Number Of Sulfonic Groups Research Articles

Towards Photothermal Acid Catalysts Using Eco-Sustainable Sulfonated Carbon Nanoparticles—Part I: Synthesis, Characterization and Catalytic Activity towards Fischer Esterification

The development of photothermal catalysts for biodiesel synthesis reaction (transesterification) requires the production of light-absorbing nanoparticles functionalized with catalytic (acid) groups. Using Stöber method, it is possible to produce resorcinol/formaldehyde resin (RF) nanoparticles, which can be carbonized (pyrolysis in an inert atmosphere) and sulfonated. In this work, vegetable tannins are used as a replacement for synthetic resorcinol in the Stöber synthesis of resin (TF) nanoparticles. The nanoparticles are characterized using DLS, FESEM, TEM and N2 adsorption-desorption isotherms. Both resin and carbon nanoparticles are sulfonated by reaction with concentrated sulfuric acid. The attachment of sulfonic groups is verified by FTIR and EDX. The number of sulfonic groups is measured by acid/base titration and TGA. All sulfonated nanoparticles show catalytic activities towards Fischer esterification of ethanoic acid with ethanol, and high (up to 70%) conversion is obtained. The conversion is lower with TF-based nanoparticles, but the turnover numbers are similar in the RF- and TF-based materials. Sulfonated carbon and resin nanoparticles show higher catalytic activity compared to commercial acidic catalysts (e.g., Nafion®). Photothermal heating of carbon nanoparticles is observed. In Part II, sunflower oil transesterification, catalyzed by sulfonated nanoparticles, is observed. Photothermal catalysis of acetic acid esterification and sunflower oil transesterification is demonstrated.

NIR dye‐encoded nanotags for biosensing: Role of functional groups on sensitivity and performance in SERRS‐based LFA

AbstractSurface‐enhanced resonance Raman scattering (SERRS) is based on nanostructures supporting localized surface plasmon resonances as well as electronic resonances of the molecular adsorbate. Bright NIR‐SERRS nanotags require dyes with high Raman scattering cross‐sections upon NIR laser excitation in combination with functional groups for chemisorption. Here, we report on the role of isothiocyanate (ITC) and sulfonate (SO) groups in five cyanine dyes on sensitivity and performance of nanotags in SERRS‐based LFA. Dye concentration‐dependent SERRS and zeta potential measurements on bare gold nanostars (AuNS) revealed strong differences in their sensitivity and stability as a function of the number of ITC and SO groups. A positive correlation with the number of ITC groups due to stronger chemisorption and a negative correlation with the number of SO groups due to stronger desorption because of higher water solubility was observed. The application in SERRS‐based biosensing requires additional functionalization steps, for example, co‐adsorption of PEG with the NIR dye. The comparison of the Raman intensities before and after bioconjugation showed that the presence of at least one ITC group is necessary for minimizing Raman signal losses, irrespective of the additional presence of SO groups. In a SERRS‐based lateral flow assay (LFA) for sensing the pregnancy marker beta‐hCG, the two dyes NIR 4f and NIR 5e (both ITC = 2, SO = 0) showed the best performance. In contrast, we do not recommend to use IR‐783 (ITC = 0, SO = 2) for SERRS‐based biosensing. Overall, this study highlights the importance of surface‐seeking moieties such as the common ITC group for optimal performance in SERRS‐based biosensing platforms.

Application of modified cellulose-based antiscalant in reverse osmosis membrane scaling control

