Number Of Sulfonic Groups Research Articles

Dye-resist properties of hetero-multifunctional dye-resist agents in acid dyeing of wool

The dye-resist effect and leveling properties of hetero-mulifunctional dye-resist agents in acid dyeing of wool were investigated. The dye-resist agent with dichlorotriazinyl group achieved better resist effectiveness than those with monochlorotriazinyl group. The resist effectiveness was improved by increasing the number of sulfonate group in dye-resist agents. Also, the resist agents with more sulfonate groups showed better dye-assist effectivness, attributable to the increased electrostatic attraction between dye-resist agents and the cationic dye. However, the leveling properties of dye-resist agents decreased with the number of sulfonate groups in the molecule.

Preparation of nanosilver particles into sulfonated poly(ether ether ketone) (S-PEEK) nanostructures by electrospinning

By using the interaction between the sulfonated groups and silver ions, nanosilver particles were successfully introduced into S-PEEK nanostructures (nanospheres and nanofibers) by electrospinning. The nanoparticles were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectra (XPS), UV/vis, etc. The size of the spheres increases with the weight concentration of silver exchanged sulfonated poly(ether ether ketone) (S-PEEK-Ag) increasing. The size of the silver particles can be controlled by adjusting the sulfonated degree (number of sulfonate groups per repeating unit) of sulfonated poly(ether ether ketone) (S-PEEK) and the weight ratio of the S-PEEK solutions. This paper provides a new method for the preparation of nanometal particles into nanostructures.

Adsorption and desorption properties of cationic polyethylene film gels to organic anions and their regeneration

AbstractAn investigation was undertaken on the adsorption and desorption properties of 2‐(dimethylamino)ethyl methacrylate grafted polyethylene (PE‐g‐PDMAEMA) films to anionic dye anions with one to three sulfonic groups in response to pH and temperature changes. The amounts of dye anions adsorbed on the PE‐g‐PDMAEMA films passed through the maximum values at about pH 3 because of an increase in the protonation of dimethylamino groups caused by a decrease in the pH value. The amounts of adsorbed dye anions decreased below pH 3 because the ionic strength increased with the addition of HCl to adjust the initial pH values of the aqueous dye solutions. The amounts of adsorbed dye anions decreased with an increase in the number of sulfonic groups in the dye molecules at the same pH value because electrostatic repulsion was generated between free sulfonic groups of the dye anions adsorbed onto the PE‐g‐PDMAEMA films and free dye anions in the medium. A large number of dye anions adsorbed were desorbed from the PE‐g‐PDMAEMA film with initial pH values above 11.0. The cyclic processes of adsorption at pH 3.0 and desorption at pH 11.0 were repeated without considerable fatigue. The PE‐g‐PDMAEMA films showed practically regenerative adsorption and desorption behavior in response to the pH changes. In addition, when the dye‐anion‐adsorbed PE‐g‐PDMAEMA films were alternately immersed in water at two different temperatures, dye anions were desorbed in water at higher temperatures without any chemical agents because of the deprotonation of dimethylamino groups and thermosensitive contraction of grafted PDMAEMA chains. These results indicate that PE‐g‐PDMAEMA films can be applied as regenerative ion‐exchange membranes for adsorption and desorption processes of anionic compounds in response to the pH and temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 381–391, 2006

On metallic characteristics in some conducting polymers

Polyaniline (PANI) exhibits a dc conductivity σ ≈ 10 −1 S/cm when it is doped with poly(styrenesulfonic acid) (PSSA) such that the number of sulfonate groups per two-ring PANI unit ( y) is 2. On increasing the dopant amount to y = 12, σ drops to 10 −5 S/cm. The EPR-derived magnetic susceptibility of these two conducting polymers gives nearly the same density of states at the Fermi level N( E F) ≈ 0.65 ± 0.05 states/eV 2-rings. The corresponding electronic specific heat coefficient as calculated from this N( E F) value does not appear to be inconsistent with the results from low temperature calorimetric measurements. Similarly, with y′ defined as the number of sulfonate groups per three-ring PEDOT unit, PSSA-doping of poly(ethylenedioxythiophene) (PEDOT) yields different σ ≈ 10 −1 and 10 −5 S/cm at y′ = 5.7 and 45.9, respectively, but the same N( E F) ≈ 0.55 ± 0.05 states/eV 3-rings. These observations suggest that the additional dopants, which help with dispersion in processing conducting polymers, do not alter the metallic domains but are located in the disordered regions surrounding them. The N( E F) values also remain practically the same between p-toluenesulfonic acid (PTSA) doped PANI and its dispersed blend in poly(methylmethacrylate) (PMMA), as well as for PEDOT–PTSA before and after its being subjected to an additional dispersion step.

