Hydrophilic Media Research Articles

Investigation of temperature-driven water transport in polymer electrolyte fuel cell: Thermo-osmosis in membranes

The objective of this work is to investigate water transport in polymer electrolyte fuel cell membranes subjected to a temperature gradient. Direct thermo-osmotic experiments on different polymer membrane types (non-reinforced Nafion ®, and reinforced Gore-Select ® and Flemion ® membranes) were performed using an in-house fuel cell fixture with a parallel flow field and pure membrane sheet without catalyst layers. Thermo-osmotic flow was observed in all membranes, and the water flow direction in the membrane was determined to always flow from the cold to hot side, as anticipated for a small pore hydrophilic porous medium. The water flux was found to be proportional to temperature gradient, and increase with average membrane temperature. The dependency of the thermo-osmotic diffusivity on average temperature showed predictable Arrhenius-type behavior. True interfacial temperatures of the membrane were estimated using a two-dimensional thermal model, and empirical relations for the thermo-osmotic diffusivity for the membrane types tested were developed. These can be of use to design engineers concerned about achieving optimal water balance during steady and transient operation.

Antioxidant activity evaluation of alkyl hydroxytyrosyl ethers, a new class of hydroxytyrosol derivatives

The antioxidant activity of a new series of alkyl hydroxytyrosyl ethers was evaluated by the Rancimat test in a lipophilic food matrix and by the FRAP, ABTS and DPPH assays in a hydrophilic medium, and compared to free hydroxytyrosol (HTy), butylhydroxytoluene (BHT) and α-tocopherol. All methods used to assess the antioxidant activity of the new compounds emphasised the importance of the ortho-diphenolic structure on the maintenance of the high antioxidant activity associated with free HTy. The results obtained support the ‘polar paradox’ since the antioxidant activity of the lipophilic hydroxytyrosyl ethers was slightly lower in bulk oils and higher in hydrophilic media in comparison with their reference HTy. Although the length of the alkyl chain did not significantly affect the antioxidant activity in bulk oils, it did have a positive influence in hydrophilic medium for ethers with a short alkyl chain (methyl, ethyl and propyl), while ethers with longer alkyl chain (butyl, hexyl, octyl, dodecyl and octadecyl) maintained or even decreased their antioxidant activity, probably due to the steric effect of the side chains. In conclusion, these results show the strong antioxidant activity of a new group of lipophilic HTy derivatives that satisfies the food industry demands for new antioxidants with potential use as functional ingredients to improve the quality and nutritional properties of foods.

Applications of cationic gemini surfactant in preparing multi-walled carbon nanotube contained nanofluids

Stable homogeneous nanofluids of multi-walled carbon nanotubes (MWNTs) were prepared by using gemini cationic surfactant trimethylene-1,3-bis (dodecyldimethyl ammonium bromide), abbreviated as 12-3-12,2Br −1, as dispersing agents. Zeta potential and FT-IR measurements were employed to investigate the adsorption mechanism of 12-3-12,2Br −1 on MWNTs. The interactions between MWNTs and 12-3-12,2Br −1 through hydrophobic segments cause hydrophilic MWNT-suspended medium interfaces with high positive charges, which enables the nanofluids to be stable for long periods. At relatively low temperatures the superfluous surfactant molecules form stable layer or column micelles, making an increase in the viscosity of nanofluids. Only 0.6 wt% gemini surfactant was used to obtain 0.5 wt% MWNT dispersions. The dispersions show no MWNTs precipitation for at least 5 weeks.

