Search

A new, simple and rapid method for the quantitative determination of the antimicrobial preservative 2-phenoxyethanol, based on reverse phase ultra-high-performance liquid chromatography has been developed. The validation was performed according the ICH Q2 guideline "Validation of Analytical Procedures". The desired chromatographic separation was achieved on a Waters Symmetry C18 (150 × 4.6 mm, 5 μm) column using an isocratic elution, with detection at 270 nm wavelength. The mobile phase consisted of acetonitrile/water (55:45, v/v), pumped at a flow rate of 1 mL/min. The calibration curve and the analytical procedure are linear (r 2  = 0.999) from the concentration of 0.07 mg/mL to 1.1 mg/mL. The percent relative standard deviation for intra- and inter-day precision was <1%. The recovery of 2-phenoxyethanol in vaccines ranged between 96.5 and 100.60%. The limits of detection and quantitation were 1.3 × 10 -4 and 2.7 × 10 -4  mg/mL, respectively. The method was found to be robust by changing the column working temperature, the percentage of acetonitrile of the mobile phase and the flow rate. The validated method can be successfully and reliably used to quantify as well as to exclude presence of 2-phenoxyethanol preservative in marketed vaccines., (Copyright © 2021 International Alliance for Biological Standardization. Published by Elsevier Ltd. All rights reserved.)

Glycerol carbonate is one of the most potentially multifunction glycerol-derived compounds. Glycerol is an important by-product of the oleochemical industry. The oligomerization of glycerol carbonate, assisted by the glycerol, results in the production of polyhydroxylated oligomers rich in linear carbonate groups. The polar moieties of these oligomers (M w <1000Da) were supplied by glycerol and glycerol carbonate rather than ethylene oxide as in most commercial surfactants. The insertion of linear carbonate groups into the glycerol-based skeleton rendered the oligomers amphiphilic, resulting in a decrease in air/water surface tension to 57mN/m. We improved the physical and chemical properties of the oligomers, by altering the type of acylation reaction and the nature of the acyl donor. The polar head is constituted of homo-oligomers and hetero-oligomers. Homo-oligomers are oligoglycerol and/or oligocarbonate, hetero-oligomers are oligo(glycerol-glycerol carbonate). Coprah oligoesters had the best surfactant properties (CMC<1mg/mL, π cmc <30mN/m), outperforming molecules of fossil origin, such as ethylene glycol monododecyl ether, glycol ethers and fatty acid esters of sorbitan polyethoxylates. The self-assembling properties of oligocarbonate esters were highlighted by their ability to stabilize inverse and multiple emulsions. The oligo-(glycerol carbonate-glycerol ether) with relatively low molecular weights showed properties of relatively high-molecular weight molecules, and constitute a viable "green" alternative to ethoxylated surfactants., (Copyright © 2016 Elsevier Inc. All rights reserved.)

In the development of transdermal and topical products it is important to understand how formulation ingredients interact with the molecular components of the upper layer of the skin, the stratum corneum (SC), and thereby influence its macroscopic barrier properties. The aim here was to investigate the effect of two commonly used excipients, transcutol and dexpanthenol, on the molecular as well as the macroscopic properties of the skin membrane. Polarization transfer solid-state NMR methods were combined with steady-state flux and impedance spectroscopy measurements to investigate how these common excipients influence the molecular components of SC and its barrier function at strictly controlled hydration conditions in vitro with excised porcine skin. The NMR results provide completely new molecular insight into how transcutol and dexpanthenol affect specific molecular segments of both SC lipids and proteins. The presence of transcutol or dexpanthenol in the formulation at fixed water activity results in increased effective skin permeability of the model drug metronidazole. Finally, impedance spectroscopy data show clear changes of the effective skin capacitance after treatment with transcutol or dexpanthenol. Based on the complementary data, we are able to draw direct links between effects on the molecular properties and on the macroscopic barrier function of the skin barrier under treatment with formulations containing transcutol or dexpanthenol., (Copyright © 2016 Elsevier Inc. All rights reserved.)

