Synthesis, Modification, and Application of Siloxane Materials for Environmental Sensing

As human populations and resource consumption increase, it is increasingly important to monitor the quality of our environment. While laboratory instruments offer useful information, portable, easy to use sensors would allow environmental analysis to occur on-site, at lower cost, and with minimal operator training. We explore the synthesis, modification, and applications of modified polysiloxane in environmental sensing. Multiple methods of producing modified siloxanes were investigated. Oligomers were formed by using functionalized monomers, producing siloxane materials containing silicon hydride, methyl, and phenyl side chains. Silicon hydride-functionalized oligomers were further modified by hydrosilylation to incorporate methyl ester and naphthyl side chains. Modifications to the siloxane materials were also carried out using post-curing treatments. Methyl ester-functionalized siloxane was incorporated into the surface of a cured poly(dimethylsiloxane) film by siloxane equilibration. The materials containing methyl esters were hydrolyzed to reveal carboxylic acids, which could later be used for covalent protein immobilization. Finally, the siloxane surfaces were modified to incorporate antibodies by covalent, affinity, and adsorption-based attachment. These modifications were characterized by a variety of methods, including contact angle, attenuated total reflectance Fourier transform infrared spectroscopy, dye labels, and 1H nuclear magnetic resonance spectroscopy. The modified siloxane materials were employed in a variety of sensing schemes. Volatile organic compounds were detected using methyl, phenyl, and naphthyl-functionalized materials on a Fabry-Perot interferometer and a refractometer. The Fabry-Perot interferometer was found to detect the analytes upon siloxane extraction by deformation of the Bragg reflectors. The refractometer was used to determine that naphthyl-functionalized siloxanes had elevated refractive indices, rendering these materials more sensitive to some analytes. Antibody-modified siloxanes were used to detect biological analytes through a solid phase microextraction-mediated enzyme linked immunosorbent assay (SPME ELISA). The SPME ELISA was found to have higher analyte sensitivity compared to a conventional ELISA system. The detection scheme was used to detect Escherichia coli at 8500 CFU/mL. These results demonstrate the variety of methods that can be used to modify siloxanes and the wide range of applications of modified siloxanes has been demonstrated through chemical and biological sensing schemes.

Equilibrium swelling measurements of network and semicrystalline polymers in supercritical carbon dioxide using high-pressure NMR

The extent of swelling of cross-linked poly(dimethylsiloxane) and linear low-density poly(ethylene) in supercritical CO2 has been investigated using high-pressure NMR spectroscopy and microscopy. Poly(dimethylsiloxane) was cross-linked to four different cross-link densities and swollen in supercritical CO2. The Flory-Huggins interaction parameter, x, was found to be 0.62 at 300 bar and 45 degrees C, indicating that supercritical CO2 is a relatively poor solvent compared to toluene or benzene. Linear low-density poly(ethylene) was shown to exhibit negligible swelling upon exposure to supercritical CO2 up to 300 bar. The effect Of CO2 pressure on the amorphous region of the poly(ethylene) was investigated by observing changes in the H-1 T-2 relaxation times of the polymer. These relaxation times decreased with increasing pressure, which was attributed to a decrease in mobility of the polymer chains as a result of compressive pressure.

An experimental and modelling study of the capture of CO2 from gas mixtures with different techniques, with focus on multicomponent effects.

In the present work, the deviations in the solubility of CO2, CH4, and N2 at 30 °c in the mixed gases (CO2/CH4) and (CO2/N2) from the pure gas behavior were studied using the dual-mode model over a wide range of equilibrium composition and pressure values in two glassy polymers. The first of which was PI-DAR which is the polyimide formed by the reaction between 4, 6-diaminoresorcinol dihydrochloride (DAR-Cl) and 2, 2’-bis-(3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA). The other glassy polymer was TR-DAR which is the corresponding thermally rearranged polymer of PI-DAR. Also, mixed gas sorption experiments for the gas mixture (CO2/CH4) in TR-DAR at 30°c took place in order to assess the degree of accuracy of the dual-mode model in predicting the true mixed gas behavior. The experiments were conducted on a pressure decay apparatus coupled with a gas chromatography column. On the other hand, the solubility of CO2 and CH4 in two rubbery polymers at 30⁰c in the mixed gas (CO2/CH4) was modelled using the Lacombe and Sanchez equation of state at various values of equilibrium composition and pressure. These two rubbery polymers were cross-linked poly (ethylene oxide) (XLPEO) and poly (dimethylsiloxane) (PDMS). Moreover, data about the sorption of CO2 and CH4 in liquid methyl dietahnolamine MDEA that was collected from literature65-67 was used to determine the deviations in the sorption behavior in the mixed gas from that in the pure gases. It was observed that the competition effects between the penetrants were prevailing in the glassy polymers while swelling effects were predominant in the rubbery polymers above a certain value of the fugacity of CO2. Also, it was found that the dual-mode model showed a good prediction of the sorption of CH4 in the mixed gas for small pressure values but in general, it failed to predict the actual sorption of the penetrants in the mixed gas.

