Investigation of adhesion hysteresis in poly(dimethylsiloxane) networks using the JKR technique

The JKR technique was used to determine the source and nature of the adhesion hysteresis present in modified poly(dimethylsiloxane) (PDMS) networks. As controlled excess amounts of the tetrafunctional crosslinker were added to the networks, the adhesion hysteresis increased. It was found that by poisoning the catalyst with a thiol the hysteresis could be significantly lowered, and completely removed in some cases. We believe that the adhesion hysteresis in this system stems from a complexation between the excess crosslinker and the catalyst. We found that the work of adhesion in this case is a function of the unloading rate. The unloading rate dependence of this chemical adhesion hysteresis was attributed to the rate of bond dissociation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2129–2139, 1998     

Development of an ultra-low volume flow cell for surface plasmon resonance detection in a miniaturized capillary electrophoresis system

A miniaturized capillary electrophoresis system coupled to a surface plasmon resonance (SPR) sensor on a microfluidic platform fabricated from PDMS is detailed. A previously described split-flow injection technique is first utilized to manipulate sample into the microfluidic chip, followed by separation within the fused-silica capillary and final off-capillary detection of analytes via SPR. Instead of using commercial SPR flow cells requiring relatively large detection volumes, samples of less than 1 nL volume are utilized. The interface between the CE system and SPR sensor made it possible to detect minute volumes of sample with minimal dispersion. The flow cell has the potential to be applicable to miniaturized flow-injection (FI) systems where submicroliter volumes of sample are frequently only available for analysis. The components present in solution, but not bound to the sensor surface, were also investigated. The sensitivity of the CE-SPR system was similar to that found in UV-spectrometric instruments and nonchromophoric components could also be measured.     

Wettability of tri-block copolymer coated hydrophobic surfaces Predictions and measurements

Hydrophobic surfaces with adsorbed tri-block copolymers are wetted by oil in spite of the hydrophilic buoy groups of the block copolymer that are present near the surface. The effect of the buoy group length of the adsorbed molecules on the wettability of hydrophobic surfaces is studied by contact angle measurements and by computer modelling.

The computer model predicts an increase in interfacial free energy with increasing buoy group length for equilibrium adsorption of block copolymer from water. Molecules with large buoy groups occupy more lateral space; therefore the “bare” surface gets more exposed and the anchor groups contribute less to the interfacial free energy which thus increases with the buoy group length.

The calculations showed that the variation of the interaction parameter between solvent and buoy group hardly influences the interfacial free energy. In contrast the interaction parameter between solvent and surface influences the interfacial free energy to a large extent because the oil/surface interactions have a lower energetic value as compared to water/surface interactions and therefore the interfacial free energy is lower than in water. The interfacial free energy varies slightly with increasing buoy group length, depending on the value chosen for the solvent/surface interaction parameter.

Advancing and receding contact angles of hexadecane, sunflower oil and hydrolysate (partly hydrolysed sunflower oil) were measured on hydrophobic surfaces. All oil/water contact angles were small, indicating a hydrophobic apolar surface character. It was found that, for oils with a “good” interaction with the surface (hexadecane and sunflower oil), the contact angle has a minimum value at a certain buoy group length. For hydrolysate (less-strong interaction with the surface) the contact angle decreases monotonically with increasing buoy group length. The results for hexadecane, sunflower oil and hydrolysate are in reasonable agreement with the model predictions. The effect of increasing buoy group length is weak; both decreasing and increasing angles are found, depending on the type of oil used.     

Isoelectric focusing in an ordered micropillar array

An original micropillar array dedicated to electrophoretic separations has been developed. It consists of a rectangular zone of PDMS micropillars protruding on a PDMS block. This area has been chosen to mimic a diluted gel structure and remains uncovered to keep the ability to perform an immunoblot after the protein separation for further applications in the field of allergy diagnosis. The micropillar array geometry has been optimized by evaluating the influence of pillar shape, pillar size and interpillar distance on evaporation and IEF separation. The separation conditions namely electrolyte composition, temperature and sample loading have been studied. Finally a protein mixture with pI ranging from 4.7 to 10.6 has been successfully separated within this microdevice by IEF without decreasing the resolving power obtained with conventional minigel. The micropillar array developed for electrophoretic separations leads to much shorter analysis times and can be reused several times while gels are disposable.     