In order to improve curcumin's low water-solubility and selective delivery to cancer, we reported ligand-mediated micelles based on a Y-shaped biotin-poly (ethylene glycol)-poly (epsilon-caprolactone)2 (biotin-PEG-PCL2) copolymer. Its structure was characterized by (1)H NMR. The blank and drug-loaded micelles obtained by way of thin-film hydration were characterized by dynamic light scattering, X-ray diffraction, infrared spectroscopy and hemolytic test. Curcumin was loaded into micelles with a high encapsulating efficiency (93.83%). Curcumin's water-solubility was enhanced 170,400 times higher than free curcumin. Biotin-PEG-PCL2 micelles showed slower drug release in vitro than H2N-PEG-PCL2 micelles. In vitro cellular uptake and cytotoxicity tests showed that higher dosage of curcumin might overcome the effect of slow release on cytotoxicities because of its higher uptake induced by biotin, resulting in higher anticancer activities against MDA-MB-436 cells. In brief, Y-shaped biotin-PEG-PCL2 is a promising delivery carrier for anticancer drug., (Copyright © 2014 Elsevier Inc. All rights reserved.)

We have studied oligo(ethylene glycol) (OEG) thiol self-assembled monolayer (SAM) coated gold nanoparticles (AuOEG) and their interactions with proteins in solutions using electrophoretic and dynamic light scattering (ELS and DLS). The results are compared with poly(ethylene glycol) (PEG) thiol coated AuNPs (AuPEG). We show that both AuOEG and AuPEG particles carry a low net negative charge and are very stable (remaining so for more than one year), but long-term aging or dialysis can reduce the stability. If the decorated AuNPs are mixed with bovine serum albumin (BSA), both effective size and zeta-potential of the AuNPs remain unchanged, indicating no adsorption of BSA to the colloid surface. However, when mixed with lysozyme, zeta-potential values increase with protein concentrations and lead to a charge inversion, indicating adsorption of lysozyme to the colloid surface. The colloidal solutions of AuOEG become unstable near zero charge, indicated by a cluster peak in the DLS measurements. The AuPEG solutions show similar charge inversion upon addition of lysozyme, but the solutions are stable under all experimental conditions, presumably because of the strong steric effect of PEG. Washing the protein bound colloids by centrifugation can remove only part of the adsorbed lysozyme molecules indicating that a few proteins adsorb strongly to the colloids. The effective charge inversion and rather strongly bound lysozyme on the colloid surface may suggest that in addition to the charges formed at the SAM-water interface, there are defects on the surface of the colloid, which are accessible to the proteins. The results of this study of surface charge, and stability shed light on the interaction with proteins of SAM coated AuNPs and their applications., (Copyright © 2014 Elsevier Inc. All rights reserved.)

The decomposition of iron(III) acetylacetonate in high-boiling polyols such as diethylene glycole is an efficient way to produce water-soluble iron oxide nanoparticles (IONPs) with small sizes. We present an extension of this method by introducing ethylene diamine (EDA) or diethylene triamine (DTA) as a structure-directing agent and adding polyvinylpyrrolidone (PVP) as a stabilizing agent. The synthesis was studied with respect to effects of the chain length of the polyol used as solvent, the chain length of the structure-directing agent, the presence of PVP, the heating rate, and the nature of the precursor. By varying these parameters, we were able to show, that probably an interplay of the structure-directing agent and the polyol plays an important role for the stabilization and growth of the different facets of the IONP crystal. The chain length of the polyol used as solvent alters the influence of EDA or DTA as stabilizer of {111} facets, leading to IONPs with spherical, tetrahedral, or nanoplate morphology and mean diameters ranging from 4 nm up to 25 nm. PVP in the reaction medium narrows down particle size and shape distributions and promotes the formation of very stable, water-based colloidal solutions. The saturation magnetization of the particles was determined by a superconducting quantum interference device (SQUID) and their ability to act as a T2-contrast agent was tested by magnetic resonance imaging (MRI)., (Copyright © 2013 Elsevier Inc. All rights reserved.)

