Effect of carrier concentration on the facilitated oxygen transport in a polymer membrane

Facilitated transport of oxygen in a solid Polymer membrane containing cobaltporphyrin (CoP) which carries oxygen specifically and reversibly, leads to permselectivity of oxygen against nitrogen in the membrane. The increase in concentration of the CoP carrier is expected to enhance the oxygen transport. The membranes of poly(octylmethacrylate-co-vinylimidazole) containing 0.8 ～ 10 wt% CoP were prepared, and the effects of the CoP-concentration on the transport and the diffusion constants of oxygen are studied. Although the induction period before the steady state of oxygen permeation was prolonged with the CoP concentration in the polymer membrane, the glass transition temperature (T_g) of the membrane was increased and the diffusion constants of oxygen were decreased with the CoP concentration to yield unexpected reduction of the oxygen permeation in the highly CoP loaded membrane.     

Photoregulation of polymer conformation by photochromic moieties. I. Anionic ligand to an anionic polymer

Abstract— Photoregulated biological processes appear to make use of membrane-bound photochromic macromolecules. In order to elucidate various physicochemical pathways by which these processes can be triggered, model studies have been undertaken employing photochromic moieties bound to synthetic macromolecules with a labile fold structure. Inspired by Lovrien's 1967 work, attention was first focused on the anionic dis-azo stilbene dye chrysophenine (CHP) and poly(methacrylic acid) (PMA) in aqueous solution. This ligand is found to bind to and unfold PMA only if the degree of ionization of the polymer is below 0·75. Viscosity as well as equilibrium dialysis data indicate that maximally one CHP per ten monomer units PMA is bound. The apparent degree of ionization conferred to PMA by the ionic CHP ligand leading to polymer unfolding is the same as the known real degree of ionization leading to polymer unfolding in the absence of CHP. Upon trans→cis photoisomerization, the ligand either desorbs or creates a higher local dielectric constant because of the large cis-azo dipole moments. As a result some refolding to a more compact hydrodynamic volume occurs, as deduced from the viscosity measurements at a low degree of ionization. Simultaneously a lowering of the pK_app by 0·1 pK unit is observed at degrees of ionization below 0·075. Photoregulation of conformation as well as of pK_app indicates two possible pathways for the regulation of ionic fluxes such as have been postulated for photobiological transducers.     

氧在甲基丙烯酸辛酯-乙烯基咪唑共聚物/钴卟啉复合膜中的溶解和扩散过程

讨论了氧在甲基丙烯酸辛酯 乙烯基咪唑共聚物 钴卟啉复合膜中的溶解和扩散过程,用二元输送模型分析了间α,α,α,α-四(邻三甲基乙酰胺苯基)钴卟啉(CoP)作为氧载体的复合膜氧输送性能.研究发现,固定在聚合物中的CoP与氧可逆地络合和解络合,其络合平衡常数K为14mol- 1 L ,根据吸附实验结果计算出氧在基体聚合物中的物理溶解度系数kD 为4 4×10 - 5cm3(STP)cm- 3Pa- 1 .聚合物 载体复合膜除了物理渗透外,氧还可通过与载体的络合和解络合而扩散,从而促进氧的输送.氧通过载体的扩散系数(DC)和通过基体聚合物的物理扩散系数(DD)的比值为0 0 8.     

Photoregulation of polymer conformation by photochromic moieties. II. Cationic and neutral moieties on an anionic polymer

