Effect of water constituents on the degradation of sulfaclozine in the three systems: UV/TiO2, UV/K2S2O8, and UV/TiO2/K2S2O8.

Bicarbonate, phosphate, chloride ions, and humic substances are among the constituents most widely present in natural waters. These non-target constituents can greatly affect the efficiency of advanced oxidation processes used for water decontamination due to their capacity to interfere with the adsorption of the target compounds on the surface of TiO2, absorb photons, scavenge hydroxyl radicals (·OH), and generate photochemical reactive intermediates. In this work, the effect of these constituents on the degradation of sulfaclozine (SCL) was monitored in three different AOPs systems: UV/TiO2, UV/K2S2O8, and UV/TiO2/K2S2O8. It was shown that bicarbonate (HCO3-) and phosphate (HPO42-) ions enhanced the degradation of SCL in UV/TiO2 and UV/TiO2/K2S2O8 systems whereas the addition of humic substances influenced these rates with a much smaller extent. On the other hand, the degradation rate of SCL in the UV/K2S2O8 system was not affected by the presence of HCO3- and HPO42- but was inhibited in the presence of humic substances. In addition, the different mechanisms that can take place in the presence of these constituents were discussed and the degradation rate enhancement in presence of HCO3- and HPO42- was attributed to the formation of new reactive species such as carbonate (CO3·-) and hydroxyl (·OH) radicals activated by TiO2 holes (h+). In the presence of chloride (Cl-) and nitrate (NO3-) ions, an enhancement of SCL adsorption on the surface of TiO2 was observed. Finally, a comparative study of the degradation of SCL in river water and ultrapure water was reported.

Ag loaded WO3 nanoplates for efficient photocatalytic degradation of sulfanilamide and their bactericidal effect under visible light irradiation.

Sulfonamides (SAs) are extensively used antibiotics and their residues in the water bodies propose potential threat to the public. In this study, degradation efficiency of sulfanilamide (SAM), which is the precursor of SAs, using WO3 nanoplates and their Ag heterogeneous as photocatalysts was investigated. WO3 nanoplates with uniform size were synthesized by a facile one step hydrothermal method. Different amount of Ag nanoparticles (Ag NPs) were loaded onto WO3 nanoplates using a photo-reduction method to generate WO3/Ag composites. The physio-chemical properties of synthesized nanomaterials were systematically characterized. Photodegradation of SAM by WO3 and WO3/Ag composites was conducted under visible light irradiation. The results show that WO3/Ag composites performed much better than pure WO3 where the highest removal rate was 96.2% in 5h. Ag as excellent antibacterial agent also endows certain antibacterial efficiency to WO3, and 100% removal efficiency against Escherichia Coli and Bacillus subtilis could be achieved in 2h under visible light irradiation for all three WO3/Ag composites synthesized. The improved performance in terms of SAM degradation and antibacterial activity of WO3/Ag can be attributed to the improved electron-hole pair separation rate where Ag NPs act as effective electron trapper during the photocatalytic process.

Conformational landscape, photochemistry, and infrared spectra of sulfanilamide.

A combined matrix isolation FTIR and theoretical DFT(B3LYP)/6-311++G(3df,3pd) study of sulfanilamide (SA) was performed. The full conformational search on the potential energy surface of the compound allowed the identification of four different minima, all of them bearing the sulfamide nitrogen atom placed in the perpendicular orientation relatively to the aromatic ring and differing from each other in the orientation of the hydrogen atoms connected to the two nitrogen atoms of the molecule. All conformers were predicted to be significantly populated in the gas phase (at 100 °C, their relative populations were estimated as being 1:0.9:0.3:0.2). However, in agreement with the theoretically calculated low-energy barriers for conformational isomerization, in the low-temperature matrices, only the most stable conformer could be observed, with the remaining forms being converted into this form during matrix deposition (conformational cooling). The unimolecular photochemistry of matrix-isolated SA (in both argon and xenon) was also investigated. Upon broadband UV irradiation (λ > 215 nm), two photofragmentation pathways were observed: the prevalent pathway (A), leading to extrusion of sulfur dioxide and simultaneous formation of benzene-1,4-diamine, which then converts to 2,5-cyclohexadiene-1,4-diimine, and the minor pathway (B), conducting an γ-cleavage plus [1,3] H-atom migration from the sulfamide group to the aromatic ring, which leads to formation of iminosulfane dioxide and aniline, the latter undergoing subsequent phototransformation into cyclohexa-2,5-dien-1-imine. Finally, the crystalline polymorph of SA resulting from warming (265 K) the amorphous solid obtained from fast cooling of the vapor of the compound onto the cold (13 K) substrate of the cryostat was identified spectroscopically, and found to be the γ-crystalline phase, the one exhibiting in average longer H-bonds and an infrared spectrum resembling more that of the low temperature SA glass. Full assignment of the infrared spectra of this crystalline variety as well as of those of the ß-polymorph room temperature crystalline sample and low temperature amorphous state was undertaken with help of theoretical results obtained for the crystallographically relevant dimer of SA.

Determination of sulphathiazole and sulphanilamide by photochemically induced fluorescence and first-derivative fluorescence.