Synthesis, Modification, and Application of Siloxane Materials for Environmental Sensing

As human populations and resource consumption increase, it is increasingly important to monitor the quality of our environment. While laboratory instruments offer useful information, portable, easy to use sensors would allow environmental analysis to occur on-site, at lower cost, and with minimal operator training. We explore the synthesis, modification, and applications of modified polysiloxane in environmental sensing. Multiple methods of producing modified siloxanes were investigated. Oligomers were formed by using functionalized monomers, producing siloxane materials containing silicon hydride, methyl, and phenyl side chains. Silicon hydride-functionalized oligomers were further modified by hydrosilylation to incorporate methyl ester and naphthyl side chains. Modifications to the siloxane materials were also carried out using post-curing treatments. Methyl ester-functionalized siloxane was incorporated into the surface of a cured poly(dimethylsiloxane) film by siloxane equilibration. The materials containing methyl esters were hydrolyzed to reveal carboxylic acids, which could later be used for covalent protein immobilization. Finally, the siloxane surfaces were modified to incorporate antibodies by covalent, affinity, and adsorption-based attachment. These modifications were characterized by a variety of methods, including contact angle, attenuated total reflectance Fourier transform infrared spectroscopy, dye labels, and 1H nuclear magnetic resonance spectroscopy. The modified siloxane materials were employed in a variety of sensing schemes. Volatile organic compounds were detected using methyl, phenyl, and naphthyl-functionalized materials on a Fabry-Perot interferometer and a refractometer. The Fabry-Perot interferometer was found to detect the analytes upon siloxane extraction by deformation of the Bragg reflectors. The refractometer was used to determine that naphthyl-functionalized siloxanes had elevated refractive indices, rendering these materials more sensitive to some analytes. Antibody-modified siloxanes were used to detect biological analytes through a solid phase microextraction-mediated enzyme linked immunosorbent assay (SPME ELISA). The SPME ELISA was found to have higher analyte sensitivity compared to a conventional ELISA system. The detection scheme was used to detect Escherichia coli at 8500 CFU/mL. These results demonstrate the variety of methods that can be used to modify siloxanes and the wide range of applications of modified siloxanes has been demonstrated through chemical and biological sensing schemes.

BLOCK COPOLYMERS CONTAINING A LOW-SURFACE-ENERGY BLOCK AND THEIR APPLICATIONS

This thesis reports the synthesis and/or applications of three types of block copolymers that each bear a low-surface-energy block. First, poly(dimethylsiloxane)-block-poly(2-cinnamoyloxyethyl acrylate) (PDMS-b-PCEA) was synthesized and characterized. Cotton coating using a micellar solution of this block copolymer yielded superhydrophobic cotton fabrics. X-ray photoelectron spectroscopy (XPS) and surface property analyses indicated that the PDMS block topped the polymer coating. Photocuring the cotton swatches crosslinked the underlying PCEA layer and yielded permanent coatings. More interestingly, hydrophilically patterned superhydrophobic cotton fabrics were produced using photolithography that allowed the crosslinking of the coating around irradiated fibers but the removal, by solvent extraction, of the coating on fibers that were not irradiated. Since water-based ink only permeated the uncoated regions, such patterned fabric was further used to print ink patterns onto substrates such as fabrics, cardboard, paper, wood, and aluminum foil. Then, another PDMS-based diblock copolymer poly(dimethylsiloxane)-block-poly(glycidyl methacrylate) (PDMS-b-PGMA) was prepared. Different from PCEA that photocrosslinked around cotton fibers, PGMA reacted with hydroxyl groups on cotton fiber surfaces to get covalently attached. Further, different PGMA chains crosslinked with each other. PDMS-b-PGMA-coated cotton fabrics have been used for oil-water separations. In addition, polymeric nanoparticles were grafted onto cotton fiber surface before PDMS-b-PGMA was used to cover the surfaces of the grafted spheres and the residual surfaces of the cotton fibers. These two types of fabrics, coated by the block copolymer alone or by the polymer nanospheres and then the copolymer, were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR), and water repellency analyses. A comprehensive comparative study was made of their performances in oil-water separation. Finally, a fluorinated ABC triblock copolymer poly(acrylic acid)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(2-perfluorooctylethyl methacrylate) (PAA-b-PCEMA-b-PFOEMA) was used to iii encapsulate air nanobubbles. The produced air nanobubbles were thermodynamically stable in water and were some 100 times more stable than commercially available perfluorocarbon-filled microbubbles under ultrasound. These nanobubbles, due to their small sizes and thus ability to permeate the capillary networks of organs and to reach tumors, may expand the applications of microbubbles in diagnostic ultrasonography and find new applications in ultrasound-regulated drug delivery.