<p indent=0mm>Applying membrane scaling is a key problem in reverse osmosis (RO) desalination processes. By dosing antiscalant, we can effectively inhibit inorganic scale and control RO membrane scaling. Accordingly, in this work, an environmentally friendly modified cellulose-based antiscalant is synthesized by the etherification of cellulose and subsequent graft copolymerization using the etherification product carboxymethyl cellulose (CMC), acrylic acid (AA), and sodium allyl sulfonate (SAS): CMC-<italic>g</italic>-P(AA-<italic>co</italic>-SAS). The influence of molecular structure, CMC-<italic>g</italic>-P(AA-<italic>co</italic>-SAS) dose, and coexisting anions with respect to inhibiting the calcium-sulfate scale in the RO system are investigated. The results indicate that dosing CMC-<italic>g</italic>-P(AA-<italic>co</italic>-SAS) can significantly prolong the induction time of calcium-sulfate crystallization, inhibit the formation of calcium-sulfate scale, greatly alleviate both membrane fouling and membrane flux decline caused by membrane-surface scale formation, and effectively improve the membrane filtration efficiency. Static tests, scanning electron microscopy, optical microscopy, X-ray diffraction, conductivity measurements, and dispersion experiments suggest that the scale inhibition mechanism of CMC-<italic>g</italic>-P(AA-<italic>co</italic>-SAS) can be attributed to the chelation and dispersion effects of the introduced anionic groups, and that the carboxyl groups are more efficient in the inhibition of calcium-sulfate scale than the sulfonic groups. In addition, an appropriate number of sulfonic groups on the graft chain of CMC-<italic>g</italic>-P(AA-<italic>co</italic>-SAS) can improve the water solubility of CMC-<italic>g</italic>-P(AA-<italic>co</italic>-SAS), as well as effectively stabilize the scale-formed substances and enhance the scale inhibition efficiency. If the proportion of sulfonic groups is too high, the content of the carboxyl groups decreases accordingly, which reduces the chelation and dispersion effects of CMC-<italic>g</italic>-P(AA-<italic>co</italic>-SAS), which, in turn, reduces the scale inhibition performance.

Effect of Reactive Dye Structures and Substituents on Cellulose Fabric Dyeing

Traditional dyeing of cotton fabrics with reactive dyes has produced many environmental problems. Therefore, it is important to investigate the relationship between dye molecular structures and dyeing properties for cleaner procedures. Here, the properties of five azo-based reactive dyes with different substituents and reactive groups were studied. The dyes had similar molecular shapes, sizes, and chromophore structures. Differences were in the aromatic rings, the number of sulfonate groups, and the position of vinyl sulfonate on the benzene ring. The dye substantivity (S%), exhaustion (E%), reactivity (R%), fixation (F%), color strength, salt effects, alkali effects, and color fastness were investigated and analyzed. Different substituents on the dyes had a little effect on the ultraviolet-visible absorption maximum wavelength. In addition, the requirements of salt and alkali to produce the maximum color strength varied for different dye structures. The dye containing a naphthalene ring, three sulfonate groups, and a vinyl sulfonate at the para-position of the benzene ring produced the highest color strength and fixation values. Color fastness was almost the same for each dyed sample, except for the wet-rubbing fastness. The results should be useful for developing new dyes and environmentally friendly dyeing techniques.

Optimizing the Biodistribution of Radiofluorinated Barbiturate Tracers for Matrix Metalloproteinase Imaging by Introduction of Fluorescent Dyes as Pharmacokinetic Modulators.

