Spectrophotometric investigations and computational calculations of prototropic tautomerism and acid-base properties of some new azo dyes

The prototropic tautomerism in four novel azo compounds derived from pyrazolo[1,5-a]pyrimidin-7(4H)-one was intensively examined. Tautomeric structures which result from annular and azo-hydrazone tautomerism were exposed to semiempirical and density functional theory (DFT) calculations, allowing the recording of structural parameters, physicochemical properties and equilibrium constants to be recorded. The values of the equilibrium constants determined among the most stable forms clearly showed that compounds 1 and 2 co-exist in the NH and hydrazone forms. However, NH tautomers were strongly preferred to other forms in compounds 3 and 4. The observed electronic absorption bands were assigned and compared with the predicted transitions using a time-dependent DFT method (TDDFT). In all solvents employed, except for DMF and acetonitrile, compounds 1 and 2 exhibited azo-hydrazone tautomerism. However, the ionized species were predominant in highly polar solvents for compounds 3 and 4. In DMF, all the investigated dyes exist either in acid-base equilibrium or in the ionized form depending on the molecular structure. Hence, the values of the ionization constant (K_ion) and Gibbs free energy (ΔG) of the equilibrium existing in solution were calculated. In addition, the pK_a values of the investigated dyes were determined spectrophotometrically.     

The synthesis, characterization, thermal and optical properties of copper, nickel, and vanadyl complexes derived from azo dyes

Two, novel, tetradentate Schiff-base ligands, namely bis-5-phenylazosalicylaldehyde diethylenetriimine and bis-5-[(4-methoxyphenyl)azo]salicylaldehyde diethylenetriimine, as well as their Cu²⁺, Ni²⁺, and VO²⁺ complexes, were synthesized and characterized using elemental analysis, infrared and also UV–Visible spectroscopy, ¹HNMR and mass spectra. The thermal stability of the free ligands and the related metal complexes, as determined using differential scanning calorimetry and thermal gravimetric analysis, were found to be thermally stable upto 240–275 °C depending on the type of ligand and the central metal atom. The λ_max of the ligands and their transition metal complexes in the region 300–800 nm are discussed. The novel metal complexes offer potential for application as recording media owing to both their absorption spectra in the blue-violet light region and high thermal stability.     

Nanoparticles of organosilane-based nitrite ionic liquid immobilized on silica for the diazotization of aniline derivatives and subsequent synthesis of azo dyes

Imidazolium based nitrite ionic liquid containing trimethoxysilyl group was prepared from the reaction of N-methylimidazole and (3-chloropropyl) trimethoxysilane. This ionic liquid was immobilized on silica covalently to give nanoparticles with the imidazolium nitrite moiety remaining intact. The diazotization reaction was performed as a model reaction to examine the activity of these nanoparticles as a nitrosonium source. Excellent performance was exhibited in the diazotization reaction of various aniline derivatives in the presence of HCl under mild heterogeneous conditions (room temperature and short reaction time). In-situ coupling of diazonium salts to a range of tertiary anilines, phenols and naphthols afforded the requisite azo dyes in good yield, using standard experimental procedures.     

The effect of perspiration on photo-induced chemical reaction of azo dyes and the determination of aromatic amine products

In order to investigate the impact of perspiration on photo-induced chemical reaction of azo dyes and the carcinogenic aromatic amine products produced from the reaction, we have carried out experimental studies on the photochemical reaction of C.I. Reactive Red 2 mixed with American Association of Textile Chemists and Colorists（AATCC）standard artificial perspiration. UV-vis spectroscopic technique was employed to monitor the reaction processes, and the reaction products were analyzed by hollow fiber protected liquid-liquid-liquid phase micro-extraction with capillary electrophoresis（HF-LLLME-CE). The results showed that perspiration had remarkable influence on the photochemical reaction of azo dyes. Aromtic amines formed during the photochemical process as a result of reduction of azo dyes by organic components in perspiration. The HF-LLLME-CE methodology was validated in analyzing aromatic amines produced from the photochemical degradation of azo dye C.I. Reactive Red 2 and C.I. Acid Red 35 mixed with artificial perspiration.     

