Efficient removal of sparfloxacin antibiotic from water using sulfonated graphene oxide: Kinetics, thermodynamics, and environmental implications.

Pharmaceutical contamination poses a significant threat to global health. Due to their high solubility in water, antibiotics are difficult to remove. This study produced and used sulfonated graphene oxide (SGO) to adsorb sparfloxacin from aquatic environments. UV-Visible, Fourier transform infrared (FTIR), X-ray diffraction (XRD), XPS, SEM, TEM, EDX, particle size, Thermogravimetric analysis (TGA), and acid-base titration were used to characterize synthesized SGO particles. The BET technique determined SGO's surface area (32.25 m2/g). The calculated pHPZC of SGO was 2.5. Sparfloxacin adsorption onto SGO was analyzed using adsorption duration, medium pH, adsorbent dosages, antibiotic concentration, cations, and solution temperature. The pseudo-second-order kinetic model better described experimental kinetic data than the pseudo-first-order and Elovich models. Equilibrium isotherm data supported the Langmuir model, revealing a peak absorption capacity of 1428.57 µmol/g at 25 °C. The kinetic and isotherm models' applicability was assessed using error analysis. A thermodynamic analysis revealed an endothermic, spontaneous adsorption process with a change in entropy (ΔS) of 114.15 J/mol K and enthalpy (ΔH) of 8.44 kJ/mol. A regeneration analysis showed that SGO adsorption efficiency topped 86.4 % after five cycles.

Kinetics, Equilibrium, and Thermodynamics for Conjugation of Chitosan with Insulin-Mimetic [meso-Tetrakis(4-sulfonatophenyl)porphyrinato]oxovanadate(IV)(4-) in an Aqueous Solution.

This study investigated the conjugation of chitosan with the insulin-mimetic [meso-tetrakis(4-sulfonatophenyl)porphyrinato]oxovanadate(IV)(4-), VO(tpps), in an aqueous medium as a function of conjugation time, VO(tpps) concentrations, and temperatures. To validate the synthesis of chitosan-VO(tpps) conjugate, UV-visible and Fourier transform infrared spectrophotometric techniques were utilized. Conjugate formation is ascribed to the electrostatic interaction between the NH3+ units of chitosan and the SO3- units of VO(tpps). Chitosan enhances the stability of VO(tpps) in an aqueous medium (pH 2.5). VO(tpps) conjugation with chitosan was best explained by pseudo-second-order kinetic and Langmuir isotherm models based on kinetic and isotherm studies. The Langmuir equation determined that the maximal ability of VO(tpps) conjugated with each gram of chitosan was 39.22 µmol at a solution temperature of 45 °C. Activation energy and thermodynamic studies (Ea: 8.78 kJ/mol, ΔG: -24.52 to -27.55 kJ/mol, ΔS: 204.22 J/(mol K), and ΔH: 37.30 kJ/mol) reveal that conjugation is endothermic and physical in nature. The discharge of VO(tpps) from conjugate was analyzed in freshly prepared 0.1 mol/L phosphate buffer (pH 7.4) at 37 °C. The release of VO(tpps) from the conjugate is a two-phase process best explained by the Higuchi model, according to a kinetic analysis of the release data. Taking into consideration all experimental findings, it is proposed that chitosan can be used to formulate both solid and liquid insulin-mimetic chitosan-VO(tpps) conjugates.

Adsorption Characteristics of Allura Red AC onto Sawdust and Hexadecylpyridinium Bromide-Treated Sawdust in Aqueous Solution.

The Allura red AC (ARAC) dye adsorption onto natural sawdust (NSD) and hexadecylpyridinium bromide-treated sawdust (MSD) was investigated in aqueous solution as a function of contact time, solution pH, particle size, adsorbent dosage, dye concentration, temperature, and ionic strength. The adsorbents were characterized by Fourier transform infrared spectroscopy and X-ray diffraction crystallography. The dye adsorption onto both adsorbents was confirmed by field emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. The maximum dye adsorption was found within 120 min at pH 2.0 for NSD and pH 3.0 for MSD, respectively, with a particle size of 0-75 µm and an adsorbent dosage of 0.07 g/50 mL ARAC dye solution (50 µmol/L). The batch adsorption kinetic data were followed by the pseudo-second-order kinetic model rather than the pseudo-first-order and Elovich kinetic models. Equilibrium adsorption isotherms were explained by the Langmuir isotherm model, and the maximum extent of adsorption was found to be 52.14 µmol/g for NSD and 151.88 µmol/g for MSD at 55 °C. The values of activation energy (E a) and thermodynamic parameters (ΔG ⧧, ΔH ⧧, ΔS ⧧, ΔG°, ΔH° and ΔS°) proved that the ARAC dye adsorption onto both adsorbents NSD and MSD is a spontaneous-endothermic physisorption process. ARAC (98-99%) was released from dye-loaded adsorbents in aqueous solution (pH ≥ 12) within 120 min. The adsorbents NSD and MSD were reused for a second time without significant loss of their adsorption efficiency.