Abstract— Photoregulation of the conformation of poly (methacrylic acid) (PMA) in the range 4·5 < pH > 6·5 has been achieved by means of the cationic photochromic ligand, p-phenyl-azophenyl trimethyl ammonium iodide (PTA), as well as by means of copolymerization of methacrylic acid (MA) with the neutral photochromic co-monomer, p-phenyl azomethacrylanilid (PM). At degrees of ionization α, corresponding to the conformational unfolding of PMA, the pK_app is 0·2 units higher when the ligand PTA is trans than when PTA is in the photostationary 80%“cis” state. Equilibrium dialysis shows that the binding of PTA is independent of the cis/trans ratio at high α (after the conformational unfolding), but at lower αtrans-PTA binds positively and cis-PTA negatively. In the transition region, the presence of non-polar trans-azo ligand is therefore held responsible for a shift of the conformational equilibrium toward the more compact, folded form, which is harder to ionize than the unfolded form. Because of the relation pK_app# pH + log [(1 –α)/α], the degree of ionization of PMA, and thus the polymer conformation, as reflected in the reduced viscosity, can be photochemically regulated in pH buffers. At pH # 5·5 (α# 0·20) a maximal relative shift of Δα/α= 20 per cent was found, with a corresponding relative shift in reduced viscosity of 20·5 per cent. In the photochromic copolymer a pK_app switch of similar magnitude was found. In this case the azo-moiety is permanently affixed to the PMA so that the photosensitivity of the pK_app in the range of the conformational unfolding is due to a shift in the conformational equilibrium induced by the presence of non-polar trans-azo and polar “cis” azo, respectively. In both cases only about 1 photochromic moiety per 100 monomer units is capable of appreciably shifting the conformational manifold of PMA and/or the degree of ionization in constant pH buffers, provided one stays close to the unfolding transition. Mention is made of the implications for photoregulation of the permeability of, and the potential across. model membranes made of photochromic PMA molecules.     

Design variations of a polymer–enzyme composite biosensor for glucose: Enhanced analyte sensitivity without increased oxygen dependence

The glucose sensitivity and oxygen dependence of a variety of implantable biosensors based on glucose oxidase (GOx), incorporating an electrosynthesized poly-o-phenylenediamine (PPD) permselective barrier on 125-μm diameter Pt disks (Pt_D) and cylinders (Pt_C, 1-mm length), were measured and compared. Full glucose calibrations and experimental monitoring of solution oxygen concentration allowed us to determine apparent Michaelis–Menten parameters for glucose and oxygen. In the linear region of glucose response, the most sensitive biosensor design studied was Pt_D/PPD/GOx (enzyme deposited over polymer) that was 20 times more sensitive than the more widely used Pt_C/GOx/PPD (enzyme immobilized before polymer deposition) configuration. The oxygen dependence, quantified as K_M(O₂), of both active and less active designs was surprisingly similar, a finding that could be rationalized in terms of an increase in K_M(G) with increased enzyme loading. The Pt_D/PPD/GOx design will now enable us to explore glucose concentration dynamics in smaller and layered brain regions with good sensitivity and minimal interference from fluctuations in tissue pO₂.     

Oxygen Gas Permeability of Poly (Aminophosphazene) Films in Water

Abstract

Various gas permeability in dry and oxygen gas permeability in wet conditions with poly(organophosphazene) membranes have been previously reported [1–2]. To prepare the transparent poly(aminophosphazene) having the highest oxygen gas permeability value (D) in water, chlorine atoms in polydichlorophosphazne (1) were substituted with amine compounds (2).     

Naphthalene Complexation by β-Cyclodextrin: Influence of Added Short Chain Branched and Linear Alcohols

Naphthalene forms 1 : 1 complexes with -cyclodextrin (-CD)in water. The binding constant is 377 ± 35 M^-1. Addition of linear or branched alcohols causes a reduction in the apparent strength of naphthalene binding (K_app) compared to the value in the absence of additives. For example, 1% 1-pentanol reduces K_app to 184 ± 31 M^-1. Branching does not alter K_app much for a given number of carbon atoms, e.g., it is 113 ± 9 M^-1for 2-pentanol and 116 ± 8 M^-1for 3-pentanol. The exception to this is tert-butanol for which K_app is 577 ± 40 M^-1. The variation in K_app as a function of [1-pentanol] yields values for the individual equilibrium constants contributing to K_app. This reveals that a ternary complex forms involving naphthalene, the CD and 1-pentanol. The constant for formation of the ternary complex is 99 ± 29 M^-2. NaI quenching of naphthalene fluorescence indicates that the CD cavity partially protects the naphthalene excited state fromthis water phase quencher. Interestingly, the Stern–Volmer constant is lower in the presence of 1-pentanol than in its absence, although there should be more unbound (and therefore more NaI accessible) naphthalene in the former system than in the latter. These apparently contradictory results are discussed in terms of ternary complex formation.     

