Dynamic permeation method to determine partition coefficients of highly hydrophobic chemicals between poly(dimethylsiloxane) and water

Measurement of partition coefficients between poly(dimethylsiloxane) (PDMS) and water (KPDMSw) becomes more and more difficult as the hydrophobicity of the compound increases. Experimental challenges include long extraction times, sorption to various surfaces and materials, and incomplete dissolution of the compound in the aqueous phase. In order to avoid these artifacts and to shorten experimental time, a dynamic permeation method was developed. According to steady-state diffusion theory, KPDMSw is inversely proportional to the permeation rate through the aqueous boundary layer (ABL) from the donor PDMS to the acceptor PDMS. A simple ABL permeation reactor can thus be applied to determine KPDMSw values of hydrophobic chemicals within a few days. The obtained values were in good agreement with those obtained using a conventional shaking method and the partition controlled delivery system. A good linear correlation was obtained between the logarithm of the 1-octanol/water partition coefficient (log Kow) from the literature and log KPDMSw over 6 orders of magnitude.     

Sampling and Raman confocal microspectroscopic analysis of airborne particulate matter using poly(dimethylsiloxane) solid-phase microextraction fibers

Commercial poly(dimethylsiloxane) (PDMS) 7-microm solid-phase microextraction (SPME) fibers were used for sampling and Raman spectroscopic analysis of a tailpipe diesel exhaust, candle smoke, cigarette smoke, and asbestos dust. Samples were collected via direct exposure of the SPME fiber to contaminated air. The mass loading for SPME fibers was varied by changing the sampling time. Results indicate that PDMS-coated fibers provide a simple, fast, reusable, and cost-effective air sampling tool for airborne particulates. The PDMS coating was stable; Raman bands of the PDMS coating were observed exactly at the same wavenumber positions before and after air sampling. Raman spectroscopic analysis resulted in identification of several characteristic bands allowing chemical speciation of particulates. The advantage of the SPME fiber is the open bed geometry allowing for application of various spectroscopic methods of particulate analysis. This paper describes the first-ever combined application of SPME technology with Raman confocal microspectroscopy for sampling and analysis of airborne particulates. Advantages of the combination of solid-phase microextraction and Raman microspectroscopy for airborne particulate analysis are discussed. Challenges associated with combined SPME sampling and Raman analysis of single particles are also described.     

Sol-gel coating technology for the preparation of solid-phase microextraction fibers of enhanced thermal stability

A novel sol-gel method is described for the preparation of solid-phase microextraction (SPME) fibers. The protective polyimide coating was removed from a 1-cm end segment of a 200 μm o.d. fused-silica fiber, and the exposed outer surface was coated with a bonded sol-gel layer of poly(dimethylsiloxane) (PDMS). The chemistry behind this coating technique is presented. Efficient SPME-GC analyses of polycyclic aromatic hydrocarbons, alkanes, aniline derivatives, alcohols, and phenolic compounds in dilute aqueous solutions were achieved using sol-gel-coated PDMS fibers. The extracted analytes were transferred to a GC injector using an in-house-designed SPME syringe that also allowed for easy change of SPME fibers. Electron microscopy experiments suggested a porous structure for the sol-gel coating with a thickness of ～10 μm. The coating porosity provided higher surface area and allowed for the use of thinner coatings (compared with 100-μm-thick coatings for conventional SPME fibers) to achieve acceptable stationary-phase loadings and sample capacities. Enhanced surface area of sol-gel coatings, in turn, provided efficient analyte extraction rates from solution. Experimental results on thermal stability of sol-gel PDMS fibers were compared with those for commercial 100-μm PDMS fibers. Our findings suggest that sol-gel PDMS fibers possess significantly higher thermal stability (>320 °C) than conventionally coated PDMS fibers that often start bleeding at 200 °C. This is due, in part, to the strong chemical bonding between the sol-gel-generated organic-inorganic composite coating and the silica surface. Enhanced thermal stability allowed the use of higher injection port temperatures for efficient desorption of less-volatile analytes and should translate into extended range of analytes that can be handled by SPME-GC techniques. Experimental evidence is provided that supports the operational advantages of sol-gel coatings in SPME-GC analysis.     

