Mechanism of ion transfer in supported liquid membrane systems: electrochemical control over membrane distribution.
ABSTRACT: A polarization study carried out on a thin supported liquid membrane separating two aqueous compartments is presented. Transfer of both the ionized and uncharged form of an organic tracer dye, rhodamine B ([9-(2-carboxyphenyl)-6-diethylamino-3-xanthenylidene]-diethylammonium chloride), across supported liquid membranes composed of one of 1-octanol (octan-1-ol), 1,9-decadiene (deca-1,9-diene), 1,2-dichlorobenzene, or nitrophenyl octyl ether (1-(2-nitrophenoxy)octane) was studied using cyclic voltammetry and UV-vis absorption spectrophotometry. Concentration analysis indicates that the high membrane concentration of rhodamine B determines the ionic transfer observed via voltammetry, which is consistent with the low aqueous ionic concentration and large membrane/aqueous distribution of the molecule. The observed double-transfer voltammogram, although it has been largely neglected in previous literature, is a logical consequence of the presence of two liquid-liquid interfaces and is rationalized in terms of ion transfer across the two interfaces on either side of the membrane and supported by voltammograms obtained for a series of ions of varied lipophilicity. The bipolar nature of the voltammetric response offers an effective way of mass transport control via changing polarity of the applied voltage and finds immediate use in extraction, purification, and separation applications.
Project description:Short pieces of fused silica capillary tubing were used to support an electrified liquid-liquid interface. A methyl deactivated silica capillary having a diameter of 25 ?m was filled with 1,2-dichloroethane solution and served as the organic part of the liquid-liquid interface. A nondeactivated fused silica capillary having a diameter of 5, 10, or 25 ?m was filled with an aqueous HCl solution and served as the aqueous part of the electrochemical cell. For the latter, silanization of the capillary interior with chlorotrimethylsilane allowed for a successful phase reversal. All capillaries were characterized by ion transfer voltammetry using tetramethylammonium cation as a model ion. This simple, fast, and low-cost miniaturization technique was successfully applied for detection of the antibiotic ofloxacin.
Project description:The aliphatic-acid-mediated dehydration of C6-10-α,ω-alkanediols to alkadienes proceeds in a stepwise manner: C6-10-α,ω-alkanediols react with aliphatic acids first to generate diesters; subsequent pyrolysis of the latter produces alkadienes. The highest yields of 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene were up to 70.3, 74.8, and 90.3%, respectively. It turned out that pyrolysis favors the diester with a longer carbon chain more, while acetic acid outperformed the other aliphatic acids in the pyrolysis step that a relatively lower temperature was enough for a high yield of alkadienes.
Project description:Interfaces of liquid water play a critical role in a wide variety of processes that occur in biology, a variety of technologies, and the environment. Many macroscopic observations clarify that the properties of liquid water interfaces significantly differ from those of the bulk liquid. In addition to interfacial molecular structure, knowledge of the rates and mechanisms of the relaxation of excess vibrational energy is indispensable to fully understand physical and chemical processes of water and aqueous solutions, such as chemical reaction rates and pathways, proton transfer, and hydrogen bond dynamics. Here we elucidate the rate and mechanism of vibrational energy dissipation of water molecules at the air-water interface using femtosecond two-color IR-pump/vibrational sum-frequency probe spectroscopy. Vibrational relaxation of nonhydrogen-bonded OH groups occurs at a subpicosecond timescale in a manner fundamentally different from hydrogen-bonded OH groups in bulk, through two competing mechanisms: intramolecular energy transfer and ultrafast reorientational motion that leads to free OH groups becoming hydrogen bonded. Both pathways effectively lead to the transfer of the excited vibrational modes from free to hydrogen-bonded OH groups, from which relaxation readily occurs. Of the overall relaxation rate of interfacial free OH groups at the air-H2O interface, two-thirds are accounted for by intramolecular energy transfer, whereas the remaining one-third is dominated by the reorientational motion. These findings not only shed light on vibrational energy dynamics of interfacial water, but also contribute to our understanding of the impact of structural and vibrational dynamics on the vibrational sum-frequency line shapes of aqueous interfaces.
