The production and verification of pristine semi-fluorinated thiol monolayers on gold

In this work the interaction between human serum albumin (HSA) and a monofluorinated phospholipid, 1-palmitoyl-2-[16-fluoropalmitoyl-phosphatidylcholine] (F-DPPC), was studied by using Langmuir monolayer and Brewster angle microscopy (BAM) techniques. Different amounts of F-DPPC were spread on a previously formed HSA monolayer located at the air/water interface at 25 °C and the mixed monolayers thus obtained showed the existence of a liquid expanded-liquid condensed (LE-LC) phase transition (at 14 mN/m), attributed to the pure F-DPPC monolayer, coexisting with a second transition (at 22-24 mN/m) corresponding to the protein conformational change from an unfolded state to another in “loops” configuration. Relative thickness measurements recorded during the compression of the mixed monolayers showed the existence of an “exclusion” surface pressure (π_exc), above which the protein is squeezed out the interface, but not totally. BAM images reveal that some protein molecules in a packed “loops” configuration remain at the interface at surface pressures higher than the “exclusion” surface pressure. The application of the Defay-Crisp phase rule to the phase diagram of the F-DPPC/HSA system can explain the existence of certain regions of surface pressure in which the mixed monolayer components are miscible, as well as those others that they are immiscible.     

Pyrene-containing polystyrene segmented copolymer from nitroxide mediated polymerization and its application for the noncovalent functionalization of as-prepared multiwalled carbon nanotubes

This study reports simple and convenient procedures for the preparation of a novel surface modifier for multiwalled carbon nanotubes (CNTs) having uniform and controlled structure through controlled “living” free-radical polymerization technique. The technique afforded pyrene functionalized polystyrene block copolymers (PMAS) having controlled molecular weight, molecular weight distribution and length of each block for effective surface modification of CNTs. The modified CNTs exhibited much improved and stable dispersion in toluene. PMAS-CNT/polystyrene composites afforded clearer and more homogeneous films compared to those containing non-modified CNTs. The polystyrene films containing 2 wt% and 5 wt% of PMAS-CNTs showed improved AC conductivities of approximately 10⁻³ and 10⁻² S/cm, respectively, which were 10 ∼ 10⁶ times higher than those of films containing non-modified CNTs. These results demonstrated that PMAS effectively modified the surface of CNTs, which resulted in improved dispersion of CNTs in polystyrene matrices.     

Flame retardancy of silicone-based materials

This review describes some recent works related to the development of the flame retardation of silicone elastomers and/or applications of silicones as flame retardant agents in other polymers. First, the thermal degradation of silicones themselves is discussed, focussing on depolymerization mechanisms, effect of structure, heating conditions, and effect of additives (i.e. less than 5 wt% fillers) on thermal degradation of silicones. Then, the influence of several types of mineral fillers (of up to 80 wt% content) as ceramization agents of silicones is presented. Finally, the introduction of (functionalized) silicones as flame retardants into other polymers is described.     

Elastic behavior of MFI-type zeolites: Compressibility of H-ZSM-5 in penetrating and non-penetrating media

The elastic behavior of H-ZSM-5 was investigated by in-situ synchrotron X-ray powder diffraction, using both silicone oil (s.o.) and (16:3:1) methanol:ethanol:water (m.e.w.) as “non-penetrating” and “penetrating” pressure transmitting media, respectively. From P_amb to 6.2 GPa the volume reduction observed in s.o. is 16.6%. This testifies that H-ZSM-5 is one of the most flexible microporous materials up to now compressed in s.o. Volume reduction observed in m.e.w. up to 7.6 GPa is 14.6%. A strong increase in the total electron number of the extraframework system, due to the penetration of water/alcohol molecules in the pores, is observed in m.e.w. This effect is the largest up to now observed in zeolites undergoing this phenomenon without cell volume expansion. The higher compressibility in s.o. than in m.e.w. can be ascribed to the penetration of the extra-water/alcohol molecules, which stiffen the structure and contrast the channel deformations.     

Preparation and surface properties of latexes with fluorine enriched in the shell by silicon monomer crosslinking

A series of core-shell acrylic copolymer latexes containing fluorine enriched in the shell have been prepared by emulsion polymerization of a variety of hydrocarbon monomers with (perfluoroalkyl)methyl methacrylate and vinyltriethoxysilicone. In the presence of a reactive anionic and a long chain anionic-nonionic emulsifier, the core-shell latexes were prepared and characterized by transmission electron microscopy (TEM) and tapping-mode atomic force microscopy (AFM). From AFM and contact angle measurements, it was observed that the resulting fluorine and silicon-containing acrylic copolymers with surface energy as low as 15.5 mN/m formed a dense and gradient film containing a surface layer with high a fluorine content, and that the fluorinated particles can be fixed on the surface due to the crosslinking reaction of multi-functional silicon monomer even though the fluorinated carbon number was not enough to crystallize.     