Synthesis and properties of novel aziridinyl azo dyes from 2-aminothiophenes—Part 1: Synthesis and spectral properties

A series of yellow to greenish-blue aziridinyl azo dyes and their azo precursors containing a thienyl coupling moiety has been prepared from 2-aminothiophenes. The 2-aminothiophenes were readily obtained by using the Gewald reaction. It was found that cyclisation of the precursor dyes to the corresponding aziridinoazo dyes brought about bathochromic shifts in absorption maxima. Further spectral comparisons with N-phenylazo dyes derived from other terminal cyclic groups, such as four-, five-, six-, seven- and eight-membered rings, showed that the N-thienylaziridinoazo dyes are relatively bathochromic. From the viewpoint of solvatochromism, a clear contrast existed between λ_max values in different solvents; thus, a positive solvatochromism was observed in aprotic solvents, whereas a hypsochromic shift was brought about in polar protic solvents. PPP–MO calculations provided reliable predictions of absorption maxima for the various aziridinyl azo dyes and their precursor dyes.     

Comparisons between azo dyes and Schiff bases having the same benzothiazole/phenol skeleton: Syntheses, crystal structures and spectroscopic properties

Three pairs of heterocyclic azo dyes and their corresponding Schiff bases were prepared by diazotization and Schiff-base condensation reactions between substituted 2-aminobenzothiazoles and either 3-(diethylamino)phenol or 3,5-dichloro-2-hydroxybenzaldehyde in order to obtain some high performance Disperse Red dyes and compare the structural and spectral differences between the azo dyes and Schiff bases. All azo dyes and Schiff bases in this work have the same benzothiazole/phenol skeleton but different substituent group in the phenyl ring. X-ray single-crystal diffraction analyses of selected compounds reveal that they have a similar planar conformation between the benzothiazole and phenol units but dissimilar dimeric crystal packing. Electronic spectra of the dyes demonstrate that the presence of NN and CN double bond chromophore units as well as substituent effects of different auxochrome groups in the benzothiazole backbone leads to significant alterations of bathochromic and hypsochromic shifts despite only slight differences in their molecular structures.     

The adsorption of sulphonated azo‐dyes methyl orange and xylenol orange by coagulation on hollow chitosan microsphere

Chitosan (CS) can be used as adsorbent in the treatment of effluents from the textile industry, especially for negatively charged dyes, due to its cationic polyelectrolyte nature. In this work, the adsorption of a model dye, methyl orange, xylenol orange on hollow CS microsphere is analyzed. Adsorption of methyl orange, xylenol orange onto cross‐linked CS is realized by means of analysis of pH influence, agitation time, and initial concentration of the dye. The results obtained from the experiment shows that the adsorption capacities of the two dye‐hollow CS microsphere systems are higher than those stated in other literature using CS particles. The difference in the degree of adsorption may also be attributed to the size and chemical structure of the dye molecule. The results have demonstrated that monovalent and smaller dye molecular sizes have superior capacities due to the increase in dye/CS surface ratio in the system and deeper penetration of dye molecules into the internal pore structure of hollow CS microsphere. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A new nitrite ionic liquid (IL-ONO) as a nitrosonium source for the efficient diazotization of aniline derivatives and in-situ synthesis of azo dyes

A new task-specific nitrite containing ionic liquid derived from the O-nitrosation of N-methyl-N-hydroxybutylimidazolinium chloride was synthesized and used as a source of nitrosonium ion to affect the efficient diazotization of arylamines. The diazonium salts thus obtained were coupled, using standard experimental procedures, to a range of tertiary anilines, phenols and naphthols to afford the requisite azo dyes in good yield. The diazotization and subsequent azo-coupling generated the related azo dyes at 0-5 °C in short reaction times with a simple experimental procedure.     