The topology of the plasma membrane Na(+)/Ca(2+) exchanger of cardiac muscle, NCX1, is uncertain. Biochemical analyses have indicated the presence of 9 transmembrane segments (TMSs) whereas the recent crystal structure of a prokaryotic homologue has 10 TMSs. The discrepancy is towards the C-terminus of the proteins where the prokaryotic homologue has an additional TMS8. To resolve this apparent disagreement, we re-assessed the topology of the C-terminal TMSs of NCX1. We examined the ability of internal or external cysteine residues in the N-terminal portion of NCX1 to crosslink with cysteine residues, of uncertain orientation, in the C-terminal portion of the protein. The results strongly support a model of NCX1 with 10 TMSs as found in the prokaryotic homologue., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Tetra- and tri-substituted m-phenylacetylene macrocycles with diethylene glycol monoethyl ether (DEG) phenylether peripheral side chains (PAM 1 and PAM 1') were synthesized, and both of them could self-assemble into well-defined one-dimensional (1D) structures through two kinds of fabrication processing. The recrystallization approach led to similar microbelts for PAMs 1 and 1' with hundreds of microns in length, 2-4 μm in width, and 200-300 nm in thickness. But AFM, XRD, and spectrum characterizations indicated that the microbelts of PAM 1' had smaller intercolumnar distances and more favorable π-π stacking. Two different nanostructures were obtained through the other processing of solvent evaporation: nanobelts for PAM 1 and twisted nanorods for PAM 1'. The different molecular arrangement and nanostructures could be ascribed to the different molecular structures, especially the different positioning of the peripheral substituents. This research provides a potential control over the morphology and the structure of the 1D assembly by adjusting the molecular structure as well as the sample processing., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Diethyleneglycol (DEG)-stabilized calcium fluoride (CaF(2)) nanoparticles with a mean diameter of about 20 nm consist of an inorganic crystalline core, covered by a roughly monomolecular layer of organic material according to standard physico-chemical analysis. Multinuclear NMR experiments under magic angle spinning were used to identify the constituent (13)C, (1)H and (19)F atoms. All resonances were assigned (DEG, EtOH, H(2)O, H(3)O(+), OH(-), F(-), CaF(2)), and different populations could be discriminated in terms of their mobilities and correlations with neighboring atoms. We observed several different layers: mobile EtOH on the particle surface, an "interphase" containing immobile DEG molecules and fluoride ions, plus the single-crystalline CaF(2) core. It was thus possible for the first time to characterize by NMR all layered components of such core-shell particles, and the thickness of the newly discovered interphase could be estimated from the NMR intensities., (Copyright © 2012 Elsevier Inc. All rights reserved.)

To develop new matrices for the entrapment and sustained release of bioactive lysozyme, a series of supramolecular hydrogels based on α-cyclodextrin (α-CD) and water-soluble poly(ε-caprolactone)-poly(ethylene glycol) block copolymer (PCL-b-PEG) were prepared in the presence of chicken egg lysozyme. Different from commonly used polymeric microspheres and chemically crosslinked hydrogels for lysozyme encapsulation, such hydrogel matrices could be formed under mild conditions without high temperature and the use of chemical emulsifiers or crosslinkers. Their gelation rate, mechanical strength and shear viscosity as well as the release behavior for the encapsulated lysozyme could be tuned easily by the change of α-CD or PCL-b-PEG amount. For the encapsulated lysozyme, its conformation and biological activity could be well maintained when compared to native lysozyme. For the resultant supramolecular hydrogels, they were also confirmed to have a good biocompatibility by MTT assay using mice skin fibroblast (L929)., (Copyright © 2011 Elsevier Inc. All rights reserved.)

In this study, we describe the development of a facile and effective route for the synthesis of Fe(3)O(4)-based T(1) contrast agent, which can be useful for in vivo magnetic resonance (MR) imaging. Citrate-coated Fe(3)O(4) nanoparticles (6 nm) with a narrow size distribution were synthesized by "one-pot green chemistry route" in diethylene glycol (DEG) solvent. The synthesized nanoparticles were characterized by different analytical techniques including XRD, TEM, HRTEM, and FTIR. At room temperature, nanoparticles exhibited superparamagnetic nature with high saturation magnetization. The longitudinal (r(1)) and transverse (r(2)) relaxivities were found to be 35.45 and 51.81 mM(-1)s(-1), respectively. Contrast agent developed by this method showed a relatively higher longitudinal relaxivity (r(1)) and the lowest relaxivity ratio (r(2)/r(1)=1.46) at 3T MR field. The anionic nature of citric acid facilitated non-specific internalization without impairment of cell viability and functionality. The in vitro studies showed both phagocitic and non-phagocytic uptake of these NPs. In vivo MR imaging of swine showed both T(1) and T(2) contrast effect., (Copyright © 2011 Elsevier Inc. All rights reserved.)