Dysregulated expression or activation of matrix metalloproteinases (MMPs) is observed in many kinds of life-threatening diseases. Therefore, MMP imaging-for example, with radiolabeled MMP inhibitors (MMPIs)-potentially represents a valuable tool for clinical diagnostics using noninvasive single photon emission computed tomography (SPECT) or positron emission tomography (PET) imaging. Despite numerous preclinical imaging approaches, translation to a clinical setting has not yet been successful. We introduce and oppose three potential radiofluorinated MMP-targeted imaging probes, modified by the introduction of pentamethine cyanine (Cy5) dyes and therefore containing both radio- as well as fluorescent label with respect to their capability to assess MMP activity in vivo by means of scintigraphic (PET) and/or fluorescent (NIRF) imaging. New hybrid MMPI tracer candidates, structurally based on radiofluorinated pyrimidine-2,4,6-triones (barbiturates) from previous approaches, were synthesized by convenient two-step syntheses. In the first step, Cy5 dyes, varying in the number of sulfonate groups (nSO3- = 1, 2, or 4) and bearing an additional "clickable" alkyne moiety, were coupled to the barbiturate MMPI by amide formation. In the second step, the [18F]fluoride radiolabel was introduced into the resulting Cy5 dye conjugates by "radio-click" chemistry. Biodistribution studies of these hybrid tracer candidates were assessed and compared in C57BL/6 mice by PET as well as fluorescence imaging. MMP activity was imaged in a MMP-positive mouse model of irritant contact dermatitis (ICD) by PET and sequential fluorescence reflectance imaging (FRI), respectively. In vivo data were validated by scintillation counting, gelatin zymography, and MMP-histology. Three new potential hybrid MMP imaging probes were prepared, differing essentially in the number of sulfonate groups, introduced by Cy5 dye components. Although the hydrophilicity of these compounds was substantially increased, 10a (nSO3- = 1) and 10b (nSO3- = 2) were still rapidly eliminated via unfavorable hepatobiliary pathways, as observed in earlier approaches. Only 11 (nSO3- = 4) showed delayed in vivo clearance and a shift towards higher renal elimination. In the chosen mouse model of ICD, only 11 (nSO3- = 4) significantly accumulated in the inflamed mouse ear, which could be precisely visualized by means of PET and FRI.

Sulfonated Phosphine Ligands in the Ruthenium Catalyzed Biphasic Hydrogenation of Unsaturated Hydrocarbons

The hydrogenation of monocyclic aromatic hydrocarbons by ruthenium catalysts has been investigated in the presence of sulfonated monophosphine ligands with different stereoelectronic properties under biphasic conditions. The effects of (i) the number of sulfonate groups, (ii) the steric demand of the ligand and (iii) the σ-donor ability of the phosphorus atom have been investigated in the catalytic reactions. The TEM analysis of the catalytically active systems revealed that in situ formed soluble ruthenium nanoparticles (RuNPs) are responsible for the catalytic turnover. The Ru/sulfonated phosphine system with the properly tuned ligand exhibited high activity (8800 h−1) and selectivity in the hydrogenation of benzene to cyclohexane. Furthermore, the aqueous phase containing RuNPs could be recycled four times without a considerable loss of activity.Graphic

Microwave-assisted synthesis of pyrrolidinone derivatives using 1,1’-butylenebis(3-sulfo-3H-imidazol-1-ium) chloride in ethylene glycol

Abstract The energy efficiency of the microwave-assisted synthesis of pyrrolidinones was demonstrated using catalytic loading of 1,1’-butylene-bis(3-sulfo-3H-imidazol-1-ium) chloride as a sulfonic acid functionalized ionic liquid in ethylene glycol as green solvent. The effect of electron donating and electron withdrawing groups on aniline derivatives was studied under conventional heating and microwave irradiation. Furthermore, the cation effect of ionic liquids containing sulfonic groups on the catalytic efficiency for the synthesis of ethyl-1-phenyl-2-(4-chlorophenyl)-4-hydroxy-5-oxo-2,5-dihydro-1H-pyr-role-3-carboxylate was investigated under conventional heat. The experimental results exhibited that there is a relationship between catalytic efficiency and the number of sulfonic groups and imidazolium moieties linked by carbon spacer.

Biosorption of six basic and acidic dyes on brown alga Sargassum ilicifolium: optimization, kinetic and isotherm studies.