Surface modification of polymeric microspheres using glycopolymers for biorecognition

We report the synthesis and characterization of sugar-containing microspheres consisting of poly(divinylbenzene) (PDVB) cores onto which chains of galactose- or mannose-bearing polymers have been grafted. PDVB particles prepared by distillation polymerization with a diameter of 2.4 μm containing residual surface vinyl groups were used as starting material. “Grafting from”, “grafting through” and “grafting to” techniques were performed and special interest was laid towards the resulting grafting densities. The surface modification via “grafting from” was conducted by reversible addition fragmentation chain transfer (RAFT) polymerization directly from the surface, whereas thiol-ene chemistry was used to affix glycopolymer chains onto the particle surface. The resulting sugar-covered microspheres were analyzed towards their protein recognition activity with a series of lectins.     

An exonuclease-assisted amplification electrochemical aptasensor of thrombin coupling “signal on/off” strategy

In this work, a dual-signaling electrochemical aptasensor based on exonuclease-catalyzed target recycling was developed for thrombin detection. The proposed aptasensor coupled “signal-on” and “signal-off” strategies. As to the construction of the aptasensor, ferrocene (Fc) labeled thrombin binding aptamer (TBA) could perfectly hybridize with the methylene blue (MB) modified thiolated capture DNA to form double-stranded structure, hence emerged two different electrochemical signals. In the presence of thrombin, TBA could form a G-quadruplex structure with thrombin, leading to the dissociation of TBA from the duplex DNA and capture DNA formed hairpin structure. Exonuclease could selectively digest single-stranded TBA in G-quadruplex structure and released thrombin to realize target recycling. As a consequence, the electrochemical signal of MB enhanced significantly, which realized “signal on” strategy, meanwhile, the deoxidization peak current of Fc decreased distinctly, which realized “signal off” strategy. The employment of exonuclease and superposition of two signals significantly improved the sensitivity of the aptasensor. In this way, an aptasensor with high sensitivity, good stability and selectivity for quantitative detection of thrombin was constructed, which exhibited a good linear range from 5 pM to 50 nM with a detection limit of 0.9 pM (defined as S/N = 3). In addition, this design strategy could be applied to the detection of other proteins and small molecules.     

Structure modification in hen egg yolk low density lipoproteins layers between 30 and 45 mN/m observed by AFM

We have studied the structure of films made by low density lipoproteins (LDL) from hen egg yolk, which are composed of apoproteins, neutral lipids and phospholipids. These LDL have been deposited on air–water interface to form a monolayer which has been compressed to measure an isotherm using Langmuir balance. This isotherm presented three transitions (neutral lipid (surface pressure, π = 19 mN/m), apoprotein–lipid (π = 41 mN/m) and phospholipid (π = 51 mN/m) transitions). We have studied only the apoprotein–lipid transition. In order to observe the LDL film structure before (π = 30 mN/m) and after (π = 45 mN/m) the apoprotein–lipid transition, the formed films were transferred and visualised by atomic force microscopy (AFM). Our results have shown that the structures observed in the LDL film were different depending on the surface pressure. The apoproteins and neutral lipids appeared to be miscible up to the apoprotein–lipid transition, when demixing occured. The structures observed after the apoprotein–lipid transition should be due to the demixing between apoproteins and neutral lipids. On the other hand, apoproteins and phospholipids seemed miscible whatever the surface pressure. Hence, the first transition (π = 19 mN/m) should be attributed to the free neutral lipid collapse; the second transition (π = 41 mN/m) should be attributed to the demixing of apoprotein–neutral lipid complexes; and the last transition (π = 51 mN/m) should be attributed to phospholipid collapse or to demixing of apoprotein–phospholipid complexes.     

Synthesis and characterization of core–shell polyacrylate latex containing fluorine/silicone in the shell and the self-stratification film

A series of core–shell polyacrylate latexes with different fluorine/silicone monomer concentrations were prepared successfully by seeded emulsion polymerization. Dodecafluoroheptyl methacrylate and perfluorooctyl methacrylate with different fluorinated side chains were employed as fluorinated monomers, and γ-methacryloxypropyl triisopropoxidesilane (MAPTIPS) was used as a silicone-containing monomer as well as a self-cross-linking agent. The morphology and chemical structure of the latexes were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, and differential scanning calorimetry, and the self-stratification properties of the latex film were verified by X-ray photoelectron spectroscopy and static contact angle measurement. The results showed that the fluorine/silicone-containing polyacrylate latexes presented a uniformly spherical core–shell structure, and the latex films displayed a preferential distribution of fluorinated composition near the surface, which was more remarkable with the synergism effect between the fluorine monomer and MAPTIPS. Additionally, the hydrophobicity and oleophobicity of the latex films exhibited high relevance with the fluorine/silicone monomer concentrations as well as the fluorinated side-chain structure.     