Nanomechanical characterization of soft bioelectronic interfaces via modeling-informed atomic force microscopy

The field of bioelectronics involves the use of electrodes to exchange electrical signals with biological systems for diagnostic and therapeutic purposes in biomedical devices and healthcare applications. However, the mechanical compatibility of implantable devices with the human body has been a challenge, particularly with long-term implantation into target organs. Current rigid bioelectronics can trigger inflammatory responses and cause unstable device functions due to the mechanical mismatch with the surrounding soft tissue. Recent advances in flexible and stretchable electronics have shown promise in making bioelectronic interfaces more biocompatible. To fully achieve this goal, material science and engineering of soft electronic devices must be combined with quantitative characterization and modeling tools to understand the mechanical issues at the interface between electronic technology and biological tissue. Local mechanical characterization is crucial to understand the activation of failure mechanisms and optimizing the devices. Experimental techniques for testing mechanical properties at the nanoscale are emerging, and the Atomic Force Microscope (AFM) is a good candidate for in situ local mechanical characterization of soft bioelectronic interfaces. In this work, in situ experimental techniques with solely AFM supported by interpretive models for the characterization of planar and three-dimensional devices suitable for in vivo and in vitro biomedical experimentations are reported. The combination of the proposed models and experimental techniques provides access to the local mechanical properties of soft bioelectronic interfaces. The study investigates the nanomechanics of hard thin gold films on soft polymeric substrates (Poly(dimethylsiloxane) PDMS) and 3D inkjet-printed micropillars under different deformation states. The proposed characterization methods provide a rapid and precise determination of mechanical properties, thus giving the possibility to parametrize the microfabrication steps and investigate their impact on the final device.

Effect Of Daily Use Of An Enzymatic Denture Cleanser On Candida Albicans Biofilms Formed On Polyamide And Poly(methyl Methacrylate) Resins: An In Vitro Study.

Candida biofilms on denture surfaces are substantially reduced after a single immersion in denture cleanser. However, whether this effect is maintained when dentures are immersed in cleanser daily is unclear. The purpose of this study was to evaluate the effect of the daily use of enzymatic cleanser on Candida albicans biofilms on denture base materials. The surfaces of polyamide and poly(methyl methacrylate) resin specimens (n=54) were standardized and divided into 12 groups (n=9 per group), according to study factors (material type, treatment type, and periods of treatment). Candida albicans biofilms were allowed to form over 72 hours, after which the specimens were treated with enzymatic cleanser once daily for 1, 4, or 7 days. Thereafter, residual biofilm was ultrasonically removed and analyzed for viable cells (colony forming units/mm(2)) and enzymatic activity (phospholipase, aspartyl-protease, and hemolysin). Factors that interfered with the response variables were analyzed by 3-way ANOVA with the Holm-Sidak multiple comparison method (α=.05). Polyamide resin presented more viable cells of Candida albicans (P<.001) for both the evaluated treatment types and periods. Although enzymatic cleansing significantly (P<.001) reduced viable cells, daily use did not maintain this reduction (P<.001). Phospholipase activity significantly increased with time (P<.001) for both materials and treatments. However, poly(methyl methacrylate) based resin (P<.001) and enzymatic cleansing treatment (P<.001) contributed to lower phospholipase activity. Aspartyl-protease and hemolysin activities were not influenced by study factors (P>.05). Although daily use of an enzymatic cleanser reduced the number of viable cells and phospholipase activity, this treatment was not effective against residual biofilm over time.

The Effect Of Poly(methyl Methacrylate) Surface Treatments On The Adhesion Of Silicone-based Resilient Denture Liners.