Biosorption of Methyl Blue (MB), Fuchsin Acid (FA), Rhodamine B (RB), Methylene Blue (MEB), Bromocresol purple (BC) and Methyl Orange (MO) onto Sargassum ilicifolium was studied in a batch system. Effect of dye structure on biosorption by Sargassum ilicifolium was studied to define the correlation between chemical structure and biosorption capacity. Different dye groups such as triarylmethane (MB, FA and BC), monoazo (MO), thiazine (MEB) and xanthene (RB) were studied. At optimum experimental conditions for each dye, biosorption capacity was determined and compared. The results indicate that the chemical structure (triarylmethane, monoazo, thiazine, xanthene), number of sulfonic groups, basicity (element of chromophore group: S, N, O) and molecular weight of dye molecules influence their biosorption capacity. Experimental parameters such as biosorbent dose, pH, contact time, and initial dye concentration were optimized for each dye. The biosorption kinetic data were successfully described by the pseudo second-order model. The biosorption results were also analyzed by the Langmuir and Freundlich isotherms. Finally, biosorption capacities obtained using Sargassum ilicifolium were compared with the ones presented in the literature.

The effect of sulfonated graphene oxide on Sulfonated Poly (Ether Ether Ketone) membrane for direct methanol fuel cells

A novel composite membrane of sulfonated graphene oxide (s-GO) and SPEEK with various sulfonated graphene oxide contents was prepared and investigated. The sulfonation of graphene oxide and PEEK induces an increase in the number of sulfonic groups (SO3H), which significantly increases the proton conductivity of sulfonated graphene oxide/SPEEK membrane. The introduction of sulfonated graphene oxide in membranes not only improved proton conductivity, but also positively affected the mechanical properties and the blocking of methanol and water molecules passing through the membrane. Consequently, incorporation of sulfonated graphene oxide into SPEEK membrane has considerably increased the selectivity of the membrane. Therefore, this sulfonated graphene oxide/SPEEK membrane is a good candidate for usage in direct methanol fuel cells.

Effects of Polymer Molecular Weight on the Interaction between Acid Dyes and Poly(vinylpyrrolidone) in Inkjet Ink for Textiles

The detailed understanding of the interaction between dyes and additives in the practical service condition is required to develop an inkjet ink for textiles. In the present study, the interaction between three acid dyes (C. I. Acid Red 88, 13, and 27) and a water-soluble polymer, poly(vinylpyrrolidone) (PVP), with different molecular weight was investigated. The binding constants of the dyes with PVP, Kbind, were determined by means of the visible absorption spectrum measurements. The Kbind values decreased with an increase in the number of sulfonate groups in the acid dyes (an increase in the solubility of the dyes in water). This suggests that the affinity to PVP decreases with increasing water solubility. Furthermore, the binding constants were diminished by increasing molecular weight of PVP. It is presumably due to the conformation change of PVP with molecular weight. For further discussion, the thermodynamic parameters for the binding, viz. the enthalpy change, ΔHbind, and the entropy change, ΔSbind, were determined from the temperature dependence of Kbind. The ΔHbind values for all the dyes were negative, showing that the binding processes are exothermic. The absolute values of ΔHbind decreased with the increase in the number of sulfonate groups in the dye molecules. On the other hand, the increase of PVP molecular weight made the thermodynamic process to be less enthalpic and more entropic. Thus, the nature of the interaction should be affected by PVP molecular weight, because the polymer conformation is strongly influenced by the molecular weight.

Interactions between Dyes and Surfactants in Inkjet Ink Used for Textiles

Optimal preparation of inkjet ink should be possible through the elucidation of the relationship between dye/additive interactions and ink performance. In the present study, the interactions between the dyes and surfactant additives were investigated. To investigate the physical properties of the surfactants used, the critical micelle concentration (cmc) and the aggregation number (N) were determined using electron spin resonance, static light-scattering, and fluorescence spectroscopy. On the basis of the cmc and N values, the visible absorption spectra of aqueous acid dye solutions (C. I. Acid Red 88, 13, and 27) containing surfactants (i.e., Surfynol 465 (S465), octaethylene glycol monododecyl ether (OGDE), and sodium dodecyl sulfate (SDS)) were measured. From the dependence of the spectra on the surfactant concentration, the binding constants, K(bind), of the acid dyes with the surfactant micelles were calculated: the K(bind) values decreased in the order of C. I. Acid Red 88 > C. I. Acid Red 13 > C. I. Acid Red 27, which correlates with the number of sulfonate groups. For all the dyes, the K(bind) values with the nonionic surfactants, S465 and OGDE, were much larger than those with the anionic surfactant, SDS. The thermodynamic parameters of the binding, i.e., the enthalpy change, ΔH(bind), and entropy change, ΔS(bind), were determined via the temperature dependence of the binding constants. The positive ΔH(bind) value for S465 indicates an endothermic binding process, while the negative ΔH(bind) values for SDS and OGDE indicate exothermic binding processes.