Direct copolymerization of sulfonated poly(phthalazinone arylene ether)s for proton-exchange-membrane materials

Sulfonated poly(phthalazinone ether ketone) (SPPEK) copolymers and sulfonated poly(phthalazinone ether sulfone) (SPPES) copolymers containing pendant sodium sulfonate groups were prepared by direct copolymerization. The reaction of disodium 3,3′-disulfonate-4,4′-difluorobenzophenone (SDFB-Na), 4,4′-difluorobenzophenone (DFB), and 4-(4-hydroxyphenyl)-1(2H)-phthalazinone (DHPZ) at 170 °C in N-methyl-2-pyrrolidione containing anhydrous potassium carbonate gave SPPEKs. SPPESs were similarly obtained with 3,3′-disulfonate-4,4′-difluorophenyl sulfone, 4-fluorophenyl sulfone (DFS), and DHPZ as monomers. The sulfonic acid groups, being on deactivated positions of the polymer backbone, were expected to be hydrolytically more stable than postsulfonated polymers. Fourier transform infrared and 1H NMR were used to characterize the structures and degrees of sulfonation of the sulfonated polymers. Membrane films of SPPEKs with SDFB-Na/DFB molar feed ratios of up to 60/40 and SPPESs with sulfonated 4-fluorophenyl sulfone/DFS molar feed ratios of up to 50/50 were cast from N,N-dimethylacetamide polymer solutions. Membrane films in acid form were then obtained by the treatment of the sodium-form membrane films in 2 N sulfuric acid at room temperature. An increase in the number of sulfonate groups in the copolymers resulted in an increased glass-transition temperature and enhanced membrane hydrophilicity. The sodium-form copolymers were thermally more stable than their acid forms. The proton conductivities of the acid-form copolymers with sulfonated monomer/unsulfonated monomer molar feed ratios of 0.5 and 0.6 were higher than 10−2 S/cm and increased with temperature; they were less temperature-dependent than those of the postsulfonated products. SPPESH-50 showed higher conductivity than the corresponding postsulfonated poly(phthalazinone ether sulfone). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2731–2742, 2003

Polyelectrolyte complexes. V. Solid-state properties of some polycation/azo dye complexes controlled by the dye structure

The solid-state properties of some polycation/azo dye complexes according to the dye structure were studied in this work. One polycation contained about 95 mol % N,N-dimethyl-2-hydroxypropyleneammonium chloride units in the backbone (PCA5), and eight azo dyes, different in either the number of sulfonic groups or their distribution, were used as opposite components. The selected azo dyes were as Crystal Scarlet, Congo Red, Crocein Scarlet MOO, Ponceau SS, Amaranth, Ponceau S, Direct Blue 1, and Direct Red 80. Information on the compensation degree of the oppositely charges was obtained by the elemental analysis of the solid-state polycation/dye complexes (the experimental contents of chlorine, nitrogen, and sulfur were compared with the calculated values). Differential scanning calorimetry was employed to probe the strength of the intermolecular interactions in the PCA5/dye complexes. Wide-angle X-ray diffraction was used to assess the supramolecular order of the solid-state complexes. The physical properties of the PCA5/azo dye complexes (the complex stoichiometry, glass-transition temperature, decomposition temperature, and degree of supramolecular order) were influenced mainly by the dye structure but also by the polycation concentration and the presence of NaCl. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 264–272, 2003

Application of ‘waste’ metal hydroxide sludge for adsorption of azo reactive dyes