The change of the water structure in aqueous solutions of the tri-ethyleneglycol mono n-decyl ether (C(10)E(3)) was studied by micro Raman scattering. The results obtained on the O-H stretching band show that the behavior of the hydrogen bonding (H-bonds) water network can be used as a probe to follow the lamellar (L(α)) to sponge (L(3)) phase transition. In the lamellar phase, the stack of the surfactant molecules aggregated into a two-dimensional structure (membrane) acts as a soft confinement system for the H-bond water network of which the regular tetrahedral structure is perturbed. The change of the planar organization of the membranes to a highly disordered and infinite array of bilayers in the sponge phase amplifies the surface of contact between amphiphilic surfactant and water molecules which drives a strong disruption of the regular tetrahedral H-bonding water network., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Partition coefficients for a pH-degradable 1,3-dioxolane alkyl ethoxylate surfactant, 4-CH(3)O (CH(2)CH(2)O)(5.6)-CH(2), 2,2-(CH(2))(12)CH(3), 2-(CH(2)) CH(3), 1,3-dioxolane or "cyclic ketal" surfactant, CK-2,13-E(5.6,ave), between isooctane- and water-rich phases of 2- and 3-phase microemulsion systems (K(n)) were determined as functions of the ethoxylate size, n, and temperature for the neat surfactant and its binary surfactant mixtures, to understand the partitioning of alkyl ethoxylates possessing a broad distribution of ethoxylate size and to determine conditions required for formation of 3-phase microemulsion systems at an optimal temperature where phase separation occurs rapidly, important for protein purification via proteins' selective partitioning to the middle phase, driven by affinity to the second surfactant of the binary mixture. A semi-empirical thermodynamic mathematical model described the partitioning data well, provided optimal temperature values consistent with phase diagrams and theory, and demonstrated that the tail region of CK-2,13-E(5.6,ave) is more polar than the hydrophobes of fatty alcohol ethoxylates. The addition of Aerosol-OT (AOT) removed the temperature sensitivity of CK-2,13-E(5.6,ave)s partitioning, producing 3-phase microemulsion systems between 20 °C and 40 °C. Analysis of the bottom phases of the 2- and 3-phase microemulsion systems formed by CK-2,13-E(5.6,ave) via small-angle neutron scattering demonstrated the presence of spherical, monodisperse oil-in-water microemulsions., (Copyright © 2010 Elsevier Inc. All rights reserved.)

Superparamagnetic iron oxide nanoparticles, Fe(3)O(4) and gamma-Fe(2)O(3), were produced by the so-called polyol process. In order to stabilize the particles in a physiological environment as potential contrast agents for Magnetic Resonance Imaging (MRI), the as-prepared particles were successfully transferred to an aqueous medium through ligand exchange chemistry of the adsorbed polyol species with the dopamine or the catechaldehyde. The ligands were able to participate in bidentate binding to the nanoparticles surface and to improve the stability of aqueous suspensions of the nanoparticles. Analysis was performed by various techniques including X-ray diffraction, transmission electron microscopy, infrared spectroscopy and thermal analysis. The results of magnetic measurements and initial in vitro magnetic resonance imaging essays are presented for the pre- and post-surface modified nanoparticles, respectively and discussed in relation with their structure and microstructure.

Water-soluble and carboxyl-functionalized up-converting rare-earth nanoparticles (UCNPs) are obtained via an efficient surface-ligand-exchange procedure. Hexanedioic acid molecules are employed to replace the original hydrophobic ligands in diethylene glycol solvent at high temperature. Various characterizations indicate the ligand-exchange process has negligible adverse effect on the quality of the UCNPs. The resulting hydrophilic UCNPs show small size, strong up-converting emission and high water stability. The specific molecular recognition capacity of avidin-modified hydrophilic UCNPs confirms that hydrophilic UCNPs are suitable for potential biological labeling.