Proton-conducting electrolytes based on silylated and sulfonated polyetheretherketone: Synthesis and characterization

A derivative of polyetheretherketone (PEEK) having sulfonic acid groups and silicon-containing substituents covalently bound to the aromatic backbone has been prepared as proton-exchange membrane material. The polymer 4 (PhSiSPEEK) has been synthesized via (i) sulfonation of PEEK up to 0.9 degree of sulfonation (DS, the number of sulfonic groups per repeat unit), (ii) conversion of sulfonated PEEK 1 (SPEEK09) into sulfonyl chlorinated derivative 2 (PEEKSO2Cl), (iii) lithiation of 2 and subsequent addition of PhSiCl3, followed by hydrolysis. The chemical structure of the synthesized polymers has been investigated by 1H NMR and 13C NMR and ATR/FTIR spectroscopy and their thermal stability has been evaluated by thermogravimetric analysis. The presence of inorganic moieties increases the thermal stability of 4 with respect to the sulfonated and not silylated product. Despite its very high DS, PhSiSPEEK is insoluble in water but does not possess the plastic properties needed to be used as an electrolyte membrane. Blend membranes made of SPEEK05 (DS = 0.5) and containing 10 and 25 wt % of 4 (DS = 0.9, degree of silylation DSi = 0.1) have been prepared and characterized by water uptake measurements and electrochemical impedance spectroscopy. The combination of the two functionalized polymers having different properties allows to obtain proton-conducting electrolytes that are potential candidates for fuel cells applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2178–2186, 2010

Influence from the sulfonate group ( [formula omitted]) on the conversion process and emission efficiency of poly( p-phenylene vinylene)

The discovery of an alternative route to convert poly(xylyliden tetrahydrothiophenium chloride) (PTHT) into poly( p-phenylene vinylene) (PPV) using dodecylbenzenesulfonate (DBS) has allowed the formation of ultrathin films with unprecedented control of architecture and emission properties. In this work, we show that this route may be performed with several sufonated compounds where RSO 3 − replaces the counter-ion (C1 −) of PTHT, some of which are even more efficient than DBS. Spin-coating films were produced from PTHT and azo-dye molecules, an azo-polymer and organic salts as counter-ions of PTHT. The effects of the thermal annealing step of PTHT / RSO 3 − films at 110 and 230 °C were monitored by measuring the absorption and emission spectra. The results indicate that the exchange of the counter-ion Cl − of PTHT by a linear long chain with RSO 3 − group is a general procedure to obtain PPV polymer at lower conversion temperature (ca. 110 °C) with significant increase in the emission efficiency, regardless of the chemical position and the number of sulfonate groups. With the enhanced emission caused by Congo Red and Tinopal as counter-ions, it is demonstrated that the new synthetic route is entirely generic, which may allow accurate control of conversion and emission properties.

The interaction between multi-charged organic salts and poly(vinylpyridine) microgel particles

The interaction between negatively charged organic salts, with one two and three sulfonate groups respectively, and positively charged poly(2-vinylpyridine) microgel particles has been investigated. Absorption isotherms are used to describe the uptake of organic salt into the microgel network and the particle size and electrophoretic mobility of the dispersions have been discussed in terms of the electrostatic attraction between the organic salts and microgel network. The results suggest that all organic salts interact weakly with the microgel particles, and there is a tendency towards more noticeable changes in the microgel dispersion properties at lower concentration as the number of sulfonate groups within the organic salts increases.