Project description:We reported recently that amphiphilic polymers can be assembled at interfaces created between aqueous phases and thermotropic liquid crystals (LCs) in ways that: (i) couple the organization of the polymer to the order of the LC and (ii) respond to changes in the properties of aqueous phases that can be characterized as changes in the optical appearance of the LC. This investigation sought to characterize the behavior of aqueous-LC interfaces decorated with uniaxially compressed thin films of polymers transferred by Langmuir-Schaefer (LS) transfer. Here, we report physicochemical characterization of interfaces created between aqueous phases and the thermotropic LC 4-cyano-4'-pentylbiphenyl (5CB) decorated with Langmuir films of a novel amphiphilic polymer (polymer 1), synthesized by the addition of hydrophobic and hydrophilic side chains to poly(2-vinyl-4,4'-dimethylazlactone). Initial characterization of this system resulted in the unexpected observation of uniform azimuthal alignment of 5CB after LS transfer of the polymer films to aqueous-5CB interfaces. This paper describes characterization of Langmuir films of polymer 1 hosted at aqueous-5CB interfaces as well as the results of our investigations into the origins of the uniform ordering of the LC observed upon LS transfer. Our results, when combined, support the conclusion that uniform azimuthal alignment of 5CB is the result of long-range ordering of polymer chains in the Langmuir films (in a preferred direction orthogonal to the direction of compression) that is generated during uniaxial compression of the films prior to LS transfer. Although past studies of Langmuir films of polymers at aqueous-air interfaces have demonstrated that in-plane alignment of polymer backbones can be induced by uniaxial compression, these past reports have generally made use of polymers with rigid backbones. One important outcome of this current study is thus the observation of anisotropy and long-range order in Langmuir films of a novel flexible polymer. A second important outcome is the observation that the existence, extent, and dynamics of this order can be identified and characterized optically by transfer of the Langmuir film to a thin film of LC. Additional characterization of Langmuir films of two other flexible polymers [poly(methyl methacrylate) and poly(vinyl stearate)] using this method also resulted in uniform azimuthal alignment of 5CB, suggesting that the generation of long-range order in uniaxially compressed Langmuir films of polymers may also occur more generally over a broader range of polymers with flexible backbones.
Project description:We report the design of an amphiphilic polyamine (polymer 1) based on poly(2-alkenyl azlactone) that strongly couples the formation of polyelectrolyte complexes at aqueous/liquid crystal (LC) interfaces to ordering transitions in the LC. We demonstrate that the addition of a strong anionic polyelectrolyte to aqueous solutions in contact with polymer 1-laden LC interfaces (prepared by Langmuir-Schaefer transfer of monolayers of polymer 1 onto micrometer-thick films of nematic LC) triggers ordering transitions in the LCs. We further demonstrate that changes in the ordering of the LCs (i) are driven by electrostatic interactions between the polyelectrolytes, (ii) involve multivalent interactions between the polyelectrolytes, and (iii) are triggered by reorganization of the hydrophobic side chains of amphiphilic polymer 1 upon formation of the interfacial complexes. The results presented in this paper lead us to conclude that ordering transitions in LCs can be used to provide insights into the structure and dynamics of interfacial complexes formed between polyelectrolytes.
Project description:Copolymerizations of 1-decene (DC) with 1,9-decadiene (DCD), 1-dodecene (DD) with 1,11-dodecadiene (DDD), and 1-tetradecene (TD) with 1,13-tetradecadiene (TDD), using Cp*TiMe2(O-2,6-iPr2C6H3) (1)-[Ph3C][B(C6F5)4] (borate) catalyst in the presence of AliBu3/Al(n-C8H17)3 proceeded in a quasi-living manner in n-hexane at -30 to -50 °C, affording ultrahigh molecular weight (UHMW) copolymers containing terminal olefinic double bonds in the side chain with rather low PDI (Mw/Mn) values. In the DC/DCD copolymerization, the resultant copolymer prepared at -40 °C possessed UHMW (Mn = 1.40 × 106 after 45 min) with low PDI (Mw/Mn = 1.39); both the activity and the PDI value decreased at low polymerization temperature (Mn = 5.38 × 105, Mw/Mn = 1.18, after 120 min at -50 °C). UHMW poly(TD-co-TDD) was also obtained in the copolymerization at -30 °C (Mn = 9.12 × 105, Mw/Mn = 1.51, after 120 min), using this catalyst.