Electron transfer reaction of electrochemically polymerized tris-(amino-phenanthroline)-iron(II/III) complex films

New films of iron complex with 4,7-bis(2-aminophenyl)-methylaminosulfonylphenyl)-1,10-phenanthroline (APP) and 5-amino-1,10-phenanthroline (AP) are prepared on the electrode surface of In–Sn oxide conducting glass (ITO) by electrochemical oxidation. The thickness (Φ) of the films prepared on the ITO can be controlled by the number of cycles of the potential scan. The resulting film-coated electrodes show well-defined reversible vol-tammograms corresponding to the redox reaction of the Fe(II/III) complexes in 0.1 M NaClO₄ acetonitrile (AN), a mixture of butylene carbonate (BC) and propylene carbonate (PC) and poly2-hydroxyethylmethacrylate gel containing BC and PC. The electron transfer processes within the films can be treated apparently as diffusional processes characterized by the rate constants of the apparent diffusion coefficient (D_app). The value of D_app increase from 1.0 × 10^?9 to 1.6 × 10^?8 cm² sec^?1 as the Fe complex concentration (C_Fe) increases from 0.06 to 1.04 M for the [Fe(AP)₃] complex film (Φ=0.80 μm) in 0.2 M NaClO₄/AN solution. The D_app value for the [Fe(APP)₃) complex film (C_Fe = 0.19 M , Φ= 0.78 μm) is 3.5 × 10^?9 cm² sec^?1 in 0.2 M NaClO₄/AN solution. The D_app values of the [Fe(AP)₃] complex film in the PC + BC mixture and gel containing 1.0 M NaClO₄ were smaller than those obtained in AN solution by an order of magnitude. The dependence of the apparent formal potential of the Fe(II/III) redox reaction for the [Fe(AP)₃] complex film on the activity of NaClO₄ supporting electrolyte in AN shows that Na⁺ moves preferentially across the polymer/solution interfaces during the redox reaction. The Fe(II/III) redox reaction of the Fe complex films shows reversible electrochromic response between red and colorless.     

Electrode kinetics of electroactive electropolymerized polymers deposited on graphite electrode surfaces

A kinetic examination of the charge-transport processes (i.e. (i) heterogeneous electron-transfer process of electrode/film interfaces and (ii) homogeneous charge-transport process within films) at electroactive electropolymerized film-coated electrodes was conducted by normal pulse voltammetry. The films employed were of poly(o-phenylenediamine), Poly(N-methylaniline) and poly(N-ethylaniline), which were prepared on electrodes as coating films by electrooxidative polymerization of the corresponding monomers in an acidic solution. It was found that process (i) obeys the conventional Butler-Volmer equation and that process (ii) can be treated as a Fickian diffusion process. In addition, the kinetic parameters characterizing processes (i) and (ii) (i.e. the standard rate constant (k°) and transfer coefficient (α) for process (i), and the apparent diffusion coefficient (D_app for process (ii)) were estimated: D_app = ca (1–4)×10⁻⁸ cm² s⁻¹ s⁻¹, k° = ca. (4–6)×10⁻⁴ cm s⁻¹, α_a (for anodic process) = 0.83–0.86 and α_c (for cathodic process)=0.13–0.23. The are compared with the data reported previously for other electroactive polymer films.     

N-(4-乙烯基)苄基咪唑共聚物的合成及与钴卟啉络合物的氧结合性能

研究了N-(4-乙烯基)苄基咪唑单体及其与甲基丙烯酸辛酯共聚物(PBIOM)的合成与表征,以及咪唑基有机或聚合物配位体与钴卟啉(CoP)络合物的氧结合性能.合成的PBIOM重均分子量和咪唑基含量分别由GPC和元素分析方法测定,结果为3.4×105和57 mol%.PBIOM或苄基咪唑(BIm)中的咪唑基与CoP在溶液中配位,得到的CoP-PBIOM或CoP-BIm络合物具有快速、可逆的氧结合特性.相同氧气分压下CoP-BIm络合物在三氯甲烷溶液中的氧结合百分率略大于CoP-PBIOM络合物.CoP-PBIOM络合物固体膜的氧结合亲和力大于三氯甲烷溶液中的氧结合亲和力.60℃下CoP-PBIOM固体膜的氧结合半衰期为40.7 h,而CoP-BIm固体膜为8.8 h,表明聚合物配位体显著提高了CoP络合物的氧结合寿命.     