We present the formation of viscoelastic wormlike micelles in mixed amino acid-based anionic and nonionic surfactants in aqueous systems in the absence of salt. N-Dodecylglutamic acid (designated as LAD) has a higher Krafft temperature; however, on neutralization with alkaline amino acid l-lysine, it forms micelles and the solution behaves like a Newtonian fluid at 25 degrees C. Addition of tri(oxyethylene) monododecyl ether (C(12)EO(3)) and tri(oxyethylene) monotetradecyl ether (C(14)EO(3)) to the dilute aqueous solution of the LAD-lysine induces one-dimensional micellar growth. With increasing C(12)EO(3) or C(14)EO(3) concentration, the solution viscosity increases gradually, but after a certain concentration, the elongated micelles entangle forming a rigid network of wormlike micelles and the solution viscosity increases tremendously. Thus formed wormlike micelles show a viscoelastic character and follow the Maxwell model. Tri(oxyethylene) monohexadecyl ether (C(16)EO(3)), on the other hand, could not form wormlike micelles, although the solution viscosity increases too. The micelles become elongated; however, they do not appear to form a rigid network of wormlike micelles in the case of C(16)EO(3). Rheological measurements have shown that zero shear viscosity (eta(0)) increases with the C(12)EO(3) concentration gradually at first and then sharply, and finally decreases before phase separation. However, no such maximum in the eta(0) plot is observed with the C(14)EO(3). The eta(0) increases monotonously with the C(14)EO(3) concentration till phase separation. In studies of the effect of temperature on the wormlike micellar behavior it has been found that the eta(0) decays exponentially with temperature, following an Arrehenius behavior and at sufficiently higher temperatures the solutions follow a Newtonian behavior. The flow activation energy calculated from the slope of log eta(0) versus 1/T plot is very close to the value reported for typical wormlike micelles. Finally, we also present the effect of neutralization degree of lysine on the rheology and phase behavior. The formation of wormlike micelles is confirmed by the Maxwell model fit to the experimental rheological data and by Cole-Cole plots.

Ordered mesoporous carbons (OMCs) with varying pore sizes were prepared using ordered mesoporous silica SBA-15 as hard templates. The OMCs possess abundant mesopores with narrow pore size distribution, on which the adsorption behavior of bulky molecules of nonylphenol ethoxylate (NPE) were investigated. The isotherms of NPE on OMCs can be fitted by Langmuir adsorption model, evidenced by the adsorption data. The surface area of the pores larger than 1.5 nm is a crucial factor to the adsorption capacity of NPE, whereas the most probable pore diameter of OMCs is crucial to the adsorption rate of NPE. The adsorption temperature has more significant effects on adsorption rate than the adsorption capacity. Theoretical studies show that the adsorption kinetics of NPE on OMCs can be depicted with the pseudo-second-order kinetic model. In addition, thermodynamic parameters of adsorption were evaluated based on the equilibrium constants related to the equilibrium of adsorption at different temperatures.

The authors developed a simple and rapid method for quantitation of 2-phenoxyethanol (2-PE) in DTwP vaccine based on reverse phase high performance liquid chromatography (HPLC). The method was simple and reproducible. The sensitivity of the assay was confirmed by spiking known amounts of 2-phenoxyethanol to the vaccine sample.

Mesoporous carbon, CMK-3, was prepared using hexagonal SBA-15 mesoporous silica as the template and the adsorption of nonylphenol ethoxylates (NPE) onto CMK-3 was investigated. The adsorption process was well described using pseudo-second-order kinetics. At initial NPE concentrations of 107 and 530 mg l(-1), the adsorption rate constants were found to be 5.6 x 10(-3) and 8.7 x 10(-4) g mg(-1) min(-1), indicating that a higher initial concentration or adsorption amount resulted in a lower adsorption rate. NPE adsorption onto CMK-3 fitted a Langmuir-Freundlich model and the maximum amounts of NPE absorbed at 15, 25, and 35 degrees C were 923, 720, and 463 mg g(-1), suggesting an elevated adsorption capacity of CMK-3 for NPE with decreased adsorption temperature. In addition, increasing adsorption temperature led to the change of the adsorption model from the Langmuir-Freundlich to the Langmuir model. N2 adsorption results showed that the adsorption of NPE led to a decrease in the mesopore volume of CMK-3. However, the pore width of NPE-loaded CMK-3 was found to be identical to that of CMK-3.

