (SFG) vibrational spectroscopy in situ in real time. Spectroscopic results clearly reveal that the PAA molecules are adsorbed onto the P4VP surface via hydrogen bonding at the P4VP/PAA solution interface while the P4VP surface is protonated at the P4VP/HCl solution interface. Consequently, the water molecules near the interfaces are strongly perturbed by these two interactions, exhibiting different orderings at the two interfaces. This work clearly demonstrates the power of studying the interfacial molecular‐level structures via nonlinear vibrational spectroscopy when molecular adsorption happens at the solid–liquid interface and paves a way for our future study on tracing the adsorption dynamics of polymer chains onto solid surfaces. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 848–852     

Aspects of the physical chemistry of polymers, biomaterials and mineralised tissues investigated with atomic force microscopy (AFM)

Beyond being merely a tool for measuring surface topography, atomic force microscopy (AFM) has made significant contributions to various scientific areas dealing with physical chemistry processes. This paper presents aspects of the physical chemistry at surfaces and interfaces of polymers, biomaterials and tissues investigated with AFM. Selected examples presented include surface induced self-assembly of polymer blends, copolymer interfacial reinforcement of immiscible homopolymers, protein adsorption on biomaterials and erosion of mineralised human tissues. In these areas, AFM is a useful and versatile tool to study structural or dynamic sample properties including thermodynamically driven surface evolution of polymer surfaces, lateral surface composition of interfaces, adsorption processes, and the metrology of demineralisation phenomena.     

Glass bead grafting with poly(carboxylic acid) polymers and maleic anhydride copolymers

Glass beads were etched with acids and bases to increase the surface porosity and the number of silanol groups that could be used for grafting materials to the surfaces. The pretreated glass beads were functionalized using 3‐aminopropyltriethoxysilane (APS) coupling agent and then further chemically modified by reacting the carboxyl groups of carboxylic acid polymers with the amino groups of the pregrafted APS. Several carboxylic acid polymers and poly(maleic anhydride) copolymers, such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA), poly(styrene‐alt‐maleic anhydride) (PSMA), and poly(ethylene‐alt‐maleic anhydride) (PEMA) were grafted onto the bead surface. The chemical modifications were investigated and characterized by FT‐IR spectroscopy, particle size analysis, and tensiometry for contact angle and porosity changes. The amount of APS and the different polymer grafted on the surface was determined from thermal gravimetric analysis and elemental analysis data. Spectroscopic studies and elemental analysis data showed that carboxylic acid polymers and maleic anhydride copolymers were chemically attached to the glass bead surface. The improved surface properties of surface modified glass beads were determined by measuring water and hexane penetration rates and contact angle. Contact angles increased and porosity decreased as the molecular weights of the polymer increased. The contact angles increased with the hydrophobicity of the attached polymer. The surface morphology was examined by scanning electron microscopy (SEM) and showed an increase in roughness for etched glass beads. Copyright © 2007 John Wiley & Sons, Ltd.     

Adsorption of PEO-PPO-PEO triblock copolymers with end-capped cationic chains of poly(2-dimethylaminoethyl methacrylate)

