Affinity of Direct Dyes for Cellulose Film

A fast spectrophotometric method of assessing the affinity of different substances for surfaces is proposed. The effect of the dyeing temperature and concentration of the dye bath components (electrolyte and dye) on the value of the affinity of direct dyes for cellulose fibres was investigated. The optimum values of the temperature and concentrations of dye and electrolyte with respect to the affinity of the dye for the fibre were found. A series of experiments to investigate the effect of enzymes and surfactant additives on the affinity of the dye for the fibre was conducted and the insignificant effect of these components on the dyeing process was demonstrated.__________Translated from Khimicheskie Volokna, No. 2, pp. 10–12, March–April, 2005.     

Simultaneous sorption and diffusion of a 4-aminoazobenzene derivative and its conjugate acid in cellulose membrane carrying sulfonic acid groups

An azo dye, 2-methyl-N,N-bis(2-hydroxyethyl)-4-aminoazobenzene (nonionic dye) and its conjugate acid (cationic dye) are simultaneously adsorbed by the cellulose membranes carrying sulfonic acid groups from a slightly acidic aqueous solution. Sorption equilibria of the nonionic and the cationic dye are described in terms of the Henry's partition and the ionic exchange mechanism, respectively, in the latter case, the ion exchange constants obtained for the membrane with sulfonic acid group content (SAG) = 261 meq/kg at 30°C are K = 1.43 × 10^?5 and K = 0.542, respectively, where Na, H, and DH refer to sodium, hydrogen, and cationic dye ions. The diffusion coefficients of the nonionic dye (D_N) and the cationic dye (D_C) in the membranes were estimated from the permeation data of the dyes through the membrane. Both D_N and D_C decrease with increasing SAG. The ratio D_N/D_C ranged in 2.2–10, the ratio increases with the SAG.     

Copolyester studies. VII. The dyeing behavior of undrawn fibers derived from tetramethylene terephthalate: Poly(tetramethylene oxide) random block copolymers

A series of copolymers based on poly(tetramethylene terephthalate) containing poly(tetramethylene oxide) blocks whose molecular weights ranged from 1000 to 5000 in concentrations from 10 to 30% by weight was prepared. The polymers were melt spun into fibers and the undrawn fibers dyed with a disperse dye at three temperatures. The equibrium adsorption and diffusion coefficient of the dye increased with both the molecular weight and concentration of the polyether. The equilibrium adsorption varied linearly with both the molecular weight and concentration. It has been assumed that the equilibrium dye partition coefficient K_M gives a parameter of the accessibility, V, of the fiber for dye. If the diffusion coefficient D_M is given by D_M = VD_o/τ, where D_o is the diffusion coefficient of the dye in the amorphous regions and τ is a tortuosity factor, a good correlation can be obtained between K_M and D_M, suggesting that changes in D_o/τ vary in a systematic fashion.     

Molecular Mechanisms of Disperse Dyeing of Polyester and Nylon Fibres

The kinetics of the dyeing of polyester fibres with disperse dyes have previously been discussed in terms of a model in which the only forces of interaction between dye and polymer are those that give rise to mutual solubility. The rate and extent of dyeing depend on the size and shape of the dye molecules and the detailed structure of the fibre. The concentration profiles of dye within single filaments of polyesters and nylons have now been determined by a new method termed ‘optical sectioning’, in which an image of a filament is scanned by a narrow slit. The dye distributions are found by comparing experimental transmission values with those calculated by a computer for a model system in which various parameters can be adjusted. For the polyester-dye systems the rate constant of transfer of dye from dyebath to fibre (k₁) was the same as the rate constant of diffusion away from the interface (k₂). Some nylon-dye systems, on the other hand, behaved as if k₂ = k₁, whereas others behaved initially as if k₁ = k₂ but later as if k₂ > k₁. Apparent diffusion coefficients were also derived from sorption measurements and were found to fall as the dye concentration in the fibre increased. Measurement of the orientation of the dye molecules by optical dichroism showed that the dye molecules entering the filaments late in the dyeing process were more highly orientated than the earlier ones. The decrease in diffusion coefficient has been interpreted in terms of the observed higher orientation, as resulting from a greater entropy of activation in the diffusion process.     