A Zinc(II)/poly(gamma-glutamic acid) complex as an oral therapeutic for the treatment of type-2 diabetic KKAy mice.

In developing new insulin-mimetic zinc(II) complexes with various ligands including a biodegradable polymer, we prepared and characterized a Zn(gamma-pga) complex in solution as well as in solid, and investigated its in vitro insulin-mimetic activity and in vivo antidiabetic effect in type-2 diabetic KKA(y) mice. The in vitro insulin-mimetic activity of the Zn(gamma-pga) complex was considerable better than that of ZnSO(4). The Zn(gamma-pga) complex normalized the hyperglycemia in KKA(y) mice within 21 d when administrated orally at doses of 10-20 mg (0.15-0.31 mmol) Zn per kg body mass for 30 d. In addition, the impaired glucose tolerance, elevated HbA(1c) levels and metabolic syndromes were significantly improved in Zn(gamma-pga)-treated KKA(y) mice relative to those administrated with saline and ZnSO(4).

Antidiabetic activity of the orally effective vanadyl-poly (gamma-glutamic acid) complex in streptozotocin(STZ)-induced type 1 diabetic mice.

Newly synthesized vanadyl-poly(gamma-glutamic acid) complex (VO-gamma-PGA) with a VO(O4) coordination mode was found to have potent antidiabetic activity in streptozotocin (STZ)-induced type 1 diabetic mice (STZ-mice), compared with that of a solution containing only vanadyl sulfate, VOSO4. This was the first example of orally active vanadyl complex of gamma-PGA for treating STZ-mice. To better define its efficacy, we examined here the effects of VO-gamma-PGA treatment in STZ-mice by oral administration at the dose of 10 mg V/kg body mass for a longer period time than our previous study. The improvement in diabetic states in STZ-mice compared with saline-treated nondiabetic normal Std ddY mice. It was found that the elevated blood glucose levels in STZ-mice significantly decreased after 3 days and sustained the normalized blood glucose level around 180-200 mg/dL (10-11.1 mM) for the last 14 days, which is close to the blood glucose levels 100-200 mg/dL (5.6-11.1 mM) in nondiabetic normal Std ddY mice. The improvement in diabetes was strongly corelated by the improvement in oral glucose tolerance ability, glycosylated hemoglobin (HbA1c) levels and blood pressure, and serum parameters. The present results confirmed that VO-gamma-PGA complex is a promising, orally active insulin-mimetic agent to treat type 1 diabetic mice.

Chelation of vanadium(IV) by a natural and edible biopolymer poly(gamma-glutamic acid) in aqueous solution: structure and binding constant of complex.

The naturally occurring edible biopolymer poly(gamma-glutamic acid) (gamma-PGA) is shown to be an efficient chelating agent of vanadium(IV). The structure of poly(gamma-glutamic acid)oxovanadium(IV) (VO-gamma-PGA) complex in solution has been analyzed by electron spin resonance and UV-visible absorption spectra. The equatorial coordination sphere of vanadium(IV) is proposed to be [2 x carboxylate (2O)-VO-(OH2)2]. The binding isotherm is determined for suspensions of gamma-PGA in vanadium(IV) oxide sulfate (VS) solutions of different concentrations, and the data have been adjusted to fit the modified Langmuir equation. The maximum amount of vanadium bound per gram of gamma-PGA is estimated to be 141 mmol . g(-1) with a binding constant of 22 L . g(-1) at pH 3.

Amelioration of hyperglycemia and metabolic syndromes in type 2 diabetic KKA(y) mice by poly(gamma-glutamic acid)oxovanadium(IV) complex.