Analysis of passive mixing behavior in a poly(dimethylsiloxane) microfluidic channel using confocal fluorescence and Raman microscopy

Confocal fluorescence microscopy (CFM) and confocal Raman microscopy (CRM) have been applied to monitor the laminar flow mixing behavior in a poly(dimethylsiloxane) (PDMS) microfluidic channel. Two passive PDMS micromixing devices were fabricated for this purpose: a two-dimensional round-wave channel and a three-dimensional serpentine channel. The microscale laminar flow mixing of ethanol and isopropanol was evaluated using the CFM and CRM at various flow rates. The mixing behavior of confluent streams in the microchannel was assessed by determining the degree of color change in Rhodamine 6G dye on mixing using the CFM. However, it was also possible to quantitatively evaluate the mixing process without employing a fluorescence label using the CRM. The results show a strong potential for CRM as a highly sensitive detection tool to measure fundamental fluid mixing processes and to provide detailed information on chemical changes of non-fluorescent reaction mixtures in a PDMS microfluidic channel.     

Determination of hydrocarbons using sapphire fibers coated with poly(dimethylsiloxane)

A poly(dimethylsiloxane) (PDMS) coated sapphire fiber has been investigated as a sensor for hydrocarbons (HCs) in the mid-infrared region around 3000 cm(-1). In order to optimize and predict sensor response, the diffusion behavior of the analytes into the PDMS preconcentration medium has been examined. A diffusion model based on Fickian diffusion was used to quantify diffusion. The model incorporated such factors as film thickness, refractive index of the polymer and the fiber core, and principal wavelength at which the analyte absorbs. A range of hydrocarbons, from hexane to pentadecane, was analyzed at 2930 cm(-1) using both fiber-coupled Fourier transform infrared spectroscopy and a modular prototype system. Diffusion coefficients were determined for these compounds and diffusion behavior examined and related to factors such as analyte polarity and molecular size. The diffusion coefficients were found to range from 6.41 x 10(-11) 5 x 10(-12) to 5.25 x 10(-11) +/- 9 x 10(-13) cm2 s(-1) for hexane and pentadecane into a 2.9 microm PDMS film, respectively. The diffusion model was also used to examine the effect of changing system parameters such as film thickness in order to characterize sensor response.     

Polyparameter linear free energy models for polyacrylate fiber-water partition coefficients to evaluate the efficiency of solid-phase microextraction

The fiber-water partition coefficient, K(fw), is decisive for performance of solid-phase microextraction (SPME) techniques in organic chemical analyses. In this study, polyacrylate (PA)-coated fiber was evaluated for its K(fw) values toward diverse neutral organic compounds. Literature K(fw) data were thoroughly evaluated, and additional K(fw) values for 69 compounds were measured in phosphate-buffered saline (PBS) solution at 37 °C. These K(fw) data, spanning over 6 orders of magnitude, were used to construct polyparameter linear free energy relationship (PP-LFER) models. The PP-LFER models fit well to the data with a standard deviation of 0.15-0.23 log units. Additional experiments indicated that the differences in temperature (25 vs 37 °C), electrolyte concentrations (pure water vs PBS), and conditioning methods (heat vs methanol) had only minor influences (<0.3 log units) on K(fw). Using the established PP-LFERs, the SPME extraction efficiency of PA coating toward compounds of differing polarity was evaluated in comparison to poly(dimethylsiloxane) (PDMS) coating. PA exhibited higher extraction capacities for H-bond donor compounds (e.g., phenols, anilines, amides, and many drugs and pesticides) with the estimated K(fw) values being 1-4 log units higher than those of PDMS. Also, PA was shown to be more efficient than PDMS for hydrophobic aromatic compounds.     

Nonequilibrium solid-phase microextraction for determination of the freely dissolved concentration of hydrophobic organic compounds: matrix effects and limitations

Solid-phase microextraction (SPME) has recently been applied to measure the freely dissolved concentration, as opposed to the total concentration, of hydrophobic substances in aqueous solutions. This requires that only the freely dissolved analytes contribute to the concentration in the SPME fiber coating. However, for nonequilibrium SPME the sorbed analytes that diffuse into the unstirred water layer (UWL) adjacent to the SPME fiber can desorb from the matrix and contribute to the flux into the fiber. These processes were described as a model. Experimentally, an equilibrated and disconnected headspace was used as a reference for the freely dissolved concentration. The expected contribution of desorbed analytes to the uptake flux was measured for PCB no. 52 in a protein-rich solution, while it was not measured in a matrix containing artificial soil. The latter was possibly due to slow desorption of the analyte from the artificial soil. On the basis of the present study, a contribution of desorbed analytes to the uptake flux is expected only if(1) the rate-limiting step of the uptake process is diffusion through the UWL, (2) the concentration of the sorbed analyte is high, and (3) desorption from the matrix is fast.     