Diffusion and solubility of some azo dyes in swollen gelatin matrices: The effects of dye size,matrix swell,and dye–matrix interactions

The diffusion coefficient (D) and the solubility coefficient (K) of three sulfonated azo dyes were measured in swollen gelatin membranes at pH 12 by two techniques (time lag and desorption rate), with good agreement between the two. A strong correlation was established between log D and the reciprocal of the free volume of the matrix. Hence, as free volume of the matrix increased (due to increasing solvent imbibition), dye mobility increased. As dye size increased, however, mobility decreased. Dye affinity for gelatin, as measured in dilute solutions by dynamic dialysis, was small and could be related to the dye solubility in more concentrated gelatin matrices. Increasing ionic strength or decreasing alcohol content increased K without affecting the dye mobility. On the other hand, the presence of polymers with strong affinity for the dye anions, e.g., polyvinylpyrrolidone, immobilized a large fraction of the dye ions and greatly slowed the overall dye transport.     

Disperse dyeing of polyester fibers: Kinetic and equilibrium study

The effect of temperature on the dyeing rate constant k, diffusion coefficient D, and time of half‐dyeing t_1/2 was evaluated for the dyeing of polyester fibers with two disperse dyes, an azo and an anthraquinone dye. Activation energies of diffusion E were calculated. The polyester dyeing equilibrium was also studied and the partition coefficient K and standard affinity Δμ° at various temperatures were determined for the anthraquinone dye. Standard enthalpy ΔH° and standard entropy ΔS° of dyeing were also obtained. The same equilibrium parameters were not obtained for the azo dye because of its dyeing behavior. A similar kinetic and equilibrium study was made for the pure azo and anthraquinone compounds free from the dispersing agents present in the commercial dyes and the results are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 123–128, 2002     

The roles of polymer relaxation phenomena,aqueous dye solubility and the physical properties of water in the mechanism of adsorption of a disperse dye on poly(ethylene terephthalate) fibres: part 5 analysis of polymer relaxation phenomena for different polymers

The temperature dependent uptake of a commercial disperse dye on cotton and polyamide 66 fabrics at dyeing temperatures between 30°C and 130°C adhered to the Williams–Landel–Ferry equation, insofar as, very good correspondence was observed between plots of experimentally determined colour strength data points (log1/f_k) and the respective structural relaxation times of the cellulose and nylon 66 polymers (loga_T data points), as a function of the parameter (T − T_g). Adsorption of the dye on both types of fibre therefore concurs with the fundamental precept of the free volume model of dye diffusion. Comparison of the adherence of the uptake of the commercial dye on cotton and polyamide 66 fabrics with that secured on polyester fabric revealed that despite the major chemical and physical differences between the three types of fibre, the same dyeing mechanism likely applies to each fibre type. The marked temperature dependent uptake of the commercial grade disperse dye each of the three types of substrate is the consequence of two, different, but inherently interconnected, thermally activated phenomena, namely the relaxation times of the molecular rearrangements occurring within the respective cellulose, nylon 66 or poly(ethylene terephthalate) macromolecule, in which polymer glass transition assumes the principal role, and the aqueous solubility of the commercial grade disperse dye.     