Analytical complexation reactions of organic reagents with metal ions in a solidified gelatin gel

Solidified gelatin gel is an original medium for analytical complexation reactions between organic reagents and element ions. The chemical nature of this biopolymer enables the electrostatic immobilization of organic reagents bearing anionic groups, like Arsenazo III, by protonated amino groups of the macromolecule. It was shown that the exhaustive capacity of the matrix towards organic sulfonate reagents differing in the number of sulfonic groups and the geometrical size of molecules was related to the specific properties of matrices and the fractal properties of the gel surface. It was found that the conditions for the reactions of complex formation and decomposition of the reagents immobilized in the gel were identical to those for reactions in aqueous solutions. It was proved that the gel fixed on a transparent triacetylcellulose support could be used as a component of sensing elements of optical sensors and/or test systems. This was demonstrated by the examples of the determination of La(III), Th(IV), U(VI), Ca(II), and SO42−.

Single- and Dual-Component Biosorption of Reactive Black 5 and Reactive Orange 16 onto Polysulfone-Immobilized Esterified Corynebacterium glutamicum

The ability of polysulfone-immobilized esterified Corynebacterium glutamicum (PIEC) to biosorb two reactive dyes [Reactive Black 5 (RB5) and Reactive Orange 16 (RO16)] from single- and dual-dye solutions has been investigated. Single-dye biosorption isotherm experiments revealed that PIEC performed well in the biosorption of RO16, with a higher experimental uptake of 248.1 mg/g, compared to 174.1 mg/g for RB5. Conversely, the uptake of RO16 was suppressed almost 2.5 times in the presence of RB5, whereas PIEC maintained similar RB5 uptakes in both single- and dual-dye systems. Several factors might be responsible for this effect, the most important being the number of sulfonate groups and the size of each reactive dye. An attempt to achieve the continuous biosorption of reactive dyes from single- and dual-dye solutions using an upflow packed column was successful, with PIEC being regenerated and reused for three cycles.

Molecular Modeling of Proton Transport in the Short-Side-Chain Perfluorosulfonic Acid Ionomer

An explanation for the superior proton conductivity of low equivalent weight (EW) short-side-chain (SSC) perfluorosulfonic acid membranes is pursued through the determination of hydrated morphology and hydronium ion diffusion coefficients using classical molecular dynamics (MD) simulations. A unique force field set for the SSC ionomer was derived from torsion profiles determined from ab initio electronic structure calculations of an oligomeric fragment consisting of two side chains. MD simulations were performed on a system consisting of a single macromolecule of the polymer (EW of 580) with the general formula F3C-[CF(OCF2CF2SO3H)-(CF2)7]40-CF3 at hydration levels corresponding to 3, 6, and 13 water molecules per sulfonic acid group. Examination of the hydrated morphology indicates the formation of hydrogen bond "bridges" between distant sulfonate groups without significant bending of the polytetrafluoroethylene backbone. Pair correlation functions of the system identify the presence of ion cages consisting of hydronium ions hydrogen-bonded to three sulfonate groups at the lowest water content. Such structures exhibit very low S-OH3+ separations, well below 4 A and severely inhibit vehicular diffusion of the protons. The number of sulfonate groups in the first solvation shell of a given hydronium ion correlates well with the differences between Nafion and the SSC polymer (Hyflon). The calculated hydronium ion diffusion coefficients of 2.84 x 10-7, 1.36 x 10-6, and 3.47 x 10-6 cm2/s for water contents of 3, 6, and 13, respectively, show only good agreement to experimentally measured values at the lowest water content, underscoring the increasing contribution of proton shuttling or hopping at the higher hydration levels. At the highest water content, the vehicular diffusion accounts for only about 1/5 of the total proton transport similar to that observed in Nafion.