The capacity and mechanism of metal hydroxide sludge in removing azo reactive dyes from aqueous solution was investigated with different parameters, such as charge amount of dyes, system pH, adsorbent particle size, and adsorbent dosage. The three anionic dyes used were CI Reactive Red 2, CI Reactive Red 120, and CI Reactive Red 141, increasing in number of sulfonic groups, respectively. Only 0.2% (w/v) of powdered sludge (<75 μm) achieved color removal from 30 mg l −1 reactive dye solutions within 5 min without pH adjustment. The larger the charge amount of the dyes, the greater the adsorption (>90%) on the metal hydroxide sludge. The system pH played a significant role in the adsorption on metal hydroxides and formation of dye–metal complexes. The optimum system pH for dye adsorption was 8–9 which was close to the pH zpc of the sludge while the precipitation of dye–metal complexes occurred at system pH 2. The maximum adsorption capacity ( Q°) of the sludge for the reactive dyes was 48–62 mg dye g −1 adsorbent. The Langmuir and Freundlich models showed that the higher charged dyes had a higher affinity of adsorption. The smaller particle size and the greater amount of adsorbent showed the faster process, due to an increase in surface area of adsorbent. Desorption studies elucidated that metal hydroxide sludge had a tendency for ion exchange adsorption of sulfonated azo reactive dyes. Leaching data showed that the treated water was nontoxic at a system pH above 5 or a solution pH above 2.

Surface modification by self-assembled polycation/azo dye multilayers

The formation and stability of some polycation/azo dye multilayers by the alternate adsorption of one polycation of integral type having 95 mol% of N,N-dimethyl-2-hydroxypropyleneammonium chloride repeat units (PCA5) and four multicharged azo dyes: Crocein Scralet MOO (CSMOO), Ponceau SS (PSS), Direct Blue 1 (DB 1) and Direct Red 80 (DR 80) are discussed in this paper. The dyes were different either by the number of sulfonic groups (PSS, DB 1 and DR 80) or by their position (CSMOO and PSS). The multilayer growth, when PCA5 was adsorbed from 0.2 M Na2SO4 aqueous solution, was followed by UV-Vis spectroscopy and by electrokinetic measurements. Solid state polycation/azo dye complexes were also prepared to get qualitative information on the charge compensation in the multilayers.

Degradation of naphthalenesulfonic acids by oxidation with ozone in aqueous phase

Sulfonic aromatic compounds are widely used in the textile industry for the synthesis of azo dyes. The presence of the sulfonic group endows these compounds with high water-solubility and resistance to biological treatment. The present work analysed the efficacy of oxidation with ozone in the treatment of waters containing naphthalene-1-sulfonic acid, naphthalene-1,5-disulfonic acid and naphthalene-1,3,6-trisulfonic acid. The reactivity to ozone significantly decreased with an increase in the number of sulfonic groups in the aromatic ring, and naphthalene-1,3,6-trisulfonic acid showed the lowest reaction rate. The stoichiometry of the direct ozonization reaction was around one mole of sulfonic acid per mole of ozone in all cases. The activation energy value of the direct ozonization reaction was very similar in all studied cases (37–42 kJ mol−1). The contribution of the direct reaction to the global oxidation at pH 2 was observed to decrease with more sulfonic groups in the aromatic ring, from a contribution of 69% for naphthalene-1-sulfonic acid to around 20% for naphthalene-1,3,6-trisulfonic acid. The radical reaction rate constant was found to be of the order of 109×M−1 s−1 in all cases, although it showed a slight reduction as the number of sulfonic groups in the aromatic ring increased. A follow-up study of the oxidation products of each sulfonic aromatic acid revealed the presence of highly oxidized organic acids and sulfate ions. A theoretical study of the electronic density at the bond critical point showed that double bonds with highest electron density in the three acids are in positions 1–2, 3–4, 5–6 and 7–8. These bonds are initially attacked by ozone via 1,3-dipolar cycloaddition.

Chelation with metal is not essential for antitumor photodynamic activity of sulfonated phthalocyanines.

It is generally assumed that a central metal is essential for the efficiency of phthalocyanines in photodynamic therapy (PDT) of cancer. Contrary to the set opinion, the results of the present study indicate that the metal-free sulfonated phthalocyanines (H2PcSn, where n is the number of sulfonate groups per molecule) possess a considerable photoactivity. The relative phototoxicities of H2PcS1.5, H2PcS2.4, H2PcS3.1 and H2PcS3.8 on HEp2 human epidermoid carcinoma cells were 3.3, 20, 3.3 and 1, respectively, thus demonstrating dependence of the activity on the sulfonation degree, known for metallo-PcSn. A significant delay in tumor growth and a decrease in tumor regrowth rate were observed in mice after PDT with H2PcS2.4. The antitumor effect declined in the order H2PcS2.4 > H2PcS3.1 > H2PcS1.5 and vanished for H2PcS3.8. We demonstrate here that the high photodynamic activity of H2PcS2.4 can be explained by its physicochemical properties in living cells and tissues. Thus, H2PcSn (n is about 2) can be considered as a new alternative in PDT of light-accessible neoplasms and further clinic-oriented studies are warranted.