Determining chemical activity of (semi)volatile compounds by headspace solid-phase microextraction

This research introduces a new analytical methodology for measuring chemical activity of nonpolar (semi)volatile organic compounds in different sample matrices using automated solid-phase microextraction (SPME). The chemical activity of an analyte is known to determine its equilibrium concentration in the SPME fiber coating. On this basis, SPME was utilized for the analytical determination of chemical activity, fugacity, and freely dissolved concentration using these steps: (1) a sample is brought into a vial, (2) the SPME fiber is introduced into the headspace and equilibrated with the sample, (3) the SPME fiber is injected into the GC for thermal desorption and analysis, and (4) the method is calibrated by SPME above partitioning standards in methanol. Model substances were BTEX, naphthalene, and alkanes, which were measured in a variety of sample types: liquid polydimethylsiloxane (PDMS), wood, soil, and nonaqueous phase liquid (NAPL). Variable sample types (i.e., matrices) had no influence on sampling kinetics because diffusion through the headspace was rate limiting for the overall sampling process. Sampling time was 30 min, and relative standard deviations were generally below 5% for homogeneous solutions and somewhat higher for soil and NAPL. This type of activity measurement is fast, reliable, almost solvent free, and applicable for mixed-media sampling.     

Novel hydrophobicity ruler approach for determining the octanol/water partition coefficients of very hydrophobic compounds via their polymer/solvent solution distribution coefficients

A novel hydrophobicity ruler approach for determining the octanol/water partition coefficients of very hydrophobic compounds is proposed, which is an indirect method that measures the polymer/solvent solution distribution coefficients (log Kp/s) of reference and unknown compounds. The log Kp/s values of the unknown compounds can be calibrated to their log Ko/w values via the correlation of the log Kp/s values of the reference compounds with their log Ko/w values. An organic solvent was used to increase the solubility of the very hydrophobic compounds in the aqueous solution, so that their concentrations and absorption amounts were high enough to be measured precisely. The solvent also reduced the hydrophobicity scale of the very hydrophobic compounds and controlled the amounts absorbed into the polymer phase, so that compounds spanning a very wide range of log Ko/w values could be measured in a single measurement and the coexisting compounds would not interfere each other. Poly(dimethylsiloxane) (PDMS), aqueous methanol solutions, and a series of 21 PCB (polychlorinated biphenyl) compounds were used to demonstrate the principle of the hydrophobicity ruler approach. The PCB compounds with known experimental log Ko/w values served as reference compounds, whereas the PCB compounds without known log Ko/w values were determined. The log Ko/w values determined for PCB126, PCB187, PCB197, PCB180, PCB170, and PCB195 were 6.94, 7.84, 8.33, 8.17, 7.92, and 8.49, respectively. The correlation of the log Kp/s values of the reference PCB compounds with their log Ko/w values was linear (log Ko/w=2.56 log Kp/s+1.08, R2=0.95). The hydrophobicity ruler approach is also a valuable tool for validating the experimental and theoretical log Ko/w values and identifying outliers in log Ko/w databases.     

Surface biopassivation of replicated poly(dimethylsiloxane) microfluidic channels and application to heterogeneous immunoreaction with on-chip fluorescence detection

Poly(dimethylsiloxane) (PDMS) appeared recently as a material of choice for rapid and accurate replication of polymer-based microfluidic networks. However, due to its hydrophobicity, the surface strongly interacts with apolar analytes or species containing apolar domains, resulting in significant uncontrolled adsorption on channel walls. This contribution describes the application and characterization of a PDMS surface treatment that considerably decreases adsorption of low and high molecular mass substances to channel walls while maintaining a modest cathodic electroosmotic flow. Channels are modified with a three-layer biotin-neutravidin sandwich coating, made of biotinylated IgG, neutravidin, and biotinylated dextran. By replacing biotinylated dextran with any biotinylated reagent, the modified surface can be readily patterned with biochemical probes, such as antibodies. Combination of probe immobilization chemistry with low nonspecific binding enables affinity binding assays within channel networks. The example of an electrokinetic driven, heterogeneous immunoreaction for human IgG is described.     

Extending the solid-phase microextraction technique to high analyte concentrations: measurements and thermodynamic analysis

The solid-phase microextraction (SPME) technique has been used historically to quantify analytes present at the parts per million level. However, the nonintrusive nature of SPME lends itself to other applications involving analytes at higher concentration. In the current work, the possibility of using the SPME technique to measure concentrated gaseous samples was examined. Pentane concentrations between 0 and 100% saturation were studied, over a temperature range of 20-45 degrees C. The results showed that, up to a critical mole fraction in the solid phase, the concentrations of pentane in the polymeric extracting solid and vapor phases were related by a constant, equal to Henry's constant. The temperature dependence of Henry's constant was shown to follow the predicted trend with temperature, as determined from rigorous thermodynamic calculations. Above the pentane concentration in the polymeric phase, the response deviated from linearity. The nonideality was captured in an activity coefficient. An activity coefficient model developed to describe the nonideality was found to be a function of the swollen volume of the SPME polymer phase. The results indicate that the SPME technique can be applied to high analyte concentrations, although difficulties may be encountered when multiple analytes are absorbed.     