We study the adsorption of a symmetric triblock copolymer of ethylene oxide, EO, and propylene oxide, PO, end-capped with quarternized poly(2-dimethylaminoethyl methacrylate), DMAEMA (DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24)). Light scattering and tensiometry are used to measure the relative size of the associated structures and surface excess at the air-liquid interface. The adsorbed amount, the amount of coupled water, and the viscoelasticity of the adsorbed polymer layer are measured on hydrophobic and hydrophilic surfaces (polypropylene, cellulose, and silica) by using quartz crystal microgravimetry (QCM) and surface plasmon resonance (SPR) at different ionic strengths and temperatures. The results of the experiments are compared with those obtained after adsorption of the uncharged precursor copolymer, without the cationic end-caps (EO(132)PO(50)EO(132)). DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24) possesses higher affinity with the negatively charged silica and cellulose surfaces while the uncharged copolymer adsorbs to a larger extent on polypropylene surfaces. In this latter case, adsorption increases with increasing solution ionic strength and temperature. Adsorption of EO(132)PO(50)EO(132) on silica surfaces has little effect on the water contact angle (WCA), while adsorption of DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24) increases the WCA of silica to 32°, indicating a large density of exposed PPO blocks upon adsorption. After adsorption of EO(132)PO(50)EO(132) and DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24) on PP, the WCA is reduced by ≈14° and ≈28°, respectively, due to the exposed hydrophilic EO and highly water-soluble DMAEMA segments on the surfaces. The extent of surface coverage at saturation at the polypropylene/liquid interfaces (≈31 and 40 nm(2)/molecule obtained by QCM and SPR, respectively) is much lower, as expected, when compared with results obtained at the air/liquid interface, where a tighter packing is observed. The percentage of water coupled to the adsorbed cationic polymer decreases with solution ionic strength. Overall, these observations are ascribed to the effects of electrostatic screening, polymer hydrodynamic size, and solvency.     

Adsorption of linear and star-shaped polyelectrolytes to monolayers of charged amphiphiles

Adsorption of polyelectrolytes has been studied employing monolayers of ionic amphiphiles at the air water interface as model surfaces. The adsorption of polyelectrolytes from a solution brought into contact with the amphiphile monolayer results in changes of the monolayer structure and properties. Monitoring these changes can be done by recording the changes in surface pressure. The kinetics of the adsorption depends strongly on the nature of the polyelectrolyte. Depending on the structure of the polyelectrolyte a purely diffusion controlled adsorption or a sequence of diffusion controlled adsorption and ordering processes have been identified to determine the kinetics. The influence of the molecular architecture on the polyelectrolyte adsorption has been further studied employing linear and star shaped poly(acrylic acid) and poly(N-propyl-4-vinyl pyridinium bromides), respectively. An unexpected behavior with an induction period in the adsorption kinetics of both polymers has been found. Furthermore, the degree of branching has only very minor effects on the adsorption kinetics.     

Use of cellulose derivatives on gold surfaces for reduced nonspecific adsorption of immunoglobulin G

This study addresses the design of protein-repellent gold surfaces using hydroxyethyl- and ethyl(hydroxyethyl) cellulose (HEC and EHEC) and hydrophobically modified analogues of these polymers (HM-HEC and HM-EHEC). Adsorption behavior of the protein immunoglobulin G (IgG) onto pure gold and gold surfaces coated with cellulose polymers was investigated and described by quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM) and contact angle measurements (CAM). Surfaces coated with the hydrophobically modified cellulose derivatives were found to significantly outperform a reference poly(ethylene glycol) (PEG) coating, which in turn prevented 90% of non-specific protein adsorption as compared to adsorption onto pure gold. HEC and EHEC prevented around 30% and 60% of the IgG adsorption observed on pure gold, while HM-HEC and HM-EHEC were both found to completely hinder biofouling when deposited on the gold substrates. Adsorption behavior of IgG has been discussed in terms of polymer surface coverage and roughness of the applied surfaces, together with hydrophobic interactions between protein and gold, and also polymer-protein interactions.     

Protein adsorption on polymer-modified silica particle surface

Silicon substrate surface and silica particle surface were modified with five kinds of polymers, poly(2-methoxyethyl methacrylate) (pMEMA), poly(2-hydroxyethyl methacrylate) (pHEMA), poly(acrylamide) (pAAm), poly(methyl methacrylate) (pMMA), and poly(styrene) (pSt), using a combined polymerization of surface-initiated polymerization that gives dense polymer chain layers and atom transfer radical polymerization (ATRP) that yields polymers with a narrow molecular weight distribution. Measurements of water contact angle and polymer chain amount on the modified silicon substrate surface and adsorption amounts of proteins (albumin and fibrinogen) on the modified silica particle surface revealed that the amount of polymer on the modified surface greatly affects the suppression of protein adsorption on the surface.     