Diffusion of dyes in polyester fibers. II. Diffusion coefficients from the radial distribution curves

The computational method of a concentration-dependent diffusion coefficient D(C) of dyes in fibers has been presented. This method is based on concentration profiles determined with the microphotometric technique and the numerical solution of Fick's second law of diffusion for the cylindrical system. Exploiting the grid method and data of experimental concentration profiles, diffusion coefficients of disperse dye Synthene Scarlet P3GL in the anionically modified polyester fiber have been calculated. The results have been compared with those obtained by the Boltzmann–Matano method. It was stated that (1) in the investigated polymer–dye system the relation between D and C is of the form D(C) = D₀ exp(δC); (2) the allowance for the cylindrical symmetry of the fiber leads to the lower values D(C) in the total concentration range than those obtained by the Boltzmann–Matano method; and (3) values of D₀ calculated with both methods are coincident.     

Disperse dyeing of polyester fibers: Kinetic and equilibrium study

The effect of temperature on the dyeing rate constant k, diffusion coefficient D, time of half‐dyeing t_1/2 was evaluated for the dyeing of polyester fibers with two disperse dyes, an azo and an anthraquinone dye. Activation energies of diffusion E were calculated. The polyester dyeing equilibrium was also studied and the partition coefficient K and standard affinity Δμ° at various temperatures were determined for the anthraquinone dye. Standard enthalpy ΔH° and standard entropy ΔS° of dyeing were also obtained. The same equilibrium parameters were not obtained for the azo dye because of its dyeing behavior. A similar kinetic and equilibrium study was made for the pure azo and anthraquinone compounds free from the dispersing agents present in the commercial dyes and the results are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2785–2790, 2002; DOI 10.1002/app.10254     

Diffusion of dyes in polyester fibers. IV. Anomalous sorption of disperse dye synthene scarlet P3GL

The investigations on dyeing of poly(ethylene terephthalate) fibers with disperse dye Synthene Scarlet P3GL have revealed anomalous sorption of the dye in heat-treated samples. In the mathematical solution of the process it has been assumed that anomalous sorption can be treated as superposition in time of two stages of Fickian sorption. The contents of absorbed dye at quasiequilibrium C_I, at the final equilibrium C_II, and the apparent diffusion coefficients D_I, and D_II have been calculated using Hill's equation.     

Structure‐Based Virtual Screening for Dopamine D2 Receptor Ligands as Potential Antipsychotics

Structure‐based virtual screening using a D₂ receptor homology model was performed to identify dopamine D₂ receptor ligands as potential antipsychotics. From screening a library of 6.5 million compounds, 21 were selected and were subjected to experimental validation. From these 21 compounds tested, ten D₂ ligands were identified (47.6 % success rate, among them D₂ receptor antagonists, as expected) that have additional affinity for other receptors tested, in particular 5‐HT_2A receptors. The affinity (K_i values) of the compounds ranged from 58 nm to about 24 μm . Similarity and fragment analysis indicated a significant degree of structural novelty among the identified compounds. We found one D₂ receptor antagonist that did not have a protonatable nitrogen atom, which is a key structural element of the classical D₂ pharmacophore model necessary for interaction with the conserved Asp(3.32) residue. This compound exhibited greater than 20‐fold binding selectivity for the D₂ receptor over the D₃ receptor. We provide additional evidence that the amide hydrogen atom of this compound forms a hydrogen bond with Asp(3.32), as determined by tests of its derivatives that cannot maintain this interaction.     

Encapsulation of disperse dye by phase separation technique using poly(styrene‐maleic acid)

C.I. disperse dye blue 60 was encapsulated by poly(styrene‐maleic acid) using phase separation technique, followed by the preparation of the encapsulated disperse dye dispersion. The effects of process conditions on particle size of the dispersion were investigated. The results showed that the particle size of the encapsulated disperse dye dispersion was small, and the stability was excellent when mass ratio of poly(styrene‐maleic acid) to disperse dye (R_p/d), dropping speed of phase separation agent (D_s), disperse dye content in dispersion (C_d), and dispersing time (D_t) were about 20%, 7 mL/min, 5–7.5%, and 1.5 h, respectively. Transmission electron microscope (TEM), zeta potentials, and contact angle indicated that C.I. disperse dye blue 60 was successfully encapsulated by poly(styrene‐maleic acid). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