Recently, we found that poly(gamma-glutamic acid)oxovanadium(IV) complex (VO(gamma-pga)) exhibits a potent antidiabetic activity in streptozotocin (STZ)-induced type 1 diabetic mice. This result prompted us to examine its ability to treat the type 2 diabetic model KKA(y) mice with insulin resistance. We studied the in vivo antidiabetic activity of VO(gamma-pga), compared with that of vanadium(IV) oxide sulfate (VS) as control. Both compounds were orally administered at doses of 5-10 mg (0.1-0.2 mmol) V kg(-1) body mass to the KKA(y) mice for 30 days. VO(gamma-pga) normalized the hyperglycemia within 21 days, whereas VS lowered the blood glucose concentration only by a small degree. In addition, the glucose intolerance, HbA(1c) level, hyperinsulinemia, hypercholesterolemia, and hyperleptinemia were significantly improved in VO(gamma-pga)-treated KKA(y) mice compared with those treated with VS. Based on these observations, VO(gamma-pga) is proposed to be the first orally active oxovanadium(IV)-polymer complex for the efficacious treatment of not only type 2 diabetes but also metabolic syndrome in animals.

Investigation of a Cu(II)-poly(gamma-glutamic acid) complex in aqueous solution and its insulin-mimetic activity.

The complexation between cupric ions (Cu(II)) and poly(gamma-glutamic acid) (gamma-PGA) in aqueous solutions (pH 3-11) has been studied by UV-visible absorption and electron spin resonance (ESR) techniques. Formation of the Cu(II)-gamma-PGA complex is confirmed by the observation of the blue shift of the absorption band in the visible region, anisotropic line shapes in the ESR spectrum at room temperature, and a computer simulation of the visible absorption spectrum of the complex. The structure of the Cu(II)-gamma-PGA complex, depending on the pH, has been determined. The in vitro insulin-mimetic activity of the Cu(II)-gamma-PGA complex is examined by determining both inhibition of free fatty acid release and glucose uptake in isolated rat adipocytes treated with epinephrine, in which the concentration of the Cu(II)-gamma-PGA complex for 50% inhibition of free fatty acid release is very similar to that of CuSO4. However, it is significantly lower than that of a previously reported insulin-mimetic bis(3-hydroxypicolinato)copper(II), [Cu(3hpic)2], complex.

A novel drug delivery system for type 1 diabetes: insulin-mimetic vanadyl-poly(gamma-glutamic acid) complex.

Insulin-mimetic vanadyl-poly(gamma-glutamic acid) complex, VO-gamma-PGA, is proposed as a novel drug delivery system for treating type 1 diabetic animals. The structure of VO-gamma-PGA in solution as well as in solid state was analyzed by electronic absorption, infra-red, and electron spin resonance spectra, and proposed that the equatorial coordination mode of VO(2+) is in either carboxylate(O)-VO-(OH(2))(3) or 2 carboxylate(O(2))-VO-(OH(2))(2). In vitro insulin-mimetic activity, metallokinetic feature in the blood of healthy rats, and in vivo normoglycemic effect of the complex prepared in solution were evaluated in streptozotocin(STZ)-induced type 1 diabetic mice, and these effects were compared with those of a solution containing only VOSO(4) as a positive control. The in vitro insulin-mimetic activity of VO-gamma-PGA was examined by determining both inhibition of free fatty acid (FFA) release and glucose uptake in isolated rat adipocytes, in which the concentration of VO-gamma-PGA for 50% inhibition of FFA release was significantly lower than that of VOSO(4). Metallokinetic study suggested that the bioavailability of VO-gamma-PGA complex was much higher than that of VOSO(4). The complex showed a significant hypoglycemic activity within at least 4h after a single oral administration, the effect being sustained for at least 24h. Furthermore, VO-gamma-PGA normalized the hyperglycemia in STZ-mice within 3 days when it was given orally at doses of 5-10mgVkg(-1) body mass for 16 days. The improvement in diabetes was also supported by the results on oral glucose tolerance test, HbA(1c) levels, and blood pressure.

Mechanisms and kinetics of trisodium 2-hydroxy-1,1'-azonaphthalene-3,4',6-trisulfonate adsorption onto chitosan.