Single-step process to produce surface-functionalized polymeric nanoparticles

Nanoparticles (NPs) are a versatile medium for the localization of therapeutics to tumors and for cellular and tissue imaging. The ability to impart targeting capability or enhance cellular uptake is dependent in part on the presentation of relevant surface functionality, among other design parameters. Currently, the production of functionalized polymeric NPs requires the a priori synthesis of polymers bearing such functionality. Here we describe a process to produce functionalized polymeric NPs derived from nonfunctional polymers in a single step. This was achieved by tailoring the solvation of the polymer using a binary solvent system such that the addition of an aqueous phase rich in water-soluble polymer or polyelectrolytes results in the formation of NPs with the concomitant functionalization of NP surfaces with the polymeric moieties introduced into the aqueous phase. This strategy also allows for easy control over NP size independent of surface functionality. We have demonstrated that poly(lactic-co-glycolic acid) (PLGA) NPs bearing surface functionality as diverse as biological polysaccharides such as heparin, water-soluble ionic polymers, and poly(ethylene glycol) can be prepared under identical conditions in a single step, with surface coverage (mass %) ranging from 3 to >70%. We expect this novel process to enable complex surface engineering of NP chemistry that hitherto was impossible using existing approaches.     

PAA/PEO comb polymer effects on rheological properties and inter-particle forces in aqueous silica suspensions

The effects of a poly(acrylic acid) (PAA)-poly(ethylene) (PEO) comb polymer dispersant on the rheological properties and inter-particle forces in aqueous silica suspensions have been studied under varying pH conditions. The comb polymer was found to adsorb more strongly under acidic than basic conditions, indicating that the PAA backbone of the copolymer preferentially adsorbs onto silica surfaces with the PEO "teeth" extending out from the surface into the solution. In the presence of low concentrations of copolymer, the silica suspensions were stable due to electrostatic repulsions between the silica surfaces. At higher copolymer concentrations and under neutral and basic conditions, where the copolymer interacted only weakly with silica, the suspensions showed a transition from a dispersed to weakly flocculated state and attractive forces were measured between silica surfaces. Under acidic conditions, the silica dispersion also destabilized at intermediate copolymer adsorbed density and then was re-stabilized at higher adsorbed coverage. The silica suspensions were stable at high copolymer coverage due to steric repulsions between the particles. The destabilization at intermediate coverage is thought to be due to polymer bridging between particles or possibly depletion forces.     

Adsorption/Desorption Behavior of Bovine Serum Albumin and Porcine Insulin on Chemically Patterned Porous Gel Networks

Adsorption/desorption of proteins onto a biomaterial surface plays a major role on the biocompatibility of the implanted material. By modifying the biomaterial surface with specially designed functional groups one may achieve the most specific behavior of the developed material used in a biological system. Based on that, porous gel matrixes with functionalized surfaces offer unlimited possibilities to control the protein-substrate interaction behavior. In the present work, we have functionalized the surface of porous glass with several chemical groups during the synthesis of the silica matrix. The porous glass matrixes were obtained using tetraethoxysilane (TEOS)/ethanol and functionalized with 3-mercaptopropyltrimethoxysilane (MPTMS) and 3-aminopropyltriethoxysilane (APTES). In vitro tests of the kinetics of protein adsorption and desorption from the gel matrix were monitored by UV-visible spectroscopy. The bioactivity of the incorporated protein was verified by in vivo experiments with adult male rats, where they presented an acute hypoglycemic peak.     