MS Binding Assays for D1 and D5 Dopamine Receptors

MS Binding Assays are a label‐free alternative to radioligand binding assays. They provide basically the same capabilities as the latter, but an unlabeled reporter ligand is used instead of a radioligand. The study presented herein describes the development of MS Binding Assays that address D₁ and D₅ dopamine receptors. A highly sensitive, rapid and robust LC–ESI‐MS/MS quantification method for the selective D₁ dopamine receptor antagonist SCH23390 ((5R)‐8‐chloro‐3‐methyl‐5‐phenyl‐1,2,4,5‐tetrahydro‐3‐benzazepin‐7‐ol) was established and validated, using its 8‐bromo analogue SKF83566 as an internal standard. This quantification method proved to be suitable for the characterization of SCH23390 binding to human D₁ and D₅ receptors. Following the concept of MS Binding Assays, saturation experiments for D₁ and D₅ receptors were performed, as well as competition experiments for D₁ receptors. The results obtained are in good agreement with results from radioligand binding assays and therefore indicate that the established MS Binding Assays addressing D₁ and D₅ receptors are well‐suited substitutes for radioligand binding assays, the technique that has so far dominated affinity determinations toward these targets.     

Studies on dyeing and structural behavior of chemically treated polyester yarns

The dyeing behavior of poly(ethylene terephthalate) based flat, high twist, and spun yarns pretreated with trichloroacetic acid–methylene chloride (TCAMC) reagent was studied. Disperse dyes having two different energy levels were employed for the dyeing work. The effect of time, temperature, and dye diffusion transition temperature (T_D) on dye uptake was analyzed. A considerable increase in equilibrium dye uptake and decrease in T_D of all the treated yarns were observed. The variation in dye diffusion behavior of higher and lower molecular weight dyes and the difficulties encountered in calculating the diffusion coefficient of the dyes are discussed. The structural and morphological changes effected by the pretreatment were also investigated using XRD and SEM, respectively. The increase in lateral order of the treated yarns was noted. The possible reason for an unusual relationship between the increase in lateral order and increase in dye uptake was explained. The cross-sectional shape and swelling and the smoothening out of the fiber surface were evidence by SEM. © 1996 John Wiley & Sons, Inc.     

Adsorption isotherm of a disperse dye

An absorption isotherm equation similar in form to Langmuir’s equation was obtained for monomolecular adsorption of a dye on the inner surface of a fibre for the process of dissolution of a dye in amorphous regions of a fibre using the assumptions concerning formation of dye—macromolecule fragment solvates in the ratio of 1:1. Linearity of the function 1/C_F = f(1/C_S) is possible both in adsorption of the dye with formation of a monomolecular layer (Langmuir) and in dissolution of the dye in the amorphous part of the fibre-forming polymer with formation of solvates. __________ Translated from Khimicheskie Volokna, No. 2, pp. 61–63, March–April, 2006.     

Dichroism of poly(ethylene terephthalate)-disperse dye system

As an approach to the basic study on the orientation behavior of amorphous region, the dichroic orientation factor, D, of poly(ethylene terephthalate), PET, fiber or film dyed with disperse dyes was investigated in relation to Δn, birefringence of the crystalline and amorphous regions, and Δn_a, birefringence of the amorphous region. It was found that D versus Δn plot belonged to a linear relationship passing through the origin but breaking slightly toward the D axis at Δn ? 0.14, while D versus Δn_a plot was expressed by a straight line passing similarly through the origin but with no break. D₀, the value of D at the ideal parallel orientation, was obtained by extrapolating the latter plot of the samples stretched with no relaxation: 1.00 and 0.73 for the PET–C.I. Disperse Yellow 7 and PET–C.I. Disperse Red 17 systems respectively. When the sample had been relaxed, the D versus Δn_a was also linear; however, D₀'s obtained were smaller than the above mentioned respective values. Even in these cases D for Disperse Yellow 7 versus the corresponding D for Disperse Red 17 belonged to a linear relationship with the slop 1:0.73. As the result it was concluded that the transition moment of molecule of C.I. Disperse Yellow 7 coincided with the molecular axis and the dye molecule combined parallel to PET chain, while as to C.I. Disperse Red 17 any definite conclusion could not be determined. However, in the both cases the mode of combination of dye molecules with PET is definite and kept unchanged during stretching and heating.     