Observations on the swelling of cross-linked poly(dimethylsiloxane) networks by solvents

The Flory Huggins Solvent parameter (χ) previously published for a range of solvents and a cross-linked silicone polymer, have been recalculated using the original swelling data, but including a term representing the loss of configurational entropy consequent on crosslinking. From the Shore hardness of the polymer, the Young’s modulus E was calculated. E = 6(C₁ + C₂), where C₁ and C₂ are the parameters from the Mooney Rivlin equation for the elastic deformation of an elastomer. Since C₁ is related to M_c, the average molecular weight between crosslinks, revised χ values could be calculated for various values of C₂/C₁. These showed that for good solvents for the silicone polymer, the values published previously were too high.     

Quantitative determination of interfacial adhesion in composites with strong bonding

An approach was proposed for the quantitative determination of adhesion strength in composites, in which adhesion is created by other mechanisms than secondary interactions. The approach is based upon a model, which gives debonding stress as a function of interfacial adhesion. Debonding stress was determined by acoustic emission experiments. The mechanism of deformation was checked by SEM experiments and the approach was verified on composites with known interfacial adhesion. The results showed that the use of functionalized polymer in PP/CaCO₃ composites resulted in adhesion strength one order of magnitude larger than without the coupling agent. The application of various surface modification techniques in PP/glass bead composites yielded different adhesion values covering a range of about one order of magnitude. The quantitative determination of interfacial adhesion makes possible the design and optimization of most surface modification techniques in particulate filled and short fiber reinforced composites.     

A sol-gel immobilization of nano and micron size sorbents in poly(dimethylsiloxane) (PDMS) microchannels for microscale solid phase extraction (SPE)

Sorbent particles consisting of nano and micro silica, and micron size octadecylsilica (ODS) were immobilized using sol-gel chemistry onto poly(dimethylsiloxane) (PDMS) microfluidic channels to serve as μ-chip solid phase extraction (SPE) devices. Extraction, preconcentration and purification of biological and chemical analytes were carried out using these. Micro and nano scale silica-immobilized μ-SPE were used for the extraction/purification of DNA from recombinant Escherichia coli crude lysate. The average DNA recovery was 77 ± 9% (X ± R.S.D.) for the micron size silica particles and 70 ± 5% (X ± R.S.D.) for the nano silica particles. The extracted DNA could be amplified by polymerase chain reaction (PCR) whereas the DNA from the crude lysate solution could not be. This was a testimony to the purification capability of the μ-SPE device. ODS immobilized μ-SPE were used to study the extraction efficiency (EE) and enhancement factor (EF) for three groups of organic compounds, aromatics, phenols and carboxylic acids. They showed poor recovery and low enrichment because the analytes sorbed into the PDMS and were not quantitatively extracted.     

Use of surface plasmon resonance to study the adsorption of detergents on poly(dimethylsiloxane) surfaces

This paper demonstrates the use of surface plasmon resonance to study adsorption (either reversible or irreversible) of detergents on PDMS surfaces in real time. The surface plasmon resonance measurements can directly provide information about the adsorption/desorption processes of detergents on the surface revealing the durability of the adsorbed layer and the anticipated degree of the EOF. Hydroxypropyl methylcellulose very strongly adsorbs onto PDMS and can be considered both a semipermanent layer and stable semipermanent coating. Adsorbed SDS or CTAB layers were stable for several minutes upon rinsing the surface with solution not containing the detergent. It was shown that SDS coated onto PDMS in microchips has the potential to afford similar separations in PDMS as found in conventional fused silica capillaries.     

Adhesion of Cryptosporidium parvum and Giardia lamblia to solid surfaces: the role of surface charge and hydrophobicity

Adhesion of Cryptosporidium parvum and Giardia lamblia to four materials of different surface charge and hydrophobicity was investigated. Glass beads were used with and without three polymer coatings: aminosilines (A0750), fluorosilines (T2494), an amino cationic polymer. Surface charge density and hydrophobicity of the beads were characterized by measuring the zeta potential (ZP) and the contact angle, respectively. Adhesion was derived from batch experiments where negatively charged (oo)cysts were mixed with the beads and recovery was determined by counting (oo)cysts remaining in suspension using a flow cytometer. Experimental results clearly show that adhesion to solid surfaces of C. parvum is different from G. lamblia. Adhesion of C. parvum to positively charged, hydrophilic beads (82% recovery relative to control) indicated that surface charge was the more important factor for C. parvum, dominating any hydrophobic effects. Adhesion of G. lamblia cysts to negatively charged, hydrophobic beads (0% recovery relative to control) indicated that although hydrophobicity and surface charge both played a role in the adhesion of G. lamblia to solid surfaces, hydrophobicity was more important than surface charge.     