Viscoelastic properties of fibrinogen adsorbed to the surface of biomaterials used in blood-contacting medical devices

The hemocompatibility of polymeric vascular implants is in part dependent on the propensity of fibrinogen to adsorb to the implant surface. Fibrinogen surface adsorption was measured in real time using a quartz crystal microbalance with dissipation monitoring (QCM-D). Six new, biodegradable tyrosine-derived polycarbonates were used as test surfaces. Stainless steel, poly(L-lactic acid), poly(D,L-lactide-co-glycolide), and poly(ethylene terephthalate) surfaces served as controls and provided a comparison of the test surfaces with those of commonly used biomaterials. Our study addressed the question regarding to which extent systematic variations in polymer structure can be used to optimize X-ray visibility and provide tunable degradation rates while generating protein-repellant surface properties that minimize fibrinogen adsorption. QCM-D revealed surface-dependent changes in fibrinogen layer thickness (2 to 37 nm), adsorbed wet mass (0.2 to 4.3 microg/cm2), and viscosity (0.001 to 0.005 kg/ms). While we did not find an overall correlation between surface air-water contact angle measurements and fibrinogen adsorption (R2 = 0.08), our data demonstrate that gradually increasing the poly(ethylene glycol) content within a subgroup of polymers having the same polymer backbone will lead to decreased fibrinogen adsorption. Within this subgroup of polymers, there was a strong correlation between decreasing air-water contact angles and decreasing fibrinogen adsorption (R2 = 0.95). We conclude that it is possible to minimize fibrinogen adsorption to tyrosine-derived polycarbonates while optimizing X-ray visibility and degradation rates. Some of the tyrosine-derived polycarbonates were identified as useful materials for the design of blood-contacting implants on the basis of their substantially lower levels of fibrinogen adsorption relative to the commonly used controls.     

Preparation of thin surface layers by grafting of PEO

We have developed a two‐stage process to graft poly(ethylene oxide) (PEO) onto a silica surface. In the first stage the adsorption of an anchor reactive polymer to the surface is carried out, and in the second stage the grafting of compatibilizing macromolecular tails is performed via the reactions of functional groups of the polymer anchored. Random copolymers of styrene and maleic anhydride (SM) were chosen as reactive anchoring polymers. The kinetics of adsorption of SM from dilute solutions onto the silica surface as well as the grafting of PEO to SM macromolecules adsorbed was experimentally investigated by null ellipsometry. A model of the structure at the surface is proposed.     

Novel fabrication of Janus particles from the surfaces of electrospun polymer fibers

A novel synthetic approach for the efficient fabrication of Janus silica particles was demonstrated by embedment of zero-dimensional colloids on one-dimensional polymer fiber surfaces, followed by the surface modification on the exposed silica hemispheres. Electrospinning of poly(methyl methacrylate) and poly(4-vinyl pyridine) blends produced polymer fibers with high specific surface area and desired surface hydrophilicities. Fiber compositions determined the colloid adsorption density and uniformity. The colloid embedding resulted from the polymer softening was manipulated by the isothermal heat treatment. Subsequent silianization completed the amino functionalities on hemispherical surfaces of embedded silica colloids. Janus particles with uniform asymmetric chemical features were further labeled with gold nanoparticles before their recovery from fiber substrates. Fabrication of Janus particles, including colloid adsorption, temperature-driven embedding, and hemispherical surface modification, were investigated and are discussed.     

Relaxation phenomena of hydrolyzed polyvinylamine molecules adsorbed at the silica/water interface I. Saturated homogeneous polymer layers