Chitosan, a naturally abundant biopolymer, has widely been studied for metal adsorption from various solutions, but the extension of chitosan as an adsorbent to remove organic substances from water and wastewater has seldom been explored. In this study, the adsorption of an azo dye, trisodium 2-hydroxy-1,1'-azonaphthalene-3,4',6-trisulfonate (1), from aqueous solution onto the various degrees of deacetylated chitosan has been investigated. Equilibrium studies have been carried out to determine the capacity of chitosan for dye. The experimental data were analyzed using two isotherm correlations, namely, Langmuir and Freundlich equations. The linear correlation coefficients were determined for each isotherm and the Langmuir provided the best fit. The experimental adsorption isotherms were perfectly reproduced in the simulated data obtained from numerical analysis on the basis of the Langmuir model and the isotherm constants. Adsorption of (1) onto the chitosan flakes was found to be strongly depending on degrees of deacetylation in chitosan and temperatures. Significant amounts of (1) were adsorbed by chitosan 8B (higher degree of deacetylated chitosan), but the adsorption capacity was reduced remarkably with increasing solution temperatures. Thermodynamic parameters such as change in free energy (DeltaG), enthalpy (DeltaH), and entropy (DeltaS) were also determined. In addition, kinetic study indicated that the adsorption process mechanisms were both transport- and attachment-limited.

Kinetic simulation studies on the transient formation of the oxo-iron(IV) porphyrin radical cation during the reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)-porphyrin with hydrogen peroxide in aqueous solution.

High-valent oxo-iron(IV) species are commonly proposed as the key intermediates in the catalytic mechanisms of iron enzymes. Water-soluble iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin (Fe(III)TMPyP) has been used as a model of heme-enzyme to catalyse the hydrogen peroxide (H(2)O(2)) oxidation of various organic compounds. However, the mechanism of the reaction of Fe(III)TMPyP with H(2)O(2) has not been fully established. In this study, we have explored the kinetic simulation of the reaction of Fe(III)TMPyP with H(2)O(2) and of the catalytic reactivity of FeTMPyP in the luminescent peroxidation of luminol. According to the mechanism that has been established in this work, Fe(III)TMPyP is oxidized by H(2)O(2) to produce (TMPyP)(*+)Fe(IV)[double bond]O (k1 = 4.5 x 10(4)/mol/L/s) as a precursor of TMPyPFe(IV)[double bond]O. The intermediate, (TMPyP)(*+)Fe(IV)[double bond]O, represented nearly 2% of Fe(III)TMPyP but it does not accumulate in sufficient concentration to be detected because its decay rate is too fast. Kinetic simulations showed that the proposed scheme is capable of reproducing the observed time courses of FeTMPyP in various oxidation states and the decay profiles of the luminol chemiluminescence. It also shows that (TMPyP)(*+)Fe(IV)[double bond]O is 100 times more reactive than TMPyPFe(IV)[double bond]O in most of the reactions. These two species are responsible for the initial sharp and the sustained luminol emissions, respectively.

Transient formation of the oxo-iron(IV) porphyrin radical cation during the reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin with hydrogen peroxide in aqueous solution.

The reaction of iron(III) tetrakis-5,10,15,20-(N-methyl-4-pyridyl)porphyrin (Fe(III)TMPyP) with hydrogen peroxide (H(2)O(2)) and the catalytic activity of the reaction intermediates on the luminescent peroxidation of luminol in aqueous solution were studied by using a double-mixing stopped-flow system. The observed luminescence intensities showed biphasic decay depending on the conditions. The initial flashlight decayed within <1 s followed by a sustained emission for more than 30 s. Computer deconvolution of the time-resolved absorption spectra under the same conditions revealed that the initial flashlight appeared during the formation of the oxo-iron(IV) porphyrin, TMPyPFe(IV) = O, which is responsible for the sustained emission. The absorption spectra 0.0-0.5 s did not reproduce well by a simple combination of the two spectra of Fe(III)TMPyP and TMPyPFe(IV) = O, indicating that transient species was formed at the initial stage. Addition of uric acid (UA) caused a significant delay in the initiation of the luminol emission as well as in the formation of the TMPyPFe(IV) = O. Both of them were completely diminished in the presence of UA equimolar with H(2)O(2), while mannitol had no effect at all. The delay of the light emission as well as the appearance of TMPyPFe(IV) = O was directly proportional to the [UA](0) but other kinetic profiles were not changed significantly. Based on these observations and the kinetic analysis, we confirmed the involvement of the oxo-iron(IV) porphyrin radical cation, (TMPyP)(.+)Fe(IV) = O, as an obligatory intermediate in the rate-determining step of the overall reaction, Fe(III)TMPyP + H(2)O(2) --> TMPyPFe(IV) = O, with a rate constant of k = 4.3 x 10(4)/mol/L/s. The rate constants for the reaction between the (TMPyP)(.+)Fe(IV) = O and luminol, and between the TMPyPFe(IV) = O and luminol were estimated to be 3.6 x 10(6)/mol/L/s and 1.31 x 10(4)/mol/L/s, respectively.