Split injection: A simple introduction of subnanoliter sample volumes for chip electrophoresis

The ability to accurately inject small volumes of sample into microfluidic channels is of great importance in electrophoretic separations. While electrokinetic injection of nanoliter scale volumes is commonly utilized in microchip capillary electrophoresis (MCE), mobility and matrix bias makes quantitation difficult. Herein, we describe a new injection method based on the simple patterning of the crossing of channels that does not require sophisticated instrumentation. The sample volume injected into the separation channel is dependent on the ratio of the widths of the crossing channels. This injection method is capable of introducing, into a separation channel, multiple plugs of sample on a large scale. This injection technique is tested for zone electrophoresis in native and surface modified poly(dimethylsiloxane) (PDMS) chips.     

Aging of a medical device surface following cold plasma treatment: Influence of low molecular weight compounds on surface recovery

The surface of medical devices is of great importance for biocompatibility. Surface properties can evolve with a material treatment, time, and storage conditions. In this work, poly(urethane) catheters sterilised by cold nitrogen plasma treatment, were subjected to air and temperature aging in order to evaluate the influence of humidity and temperature on surface recovery. The surface of catheters was analysed by contact angle measurements and XPS. Faster surface changes upon aging were observed at high temperature (45 °C) and relative humidity (90%). For the commercial poly(urethane) catheters analysed in this work, the importance of the nature and polymorphism of additives added to the polymer (lubricant, antioxidant) in the recovery process was demonstrated. Indeed, DSC and TSC showed that additive transitions (relaxation, melting…) could govern the aging process.     

Fabrication of a novel poly(dimethylsiloxane) microchips with two sharpened stretching tips

An integrated poly(dimethylsiloxane) (PDMS) microchip with two sharpened stretching has been presented. The sample was directly introduced into the separation channel through the stretching inlet tip without complicated power switching supplies and without injection cross-channel. Operations of running buffer refreshing or channel cleaning also becomes simple by vacuumed in one end and placed another tip into solution vial. The fabrication method can be easily applied in most analytical laboratories at low cost in the absence of soft lithography and plasma bonding equipments. Characteristics of the chips were tested and it can be used to separate fluorescence labeled molecules.     

利用软模板和紫外光固化技术制备超疏水表面

研究了一种制备超疏水表面的新方法.该方法以复制了荷叶表面结构的聚二甲基硅氧烷(PDMS)弹性体为软模板.利用可紫外光交联预聚物在模板压印条件下固化成型,得到了具有微乳突结构的仿荷叶表面.制备的仿荷叶表面表现出了超疏水性能.通过对紫外光固化体系中的单体含量、交联剂含量、引发剂含量、以及紫外曝光时间等因素的研究,得到了使仿荷叶表面的疏水性优化的条件.     

聚硅氧烷侧基极性对链均方偶极矩的影响

为了改进无机高分子链偶极矩的计算,在旋转异构态模型和生成矩阵统计方法基础上,导出了可以同时考虑骨架键和侧基极性的均方偶极矩公式,应用于对称和不对称聚硅氧烷高分子链的偶极矩构象构型统计性质的分析,及聚二甲基硅氧烷(PDMS)链、聚甲基苯基硅氧烷(PMPS)链是否考虑侧基极性的偶极矩比较。计算结果表明,PDMS的偶极矩特征比值0.36与实验结果一致,它大于忽略侧基极矩的特征比值约46%,均方偶极矩温度系数为1.29×10-3K-1,无规聚甲基苯基硅氧烷链(50%i-PMPS)的均方偶极矩特征比和温度系数分别为0.61和1.73×10-3K-1.不考虑侧基极性的均方偶极矩特征比与PDMS不考虑侧基时趋于同样的值0.20.对PMPS偶极矩与链规整性关系研究发现,PMPS间同链的均方偶极矩要大于全同和无规链,而全同链温度系数最大.均方偶极矩对一级相互作用能的依赖程度依次按间同链、无规和全同链顺序增加,而间同和全同链均方偶极矩受二级相互作用能的影响要大于无规链.     

Multilayer poly(vinyl alcohol)-adsorbed coating on poly(dimethylsiloxane) microfluidic chips for biopolymer separation

A poly(dimethylsiloxane) (PDMS) microfluidic chip surface was modified by multilayer-adsorbed and heat-immobilized poly(vinyl alcohol) (PVA) after oxygen plasma treatment. The reflection absorption infrared spectrum (RAIRS) showed that 88% hydrolyzed PVA adsorbed more strongly than 100% hydrolyzed one on the oxygen plasma-pretreated PDMS surface, and they all had little adsorption on original PDMS surface. Repeating the coating procedure three times was found to produce the most robust and effective coating. PVA coating converted the original PDMS surface from a hydrophobic one into a hydrophilic surface, and suppressed electroosmotic flow (EOF) in the range of pH 3-11. More than 1,000,000 plates/m and baseline resolution were obtained for separation of fluorescently labeled basic proteins (lysozyme, ribonuclease B). Fluorescently labeled acidic proteins (bovine serum albumin, beta-lactoglobulin) and fragments of dsDNA phiX174 RF/HaeIII were also separated satisfactorily in the three-layer 88% PVA-coated PDMS microchip. Good separation of basic proteins was obtained for about 70 consecutive runs.     