Simultaneous high-throughput determination of interaction kinetics for drugs and cyclodextrins by high performance affinity chromatography with mass spectrometry detection

The individual determination of the apparent dissociation rate constant (k_d,app) using high performance affinity chromatography (HPAC) is a tedious process requiring numerous separate tests and massive data fitting, unable to provide the apparent association rate constant (k_a) and equilibrium binding constant (K_a). In this study, a HPAC with mass spectrometry detection (HPAC-MS/MS) was employed to determine the drug-cyclodextrin (CD) interaction kinetics with low sample loading quantity (<10 ng per injection for single compound) and high-throughput yield as twenty drugs determined in one injection. The k_d,app measured by HPAC-MS/MS approach were 0.89 ± 0.07, 4.34 ± 0.01, 1.48 ± 0.01 and 7.77 ± 0.04 s⁻¹ for ketoprofen, trimethoprim, indapamide and acetaminophen, with k_d,app for acetaminophen consistent with that from the HPAC method with UV detector in our previous studies. For twenty drugs with diverse structures and chemical properties, good correlationship was found between k_d,app measured by single compound analysis method and high-throughput HPAC-MS/MS approach, with the correlation coefficient of 0.987 and the significance F less than 0.001. Comprehensive quantification of k_a,app, k_d,app and K_a values was further performed based on the measurement of k_d,app by peak profiling method and K_a by the peak fitting method. And the investigation of the drug-CD interaction kinetics under different conditions indicated that the column temperature and mobile phase composition significantly affected the determination of k_a,app, k_d,app and K_a while also dependent on the acidity and basicity of drugs. In summary, the high-throughput HPAC-MS/MS approach has been demonstrated high efficiency in determination of the drug-CD primary interaction kinetic parameter, especially, k_d,app, being proven as a novel tool in screening the right CD for the solubilization of the right drug.     

Development of negligible depletion hollow fiber membrane-protected liquid-phase microextraction for simultaneous determination of partitioning coefficients and acid dissociation constants

A new method based on negligible depletion hollow fiber-protected liquid-phase microextraction coupled with high-performance liquid chromatography (HPLC) was developed for the simultaneous determination of partitioning coefficients (K_OW) and acid dissociation constants (pK_a), by using phenol, 4-chlorophenol and 2,4-dichlorophenol as model compounds. A 37-mm length polypropylene hollow fiber membranes (600 μm inner diameter, 200 μm wall-thickness, 0.2 μm pore size, ∼70% porosity) with two-end sealed were filled with 1-octanol by ultrasonic agitation to prepare the extraction device. The extraction device was deployed in sample solutions, prepared by spiking target analytes in 1-octanol saturated aqueous solutions (500 mL), for negligible depletion extraction. After equilibrium was reached (∼5 h), the 1-octanol in the lumen of the hollow fiber membrane was collected for HPLC determination of the target analytes. As the depletion of the analytes in aqueous samples was negligible, the distribution coefficient (D_OW) could be calculated based on the measured equilibrium concentration in 1-octanol (C_O) and the initial concentration (C_W) in the aqueous sample of the target analyte (D_OW = C_O/C_W). The D_OW values measured at various pH values were nonlinearly regressed with pH to obtain the K_OW and pK_a values of a compound. Results showed that the measured values of the K_OW and pK_a of these model compounds agreed well with literature data.     

Electrochemical and Electrochromic Properties of Polymer Complex Films Composed of Polytetramethyleneviologen and Poly-[p-Styrenesulfonic Acid] Containing a Conductive Powder

The electrochemical and electrochromic properties of polymer films containing a conductive powder (SnO₂/TiO₂) have been investigated. The films are complexes of polytetramethyleneviologen and poly(p-styrenesulfonic acid). It was found that the coloration (purple) and bleaching rates of the composite films increase markedly with increasing conductive powder content(x). The coloring and bleaching of the composite film with x = 95 wt% were about 7 and 44 times faster, respectively, than those for an equivalent film without conductive powder. This increase in the rate of color change by introduction of a conductive powder was found to be correlated with the apparent diffusion coefficient (D _app) for the diffusionlike charge-transport process within the composite films which increases with increasing x. The D _app for the reduction process of the film with x = 95 wt% was larger by about 3 orders of magnitude than that for the unfilled film.     