Project description:The facilitated transfer of four hydrophilic anions, i.e., Cl-, Br-, NO2-, and CH3CO2-, at the micro-water/1,2-dichloroethane interface supported at the tip of a micropipet has been observed successfully using beta-octafluoro-meso-octamethylcalixpyrrole 2 as the receptor. We have also shown for the first time that the dynamics of this process can be studied by micropipet voltammetry. The standard kinetic rate constants (kdegrees) for facilitated anion transfer at such an interface were determined to be (2.11 +/- 0.90) x 10(-2) and (0.75 +/- 0.50) x 10(-2) cm/s in the case of Cl- and CH3CO2-, respectively. These values are much smaller than those associated with the facilitated transfer of analogous alkali metal ions. This difference is thought to reflect a number of underlying factors, including the higher hydration of anions as compared to similar sized cations. Studies such as these are expected to be useful in understanding the mechanism of anion transport at soft interfaces and for the design of yet-improved anion receptors and carriers.
Project description:The uptake and sorption of charged molecules by responsive polymer membranes and hydrogels in aqueous solutions is of key importance for the development of soft functional materials. Here, we investigate the partitioning of simple monatomic (Na+, K+, Cs+, Cl-, I-) and one molecular ion (4-nitrophenolate; NP-) within a dense, electroneutral poly(N-isopropylacrylamide) membrane using explicit-water molecular dynamics simulations. Inside the predominantly hydrophobic environment, water distributes in a network of polydisperse water nanoclusters. The average cluster size determines the mean electrostatic self-energy of the simple ions, which preferably reside deeply inside them; we therefore find substantially larger partition ratios K ≃10-1 than expected from a simple Born picture using a uniform dielectric constant. Despite their irregular shapes, we observe that the water clusters possess a universal negative electrostatic potential with respect to their surroundings, as is known for aqueous liquid-vapor interfaces. This potential, which we find concealed in cases of symmetric monatomic salts, can dramatically impact the transfer free energies of larger charged molecules because of their weak hydration and increased affinity to interfaces. Consequently, and in stark contrast to the simple ions, the molecular ion NP- can have a partition ratio much larger than unity, K ≃10-30 (depending on the cation type) or even 103 in excess of monovalent salt, which explains recent observations of enhanced reaction kinetics of NP- reduction catalyzed within dense polymer networks. These results also suggest that ionizing a molecule can even enhance the partitioning in a collapsed, rather hydrophobic gel, which strongly challenges the traditional simplistic reasoning.
Project description:We present a new electrochemical system that combines paper-based sensing and ion-transfer voltammetry, bringing the latter a step closer toward point-of-care applications. Studies at the interface between two immiscible electrolyte solutions (ITIES) are often performed to detect redox-inactive species; unfortunately, due to the inherent instability of the interface, it is rather poorly explored outside specialized laboratories. Here, we address this limitation by combining a pen-like device containing the gelled organic phase with a paper-supported aqueous phase. This combination makes the system more user-friendly, potentially low-cost, and easy to assemble. We show the applicability of the new cell to analyze both simple and ionophore-facilitated transfer of ions and proteins, preconcentration of species, and analysis of mixtures through combination with paper chromatography. The native ion content of the paper also enabled measurements without added electrolytes. Those studies could broaden the scope for the application of the label-free electrochemical detection of nonredox-active species at points-of-need.
Project description:We explore anion-induced interface fluctuations near protein-water interfaces using coarse-grained representations of interfaces as proposed by Willard and Chandler ( J. Phys. Chem. B 2010 , 114 , 1954 - 1958 ). We use umbrella sampling molecular dynamics to compute potentials of mean force along a reaction coordinate bridging the state where the anion is fully solvated and one where it is biased via harmonic restraints to remain at the protein-water interface. Specifically, we focus on fluctuations of an interface between water and a hydrophobic region of hydrophobin-II (HFBII), a 71 amino acid residue protein expressed by filamentous fungi and known for its ability to form hydrophobically mediated self-assemblies at interfaces such as a water/air interface. We consider the anions chloride and iodide that have been shown previously by simulations as displaying specific-ion behaviors at aqueous liquid-vapor interfaces. We find that as in the case of a pure liquid-vapor interface, at the hydrophobic protein-water interface, the larger, less charge-dense iodide anion displays a marginal interfacial stability compared with that of the smaller, more charge-dense chloride anion. Furthermore, consistent with the results at aqueous liquid-vapor interfaces, we find that iodide induces larger fluctuations of the protein-water interface than chloride.