含氟/硅丙烯酸酯核壳型乳液的合成及性能

采用半连续种子乳液聚合法, 在十二烷基硫酸钠(SDS)/辛基苯基聚氧乙烯醚(TX-10)复合乳化剂的作用下, 合成了以丙烯酸丁酯(BA)为核, 以甲基丙烯酸甲酯(MMA)、甲基丙烯酸十二氟庚酯(DFHMA)、3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPTMS)和甲基三甲氧基硅烷(MTMS)为壳的核壳型含氟/硅丙烯酸酯聚合物乳液. 利用FTIR, TEM, SEM-EDX和DSC等手段对乳液组成、乳胶粒子结构、膜表面及断面形态等进行了表征, 讨论了氟/硅含量对聚合物膜性能的影响. 结果表明, 核-壳粒子尺寸为20~30 nm, 乳液膜的性能与膜表面氟和硅的含量及相容性有较大的相关性, 当m(氟)∶m(硅单体)=3∶1时, 形成的膜均匀透明, 吸水率较低, 尺寸稳定性较好.     

Design and development of microfabricated capillary electrophoresis devices with electrochemical detection

Our efforts have been focused on developing a self-contained and transportable microfabricated electrophoresis (CE) system with integrated electrochemical detection (ED). The current prototype includes all necessary electrodes “on-chip” and utilizes miniaturized CE and ED supporting electronics custom designed for this purpose. State-of-the-art design/modeling tools and novel microfabrication procedures were used to create recessed platinum electrodes with complex geometries and the CE/ED device from two patterned ultra-flat glass substrates. The electrodes in the bottom substrate were formed by a self-aligned etch and deposition technique followed by a photolithographic lift-off process. The microchannels (20 μm deep×65 μm wide (average)) were chemically etched into the top substrate followed by thermal bonding to complete the microchip device. CE/ED experiments were performed using 0.02 M phosphate buffer (pH 6), an analyte/buffer solution (2.2 mM dopamine, 2.3 mM catechol) and varying separation voltages (0-500 V) with a custom electronics unit interfaced to a laptop computer for data acquisition. Detection limits (S/N=3) were found to be at the micromolar level and a linear detection response was observed up to millimolar concentrations for dopamine and catechol. The microchip CE/ED system injected 50 pl volumes of sample, which corresponded to mass detection limits on the order of 200 amol. For the first time, an integrated “on-chip” multi-electrode array CE/ED device was successfully designed, fabricated and tested. The majority of the electrodes (six out of eight) in the array were capable of detecting dopamine with the amplitude of the signal (i.e., peak heights) decreasing as the electrode distance from the channel exit increased.     

Morphological evolution of multistage polymer particles in the alkali post-treatment

Multistage carboxyl-containing polymer latex particles were synthesized by multistep emulsion copolymerization using methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA) and styrene (St) as raw materials, and the latex particles with diverse morphologies including multihollow, hollow and “bowl-like” were obtained by post-treating the multistage latex particles under alkali condition. The morphological evolution of the particles in the alkali post-treatment process was characterized with electron microscopy, and effects of alkali treatment conditions including treatment temperature, time as well as initial pH on particle morphology were investigated. Results indicated that the alkali treatment temperature and initial pH were the key parameters to control the morphology of the treated particles. When the alkali treatment temperature was below 60 °C or the initial pH was lower than 8.5, the particle morphology was almost unchanged no matter how long the treatment time was prolonged. The multihollow and hollow particles could be formed as alkali treatment temperature exceeded 60 °C in the range of initial pH from 8.8 to 9.5. While the latex particles with “bowl-like” morphology were observed when the multistage latex was alkali treated at 90 °C for 3 h with initial pH 9.8. Furthermore, extending alkali treatment time was beneficial to get the swelling equilibrium of the latex particles.     