Synthesis and properties of novel aziridinyl azo dyes from 2-aminothiophenes—Part 2: Application of some disperse dyes to polyester fibres

A series of yellow to greenish-blue aziridinyl azo dyes and their azo precursors containing a thienyl coupling moiety has been applied to conventional polyester fibre as well as microdenier polyester by high temperature exhaust dyeing. Heat transferability of these dyes onto polyester fibre has also been examined, using conventional heat-transfer printing techniques. The relevant dyeing characteristics, heat transferability, build-up, dyeability on microfibre polyester, washfastness and lightfastness are given. These aziridinyl dyes are reactive to polyester fibres under HT dyeing conditions. Fabrics dyed with aziridinyl dyes are more resistant to solvent extraction than those dyed with conventional dyes. Residual liquors showed only a pale colour when fabric dyed with aziridinyl dyes was dissolved and then precipitated, whereas a coloured polyester precipitate was obtained.     

Zinc‐Catalyzed Tandem Diels–Alder Reactions of Enynals with Alkenes: Generation and Trapping of Cyclic o‐Quinodimethanes (o‐QDMs)

A systematic investigation of ZnCl₂‐catalyzed reactions of enynals with alkenes has been undertaken. Structurally unique propeller‐like products could be obtained under mild conditions. Cyclic o‐quinodimethanes (o‐QDMs) are generated through [4+2] cycloaddition between enynals and alkenes. Both electron‐poor and electron‐rich dienophiles could be used to trap the active intermediate through [4+2] cycloaddition. But [1,5]‐H shift products could also be observed when electron‐rich alkenes were used as dienophile. DFT calculations were performed to understand the reaction mechanism. A competition between the [4+2] cycloaddition and [1,5]‐H shift was proposed for the transformation of cyclic o‐QDMs. The selectivity could be affected by the properties of the substrates.

     

Density functional theory study of the electrochemical oligomerization of thiophene: transition states for radical–radical and radical–neutral pathways

Accurate density-functional-theory (DFT) calculations on oligothiophenes containing up to 6 units have been performed in order to understand the various possible mechanisms of growth. There are two possible mechanisms for this process which involve the coupling of cationic radicals with either another cationic radical or with a neutral oligomer. Most of the electronic properties of these oligomers are well understood, but there is very little known about the nature of the intermediates and the transition states leading to polymerization. The initial oxidation, forming stable intermediates, releasing protons and/or further oxidations are studied in terms of the energetics, changes in the geometry, charge distributions and possible signatures in the vibrational spectra. The radical–radical pathway is found to be the more probable one between two mechanisms. Also the attack of monomers/or shorter oligomers on the longer ones is found to be faster than the coupling of equal size chains.     

Removal of reactive blue 19 and reactive blue 49 textile dyes by citrus waste biomass from aqueous solution: Equilibrium and kinetic study

The purpose of this study was to establish the potential of inexpensive and locally available biomaterial, that is, lignocellulosic waste of Citrus sinensis as biosorbent to remove reactive anthraquinone dyes from aqueous solution. The effects of immobilisation and chemical treatment of biosorbent were also explored for the enhanced sorption of dyes. Biosorbent was chemically treated with organic and inorganic reagents of which acetic acid augmented the sorption capacities for Reactive blue 19 and Reactive blue 49 attaining equilibrium in 60 min. While immobilisation of biosorbent into calcium alginate beads reduced the sorption capacity and the time to achieve equilibrium was prolonged up to 120 min. Sorption of both reactive dyes was found to be dependent on pH of media and maximum removal was observed at pH 2. The sorption process was fast and the data followed pseudo‐second‐order kinetic rate equation (R² = 0.99). The equilibrium data were also fitted to Freundlich, Langmuir and Temkin isotherms. The mechanism of sorption was found to be physiosorption. FTIR analysis and SEM imaging of biosorbent were also carried out to study functional groups involved and morphological changes at the surface of biomass. © 2011 Canadian Society for Chemical Engineering     