Interaction of Zinc Tetrasulfonated Phthalocyanine with Cytochrome c in Water and Triton-X 100 Micelles

The interaction of a zinc tetrasulfonated phthalocyanine with cytochrome c was studied using steady-state spectroscopic techniques and time-correlated single photon counting in water and Triton-X 100 micelles. The dye forms dimers in water with a high equilibrium constant (70 x 10(6) M(-1)). Because of a specific electrostatic interaction, the presence of cytochrome c does not lead to a dissociation of this dimer, but increases its formation, with an equilibrium constant of about 7.9 x 10(9) M(-1). Triton-X 100 micelles dissociate the dimer, creating two populations of dye molecules: one in a hydrophilic media, probably on the surface of the micelles, another on a hydrophobic environment, probably inside the micelles. However, when cytochrome c is added the dye aggregation is again induced leading to a strong fluorescence quenching. This fluorescence quenching may also be caused by a photoinduced electron-transfer due to the formation of a 1:1 complex between the dye and the protein, but the present work does not give direct evidence of such an effect because the fluorescence decays did not show the presence of an extra component. The results presented here are quite different from those reported for aluminum sulfonated phthalocyanines, where aggregation does not occur and the fluorescence quenching is solely due to photoinduced electron-transfer reactions.

Syringomyelia caused by intrathecal remnants of oil-based contrast medium

Oily contrast medium had been in use since the early 19th century as a radiographic agent for detecting spinal lesions and spinal cord tumors until the late 20th century. At that point computed tomography scanning and magnetic resonance imaging, or other hydrophilic contrast medium substituted for it. Adverse effects of oil-based dye, both acute and chronic, had been reported since the middle of the 20th century. In this paper the authors report the case of syringomyelia that seemed to be caused mainly by remaining oily contrast medium for 44 years. Syringomyelia secondary to adhesive arachnoiditis caused by oily contrast medium after a long period of time is well known. In the present case, however, surgery revealed only mild arachnoiditis at the level of syringomyelia as well as both solid and liquid remnants of contrast medium. Generally, cerebrospinal fluid (CSF) blockage due to an arachnoid adhesion is considered to cause syringomyelia following adhesive arachnoiditis. The authors speculated that in the present case syringomyelia was induced by a mechanism different from that in the previously reported cases; the oily contrast medium itself seems to have induced the functional block of CSF and impaired the buffer system of the intrathecal pressure. No reports on thoracic adhesive arachnoiditis and syringomyelia caused by oil-based dye referred to this mechanism in reviewing the literature.

Two-phase flow and evaporation in model fibrous media: Application to the gas diffusion layer of PEM fuel cells

Two-phase flow dominated by capillary effects in model fibrous media is studied combining pore-network simulations and visualisations on transparent micromodels. It is shown that the process of liquid water invasion in a hydrophobic medium can be simulated using the classical invasion percolation algorithm provided that the contact angle (measured in air, which is the wetting phase) is sufficiently far below 90°. For contact angles approaching 90°, changes in the interface local growth mechanisms lead to changes in the invasion pattern. Then it is shown that the invasion pattern is dramatically different in a hydrophilic medium. Impact of wettability (hydrophobic vs. hydrophilic) on evaporation pattern is also analysed. In a last part, implications of the study findings on the water management problem in the gas diffusion layers (GDLs) of PEMFC are discussed. Our results provide pore-scale explanations to the advantages of hydrophobic GDLs.

Preparation of Medium Cation Exchange Stationary Phase of Polymeric Matrix and Their Chromatographic Properties

AbstractBased on the monodisperse poly(glycidyl methacrylate‐co‐ethylenedimethacrylate) beads (PGMA/EDMA) with macropore as a medium, a new hydrophilic medium cation exchange (MCX) stationary phase for HPLC was synthesized by a new chemically modified method. The stationary phase was evaluated with the property of ion exchange, separability, reproducibility, hydrophilicity, effect of salt concentration, salt types, column loading and pH on the separation and retention of proteins in detail. It was found that it follows ion exchange chromatographic (IEC) retention mechanism. The measured bioactivity recovery for lysozyme was (96±5)%. The dynamic protein loading capacity of the synthesized MCX packings was 21.8 mg/g. Five proteins were almost completely separated within 6.0 min at a flow rate of 4 mL/min using the synthesized MCX resin. The MCX resin was also used for the rapid separation and purification of lysozyme from egg white with only one step. The purity and specific bioactivity of the purified lysozyme was found more than 95% and 70345 U/mg, respectively.