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.

Influence of substituent of direct dye having bisphenylenebis(azo) skeletal structure on structure of nascent cellulose produced by Acetobacter xylinum [I]: different influence of Direct Red 28, Blue 1 and 15 on nascent structure

The difference of influence of a certain kind of direct dye on the structure of nascent microbial cellulose was examined, with Direct Red 28 having a biphenylenebis(azo) skeletal structure; Direct Blue 1 having two hydroxyl, two methoxy and two sulfonate groups more than Direct Red 28; and Direct Blue 15 whose sulfonate groups position are different compared to Direct Blue 1. It became clear that the product in the presence of a direct dye (in particular, Direct Red 28) has the structure in which the dye molecule is included between the monolayer in the cellulose sheets corresponding to the (110) plane of microbial cellulose. On the other hand, the structure of the product in the presence of Direct Blue l and 15 contains conceived cellulose II structure which occurred due to be removal of dye during the rinsing process as a result of larger hydrophilicity than its affinity toward cellulose. Solid state 13C NMR and deuteration-IR measurements showed that the product in the presence of direct dye is in a noncrystalline state, although X-ray measurements indicated that they are in a crystalline state. These results support the inclusion of a dye between the (1TO) planes. Solid state 13C NMR and deuteration-IR reveal that the crystal structure of cellulose regenerated from the product in the presence of Direct Red 28 is similar to cellulose IV I, while that from each Direct Blue 1 and 15 product is cellulose II. The difference of the influence of the former and the latter on the nascent cellulose seemed to be caused mainly by the number of sulfonate groups, although the influence of hydroxyl and methoxy groups is not clear at present.

Electrokinetic Properties of Modified Polyester Fibers

Electrokinetic properties of easily dyed cationic dyeable polyester (ED-CDPET) fibers of different deniers and cationic dyeable polyester (CDPET) fibers containing varying numbers of sulfonic groups are examined when cationic dye solutions are streamed through their plugs. There is a decrease in the negative zeta potential with more sulfonic groups in the chemical composition of fibers. This may be attributed to enhanced adsorption of dye cations by the increased number of polar sulfonic groups on the fibers. Of the two fibers, ED-CDPET exhibits lower negative zeta potential compared to CDPET with identical sulfonic group content, which may be attributed to the im proved accessibility of the sulfonic groups to the dye cations. Maximum denier ED- CDPET shows the least negative zeta potential of the samples of various deniers studied. Heat setting (at 180°C, 90 seconds) lowers the negative zeta potential, which may be due to decreased surface area. Results in surface charge density and surface conductivity are also discussed.

Compatibility of acid dyes on nylon

The selection of trichromatic acid dyes with good compatibility for nylon is more complicated than that for cationic-dye/acrylic-fiber dyeing because the dyeing-temperature range in nylon dyeing is much wider than that in acrylic-fiber dyeing. Forty-six commercially available acid dyes have been divided into five groups according to their change in dyeing rate with dyeing temperature, i.e. activation energy. Discussion is made in terms of the molecular weight of the dye, the number of sulfonate groups in the dye, the change in saturation value with pH, and the change in the time of half-dyeing with dyeing temperature. Trichromatic combinations in each group are described.

CELLULAR UPTAKE AND RELATIVE EFFICIENCY IN CELL INACTIVATION BY PHOTO ACTIVATED SULFONATED meso‐TETRAPHENYLPORPHINES

The cellular uptake, relative fluorescence quantum yields and photosensitizing efficiencies of meso-tetraphenylporphines sulfonated to different degrees (TPPSn) have been investigated using the human carcinoma cell line NHIK 3025. The efficiencies of these dyes in photoinactivation of cells were highly dependent on the number of sulfonate groups on the derivatives. These differences in phototoxicity were primarily due to different abilities to be taken up by cells, but were also dependent upon the cellular localization of the dyes. TPPS1 and TPPS2a were more efficiently taken up by the cells than TPPS2o and TPPS4. Plasma membrane associated TPPS4 was less efficient in cell inactivation per quantum of fluorescence emitted than intracellularly located dye. This was also to some extent the case for TPPS1 but not for TPPS2a and TPPS2o. The results presented here indicate that TPPS2a and TPPS1 are the most promising of the TPPSns for possible future use in photodynamic therapy.