The thermal degradation behaviour of polydimethylsiloxane/montmorillonite nanocomposites

A series of novel polydimethylsiloxane/montmorillonite (PDMS/MMT) nanocomposites was prepared. The thermal degradation behaviour of these nanocomposites was studied by means of Thermal Volatilization Analysis (TVA) and Thermogravimetric Analysis (TGA). The major degradation products were identified as cyclic oligomeric siloxanes from D₃ to D_7, and higher oligomeric siloxane residues. Other minor degradation products include methane, bis-pentamethylcyclotrisiloxane, propene, propanal, benzene and dimethylsilanone. The results demonstrate that the nanoclay significantly alters the degradation behaviour of the PDMS network, modifying the profile of the thermal degradation and reducing the overall rate of volatiles evolution. The results also indicate that the nanoclay promotes the formation of dimethylsilanone and benzene by inducing low levels of radical chain scission.     

PDMS微流体系统的加工制作

目前,微流体装置越来越多地应用到分析系统、生物医学、化学等基础研究领域。传统的微流体系统制作方法是对玻璃和硅片进行刻蚀。用软刻法制作PDMS(Poly(dimethylsiloxane)：聚二甲基硅氧烷)微流体装置比传统的制作方法更快速,成本更低廉,并且对于通道的密封也不需要玻璃或硅芯片键合密封等复杂工艺。这类软刻法的核心技术是快速原样制作法和复制压模技术。相对于微电子加工工艺,软刻法制作过程不需要超静环境,化学家和生物学家可在普通的实验室实现加工制作。本文介绍了PDMS微装置在分离和生物材料模式化等方面的应用。     

CONFIGURATION-DEPENDENT PROPERTIES OF POLY(DIMETHYLSILOXANE) CHAIN*

The intermolecular rotational potential energies for poly(dimethylsiloxane) (PDMS) chains aredirectly obtained from a priori probability P_(αβ). Here the differing statistical weight matrices for the Si-Oand O-Si bonds are considered in calculating the configuration partition function. In the Bahar's model, asthe same statistical weight matrices for the Si -O and O- Si bonds are adopted, there exists a large deviationof αpriori probability P_(αβ) between the theory and the molecular dynamics (MD) simulation. Our model givessatisfactory agreement with experiment on the mean-square unperturbed end-to-end distance, the mean-square dipole moment and its temperature dependence, and the molar cyclization equilibrium constants fordimethylsiloxane oligomers. This new rotational isomeric state approach can be widely applied to otherchains, such as -CH_2-C[(CH_2)_mH]_2- and -O-Si[(CH_2)_mH]_2 for arbitrary m.     

溶菌酶蛋白在聚合物防污膜表面的吸附

采用分子动力学模拟方法比较了溶菌酶蛋白在两种典型聚合物防污材料聚乙二醇(PEG)和聚二甲基硅氧烷(PDMS)表面的吸附行为, 在微观上探讨了聚合物膜表面性质对蛋白质吸附的影响. 根据蛋白质与聚合物膜之间的相互作用、能量变化及表面水化层分子的动力学行为, 解释了PEG防污涂层相对于PDMS表面具有更佳防污效果的原因: (1) 相比PDMS涂层, 蛋白质与PEG涂层的结合能量较低, 使其结合更加疏松; (2) 蛋白质吸附到材料表面要克服表面水化层分子引起的能障, PEG表面与水分子之间结合紧密, 结合水难于脱附, 造成蛋白质在其表面的吸附需要克服更高的能量, 不利于蛋白质的吸附.     

PEG-covered lipid surfaces: bilayers and monolayers

In this review paper we survey the ways in which various micropipet techniques have been used to study the mechanochemical and interactive features of lipid bilayer vesicles and monolayer-coated gas bubbles. Special emphasis will be made on characterizing the barrier properties of grafted PEG layers and how a hierarchical approach that uses a short barrier and extended ligand allows us to start to mimic nature's own solution to the problem of ubiquitous repulsion and specific attraction. The information gained from such studies not only characterizes the membrane and other lipid surfaces and their intersurface interactions from a fundamental materials science perspective, but also provides essential materials property data that are required for the successful design and deployment of lipid-based carriers and other capsules in applications involving this so-called ‘stealthy’ surface.