The analysis of the available bubble life times and dead times for the bubble pressure tensiometer BPA-1S shows that dynamic surface tensions can be measured also for surfactant solutions at concentrations many times higher than the corresponding CMC. For the three nonionic surfactants Triton X-100, Triton X-45, and C14EO8 experiments are performed for solutions with a concentration of up to 200 times the CMC (C14EO8). Comparison of the experimental data with micelle kinetics models yields rate constants for the fast micelle dissolution process, which are in a good agreement with values obtained by other experimental methodologies.

Monolayers from the newly synthesized compound methoxy-tri(ethylene glycol)-undecenyldimethylchlorosilane (CH3O(CH2CH2O)3(CH2)11Si(CH3)2Cl, MeO(EG)3C11DMS) and dodecyldimethylchlorosilane (DDMS), both pure and mixed, were prepared by self-assembly from organic solution in the presence of an organic base. The films obtained were characterized by advancing and receding contact angle measurements and ellipsometry to confirm the formation of self-assembled monolayers (SAMs). The resulting data on the covalently attached dimethylsilanes were compared to known oligo(ethylene glycol) (OEG)-terminated SAM systems based on terminal alkenes, thiolates or trihydrolyzable silanes. The composition of the mixed SAMs was found to depend directly and linearly on the composition of the silanization solution. Enhanced protein repellent properties were found for the SAMs using a variety of proteins, including the Ras Binding Domain (RBD), a protein with high relevance for cancer diagnostics. Roughly a RBD protein monolayer amount was adsorbed to silicon oxide surfaces silanized with DDMS or non-silanized silicon wafers, and in contrast, no RBD was adsorbed to surfaces silanized with MeO(EG)3C11DMS or to mixed monolayers consisting of DDMS and MeO(EG)3C11DMS if the content of OEG-silane overcame a critical content of X(EG) approximately 0.9.

The equilibrium residence times of the nonionic surfactant nonylphenol ethoxylate (NP100) in a latex dispersion were determined using NMR diffusometry. At 16% w/w particle concentration and 0.12, 0.43 and 0.81% w/w NP100, the residence times of the surfactant were 0.16, 1.02 and 4.73 s in solution (tau(A)) and 0.3, 0.37 and 0.61 s on the surface of the particles (tau(B)), respectively. At even higher particle concentration (>45% w/w), tau(A) and tau(B) were 1.47 and 2.2 s. Calculating the number of collisions that ought to result in adsorbed species, at 16% w/w, only 2, 5 and 2 per thousand (corresponding to 0.12, 0.43 and 0.81% w/w NP100) resulted in adsorption, whereas at >45% w/w, only 12 per thousand resulted in adsorption, which suggested that the surfactant was irreversibly adsorbed on the particles. The small increase in collision frequency with increased particle concentration could be a result of a diffusion controlled adsorption, while an energy barrier for desorption controlled the overall exchange dynamics in the dispersion. The slow dynamics in the dispersion was controlled, mainly by the nonylphenol group, which gave NP100 a strong preference to surfaces. In addition, the chain length of the poly(ethylene glycol) (PEG) group changed the solution behavior from being that of a typical surfactant to that of a polymer.