Self-Controlled Synthesis of Hyperbranched Poly(ether ketone)s from A3 + B2 Approach via Different Solubilities of Monomers in the Reaction Medium

Hyperbranched poly(ether ketone)s (PEK's) were synthesized via A3 + B2 polymerization approach without forming cross-linked products, because the polymer-forming process based on Friedel−Crafts reaction was kinetically controlled by the solubility difference of monomers in the viscous hydrophilic reaction medium, poly(phosphoric acid) (PPA)/phosphorus pentoxide (P2O5). The hydrophilic trimesic acid as an A3 monomer is soluble in the reaction medium, while hydrophobic diphenyl ether and 1,4-diphenoxybenzene as B2 monomers are marginally soluble. It is hypothesized that the gelation was avoided because of the following two factors: (i) self-regulated feeding of the arylether monomers into the system driven by their poor solubility and phase separation from PPA/P2O5 medium; (ii) reaction-medium-induced isolation of growing macromolecules promoted by the high bulk viscosity. Both polymerization experiments based on equimolar or equifunctional stoichiometry (A3:B2) resulted in completely soluble hyperbranched...

Optical biochemical sensor for determining hydroperoxides in nonpolar organic liquids as archetype for sensors consisting of amphiphilic conetworks as immobilisation matrices

This paper reports the successful design of a prototype of an optical biochemical sensor for the determination of hydroperoxides in nonpolar organic liquids. The sensor consists of a matrix of an amphiphilic polymer conetwork (APCN), a novel class of very promising polymeric materials for easy preparation of biochemical sensor matrices. APCNs are characterised by nanoscopic phase separation between the hydrophilic and the hydrophobic phases. For medium ratios of conetwork composition, the domains of both phases are interconnected both on the surface of the conetworks and throughout the bulk. The APCNs have peculiar swelling properties-the hydrophilic phase swells in hydrophilic media and the hydrophobic phase swells in hydrophobic media. In both types of media dissolved reagents can diffuse from the solution into the swollen phase of the polymeric conetwork. This enables loading of the hydrophilic phase of the APCNs with enzymes and indicator reagents by simple impregnation. Hydrophobic analytes can diffuse into the polymeric conetwork via its hydrophobic phase and react with indicator reagents immobilised in the hydrophilic phase at the huge internal interface between the two opposite phases.To prepare the described hydroperoxide-sensitive biosensors, we used APCN films consisting of 58% (w/w) poly(2-hydroxyethyl acrylate) (PHEA) as hydrophilic chains and 42% (w/w) polydimethylsiloxane (PDMS) as hydrophobic linkers. Horseradish peroxidase (HRP) and diammonium 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as indicator reagent were co-immobilised in this optically clear and transparent matrix. In this feasibility study the conditions investigated were principally those relevant to characterisation of the innovative matrix material and the disposable biosensor produced from it; the biosensor was not optimised. Sensitivity toward tert-butylhydroperoxide (tBuOOH) dissolved in n-heptane was acceptable, between approximately 1 and at least 50 mmol L(-1), even in the dry state. The response time was 1.7 to 5.0 min. No leaching of immobilised reagents was observed during a period of at least one hour. Pre-swelling the sensors with water increased the reaction rate and the total turnover number of the enzyme. In a dry atmosphere at 4 degrees C the sensors were found to be stable for at least two weeks.