Surface area exclusion chromatography was used to investigate the adsorption and reconformation characteristics of hydrolyzed polyvinylamine molecules at silica/water interfaces employing radiolabeled polymers. The polymer solution was injected at the inlet of the column, whereas the polymer was successively adsorbed on the stacked glass-fiber filters constituting the stationary phase of the column. The filters and effluent samples collected at the outlet were individually analyzed for radioactivity content, which provided the adsorption histogram and the relative affinity of the various polymers. For saturated polymer layers, the relaxation process was demonstrated when the exceedingly adsorbed molecules desorbed. Modifications in the adsorption on the successive filters were thus converted into changes in the interfacial area of adsorbed molecules, taking into account the deviation from the plateau adsorption expected for nonrelaxing systems. Adsorption characteristics of nonrelaxed polymer layers were determined from the adsorption values determined before relaxation occurred. Adsorption and relaxation characteristics were determined to depend strongly on molecular weight and degree of hydrolysis of the polyvinylamine molecules. Half-hydrolyzed polymers had adsorption and relaxation characteristics close to those of the fully hydrolyzed polyvinylamine. Accordingly, adsorption isotherms on the cellulose/water interface were carried out to possibly extend the main conclusions of the study.     

Liquid chromatography of macromolecules at the critical adsorption point. II. Role of column packing: Bare silica gel

Liquid chromatography of macromolecules at the critical adsorption point (LC CAP) presents a potentially very powerful method for molecular characterization of complex polymers. However, LC CAP applicability is limited due to various experimental problems. The pore sizes and surface chemistry of the column packings belong to the most important weak points of the method. The LC CAP behavior of poly(methyl methacrylate)s was investigated using bare silica gels of 6, 12, and 100 nm pore sizes and with various amounts of surface silanols. Tetrahydrofuran as the adsorption suppressing liquid and toluene as the adsorption promoting liquid were mixed to form the “nearly critical” eluents. Both pore size and surface chemistry of silica were found to strongly influence the retentive characteristics of the system in the critical adsorption area. Macromolecules that were large enough to be excluded from the packing pores hardly followed the LC CAP rules: their retention volumes changed irregularly with the polymer molar mass and their recovery dropped sharply. The narrow pore silica gel-packed column governed the elution patterns of the whole column set composed of silica gels with different pore sizes. This makes the conventional LC CAP characterization of common polymers with broader molar mass distribution impractical and even not feasible. A hybrid column system was proposed containing narrow pore nonadsorptive column added in series to the meso- and macroporous LC CAP silica gels. This narrow pore column would allow separation of gas, impurities, and system peaks from the polymer peaks. The possible successive changes of the surface of silica gel, e.g., due to formation of silanols by hydrolysis or due to irreversible adsorption of some admixtures from the sample or eluent may make the LC CAP irrepeatable. Pronounced peak broadening was observed in the critical adsorption area and this effect increased strongly with the polymer molar mass. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1363–1371, 1998     

Unique Possibilities of Dynamic Metal–Polymer Interactions in Selective Hydrogenation

Rationally designed polymers can function as supports or promoters for metal catalysts, imparting distinct catalytic properties in selective hydrogenation. With strongly metal–ligating functional groups, mobile polymer chains can spontaneously decorate the metal catalyst surfaces under mild conditions, forming stable metal–polymer interfaces. We have termed this phenomenon ‘dynamic metal–polymer interaction (DMPI),’ which can be roughly considered as an organic version of the strong metal–support interaction (SMSI) concept. The polymer chains that dynamically interact with the metal surface can control the adsorption of reactants and products through competitive adsorption, significantly improving selectivity and catalyst stability. One of the remarkable advantages of using polymers as catalytic materials is that their molecular structures, such as molecular weight, crystallinity, and chemical functionality, can be tailored using rich organic chemistry. This, in turn, allows us to precisely tune the metal–polymer interactions and catalytic properties. In this Concept, we will discuss how metal–polymer interfaces can be designed and utilized for selective hydrogenation, with a particular emphasis on the industrially relevant acetylene partial hydrogenation reaction.     

Contact angles as indicators of the polymer surface structure

The capacities of the wetting method for the characterization of the surface structure of polymers and surfactant adsorption layers on polymer surfaces and also the determination of the energy characteristics of polymer surfaces at different interfaces, which are used to optimize the choice of polymers in the solution of actual practical problems, are demonstrated.     