This manuscript reports the usefulness of the determination of sulphathiazole (ST) using photochemically induced fluorescence (RTPF) and RTPF coupling with first derivative (D1-RTPF), and the determination of sulphanilamide (SAN) by meaning first derivative of the emission spectrum. By irradiating 5 min, with intense UV radiation, sulphathiazole, in ethanol:water 20:80 (v/v) solutions at pH 4.5-5.0, show fluorescence emission at 342 nm (lambdaex=251 nm). Under these conditions, a linear relation, fluorescence intensity-ST concentration, was found between 0.23 and 3.00 microg mL(-1) of ST. The method was applied for determining ST in a pharmaceutical drug. ST was also determined in honey by using the D1-RTPF signal, applying the standard addition method, and measuring at 324.8 nm. Under the same experimental conditions of pH and solvent, a fluorimetric method for determining SAN in presence of ST is proposed. Calibration graphs for SAN determination were established using the amplitude of the first derivative of the emission spectrum measured at 324.4 nm, as the analytical signal. This method has been applied to determining SAN in a pharmaceutical formulation.

Triplet-sensitized photodegradation of sulfa drugs containing six-membered heterocyclic groups: identification of an SO2 extrusion photoproduct.

The aquatic photochemical behavior of a class of sulfa drugs containing six-membered heterocyclic substituents (sulfamethazine, sulfamerazine, sulfadiazine, sulfachloropyridazine, and sulfadimethoxine) was investigated. Photodegradation of the sulfa drugs in a natural water sample was significantly enhanced relative to the degradation in deionized water, with the exception of sulfadimethoxine. This indicated an indirect photochemical process that was identified through the use of quenchers to be attributable to interaction with triplet excited-state dissolved organic matter (3DOM). The direct photolysis rate constant and quantum yield for both the neutral and anionic species of each sulfa drug were calculated using matrix deconvolution methods. The quantum yield values range from 0.01 x 10(-3) for the neutral form of sulfadimethoxine to 5 x 10(-3) for the anionic form of sulfamethazine and are significantly lower than those observed in a previous study for sulfa drugs containing five-membered heterocyclic substituents, although the rate constants are of similar magnitude. The primary product formed in both direct and indirect photodegradation for all five compounds was identified as a sulfur dioxide extrusion product. The predicted environmental half-lives solely attributable to direct photolysis range from 8.6 h in midsummer at 30 degrees latitude in pH 7 surface water for sulfachloropyridazine to 420 h in midwinter at 45 degrees in pH 7 surface water for sulfadimethoxine. These half-lives, except for sulfadimethoxine, will be decreased by interaction with 3DOM.

Photochemical fate of sulfa drugs in the aquatic environment: sulfa drugs containing five-membered heterocyclic groups.

The photochemical fate of five sulfa drugs with varying five-membered heterocyclic substituents (sulfamethoxazole, sulfisoxazole, sulfamethizole, sulfathiazole, and sulfamoxole) was investigated in aqueous solution. The rate of direct photolysis of these compounds is dependent upon the identity of the heterocyclic R group as well as the pH of the solution. Matrix deconvolution methods were employed to determine the absorption spectrum and photolysis rate of each protonation state (cationic, neutral, and anionic). From these data, quantum yields for direct photodegradation were calculated for each protonation state of the sulfa drugs. The quantum yields calculated range from <0.005 for the neutral state of sulfamethizole to 0.7 +/- 0.3 for the protonated state of sulfisoxazole. The protonation state that is most photoreactive varies among the sulfa drugs and cannot be attributed to the rate of photon absorption. Products arising from the direct photolysis of the sulfa drugs were also investigated. For all the compounds, sulfanilic acid was observed as a common product. The singlet oxygen quenching rates of the sulfa drugs were determined by laser flash photolysis and range from (2 +/- 1) x 10(4) M(-1) s(-1) for sulfamethoxazole to (3.0 +/- 0.7) x 10(8) M(-1) s(-1) for sulfamoxole. Reaction of the sulfa drugs with hydroxyl radical is not modulated by the R group, and the rate constants are all near the bimolecular diffusion-controlled limit of 10(10) M(-1) s(-1). The photodegradation of the sulfa drugs in natural water samples of Lake Josephine (St. Paul, MN) and Lake Superior was attributed solely to direct photolysis. This study indicates thatthese similarly structured antibiotics will be subject to a wide range of photodegradation rates with sulfathiazole degrading relatively quickly, sulfisoxazole and sulfamethizole degrading moderately, and sulfamethoxazole degrading much more slowly.

Investigation of structural and dynamic features of the radicals produced in gamma irradiated sulfanilamide: an ESR study.

Characteristic features of the radiolytical intermediates produced in gamma irradiated solid sulfanilamide (SA) were investigated in the present work using ESR spectroscopy. SO(2), which is the most sensitive group to radiation of SA molecule, was found to be at the origin of radiation produced ionic radical species. The latters give rise to an axially symmetric and an isotropic ESR spectra so that their sum appears as a three line antisymmetric ESR spectrum. Heights of these lines measured with respect to the base line were used to monitor microwave, temperature, time-dependent and kinetic features of the radical species contributing to ESR spectrum. Based on the experimental results derived from this study, it was concluded that as in the case of other solid sulfonamides radiation, yield of solid SA is very low (G=0.5) compared with those obtained for sulfonamide aqueous solutions (G=3.5-5.1), so that SA and SA-containing drugs could be safely sterilized by radiation.

The effect of antioxidants on the photolysis of aqueous sulfacetamide and sulfanilamide solutions.

Aqueous sulfacetamide and sulfanilamide solutions were photolyzed at pH 1-13 and in the presence of various antioxidants and a chelating agent (pH 7.0). The rate constants for the photodegradation of sulfacetamide and sulfanilamide were determined. Sodium metabisulfite and thiourea were the best antioxidants for the photostabilization of sulfacetamide and sulfanilamide solutions respectively. Sodium edetate is also an effective stabilizer in sulfacetamide solutions. The efficiency of the antioxidants on the basis of product distribution and the kinetic results is discussed.