An experimental study about the imbibition of aqueous solutions of low concentration of a non-adsorbable surfactant in a hydrophilic porous medium

The imbibition of aqueous solutions of Triton X-100 in calcium fluoride columns has been studied in order to determine the influence of the interfacial adsorption of the surfactant in the capillary rise of the solutions. This system has been chosen because this surfactant behaves as non-adsorbable at the surface of this solid when it is in aqueous solution. The experiments have consisted of the measurement of the increase in the weight of the porous columns caused by the capillary rise of the solutions. The analysis of the results has been made through a modified expression of Washburn's equation that takes into account that the experimental increase in the weight is caused by the imbibition as well as by the development of a liquid meniscus around the bottom base of the columns. From this analysis, it has been deduced that the surfactant concentration does not influence on the imbibition rate, it being equal to the observed for water. However, it has been also proved that the contact angle depends on the surfactant concentration, taking decreasing values as the surface tension of the solutions decreases. In order to justify these findings, a study about the influence of the interfacial adsorption on the imbibition has been carried out. By means of them, it has been proved that the absence of adsorption at the solid–liquid interface is the reason that explains both the independence of the imbibition rate from the surfactant concentration and the decrease of the contact angle. Moreover, this fact indicates that the depletion of the surfactant molecules from the advancing meniscus, which has been normally adduced as the phenomenon causing the observed behaviour, has to be ruled out as the physical cause that justifies the behaviour found from the analysis of the imbibition experiments. As a corollary, it has been also stated that only if the adsorption at the solid interfaces happened, the imbibition of aqueous solution of surfactant in hydrophilic media could be influenced by the surfactant concentration.

Sensitivity and specificity of Congo red staining according to Romhányi. Comparison with Puchtler's or Bennhold's methods

The sensitivity and specificity of various Congo red staining methods is very important in the diagnosis of amyloidosis. When using a less sensitive staining method, some true positive cases of amyloidosis remain undetected. A more highly specific method potentially detects more cases and reveals amyloidosis in an earlier stage of deposition. In this paper, the Congo red staining method according to Romhányi is discussed in comparison with Puchtler's and Bennhold's methods. Using Romhányi's technique, there is no alcoholic differentiation, and thus no dye molecules are washed off the amyloid filaments. The binding of the oriented dye molecules is optimal for polarization microscopy. With this method, the polar hydrophilic mounting medium, gum Arabic is used. Mounted in this carbohydrate-containing, hydrophilic medium, the Congo red molecules are oriented parallel to the surface of the amyloid filaments and the sign is linear positive, corresponding to an additive character of topo-optical staining reactions. Otherwise, the Congo red molecules are oriented perpendicular to the surface of collagen, reducing the intensity of birefringence and even inducing an inversion of the original sign of the collagen birefringence. With alcoholic differentiation, Congo red dye molecules are extracted and this decreases the birefringence of amyloid deposits, i.e. minimal amyloid deposits may be missed. Using the apolar hydrophobic mounting medium, Canada balsam, an axis-parallel arrangement of Congo red dye molecules on the surface of collagen fibers and amyloid will occur, resulting in an additive topo-optical reaction with a green polarization color and a false positive diagnosis of amyloidosis ("phantom amyloidosis").

Application of Media Manufactural by Waste Plastic to Stormwater Treatment in Urban Drainage System

While more attention has been paid in recent years to urban point source pollution control, no considerable measures have been taken to control urban non-point source pollution. Contaminants from non-point sources deposited on urban impermeable surfaces such as road and highway are easily released to the public waters by rainfall, leading to the deterioration in water quality in urban area. Experiments were performed using a reactor and real rainwater runoff obtained from road surfaces at various pollutant loading and rainfall intensity to determine the criteria for the first flush rainwater and to evaluate the applicability of the reactor for treating road runoff. The results at different rainfall intensities show that the medium PPB is superior to the other media for water permeability. PPB was not blocked at 10 mm/hr rainfall, and its permeability was stable. On the other hand, PVS and PPF resulted in a substantial overflow ratio even at 1 mm/hr rainfall intensity. Comparison of treatment efficiencies for suspended solids showed that all media showed similar removal efficiency ranging from 91% to 95%. However, PPB seems to be better than the other media considering its higher water permeability. PPB and PPF, both hydrophobic, yielded over 76% of heavy metal removal. But the hydrophilic media PVS showed much smaller removal efficiency ranging from 26% to 47%. The treatment efficiencies over PAHs (Poly Aromatic Hydrocarbons) showed the similar removal efficiency ranging from 66% to 97% for all three media. In this study a reactor using filter media was investigated to reduce the level of contamination in urban road runoff.