High-efficiency single-cell entrapment and fluorescence in situ hybridization analysis using a poly(dimethylsiloxane) microfluidic device integrated with a black poly(ethylene terephthalate) micromesh

Here, we report a high-efficiency single-cell entrapment system with a poly(dimethylsiloxane) (PDMS) microfluidic device integrated with a micromesh, and its application to single-cell fluorescence in situ hybridization (FISH) analysis. A micromesh comprising of 10 x 10 microcavities was fabricated on a black poly(ethylene terephthalate) (PET) substrate by laser ablation. The cavity was approximately 2 microm in diameter. Mammalian cells were driven and trapped onto the microcavities by applying negative pressure. Trapped cells were uniformly arrayed on the micromesh, enabling high-throughput microscopic analysis. Furthermore, we developed a method of PDMS surface modification by using air plasma and the copolymer Pluronic F-127 to prevent nonspecific adsorption on the PDMS microchannel. This method decreased the nonspecific adsorption of cells onto the microchannel to less than 1%. When cells were introduced into the microfluidic device integrated with the black PET micromesh, approximately 70-80% of the introduced cells were successfully trapped. Moreover, for mRNA expression analysis, on-chip fluorescence in situ hybridization (e.g., membrane permeabilization, hybridization, washing) can be performed in a microfluidic assay on an integrated device. This microfluidic device has been employed for the detection of beta-actin mRNA expression in individual Raji cells. Differences in the levels of beta-actin mRNA expression were observed in serum-supplied or serum-starved cell populations.     

Sol-gel modified poly(dimethylsiloxane) microfluidic devices with high electroosmotic mobilities and hydrophilic channel wall characteristics

Using a sol-gel method, we have fabricated poly(dimethylsiloxane) (PDMS) microchips with SiO2 particles homogeneously distributed within the PDMS polymer matrix. These particles are approximately 10 nm in diameter. To fabricate such devices, PDMS (Sylgard 184) was cast against SU-8 molds. After curing, the chips were carefully removed from the mold and sealed against flat, cured pieces of PDMS to form enclosed channel manifolds. These chips were then solvated in tetraethyl orthosilicate (TEOS), causing them to expand. Subsequently, the chips were placed in an aqueous solution containing 2.8% ethylamine and heated to form nanometer-sized SiO2 particles within the cross-linked PDMS polymer. The water contact angle for the PDMS-SiO2 chips was approximately 90.2 degrees compared to a water contact angle for Sylgard 184 of approximately 108.5 degrees . More importantly, the SiO2 modified PDMS chips showed no rhodamine B absorption after 4 h, indicating a substantially more hydrophilic and nonabsorptive surface than native PDMS. Initial electroosmotic mobilities (EOM) of (8.3+/-0.2)x10(-4) cm2/(V.s) (RSD=2.6% (RSD is relative standard deviation); n=10) were measured. This value was approximately twice that of native Sylgard 184 PDMS chips (4.21+/-0.09)x10(-4) cm2/(V.s) (RSD=2.2%; n=10) and 55% greater than glass chips (5.3+/-0.4)x10(-4) cm2/(V.s) (RSD=7.7%; n=5). After 60 days of dry storage, the EOM was (7.6+/-0.3)x10(-4) cm2/(V.s) (RSD=3.9%; n=3), a decrease of only 8% below that of the initially measured value. Separations performed on these devices generated 80,000-100,000 theoretical plates in 6-14 s for both tetramethylrhodamine succidimidyl ester and fluorescein-5-isothiocyanate derivatized amino acids. The separation distance was 3.5 cm. Plots of peak variance vs analyte migration times gave diffusion coefficients which indicate that the separation efficiencies are within 15% of the diffusion limit.     