Biological activities of phthalocyanines--X. Syntheses and analyses of sulfonated phthalocyanines.

Abstract— Synthetic methods to obtain selectively sulfonated metallo phthalocyanines are compared. Both condensation and direct sulfonation procedures lead to mixtures of mono‐ to tetrasulfonated products which are resolved by reverse phase liquid chromatography in buffered aqueous‐methanol. The proportion of sulfonated derivatives is examined as a function of the starting reagents in the case of the condensation method, and as a function of the temperature and reaction time in the case of the direct sulfonation procedure. The number of sulfonate groups per phthalocyanine molecule is determined by oxidative degradation of the phthalocyanine ring followed by quantitative chromatographic analysis of the sulfophthalamide and phthalamide fragments.

The influence of molecular weight of acid dyes on the yield stress of dyed nylon monofilament

The yield stress of nylon filament dyed with several acid dyes has been determined as a function of dye content and the molecular weight of acid dyes. The nylon filament dyes with acid dye has greater yield stress than undyed one. The relation between the increment of the yield stress (f) due to the adsorption of acid dye and the dye content (C) in the filament can be expressed by parameters A and B as log f = A log(C − C) + B, where C0 is the dye content under which no contribution to the yield stress is observed and C0 depends on the number of sulfonic groups in acid dye. It is found that these parameters A and B are expressed by M (the difference between the molecular weight of acid dye and the weight of SO3Na groups in it) as A = 1 − 100/M, B = k1Mk2, where k1 and k2 are the constants which depend on the parent chemical structure of dyes. The parameters A and B are expected to give available informations as to the physical state of adsorbed dye on nylon filament.

Paper chromatography of some chelating reagents containing sulfonic groups in liquid-liquid anion exchange systems

Chromatographic behaviour of nine chelating reagents in chloride and perchlorate systems was investigated with two methods: paper extraction chromatography and moist paper technique. It was found that the affinity of the reagents to cellulose treated with liquid anion exchangers decrease in the following orders: Eriochrome cyanine R>Chromazurol S>Pyrocatechol violet, and Alizarin S>ferron>chromotropic acid ∼ nitroso-R-salt>sulfosalicylic acid>tiron. The results obtained suggest that the retention of reagents in extraction chromatography is caused not only by anion-exchange process but also by adsorption and probably also by partition phenomena. The number of alkylammonium cations forming extracted species with reagents depends on the number of sulfonic groups in the reagent molecule but in sulfosalicylic acid carboxylic group can also be partially bound.

Basic dyeability and acid content of high‐conversion polyacrylonitrile

AbstractPrevious data have shown that the basic dyeability of acrylic polymers increases at a given specific viscosity as the peroxydisulfate‐to‐bisulfite ratio, that is, the catalyst‐toactivator (C/A) ratio, is increased. This study represents an effort to understand better the role of the initiator system on the basic dyeability, the acid group composition, and the chain composition of acrylic polymers by preparing model polymers with radioactive initiators. As the C/A ratio is increased, the molecular weight distribution broadens as measured by the M̄v/M̄n ratio, the latter obtained by osmometry. There is also a significant effect of both C/A ratio and molecular weight on the sulfate group content per molecule, but there is no effect of C/A ratio on the number of basic dye sites per molecule, the number of sulfonate groups per molecule, or the weak acid groups per molecule. These effects can be explained by invoking a chain transfer to activator reaction in addition to the usual method of chain termination by recombination. The basic dyeability is found to correlate with the number‐average molecular weight and with the number of strong acid groups plus the nonchromophoric weak acid groups.

Preparation of polyacrylic dyes

AbstractPolyacrylic chloride was reacted with aminonaphthol sulfonic acid to give a polymeric intermediate, from which the corresponding dyestuff was prepared by coupling with an aromatic diazonium salt. The water‐solubility of the polymeric azo dye was found to depend mainly on the number of sulfonic groups in the molecular chain, and the colouring of dye was comparatively rich in variety. A copolymer of acrylic chloride with methyl methacrylate was directly reacted with a dyestuff containing amino groups to give a polymeric dye. In the molecular chain of those polymeric dyes, the functional structure of the dyestuff was kept by its incorporation to the acrylic polymer chain.