疏水/亲水性聚二乙烯基苯/聚丙烯酸大孔互穿聚合物网络树脂对苯胺的吸附性能

采用分步悬浮聚合法制备了聚二乙烯基苯/聚丙烯酸甲酯（PDVB/PMA）大孔互穿聚合物网络,将其中的聚丙烯酸甲酯转化为聚丙烯酸,得到具有疏水/亲水性能的聚二乙烯基苯/聚丙烯酸（PDVB/PAA）大孔互穿聚合物网络（IPN）,研究了这类疏水/亲水大孔PDVB/PAA IPN对苯胺的吸附热力学和吸附动力学,测定了该树脂的孔结构、含水量、弱酸交换量和溶胀性能;测定了该树脂对苯胺在不同温度下的吸附等温线,利用热力学函数关系计算了吸附焓、自由能和熵。 红外光谱显示,成功合成了疏水/亲水PDVB/PAA IPN,与PDVB、PDVB/PMA IPN树脂相比,其BET表面积以及孔容均减小,含水量为62.73％,弱酸交换量为1.91 mmol/g;对苯胺的吸附为放热、自发的过程;溶胀实验、静态解吸实验表明,PDVB/PAA IPN树脂中疏水性的PDVB网具有疏水作用吸附能力,亲水性的PAA网具有氢键作用吸附能力。 对苯胺的吸附在90 min时即可达到吸附平衡,树脂吸附苯胺符合一级速率方程,吸附速率主要受颗粒内扩散的控制,同时还受液膜扩散的影响,吸附动力学可采用HSDM模型描述。     

Adsorption of hydrophilic-hydrophobic block copolymers on silica from aqueous solutions

Adsorption of a water-soluble diblock copolymer, poly(t-butylstyrene)-sodium poly(styrene sulfonate) (PtBS-NaPSS), on silica surfaces in aqueous solutions was studied using ellipsometry and atomic-force microscopy (AFM). Molar masses of 87 000 and 160 000 g/mol were used. The block copolymers used were compositionally asymmetric, with large, hydrophilic, PSS blocks and small, hydrophobic, PtBS blocks. Adsorption could not be observed in pure water without added salt. When the NaCl concentration was increased to 1 mol/L, adsorption could be readily observed. The measured adsorbed amount at long times was significantly larger for the 87 000 diblock compared with that for a polyelectrolyte homopolymer of comparable molecular size, demonstrating the role played by the uncharged block in anchoring the diblock at the solid surface. The kinetics of adsorption showed a two-stage process, an initial diffusion-limited stage, followed by a slower buildup of surface coverage in a brush-limited stage. The number density of molecules at the surface was smaller for the higher molecular weight species, in agreement with simple scaling arguments.     

Silica Polyamine Composites: New Supramolecular Materials for Cation and Anion Recovery and Remediation

Summary: The surface coverage of amorphous silica gels used in the synthesis of silica polyamine composites has been investigated by ²⁹Si NMR. By diluting the polyamine anchor silane, chloropropyl trichlorosilane, with methyl trichlorosilane it was found that surface coverage could be markedly improved for a range of amine polymers after grafting to the silica surface. The commensurate decrease in the number of anchor points and increase in the number of free amines results in an increase in metal capacity and/or an improvement in capture kinetics. Solid state CPMAS-¹³C NMR has been employed to investigate the structure and metal ion binding of a series of these composite materials. It is reported that the highly branched polymer, poly(ethyleneimine) (PEI) exhibits much broader ¹³C NMR resonances than the linear polymers poly(allylamine) (PAA) and poly(vinylamine) (PVA). These results are understood in terms of the low energy conformations calculated from molecular modeling studies. Three new applications of the technology are also presented: 1) separation of lanthanides as a group from ferric ion and all other divalent ions; 2) a multi step process for recovering and concentrating the valuable metals in acid mine drainage; 3) a process for removing low level arsenic and selenium in the presence of sulfate using immobilized cations on the composite materials.