Biomimetic Approach to Biomembrane Models Studies: Medium Influence on the Interaction Kinetics of Some Phenylurea Derivatives Herbicides

The ability of herbicides to interact with cell membranes outer lipid layer and subsequently to penetrate inside cells can be a prerequisite for exhibiting a toxic activity for both the directly exposed workers and the end consumers as the herbicides are present in the soil and water. The effect exerted by fenuron, chlorotoluron, metobromuron, monolinuron, and chlorbromuron, five structurally similar phenylurea herbicides, on the thermotropic behavior of model membranes, represented by dimyristoylphosphatidylcholine (DMPC) vesicles, was investigated by differential scanning calorimetry. The examined compounds, when dispersed in liposomes during their preparation, exerted a different action on the gel-to-liquid crystal phase transition of DMPC multilamellar vesicles. The ability of phenylurea herbicides, as a finely powdered solid, to migrate through an aqueous medium and interact with biomembrane models was also studied. This transfer process was compared with these compounds intermembrane transfer from herbicide-loaded liposomes to empty ones. These processes can mimic absorption kinetics mediated by hydrophilic or lipophilic media. Different rate and entity of interaction occurred between model membranes and solid phenylurea herbicides. Different behavior was observed by considering the time-dependent studies carried out by contacting, for increasing times, equivalent amounts of empty DMPC vesicles with phenylurea herbicide-loaded ones; all compounds were able to migrate from loaded to empty DMPC vesicles. Thus, phenylurea herbicides are able to reach and penetrate biological membranes when dispersed in a lipophilic or hydrophilic medium; these processes are related to the substituents present on the compounds backbone. The obtained experimental results seem to validate the employed strategy to study the ability of bioactive compounds to both interact with biological membranes and be adsorbed inside a membrane mimicking a biological cell when dispersed in a lipophilic or hydrophilic medium.

Triclosan Release from Coated Polyglycolide Threads

Copolymerization of lactide, epsilon-caprolactone, and trimethylene carbonate is performed. The synthesis is focused on obtaining materials with adequate properties for application as a suture coating that could contain an antimicrobial agent like triclosan. An amorphous character, a low glass transition temperature, a moderate susceptibility to degradation, and a hydrophobic nature are the conditions required for the optimal behavior of this coating. These properties can be attained with a copolymer of composition 10:60:30. Triclosan is added to the surface of polyglycolide threads and its release is studied in different media with high-performance liquid chromatography. The influence of the temperature, the diameter of the thread, the initial concentration of the antibacterial agent, and the applied procedure on the incorporation of triclosan is also evaluated. A total release of triclosan is attained after a few days of exposure to a Dulbecco's based medium, whereas equilibrium concentrations are reached when a Sörensen hydrophilic medium is used. Partition and diffusion coefficients are also estimated.

Activity of a modified redox system for polymerization of unsaturated polyester resins

A modified redox system intended for initiation of radical polymerization of unsaturated polyester resins was investigated. The main feature of this modification was the presence of an additional accelerator—sodium formaldehyde sulfoxylate (also known as ‘Rongalit’). Rongalit acts as a reducer in hydrophilic medium. The interaction between Rongalit and the hydrophobic ingredients of the reactive mixture occur at the boundary surfaces between the different phases. The specific influence of the initiating system’s components over the polymerization kinetics was estimated. The technological time needed for gelling and then—for complete hardening of the resin was determined. The end properties of the cured polyesters as well as those of their derivative glass-fibres-reinforced composites were not found to be dependent on the mode of initiation of the polymerization process.