Studies on the Distribution of Phenoxyacetic Acid in Two-Phase Systems: n -Aliphatic Hydrocarbon – Water

Phenoxyacetic acid distribution in two-phase systems n-aliphatic hydrocarbon (C₅–C₈) – water and its dimerization in organic phase were investigated. The values of distribution coefficient (D _HR), distribution constant (K _D), and dimerization constant (K _dim) of acid were obtained. The empirical correlations of these quantities with Hildebrand solubility parameter of organic solvents were established. The influence of pH of the aqueous phase as well as the polarity of the applied organic solvents on phenoxyacetic acid physical chemistry in the two-phase systems was described.     

Extraction of certain actinide and lanthanide elements from different acidic media by polyurethane foams loaded with di-(2-ethylhexyl)phosphoric acid (HDEHP)

The extraction of cerium(III) from weakly acidic chloride solutions by HDEHP-nitrobenzene-loaded polyurethane foams could be analyzed quantitatively in terms of the equation: log(9.056 D_c)=log K_c+2.14 log (C_d?6C_c)+3 pH+log f_c where D_c is the distribution ratio of cerium(III) between the foam and aqueous phases, C_d and C_c are the total HDEHP and Ce(III) concentrations on the foam, respectively, log f_c=[Ce³⁺]_(sq)/[ΣCe(III)]_(aq), and K_c is the equilibrium constant of the equation: Ce _(aq) ³⁺ +2.14(HX)_2.8(o) ? ? CeX₆·H_3(o)+3H _(aq) ⁺ . Values of K_c under the different extraction conditions tested are given.     

Naproxen: Hydroxypropyl-β-Cyclodextrin:Polyvinylpyrrolidone Ternary Complex Formation

The aim of the present study was to investigate the effect of the presence of thewater-soluble polymer polyvinylpyrrolidone (PVP) MW = 24000 g/mol, on thecomplexation of the phototoxic anti-inflammatory drug naproxen, in its sodiumsalt form, with hydroxypropil-β-cyclodextrin (HP-β-CD). The datashown that the polymer interacts with the free naproxen and with thenaproxen:HP-β-CD inclusion complex. The presence of different proportions of PVP, in the 0–1%(w/w) rangesystematically increased the K_app of the naproxen:HP-β-CD inclusioncomplex formation. The cause of this increase is that the polymer interactswith the HP-β-CD with a binding constant of K₂ = 29000 ± 53 M^-1; and with the naproxen:HP-β-CD inclusion complex, to givea ternary complex naproxen:HP-β-CD:PVP. The binding constant of thisprocess was K₃ = 5350 ± 1 M^-1. NMR data revealed that in the ternary system, PVP is outside of the cyclodextrin, and therefore must be wholly or partially recovering the naproxen:HP-β-CD inclusion complex.     

Studies on the Distribution of Phenoxyacetic Acid in Two-Phase Systems: <Emphasis Type="Italic">n</Emphasis>-Aliphatic Hydrocarbon – Water

Summary. Phenoxyacetic acid distribution in two-phase systems n-aliphatic hydrocarbon (C₅–C₈) – water and its dimerization in organic phase were investigated. The values of distribution coefficient (D _HR), distribution constant (K _D), and dimerization constant (K _dim) of acid were obtained. The empirical correlations of these quantities with Hildebrand solubility parameter of organic solvents were established. The influence of pH of the aqueous phase as well as the polarity of the applied organic solvents on phenoxyacetic acid physical chemistry in the two-phase systems was described.     