Degradation of azo dye by three clean advanced oxidation processes: Wet oxidation, electrochemical oxidation and wet electrochemical oxidation—A comparative study

This work compared the degradation behaviors of an azo dye, cationic red X-GRL, by three clean advanced oxidation processes: wet oxidation (WO), electrochemical oxidation (EO) and wet electrochemical oxidation (WEO). It was found that the WO process was readily to remove color while the EO process was prone to decompose pollutants. Integrated with the advantage of two processes, the WEO process posed synergetic effects for both efficient removal of color and COD. Even at the low temperature of 120 °C, the color could be almost completely removed at 60 min, and the COD removal was about 43.2% at 120 min, which was greatly protomted from that by WO at similar conditions (about 7.8%). And it demonstrated a better performance under a reduced temperature and a wider dye concentration range, representing the most promising alternative for environmental application among the three processes. The main degradation products for three processes were detected and a simplified five-stages degradation pathway was suggested, which indicated that the WEO process mineralized much more completely than the other two processes.     

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.     

Experimental and first‐principles study of Ti–C–O system: Interplay of thermodynamic and structural properties

The thermodynamic properties and vacancy formation mechanism of Ti–C–O system were investigated by means of empirical calorimetry method and first‐principles calculations. The heat of combustion of titanium oxycarbides (TiC_1?xO_x, 0≤x≤1) solid solution were first measured by burning the materials in oxygen bomb calorimeter through sophisticated design experimental environment. The mixing enthalpy of the reaction (1?x)TiC + xTiO=TiC_1?xO_x was further calculated based on the measured data. Mixing enthalpy was also calculated via efficient first‐principles method based on the density functional theory. The vacancies in TiC_1?xO_x were described as two kinds of models that are disordered and segregated vacancies in titanium oxycarbides solid solution. The calculation results with segregation model show good agreement with the calorimetric results. The heat capacity values were further calculated to deduce the mixing and formation Gibbs free energy. The additive law of the heat capacity and entropy means that the structure of titanium oxycarbides tends to be in order, and this result shows a good agreement with the segregated model in TiC_1?xO_x. These results are explained on the basis of the interplay between thermodynamic and structural properties, which offered the important theoretic foundation for the novel titanium production process.     

The role of hydrogen-bond in solubilizing drugs by ionic liquids: A molecular dynamics and density functional theory study

The solvation mechanisms of aspirin and etomidate in four combinations of [Emim]⁺ and [BuGun]⁺ paired with [OAc]⁻ and [NTf₂]⁻ were systematically studied by molecular dynamics simulations and DFT calculations. It was shown that the favorable solvation of aspirin and etomidate correlated well with hydrogen-bond (H-bond) basicity of anions and the H-bond acidity of cations, respectively. Wherein, the H-bond between aspirin and [OAc]⁻ anion with high H-bond basicity possessed covalent feature, so ILs containing [OAc]⁻ anion has the best effective in solubilizing aspirin. However, H-bond interactions between etomidate and cations exhibited an electrostatic dominant, and moderate cation–anion interaction could weaken it. Accordingly, for etomidate, the best ILs solvent comprised a weakly interacting anion and a cation with strong H-bond acidity, that is, [BuGun][NTf₂]. This solvation difference was because aspirin with carboxyl group displayed strongly H-bond donating characteristic, whereas etomidate with no active hydrogen protons mainly formed H-bond with cations. Additionally, we found that π–π stacking interactions were of secondary importance for the solubilization of etomidate, but little for aspirin. These simulations will be helpful for experimental design new ILs to solubilize some drugs with aspirin-like or etomidate-like structures.     