Degradation behaviors of polyester monolayers at the air/water interface: Alkaline and enzymatic degradations

The degradation kinetics of Langmuir monolayer films of a series of biodegradable polyesters has been studied to investigate the effect of degradation medium, alkalinity and enzymes. The degradation behavior of polyester monolayers strongly depended on both degradation medium and surface pressure. As the surface pressure was increased, the degradation rates of poly(l-lactide) (PLLA) and poly[(R)-3-hydroxybutyrate] (P(3HB)) increased in both degradation media. When monolayers were exposed to an alkaline subphase, the degradation of PLLA monolayers occurred at relatively low surface pressures; the PLLA monolayers were hydrolyzed at pH 10.5 regardless of surface pressure, while the alkaline degradation of P(3HB) monolayer occurred over a constant surface pressure of 7 mN/m at pH 11.8. These results have been explained by the difference in hydrophilic/hydrophobic balance of the polymers; PLLA is more hydrophilic than P(3HB). In contrast, the enzymatic degradations of both polymer monolayers occurred at higher constant surface pressures than those of the alkaline treatment; 7 mN/m for PLLA and 10 mN/m for P(3HB). This behavior was attributed to the enzymes being much larger than the alkaline ions: the enzymes need a larger contact area with the submerged monolayers to be activated.     

SEED SEMICONTINUOUS EMULSION MULTI-COPOLYMERIZATION OF (METH) ACRYLATES WITH HIGH-SOLID CONTENT: EFFECT OF THE OPERATION CONDITIONS

The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA),2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate(HOPA) and acrylic acid (AA) was used to prepare the acrylic latexes with high-solidcontent. The effects of monomer emulsion feed rates (R_a) and (R/E)_E values, the ratio ofemulsifier amount between the initial charge (R) and the addition monomer emulsion (E),on the polymerization reaction features, the viscosities, surface tensions,particle sizes andparticle sizes distributions of latexes,T_g and the insoluble fractions of films, the 180° peelstrength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, preparedfrom the latexes, were studied. Experimental study shows that the grafting and cross-linking fraction in the PSA tapes must be controlled within a suitable range to keep thebalance of the 180° peel strength, tack and holding power.     

Mechanical Properties and Structure of Zinc-Containing Latex-Silicate Composites

The sol-gel technology is highly efficient for improving mechanical and thermal properties of polydiene elastomers by creating in them additional inorganic networks composed mainly of silica or silicates. The incorporation of modifying Zn ions into polydiene latex-silica systems increases considerably their mechanical characteristics due to an increase of the interaction between the organic and inorganic networks. Interpenetrating polydiene-silica networks were prepared by cohydrolysis of tetraethoxysilane and zinc acetate in natural Qualitex or synthetic butadiene-styrene latexes and then by aging and drying the liquid compositions at room temperature and vulcanizing at 90°C. Their structure and properties were studied by the IR spectroscopy, TMA and by tensile testing of the prepared films. The studied system was shown to be extremely suitable for obtaining latex films with improved elastic and strength characteristics. For example, the elastic modulus values of the Qualitex films containing 2–5% SiO₂ and 0.1–0.2% ZnO, are 4–9 and 6–11 times higher than those of the films prepared without zinc and of the pure latex films respectively. The possible structure roles of zinc ions at various stages of film preparation and vulcanization are discussed on the base of the results of IR and TMA studies.     

Microstructured proton-conducting membranes by synchrotron-radiation-induced grafting

Selective exposures of poly(ethylene-alt-tetrafluoroethylene) (ETFE) films with hard X-rays through high aspect ratio Ni-masks were performed at the LIGA3 beamline of the “Angström Quelle Karlsruhe” (ANKA) to create patterns of radicals used as initiators for the grafting of styrene into the bulk of the ETFE films. Grafted films were then sulfonated to obtain proton-conducting membranes. The structure definition, as investigated by scanning electron microscopy (SEM), showed a perfect discrimination between exposed and shaded areas through all the film thickness. Structuring results in a more homogeneous appearance of the membrane without affecting the degree of grafting and proton conductivity in the grafted areas. In fuel cell tests the structured membranes showed slightly lower performance due to 10% lower active area, but had a significantly higher lifetime.     

Synthesis of silicone–acrylate copolymer latexes and their film properties

Emulsion copolymerization of silicones (octomethyl tetracyclosiloxane, D₄ and methacryloxypropyl trimethoxy silane, MATS) and acrylics was carried out using three different polymerization processes: semicontinuous monomer emulsion addition, batch and initiator solution addition. Results showed that only the semicontinuous process led to a stable latex with monodisperse particles. Various polymerizations were carried out through this process with varying silicone/acrylic ratios and MATS content. Films were obtained from different latexes: their properties are significantly influenced by silicone and MATS contents in copolymers.     