Vitamin A palmitate photostability and stability over time

Vitamin A palmitate photostability in relation to UVA and UVB was tested in hydroxy ethyl cellulose hydrogels at pH 4.0, 5.6, 7.0, and 8.0, alone and with the addition of sunscreens (3,4-methylbenzilidencamphor or butyl methoxy dibenzoylmethane) or an antioxidant (butylated hydroxy toluene). The photostability of vitamin A palmitate was also tested in encapsulated systems (Tagravit A1 microcapsules, Lipotec liposomes, phosphatidylcholine liposomes, and Lipotec nanocapsules) dispersed in gels at pH 5.6 and 7.0. The stability of retinyl palmitate over time in hydroxy ethyl cellulose hydrogels at pH 5.6 and 7.0 (stored one month at 25 degrees C or 40 degrees C), alone or with butylated hydroxy toluene, was also tested. The stability of retinyl palmitate over time in encapsulated systems, dispersed in gels at pH 5.6 and 7.0, was also studied. O/W emulsions were also prepared to compare the stability of vitamin A palmitate introduced in a lipophilic/hydrophilic medium (O/W emulsions) and a hydrophilic medium (hydrogels). HPLC analysis showed that encapsulated systems such as Lipotec nanocapsules, Tagravit A1 microcapsules, phosphatidylcholine liposomes, and Lipotec liposomes protect the vitamin A ester over time from hydrolysis and from oxidation to retinaldeide and retinoic acid, and that Lipotec nanocapsules and phosphatidylcholine liposomes also improve the vitamin's photostability. A change in pH (from 5.6 to 7.0) of the gels did not influence the vitamin ester's stability. pH levels of 4.0 and 8.0 determined a decrease in the stability of retinyl palmitate in the gels. A high concentration of sunscreens improved the photostability of retinyl palmitate in the gels at pH 5.6 and 7.0. Butylated hydroxy toluene protected retinyl palmitate from degradation induced by light at all the pH levels studied and by heat at pH 5.6 and 7.0, as can be seen from the study of the photostability of vitamin A palmitate under UVB and UVA and of stability over time. Rheological studies showed a slight decrease in the viscosity of the gels after UVB-UVA irradiation and a higher decrease in the viscosity of the gels and the emulsions after storage at 25 degrees C and 40 degrees C. This decrease can be attributed to a partial degradation of hydroxy ethyl cellulose and of emulsifier, as can be seen from the decrease in shear stress versus shear rate values under these conditions of storage, denoting a depolymerization of the rheological modifier.

Synthesis and characterization of new alternating, amphiphilic, comblike copolymers of poly(ethylene oxide) macromonomer andN-phenylmaleimide

A surface-active p-vinyl benzyloxy--hydroxy-poly(ethylene oxide) mac- romonomer containing 22 pendant structural units of ethylene oxide (St-PEO22) was synthesized with an initiation method. Because of its solubility in a large variety of solvents, the free-radical copolymerization with electron-acceptor N-phenylmaleimide (NPMI) was performed at 60 °C in benzene and tetrahydrofuran (THF) as isotropic media and in a water-THF mixture or water as a heterogeneous medium. Oil-soluble 2,2-azobisisobutyronitrile and water-soluble 4,4-azobis(4-cyanovaleric acid) were used as the initiators at fixed concentrations. Two different St-PEO22/NPMI comonomer ratios (1/1 and 3/7) at a fixed total comonomer concentration in the polymerization system were used. The structures, compositions, and microstructure peculiarities of the obtained alternating, amphiphilic, comblike copolymers were determined by NMR analysis. For the copolymers synthesized in hydrophilic media, differential scanning calorimetry showed, near the endothermic peak attributed to the melting of the poly- (ethylene oxide) side chains, the presence of a second peak due to the partially ordered phase that could exist between the crystalline state and the isotropic melt. Also, the thermal stability of the obtained copolymers was studied with thermogravimetric analysis. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 479 - 492, 2005

Detection of Interfacial Structures of Poly(ethylene glycol), Poly(propylene glycol) and Their Copolymers at Liquid/Solid Interfaces Using Sum Frequency Generation Vibrational Spectroscopy