Surface tensions were measured for several binary mixtures of a multidegree polymerized alkyl polyglycoside, C12G1.46' with different types of surfactants in 0.1 M NaCl at 25 degrees C. Based on regular solution theory, using a dimensional crystal model and a phase separation model, the molecule exchange energy in mixed monolayer formation (epsilon) and mixed micellization (epsilon(m)) were determined. Surfactants used in the mixtures with C12G1.46 in this study are C12E3S (trioxyethylenated dodecyl sulfonate), C12TAC (dodecyl trimethylammonium chloride), BE-6 (hexaoxyethylenated trisiloxane surfactant), and TMN-6 (hexaoxyethylenated-2,6,8-trimethylnonanol). The mixtures show exchange energy in mixed monolayer formation (epsilon) and mixed micellization (epsilon(m)) ranging from -660 to -1410 J/mol, indicating a decrease in surface energy upon mixing. The decreases in surface energy are in the order C12G1.46/C12E3S > C12G1.46/C12TAC, C12G1.46/C12TAC > C12G2/C12TAC and C12G1.46/BE-6 > C12G1.46/TMN-6. The ability of the mixed monolayer formation relative to the mixed micelle formation of the same binary mixture, measured by the (epsilon-epsilon(m)) values, is in the order C12G1.46/BE-6 > C12G1.46/TMN-6 > C12G1.46/C12E3S-->0 > C12G1.46/C12TAC.

We examined the morphologies of two-phase emulsions in the ternary 2-butoxyethanol/n-decane/water system at various temperatures and water-to-oil ratios (WORs). The two-phase emulsion morphologies depended on temperature, WOR, and amphiphile concentration, and the results are presented in a temperature-amphiphile concentration coordinate system or a "fish" diagram. The observations made in this work contradict the predictions by the phase-inversion-temperature (PIT) concept. At WOR<1, a vertical inversion line was observed at TT(uc) (upper critical endpoint temperature) and at low amphiphile concentrations, only B/T emulsions appeared, irrespective of temperature. At WOR>1, the situation was reversed; T/B emulsions at TT(uc), and T/B emulsions at low amphiphile concentrations, irrespective of temperature. At WOR=1, two horizontal inversion lines, one each at TT(uc), were observed. The morphologies of the two-phase emulsions were B/T or T/B emulsions at low amphiphile concentrations, and at higher amphiphile concentrations T/B at TT(uc). All these findings along with three-phase emulsion data result in complete emulsion morphology diagrams in the temperature-amphiphile concentration space or fish diagram.

We study the surface adsorption and bulk micellization of a mixed system of two nonionic surfactants, namely, ethylene glycol mono-n-dodecyl ether (C12E1) and tetraethylene glycol mono-n-tetradecyl ether (C14E4), at different mixing ratios at 15 degrees C. The pure C14E4 monolayer cannot show any indicative features of phase transition because of both hydration-induced and dipolar repulsive interactions between the bulky head groups. On the other hand, the monolayers of pure C12E1 and its mixture with C14E4 undergo a first-order phase transition, showing a variety of surface patterns in the coexistence region between the liquid expanded (LE) and liquid condensed (LC) phases under the same experimental conditions. For pure C12E1, the domains are of a fingering pattern while those for the C12E1/C14E4 mixed system are found to be compact circular and small irregular structures at 2:1 and 1:1 molar ratios, respectively. The critical micelle concentration (cmc) values of both the pure and the mixed systems were measured to understand the micellar behavior of the surfactants in the mixture. The cmc values of the mixed system were also calculated assuming ideal behavior of the surfactants in the mixture. The experimental and calculated values are found to be very close to each other, suggesting an almost ideal nature of mixing. The interaction parameters for mixed monolayer and micelle formation were calculated to understand the mutual behavior of the surfactants in the mixture. It is observed that the interaction parameters for mixed monolayer formation are more negative than those of micelle formation, indicating a stronger interaction between the surfactants during monolayer formation. It is concluded that since both the surfactants bear EO units in their head groups, structural parity and hydrogen bonding between the surfactants allow them to be closely packed during monolayer and micelle formation.

Oligo(ethylene glycol)-terminated thin films were prepared by photo-induced hydrosilylation of alpha-hepta-(ethylene glycol) methyl omega-undecenyl ether (EG(7)) on hydrogen-terminated silicon (111) and (100) surfaces. Their resistance to protein adsorption, and stabilities (from hours to days) under a wide variety of conditions, such as air, water, biological buffer, acid, and base, were investigated using contact-angle goniometry and ellipsometry techniques. Results indicated higher stability of the films chemisorbed on Si(111) than on Si(100). Furthermore, micron-sized patterns were fabricated on the films via AFM anodization lithography. Using atomic force microscopy (AFM) and fluorescence microscopy, we demonstrated that various proteins including fibrinogen, avidin, and bovine serum albumin (BSA) predominately adsorbed onto the patterns, but not the rest of the film surfaces.