Electrochemically Polymerized N,N-Dimethylaniline Films Containing Tris-(Bathophenanthroline Disulfonato)Iron(II/III) Complexes

The electropolymerization of N, N-dimethylaniline (DMA) was carried out in an aqueous CF₃COONa solution (pH 1.0) containing DMA in the presence of tris(bathophenanthroline disulfonato)iron(II), Fe(bphen)₃ ^4-. Poly(N, N-dimethylanilinium trifluoroacetate) (PDMA) film was formed on electrode surfaces and, at the same time, Fe(bphen)₃ ^4- ions were stably confined in the formed PDMA film by electrostatic interaction between them and the positively charged quaternary ammonium sites of the PDMA film. The PDMA-Fe(bphen)₃ ^4-/3- film thus prepared displayed well-defined reversible electroactivity and electrochromic properties ascribable to those of the Fe(bphen)₃ ^4-/3- couple confined in the film. The PDMA-Fe(bphen)₃ ^4- film is red, and the PDMA-Fe(bphen)₃ ^3- film is colorless. The response rate of the color change to a potential pulse was found to be correlated with the kinetic parameters characterizing the rate of the overall charge-transfer reaction at the PDMA-Fe(bphen)₃ ^4-/3- film-coated electrode, that is, the apparent diffusion coefficient (D _app) for the homogeneous charge-transport process within the film and the standard rate constant (k) of the heterogeneous electron-transfer reaction at the electrode/film interface. For the PDMA-Fe(bphen)₃ ^4-/3- film with larger k° and D _app values, the response rate of the color change was larger, Further, k°, D _app, and response rate depended on the concentration (C°) of the Fe(bphen)₃ ^4- (or Fe(bphen)₃ ^3-) confined in the PDMA film; and at a given film thickness, the lower C°, the higher were k°, D _app, and response rate. At a given C°, the thinner the film thickness, the greater was the response rate.     

Dielectric and Viscoelastic Behavior of Poly-(n-Butyl Methacrylate) Containing Cholesteric Compounds

Dielectric and dynamic mechanical behavior of poly(n-butyl methacrylate) (PBMA) containing small concentrations of cholesteryl chloride (ChCl), cholesteryl caprylate (ChCp), and cholesteryl laurate (ChL) have been studied in the temperature range -20 to 80°C. Tan αmax (dielectric and mechanical) in all systems containing an additive shifts to lower temperature compared to that in pure PBMA. In the glassy region, the dynamic storage modulus E′ for all the PBMA plus additive systems is higher than that for pure PBMA. This behavior is similar to the β-peak suppression and the increase in tensile strength of poly(vinyl chloride) on addition of a small concentration of plasticizer. Using the WLF equation with C₁ and C₂ obtained from the data on pure PBMA, the reference temperature T_o for PBMA plus additive systems are determined for the best fit of the experimental points to the WLF curve and are in agreement with measured glass-transition temperatures. With respect to T_o of pure PBMA, the T_o of PBMA plus additive systems are lowered, and the lowering due to these additives is in the order ChL < ChCp < ChCl. From spectrophotometric studies in solutions of polymer plus additives, equilibrium constants for the 1:1 and 1:2 complexes between the polymer and the additive are evaluated. The magnitude of the equilibrium constant K₁ increases in the order ChL > ChCp > ChCl, and hence it is concluded that the extent of β-peak suppression depends on the strength of polymer-additive interaction.     

Ion-transport and diffusion coefficients of non-plasticised methacrylic-acrylic ion-selective membranes

The ion-transport behaviour of methacrylic-acrylic-based polymers for ion-selective electrode (ISE) membranes was investigated by a spectrophotometric method to determine the apparent diffusion coefficient. By observing the degree of deprotonation of the chromoionophore or chromogenic ionophore, the extent of penetration of cations into the polymer films was determined. The transport of the cations into the optode films depended on the stoichiometry of complexation by the ionophores. The apparent diffusion coefficients, estimated from the deprotonation data were of the order of 10⁻¹² to 10⁻¹¹ cm² s⁻¹. These values indicate that the apparent ion mobility in the methacrylic-acrylic ISE membranes is approximately a thousand times lower than that in plasticised PVC ISE membranes. For some ionophores, the value of the apparent diffusion coefficient could be modulated according to the ionophore content in the membrane and the data obtained for a calixarene containing membrane were tested against a model for facilitated diffusion with chained carriers. The data did not fit a model where intramolecular diffusion was limiting, but were consistent with a first-order rate-limiting mechanism involving an intermediate 1:2 complex between ion and ionophore. In this instance, the lowest values for D_app were thus not necessarily obtained for lowest ionophore loading and in the range examined, a trend of decreasing D_app with increasing ionophore was noted.