Different surface treatment protocols of poly(methyl methacrylate) have been proposed to improve the adhesion of silicone-based resilient denture liners to poly(methyl methacrylate) surfaces. The purpose of this study was to evaluate the effect of different poly(methyl methacrylate) surface treatments on the adhesion of silicone-based resilient denture liners. Poly(methyl methacrylate) specimens were prepared and divided into 4 treatment groups: no treatment (control), methyl methacrylate for 180 seconds, acetone for 30 seconds, and ethyl acetate for 60 seconds. Poly(methyl methacrylate) disks (30.0 × 5.0 mm; n = 10) were evaluated regarding surface roughness and surface free energy. To evaluate tensile bond strength, the resilient material was applied between 2 treated poly(methyl methacrylate) bars (60.0 × 5.0 × 5.0 mm; n = 20 for each group) to form a 2-mm-thick layer. Data were analyzed by 1-way ANOVA and the Tukey honestly significant difference tests (α = .05). A Pearson correlation test verified the influence of surface properties on tensile bond strength. Failure type was assessed, and the poly(methyl methacrylate) surface treatment modifications were visualized with scanning electron microscopy. The surface roughness was increased (P < .05) by methyl methacrylate treatment. For the acetone and ethyl acetate groups, the surface free energy decreased (P < .05). The tensile bond strength was higher for the methyl methacrylate and ethyl acetate groups (P < .05). No correlation was found regarding surface properties and tensile bond strength. Specimens treated with acetone and methyl methacrylate presented a cleaner surface, whereas the ethyl acetate treatment produced a porous topography. The methyl methacrylate and ethyl acetate surface treatment protocols improved the adhesion of a silicone-based resilient denture liner to poly(methyl methacrylate).

Improved Selective Cholesterol Adsorption By Molecularly Imprinted Poly(methacrylic Acid)/silica (pmaa-sio₂) Hybrid Material Synthesized With Different Molar Ratios.

The present paper describes the synthesis of molecularly imprinted polymer - poly(methacrylic acid)/silica and reports its performance feasibility with desired adsorption capacity and selectivity for cholesterol extraction. Two imprinted hybrid materials were synthesized at different methacrylic acid (MAA)/tetraethoxysilane (TEOS) molar ratios (6:1 and 1:5) and characterized by FT-IR, TGA, SEM and textural data. Cholesterol adsorption on hybrid materials took place preferably in apolar solvent medium, especially in chloroform. From the kinetic data, the equilibrium time was reached quickly, being 12 and 20 min for the polymers synthesized at MAA/TEOS molar ratio of 6:1 and 1:5, respectively. The pseudo-second-order model provided the best fit for cholesterol adsorption on polymers, confirming the chemical nature of the adsorption process, while the dual-site Langmuir-Freundlich equation presented the best fit to the experimental data, suggesting the existence of two kinds of adsorption sites on both polymers. The maximum adsorption capacities obtained for the polymers synthesized at MAA/TEOS molar ratios of 6:1 and 1:5 were found to be 214.8 and 166.4 mg g(-1), respectively. The results from isotherm data also indicated higher adsorption capacity for both imprinted polymers regarding to corresponding non-imprinted polymers. Nevertheless, taking into account the retention parameters and selectivity of cholesterol in the presence of structurally analogue compounds (5-α-cholestane and 7-dehydrocholesterol), it was observed that the polymer synthesized at the MAA/TEOS molar ratio of 6:1 was much more selective for cholesterol than the one prepared at the ratio of 1:5, thus suggesting that selective binding sites ascribed to the carboxyl group from MAA play a central role in the imprinting effect created on MIP.

Nitric Oxide-releasing Poly(vinyl Alcohol) Film For Increasing Dermal Vasodilation.

Pathological conditions associated with the impairment of nitric oxide (NO) production in the vasculature, such as Raynaud's syndrome and diabetic angiopathy, have stimulated the development of new biomaterials capable of delivering NO topically. With this purpose, we modified poly(vinyl-alcohol) (PVA) by chemically crosslinking it via esterification with mercaptosuccinic acid. This reaction allowed the casting of sulfhydrylated PVA (PVA-SH) films. Differential scanning calorimetry and X-ray diffractometry showed that the crosslinking reaction completely suppressed the crystallization of PVA, leading to a non-porous film with a homogeneous distribution of -SH groups. The remaining free hydroxyl groups in the PVA-SH network conferred partial hydrophylicity to the material, which was responsible for a swelling degree of ca. 110%. The PVA-SH films were subjected to an S-nitrosation reaction of the -SH groups, yielding a PVA containing S-nitrosothiol groups (PVA-SNO). Amperometric and chemiluminescence measurements showed that the PVA-SNO films were capable of releasing NO spontaneously after immersion in physiological medium. Laser Doppler-flowmetry, used to assess the blood flow in the dermal microcirculation, showed that the topical application of hydrated PVA-SNO films on the health skin led to a dose- and time-dependent increase of more than 5-fold in the dermal baseline blood flow in less than 10min, with a prolonged action of more than 4h during continuous application. These results show that PVA-SNO films might emerge as a new material with potential for the topical treatment of microvascular skin disorders.