Electrophoretic effects of the adsorption of anionic surfactants to poly(dimethylsiloxane)-coated capillaries

Poly(dimethylsiloxane) (PDMS) is one of the most convenient materials to construct capillary electrophoresis microchips. Even though PDMS has many advantages, its use is often limited by its hydrophobicity. Although it is well-known that the surface properties of PDMS can be modified by anionic surfactants, very little is known regarding the driving forces or the electrophoretic consequences of the adsorption of anionic surfactants. In this work, the adsorption of alkyl surfactants on PDMS was studied by performing electroosmotic flow (microEOF) measurements. In order to mimic the behavior of PDMS microchannels, fused-silica capillaries were coated with PDMS and used for the microEOF measurements. This approach allowed using standard CE instrumentation and provided significant advantages over similar experiments performed on microchips. The change in the microEOF in the presence of surfactants was correlated to the surfactant adsorbed amount which, plotted versus surfactant concentration, gives an adsorption isotherm. The adsorption isotherms were obtained using alkyl surfactants with different chain lengths and head groups. According to our results, the interaction of alkyl surfactants with the PDMS surface is determined by a combination of hydrophobic and electrostatic interactions, where the former is more significant than the latter. The affinity of each surfactant for the PDMS surface was calculated by fitting the adsorption profiles with a Langmuir equation and, in the case of single-charged surfactants, correlated to the corresponding cmc value.     

Characterization of electrospun poly(p-dioxanone) and poly(p-dioxanone)/clay nanocomposite fibers

PPDO was successfully electrospun into continuous, ultrafine fibers by using DMSO as solvent for the first time. The concentration of PPDO in DMSO and the electrospinning temperature were optimized. PPDO/LAP nanocomposites were also electrospun in DMSO. At 70 degrees C, ultrafine PPDO fibers were obtained from 35 wt% solution and the PPDO/LAP nanocomposite fibers were yielded from 55 wt% solution. Electrospun fibers of the PPDO/LAP nanocomposites showed higher degree of crystallinity due to the presence of embedded nanoparticles.     

Formation and properties of surface-anchored amine-terminated poly(dimethylsiloxane) assemblies with tunable physico-chemical characteristics

Surface-anchored amine-terminated poly(dimethysiloxane) (PDMS) assemblies with tunable physico-chemical characteristics were fabricated with a simple two-step procedure. Firstly, 3-glycidoxypropylmethyldimethoxysilane (GPDMS) molecules were self-assembled on silicon surface, and then coupled to PDMS through a surface ring-opening reaction. The structure and morphology of the amine-terminated PDMS assemblies were characterized with various techniques such as ellipsometry, contact angle goniometer, grazing angle attenuated total reflectance-Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The GPDMS monolayers were truly monomolecular films with a virtually normal molecular orientation of densely packed molecules, which were firmly tethered to the hydroxylated silicon substrate. Self-assembly of PDMS molecules resulted in the formation of homogeneous films ~ 6.3 nm thick with the surface roughness ~ 0.898 nm. The calculation of grafting parameters from experimental measurements indicated that the presence of homogeneous and densely grafted PDMS films allowed us to predict a “brushlike” regime for the polymer chains in good solvents.     

Electrohydrodynamic generation and delivery of monodisperse picoliter droplets using a poly(dimethylsiloxane) microchip

We developed a drop-on-demand microdroplet generator for the discrete dispensing of biosamples into a bioanalytical unit. This disposable PDMS microfluidic device can generate monodisperse droplets of picoliter volume directly out of a plane sidewall of the microfluidic chip by an electrohydrodynamic mechanism. The droplet generation was accomplished without using either an inserted capillary or a monolithically built-in tip. The minimum droplet volume was approximately 4 pL, and the droplet generation was repeatable and stable for at least 30 min, with a typical variation of less than 2.0% of drop size. The Taylor cone, which is usually observed in electrospray, was suppressed by controlling the surface wetting property of the PDMS device as well as the surface tension of the sample liquids. A modification of the channel geometry right before the opening of the microchannel also enhanced the continuous droplet generation without applying any external pumping. A simple numerical simulation of the droplet generation verified the importance of controlling the surface wetting conditions for the droplet formation. Our microdroplet generator can be effectively applied to a direct interface of a microfluidic chip to a biosensing unit, such as AMS, MALDI-MS or protein microarray-type biochips.     

Mechanical properties and structural characterization of poly(dimethylsiloxane) elastomers reinforced with zeolite fillers

Poly(dimethylsiloxane) elastomers were filled with two zeolites which were both silicates of sodium and aluminum, but which had different cavity sizes. The reinforcement of the particles provided was characterized by stress-strain measurements in elongation at room temperature. The results indicated that the ultimate properties of the networks were increased by both types of zeolites, but that the increase was larger in the case of the zeolite with the larger cavity size. Small-angle-neutron-scattering results confirmed that the interface between the elastomeric phase and the zeolite particles was smooth, but gave no evidence for increased polymer penetration into the larger-cavity zeolite. Transmission electron microscopy (TEM) showed that the zeolite with a larger pore size also had a smaller particle size, and this is probably the origin of its superior reinforcing ability.