ABSTRACTWe have applied sum frequency generation (SFG) vibrational spectroscopy, a submonolayer surface sensitive analytical technique, to study interfacial structures of poly (ethylene glycol) (PEG), poly (propylene glycol) (PPG), their solutions, their copolymers, and copolymer solutions while contacting different media including air, fused silica, and various polymers.For the first time, conformations of polyether materials at various interfaces have been shown at the molecular level in situ. Depending on the hydrophobicity of the solid contacting media, the liquid polymers PEG and PPG show different conformations at different interfaces, which can be correlated to molecular interactions at these interfaces. The favorable interaction between hydrophobic media and the hydrophobic segments, methylene or methyl groups, of polyethers causes an ordered conformation with these groups standing up at the interface. The unfavorable interaction between hydrophilic media and hydrophobic segments of the polyethers induces interfacial methylene or methyl groups to have a random structure or to lie down at the interfaces, indicated by the weakening or even absence of SFG signals. For comparison, interfaces between aqueous PEG or PPG solutions and air, polystyrene (PS), poly(methyl methacrylate) (PMMA), and fused silica have also been investigated. In addition, we have studied conformations of pluronics at various interfaces, showing that different blocks have different interface activities. The interfaces are always dominated by the PPG segments. The studies on molecular level interfacial structures of PEG, PPG and pluronics will help us to understand and control the interfacial behavior of liquids at interfaces.

Microviscosity in poly(ethylene oxide)‐polypropylene oxide‐poly(ethylene oxide) block copolymers probed by fluorescence depolarization kinetics

AbstractTriblock copolymers [poly(ethylene oxide) (PEO) and polypropylene oxide (PPO)], Pluronic F127 with 100 PEO blocks on each end, and 65 blocks of PPO in the center were examined in aqueous solution. The “sol” and “gel” phase diagram was determined as a function of concentration and temperature. For further study, the concentration was fixed at 20 wt %, and the temperature dependence of the dynamic viscosity differed from the temperature dependence of fluorescence emission spectra and the microviscosity probed by the fluorescence depolarization kinetics of rhodamine 123 dye, which was dissolved in the continuous hydrophilic phase. The depolarization measurements used single‐photon counting after two‐photon excitation with a Ti‐sapphire femtosecond laser. Although the viscoelastic modulus increased by an order of magnitude when the sol‐to‐gel transition was crossed, the microviscosity of the hydrophilic continuous medium showed only minor changes. At different temperatures the fluorescence lifetime was the same with a single‐exponential time constant, but the fluorescence depolarization displayed a double‐exponential decay. After comparison with fluorescence depolarization of the dye in PPO melt and PEO whose molecular weight and aqueous concentrations were varied, the relative proportions of faster and slower components of the fluorescence depolarization were tentatively attributed to varying ratios of the dye in free solution and associated with micelles. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2883–2888, 2002

Sum Frequency Generation Vibrational Spectroscopy Studies on Molecular Conformation of Liquid Polymers Poly(ethylene glycol) and Poly(propylene glycol) at Different Interfaces

The conformation of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) molecules at various interfaces has been investigated by sum frequency generation (SFG) vibrational spectroscopy. The interfaces studied include interfaces between pure liquid PEG (or PPG) or aqueous PEG (or PPG) solutions and air, fused silica, or solid polymers such as polystyrene (PS) and poly(methyl methacrylate) (PMMA). Depending on the hydrophobicity of the solid contacting media, the liquid polymers show different conformations at different interfaces, which can be correlated to molecular interactions at these interfaces. The favorable interaction between hydrophobic media and the hydrophobic segments, methylene or methyl groups, of polyethers causes an ordered conformation with these groups standing up at the interface. The unfavorable interaction between hydrophilic media and hydrophobic segments of the polyethers induces interfacial methylene or methyl groups to have a random structure or to lie down at the interfac...