Synthesis of magnetic nanocomposite microparticles for binding of chlorinated organics in contaminated water sources

In this work, the development of novel magnetic nanocomposite microparticles (MNMs) via free radical polymerization for their application in the remediation of contaminated water is presented. Acrylated plant-based polyphenols, curcumin multiacrylate (CMA) and quercetin multiacrylate (QMA), were incorporated as functional monomers to create high affinity binding sites for the capture of polychlorinated biphenyls (PCBs), as a model pollutant. The MNMs were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, dynamic light scattering, and UV–visible spectroscopy. The affinity of these novel materials for PCB 126 was evaluated and fitted to the nonlinear Langmuir model to determine binding affinities (K_D). The results suggest the presence of the polyphenolic moieties enhances the binding affinity for PCB 126, with K_D values comparable to that of antibodies. This demonstrates that these nanocomposite materials have promising potential as environmental remediation adsorbents for harmful contaminants.     

Influence of ultrasound on diffusion through skin/leather matrix

Leather is a unique porous material, which is composed of a three-dimensional weave of tanned collagen fibre bundles. Collagen is a fibrous protein well organized in the formation of skin as building block. This paper studies the use of ultrasound in improving the diffusion process through porous skin/leather matrix. A diffusion model for leather processing has been proposed taking into account of pore characteristics in leather. Dye diffusion experiments have been carried out with leather and powdered leather to show the influence of ultrasound under two different diffusion conditions. Apparent diffusion coefficient (D) of dye through leather matrix has been calculated from the experimental dye uptake data. The results indicate that the use of ultrasound could achieve, 16.2 and 8.56 times improvement in D value for leather at 50 °C and 30 °C, respectively as compared to 2.99 and 1.55 times for powdered leather. Scanning electron microscopy (SEM) analysis of leather has also been performed which shows that fibre structure and morphology are not affected by the use of ultrasound. This study throws some light on enhanced transport through porous materials of complex nature such as skin/leather using ultrasound.     

Studies on sublimation of disperse dye out of dyed polymers. I. Rate of sublimation and amorphous transition points of poly(ethylene terephthalate)

Four samples of poly(ethylene terephthalate) film of various crystallinities and orientation were dyed with p-nitroaniline and disperse dyes. When these films were heated under a 2–3 × 10^?3 mm Hg vacuum at a specified temperature T, the dye sublimed out of the dyed specimen. The amount (M_t/M_∞) of sublimed dye is in linear proportion to the square root of the sublimation time, t^½, where M_t and M_∞ are the amounts of dye sublimed for times t and t = ∞. The diffusion coefficient D, calculated from the slope of the above plot, is independent of the dye concentration of the film. When log D is plotted against 1/T°K over the temperature range 320–520°K, the relation is composed of two to four intersecting lines with the slope decreasing with elevation of temperature and with the breaks at about 89°–98°, 122°–135°, 155° and 175°–176°C. These breaks are the amorphous transitions: the first is the glass transition temperature T_g, the second and the fourth are the amorphous transitions corresponding to the crystalline transition points, i.e., the cold crystallization temperature and the smectic–triclinic transition temperature. With some exceptions, these amorphous transitions are found also by dilatometry and electrical conductivity measurements. The apparent activation energy for diffusion decreases from about 100 kcal/mole for the glass state to 22–24 kcal/mole for the region above 180°C. The activation energy for each region changes slightly with the size of dye molecule and the crystallinity and orientation of the film.