Phase transitions in biodegradable films based on blends of gelatin and poly (vinyl alcohol)

The aim of this work was to study the effect of the hydrolysis degree (HD) and the concentration (C PVA) of two types of poly (vinyl alcohol) (PVA) and the effect of the type and the concentration of plasticizers on the phase properties of biodegradable films based on blends of gelatin and PVA, using a response-surface methodology. The films were made by casting and the studied properties were their glass (Tg) and melting (Tm) transition temperatures, which were determined by diferential scanning calorimetry (DSC). For the data obtained on the first scan, the fitting of the linear model was statistically significant and predictive only for the second melting temperature. In this case, the most important effect on the second Tm of the first scan was due to the HD of the PVA. In relation to the second scan, the linear model could be fit to Tg data with only two statistically significant parameters. Both the PVA and plasticizer concentrations had an important effect on Tg. Concerning the second Tm of the second scan, the linear model was fit to data with two statistically significant parameters, namely the HD and the plasticizer concentration. But, the most important effect was provoked by the HD of the PVA.

Photo-fenton degradation of poly(Ethyleneglycol)

Polyethyleneglycol (PEG) was photooxidized in a photo-Fenton system and results compared with the dark reaction. The products were analysed using GPC and HPLC. In the absence of light, PEG samples needed 490 min to reduce their w by 50%, whereas under UV irradiation, only 10 min were necessary. The exponential decay of w with a concomitant increase in polydispersity and number of average chain scission, characterized a random chain scission mechanism. The degradation products of PEG in both systems showed the presence of lower molecular weight products, including smaller ethyleneglycols and formic acid. The mechanism involves consecutive processes, were the larger ethyleneglycols give rise, successively, to smaller ones. This suggests that the mechanism involves successive scissions of the polymer chain. Irradiated samples decomposed faster than those kept in the dark This study proves that the foto-Fenton method associated with UV-light is a good reactant for PEG photodegradation.

The UV/H2O2 - photodegradation of poly(ethyleneglycol) and model compounds

The general mechanism for the photodegradation of polyethyleneglycol (PEG) by H2O2/UV was determined studying the photooxidation of small model molecules, like low molecular weight ethyleneglycols (tetra-, tri-, di-, and ethyleneglycol). After 30 min of irradiation the average molar mass (Mw) of the degradated PEG, analysed by GPC, fall to half of its initial value, with a concomitant increase in polydispersitivity and number of average chain scission (S), characterizing a random chain scission process yielding oligomers and smaller size ethyleneglycols. HPLC analysis of the photodegradation of the model ethyleneglycols proved that the oxidation mechanism involved consecutive reactions, where the larger ethyleneglycols gave rise, successively, to smaller ones. The photodegradation of ethyleneglycol lead to the formation of low molecular weight carboxylic acids, like glycolic, oxalic and formic acids.

Time resolved emission spectroscopy of poly(2,5-dicyano-p-phenylene-vinylene) films

Films of poly (2,5-dicyano-p-phenylene vinylene), DCNPPV, were obtained by electrochemical synthesis over gold thin layer (20 nm) transparent electrode deposited on a glass plate. The DCNPPV films of 4 µm thickness were produced by electropolymerization process of α,α,α',α'-tetrabromo-2-5-dicyano-p-xilene at different applied potentials (-0.15, -0.25, -0.40, -0.60, -0.80, and -1.0 V) using 0.1 mol L-1 of tetraethylammonium bromide in acetonitrile as the supporting electrolyte. The emission decays have three exponential components: a fast component in the picosecond range (200-400 ps), and two other of about one and five nanoseconds at 293 K. The fluorescence quenching process seems to occur by exciton trapping in a low-energy site and quenching by residual bromine monomer attached at the end of the polymer chain. However, the electrochemical synthesis generates entrapped bromide or ion pairs during the growth step of the film which also contributes to the deactivation. The change of the electrolyte from bromide to perchlorate reduces significantly this additional quenching effect by allowing ion exchange of formed bromide with the nonquenching perchloride anion.