Light-induced effects in sulfonated aluminum phthalocyanines — potential photosensitizers in the photodynamic therapy: Spectroscopic and kinetic study

Sodium salts of sulfonated hydroxyaluminum phthalocyanines [Al(OH)Pc(SO 3Na) i ] containing various numbers of sulfonate groups ( i = 1–4), were studied by spectroscopic techniques. The lifetimes of the singlet states were found to range between 5 and 8 ns, experimentally determined fluorescence quantum yields ranging between 0.45 and 0.74. Both parameters depend on the number of sulfonate groups, the singlet lifetime depending additionally on concentration. The triplet lifetime was indirectly estimated for aqueous solutions of Al(OH)Pc(SO 3Na) 3 to amount to ca. 0.6 μs. The decay time of singlet oxygen in the same system was also found to be close to 0.6 μs. The molecules were found to dimerize in acidic and neutral solutions, the second order rate constants of the dimerization being of the order of 10 mol −1 dm 3 s −1, and the equilibrium constants of the order of 10 4. The experiments were supplemented with quantum chemical calculations allowing us to assign electronic transitions in monomers and dimers.

Competition of Reactive red 4, Reactive orange 16 and Basic blue 3 during biosorption of Reactive blue 4 by polysulfone-immobilized Corynebacterium glutamicum

Competition of Reactive red 4 (RR4), Reactive orange 16 (RO16) and Basic blue 3 (BB3) during biosorption of Reactive blue 4 (RB4) by polysulfone-immobilized protonated Corynebacterium glutamicum (PIPC) was investigated in batch and column mode of operations. Through potentiometric titrations, and with the aid of proton-binding model, carboxyl, phosphonate and amine were identified as functional groups of PIPC, with apparent p K a values of 3.47 ± 0.05, 7.08 ± 0.07 and 9.90 ± 0.05 mmol/g, respectively. Since reactive dyes release dye anions (ROSO 3 −) in solutions, the positively charged amine groups were responsible for biosorption. PIPC favored biosorption at pH 3 when RB4 was studied/used as single-solute; while the presence of RR4 and RO16 severely affected the RB4 biosorption. When present as a single-solute, PIPC recorded 184.5 mg RB4/g; while PIPC exhibited 126.9, 120.9 and 169.6 mg RB4/g in the presence of RR4, RO16 and BB3, respectively. In general, the accessibility of amine group depends on the molecular size, number of sulfonate groups and reactivity of each reactive dye. Single and multicomponent Freundlich equations successfully described the biosorption isotherms. With 0.1 M NaOH, it is possible to reuse PIPC for RB4 biosorption in 10 repeated cycles. Column experiments in an up-flow packed column coincided with batch results, that is PIPC showed strong preference towards highly reactive and relatively small RB4 anions; however, the presence of competing dyes hinder the RB4 column biosorption performance.

Effect of Fluoride Anions on Gramicidin Photoinactivation Sensitized by Sulfonated Aluminum Phthalocyanines¶

Interaction of potent photodynamic agents, sulfonated aluminum phthalocyanines (AlPcSn where n is a number of sulfonic groups), with biological membranes was studied here using model systems: sensitized photoinactivation of gramicidin channels in planar lipid bilayers and adsorption on lipid monolayers. Fluoride anions known to form complexes with aluminum were found to inhibit both the adsorption of aluminum phthalocyanines on lipid monolayers, as measured with a Langmuir trough by surface pressure and surface potential changes, and photodynamic efficacy of the dyes, as studied by gramicidin channel photoinactivation. The similar effects were caused by the alkalinization of the medium. Fluoride anions appeared to be much more effective in the case of AlPcS4 as compared to AlPcS3. The suppression of the photodynamic potency of aluminum phthalocyanines was attributed to desorption of the dyes from lipid bilayers induced by fluoride or hydroxyl ions. With AlPcS4 an enhancement of the dye aggregation leading to a decrease in the sensitizing activity was probably involved in the fluoride effect as revealed by absorption and fluorescence spectral measurements. Capillary electrophoresis was employed to understand the mechanism of the dye desorption. The results of these experiments indicated that the reduction in the membrane affinity was associated with an increase in the negative charge of the dye molecules due to the binding of fluoride or hydroxyl ions.