It has generally been assumed that the skin contributes only minor amounts to the total uptake of solvent vapors, relative to the respiratory tract. Contrary to this assumption, the widely used glycol ether solvent, 2-butoxyethanol (BE), has been reported to be more effectively absorbed through the skin (75% of the total uptake) than through the lungs of humans (Johanson and Boman, 1991, Br. J. Ind. Med. 48, 788). The possibility that the finger prick blood sampling technique used in the Johanson and Boman study was confounded by locally high concentrations of BE at the site of absorption was suggested using a previously developed PBPK model (Corley et al., 1994, Toxicol. Appl. Pharmacol. 129, 61). The current study was conducted to verify the PBPK analysis and to determine whether or not the skin was the major site for absorption of BE vapor by exposing one arm from each of six human volunteers to 50 ppm 13C2-BE vapor for 2 hr. To evaluate the potential consequences of blood sampling techniques, samples were taken from both the unexposed arm (catheter; during and after exposure) and the exposed arm (finger prick; end of the exposure only) for analysis of both BE and its major metabolite, butoxyacetic acid (BAA). Butoxyacetic acid is responsible for the hemolysis observed in toxicity studies with laboratory animals. Humans, however, are significantly less sensitive to this effect. The concentration of BE in the finger prick blood samples averaged 1500 times higher than the corresponding concentration in venous blood sampled from a catheter installed in the unexposed arm at the end of the exposure. Blood BAA levels were generally within a factor of 4 of each other for the two techniques and, therefore, was considered a better indicator of systemic absorption. Urine was collected for 24 hr and analyzed for the following metabolites found in rat metabolism studies: free and conjugated BE, BAA, ethylene glycol (EG), and glycolic acid (GA), with only BAA detected in the human urine. More importantly, urinary BAA was found to be extensively conjugated ( approximately 67%) with glutamine, confirming recent reports. These results, coupled with PBPK modeling of worst-case exposure scenarios (no clothing, 100% of the body was exposed), demonstrated that no more than 15-27% (low-to-high relative temperatures and humidities), not 75%, of the total uptake of BE could be attributed to the skin of humans during simulated 8-hr exposures to the ACGIH TLV concentration of 25 ppm. Even less of the total uptake was attributed to the skin during simulations of exercise with whole-body exposures (5-9%) or by more realistic exposures of only the arms and head (1-8%). As a result, humans are unlikely to reach hemolytic concentrations of the metabolite BAA in blood following vapor exposures to BE., (Copyright 1997 Society of Toxicology.)

A number of reports in recent years have demonstrated the feasibility of detecting quadrupolar metal ions bound tightly to rather large proteins via the quadrupolar central transition (QCT) NMR approach. In this article, an in-depth investigation of several interesting properties of transferrin-bound 27Al NMR signals, namely, their dependence on temperature, viscosity, and molecular size is presented. It is shown that (1) decreasing temperature and (2) increasing viscosity by adding reagents such as glycerol and ethylene glycol perturb only the linewidths of transferrin-bound 27Al signals, and, in fact, produce a decrease in signal linewidth. These effects are in accord with quadrupolar relaxation theory, which predicts that the linewidth of the central transition of a half-integer quadrupolar nucleus should decrease with increasing correlation time of the protein under nonextreme narrowing conditions. Furthermore, it is demonstrated that these trends, which are completely opposite to those generally observed in NMR spectroscopy, can be exploited to monitor ovotransferrin half-molecule reassociation reactions. In combination with the peculiar properties of transferrin-bound quadrupolar nuclei reported in the literature to date, the phenomena described here provide the basis for understanding the conditions and experimental parameters which may facilitate the application of the QCT NMR technique to the study of other quadrupolar nuclei and proteins.