Inkjet-printed gold nanoparticle chemiresistors: Influence of film morphology and ionic strength on the detection of organics dissolved in aqueous solution

The influence of film morphology on the performance of inkjet-printed gold nanoparticle chemiresistors has been investigated. Nanoparticles deposited from a single-solvent system resulted in a “coffee ring”-like structure with most of the materials deposited at the edge. It was shown that the uniformity of the film could be improved if the nanoparticles were deposited from a mixture of solvents comprising N-methyl-2-pyrrolidone and water. Electrical conductivity measurements showed that both “coffee ring” and “flat” films were qualitatively similar suggesting that the films have similar nanoscale structures. To form the functional chemiresistor device, the 4-(dimethylamino)pyridine coating on the nanoparticle was exchanged with 1-hexanethiol to provide a hydrophobic sensing layer. The performance of 1-hexanethiol coated gold nanoparticle chemiresistors to small organic molecules, toluene, dichloromethane and ethanol dissolved in 1 M KCl in regard to changes in impedance and response times was unaffected by the film morphology. For larger hydrocarbons such as octane, the rate of uptake of the analyte into the film was significantly faster when the flatter nanoparticle film was used as opposed to the “coffee ring” film which has a thicker edge. Furthermore, the presence of potassium and chloride ions in the solution media does not significantly affect the impedance of the nanoparticle film at 1 Hz (<2% variation in film impedance over more than four orders of magnitude change in ionic strength). However, the ionic strength of the media affected the partitioning of the analyte into the hydrophobic nanoparticle film. The response of the sensor was found to increase with an increased salt concentration due to a salting-out of the analyte from the solution.     

Nanowear studies in chemically heterogeneous responsive polymeric brushes by surface force microscopy

In this study, we present nanowear studies using surface force microscopy (SFM), on nanoscopic thin films of reversibly switchable binary polymer brushes [polystyrene (PS) + poly(2-vinylpyridine) (P2VP)] and respective monobrushes [polystyrene and poly(2-vinylpyridine)] synthesized via “grafting to” method. The aim was to tune the wear in nanothin polymer brush surfaces. Therefore, the effect of conformational switching of PS + P2VP brush on treatment with selective solvents for PS and P2VP chains on the wear process was investigated. Wear process on thick spin-coated films of PS and P2VP was also investigated for comparison. Nanowear experiments were performed using SFM tip by repeating scans over the surface to follow the wear process closely. The wear process on different surfaces was explained on the basis of molecular entanglement as well as adhesion and friction on the sample surface. For spin-coated PS film as well as PS and PS + P2VP brush surfaces (treated with toluene) with molecular entanglements at surface, wear mechanism involved formation of ripples. However, in case of spin-coated P2VP films as well as P2VP and PS + P2VP brush surfaces (treated with ethanol) with no molecular entanglements at surface, wear occurred via removal of polymer chains and their accumulation at the rim. For PS + P2VP surface treated with acidic water, wear mechanism was complex and inhomogeneous ripple formation was followed by formation of heaps of polymeric material in the center of scanned area. The extent of wear as measured either by root mean square roughness of the surface or spacing between the ripples, increased with the number of scans for all the surfaces. Our study shows that wear mode of polymer brush surfaces is different for different polymers and can be controlled/tuned by the use of binary polymer brushes.     

Topography of dipalmitoyl-phosphatidyl-choline monolayers penetrated by β-casein

In this work we have analyzed the topography by atomic force microscopy (AFM) of dipalmitoyl-phosphatidyl-choline (DPPC) monolayers previously spread at the air–water interface and penetrated by β-casein. AFM images of β-casein–DPPC monolayers were taken from Langmuir–Blodgett films deposited onto hydrophilic mica substrates at different initial surface pressures (π_i) and after the compression of the mixed films. The monolayer topography depends on the initial structure of the phospholipid:liquid expanded (LE) at 3 mN/m, coexistence between LE and liquid condensed (LC) structures at 7 mN/m, at the end of the LE–LC transition at 10 mN/m, and with a LC structure at 15 mN/m. The area occupied by DPPC domains in the mixed film increases with the π_i value, especially for DPPC with a LC structure at 15 mN/m. At this surface pressure the thickness of the film is at a maximum. After the film compression at 25 mN/m, which is above the equilibrium spreading pressure of β-casein (), this protein is displaced from the interface by DPPC and the topography of the mixed monolayer depends on the initial structure of the DPPC monolayer. A notable feature of the topography of these mixed monolayers is the presence of multilayers of β-casein and DPPC of high thickness (50–70 nm) at the lower π_i values. Although the film is dominated by DPPC at the highest surface pressures (at 25 mN/m), β-casein is not displaced totally from the interface and coexists as β-casein collapsed domains within the network of the DPPC structure.