Halogen adsorption on crystallographic (1 1 1) planes of Pt, Pd, Cu and Au, and on Pd-monolayer catalyst surfaces: First-principles study

Halogen (Cl, Br and I) adsorption on crystallographic (1 1 1) planes of Pd, Pt, Cu, Au and on palladium monolayer catalysts surfaces was investigated by DFT calculations. Palladium monolayer catalyst here denotes either the Pd monolayer deposited over (1 1 1) crystallographic plane of Pt, Cu and Au monocrystals (Pd_ML/Me(1 1 1)), or the (1 1 1) crystallographic plane of Pd monocrystal with inserted one-atom thick surface underlayer of Pt, Cu and Au (Me_UND/Pd(1 1 1)). The adsorption on the 3-fold sites was found to be the strongest, and adsorption energies decreased if the size of the halogen atoms increased. For the case of Pd-monolayer catalysts it was demonstrated that energy of adsorption of halogen atoms could be correlated to the position of the d-band of surface atoms. Charge states of halogen adatoms and work function changes were evaluated. On the basis of calculated data and both experimental and theoretical data available in the literature, the changes in the catalytic activity toward oxygen reduction reaction of the Pd_ML/Pt(1 1 1) surface, caused by chloride adsorption, were discussed.     

Preparation and properties of styrene–butadiene rubber based nanocomposites: The influence of the structural and processing parameters

Rubber‐based nanocomposites were prepared with octadecyl amine modified sodium montmorillonite clay and styrene–butadiene rubber with different styrene contents (15, 23, and 40%). The solvent used to prepare the nanocomposites, the cure conditions, and the cure system were also varied to determine their effect on the properties of the nanocomposites. All the composites were characterized with X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM). The XRD studies revealed exfoliation for the modified clay–rubber composites. The TEM photomicrographs showed a uniform distribution of the modified clay in the rubber matrix. The thickness of the particles in the exfoliated composites was around 10–15 nm. Although the FTIR study of the unmodified and modified clays showed extra peaks due to the intercalation of the amine chains into the gallery, the spectra for the rubber–clay nanocomposites were almost the same because of the presence of a very small amount of clay in the rubber matrix. All the modified clay–rubber nanocomposites displayed improved mechanical strength. The styrene content of the rubber had a pronounced effect on the properties of the nanocomposites. With increasing styrene content, the improvement in the properties was greater. Dicumyl peroxide and sulfur cure systems displayed similar strength, but higher elongation and slightly lower modulus values were obtained with the sulfur cure system. The curing of the samples at four different durations at 160°C showed that the cure time affected the properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 698–709, 2004     

Electronic and structural properties of SnxTi1−xO2 solid solutions: a periodic DFT study

The structural and electronic properties of selected compositions of Sn_xTi_1−xO₂ solid solutions (x=0, 1/24, 1/16, 1/12, 1/8, 1/6, 1/4, 1/2, 3/4, 5/6, 7/8, 11/12, 15/16, 23/24 and 1) were investigated by means of periodic density functional theory (DFT) calculations at B3LYP level. The calculations show that the corresponding lattice parameters vary non-linearly with composition, supporting positive deviations from Vegard’s law in the Sn_xTi_1−xO₂ system. Our results also account for the fact that chemical decomposition in Sn_xTi_1−xO₂ system is dominated by composition fluctuations along [0 0 1] direction. A nearly continuous evolution of the direct band gap and the Fermi level with the growing value of x is predicted. Ti 3d states dominate the lower portion of the conduction band of Sn_xTi_1−xO₂ solid solutions. Sn substitution for Ti in TiO₂ increases the oxidation–reduction potential of the oxide as well as it renders the lowest energy transition to be indirect. These two effects can be the key factors controlling the rate for the photogenerated electron–hole recombination. These theoretical results are capable to explain the enhancement of photoactivity in Sn_xTi_1−xO₂ solid solutions.