Visible-light photoelectrodegradation of diuron on WO3 nanostructures.

The degradation of pesticide diuron has been explored by photoelectrocatalysis (PEC) under visible light illumination using two different WO3 nanostructures, obtained by anodization of tungsten. The highest degradation efficiency (73%) was obtained for WO3 nanosheets synthesized in the presence of small amounts of hydrogen peroxide (0.05 M). For that nanostructure, the kinetic coefficient for diuron degradation was 133% higher than that for the other nanostructure (anodized in the presence of fluoride anions). These results have been explained by taking into account the different architecture and dimensions of the two WO3 nanostructures under study.

Is photoelectrocatalysis an efficient process to degrade endocrine disruptors chemicals?

Endocrine disruptors chemicals (EDCs) pose significant health risks, including cancer, behavioral disorders, and infertility. In this study, we employed the photoelectrocatalysis (PEC) technique with optimized tungsten oxide (WO3) nanostructures as a photoanode to degrade three diverse EDCs: methiocarb, dimethyl phthalate, and 4-tert-butylphenol. PEC degradation tests were carried out for individual contaminants and a mixture of them, assessing efficiency across different EDC families. Ultra High-Performance Liquid Chromatography and Mass Spectrometry was used to control the course of the experiments. For individual solutions, 4-tert-butylphenol and methiocarb were 100% degraded at 1 hour of PEC degradation. Among the tested EDCs, dimethyl phthalate showed the highest resistance to degradation when treated individually. However, when assessed in a mixture with the other EDCs, the degradation efficiency of dimethyl phthalate increased compared to its individual treatment. Furthermore, four degradation intermediates were identified for each contaminant. Finally, toxicity tests revealed that the initial solution was more toxic than the samples treated for all the contaminants tested, except for the phthalate.

Experimental and Theoretical Tests on the Corrosion Protection of Mild Steel in Hydrochloric Acid Environment by the Use of Pyrazole Derivative.

In this study, 1,5-diallyl-1H-pyrazolo [3,4-d] pyrimidin-4 (5H)-one (PPD) was evaluated as an anticorrosion agent for mild steel (MS) in 1 M HCl. The analysis was performed by weight loss (WL), potentiodynamic polarization measurement, and electrochemical impedance spectroscopy (EIS). The Tafel polarization showed that PPD is a mixed-type inhibitor and reaches 94% of the protective efficiency at 10-3 M. EIS results indicated that the resistance to charge transfer increases with increasing inhibitor concentration and the corrosion of MS is controlled by a charge transfer process. The inhibitor adsorption on the MS surface obeyed the Langmuir's adsorption isotherm. Thermodynamic parameters were calculated to elaborate the corrosion inhibition mechanism. The micrographic analysis revealed the existence of a barrier layer on the electrode surface with the presence of PPD. Theoretical examinations performed by electronic/atomic computer simulations confirmed that the obtained results were found to be consistent with experimental findings.

Degradation of Methylparaben Using Optimal WO3 Nanostructures: Influence of the Annealing Conditions and Complexing Agent.

In this work, WO3 nanostructures were synthesized with different complexing agents (0.05 M H2O2 and 0.1 M citric acid) and annealing conditions (400 °C, 500 °C and 600 °C) to obtain optimal WO3 nanostructures to use them as a photoanode in the photoelectrochemical (PEC) degradation of an endocrine disruptor chemical. These nanostructures were studied morphologically by a field emission scanning electron microscope. X-ray photoelectron spectroscopy was performed to provide information of the electronic states of the nanostructures. The crystallinity of the samples was observed by a confocal Raman laser microscope and X-ray diffraction. Furthermore, photoelectrochemical measurements (photostability, photoelectrochemical impedance spectroscopy, Mott-Schottky and water-splitting test) were also performed using a solar simulator with AM 1.5 conditions at 100 mW·cm-2. Once the optimal nanostructure was obtained (citric acid 0.01 M at an annealing temperature of 600 °C), the PEC degradation of methylparaben (CO 10 ppm) was carried out. It was followed by ultra-high-performance liquid chromatography and mass spectrometry, which allowed to obtain the concentration of the contaminant during degradation and the identification of degradation intermediates. The optimized nanostructure was proved to be an efficient photocatalyst since the degradation of methylparaben was performed in less than 4 h and the kinetic coefficient of degradation was 0.02 min-1.

Photoelectrocatalyzed degradation of organophosphorus pesticide fenamiphos using WO3 nanorods as photoanode.

In this study, WO3 nanostructures were synthesized by the electrochemical anodization technique to use them on the degradation of persistent organic compounds such as the pesticide fenamiphos. The acids electrolyte used during the anodization were two different: 1.5 M H2SO4 - 0.05 M H2O2 and 1.5 M CH4O3S - 0.05 M H2O2. Once the samples have been manufactured, they have been subjected to different tests to analyze the properties of the nanostructures. With Field Emission Scanning Electron Microscopy (FE-SEM) the samples have been examined morphologically, their composition and crystallinity has been studied through Raman Spectroscopy and their photoelectrochemical behaviour by Photoelectrochemical Impedance Spectroscopy (PEIS). Finally, degradation tests have been carried out using the technique known as photoelectrocatalysis (PEC). The conditions that were applied in this technique were a potential of 1 VAg/AgCl and simulated solar illumination. The degradation process was monitored by UV-Visible and High-Performance liquid Chromatography (HPLC) to control the course of the experiment. The nanostructures obtained with 1.5 M CH4O3S - 0.05 M H2O2 electrolyte showed a better photoelectrochemical behaviour than nanostructures synthesized with 1.5 M H2SO4 - 0.05 M H2O2. The fenamiphos degradation was achieved at 2 h of experiment and the intermediate formation was noticed at 1 h of PEC experiment.

Photoelectrocatalyzed degradation of a pesticides mixture solution (chlorfenvinphos and bromacil) by WO3 nanosheets.

A photoelectrocatalyst consisting of WO3 nanosheets or nanorods has been synthesized by electrochemical anodization under hydrodynamic conditions, and has been used for the degradation of two toxic pesticides: chlorfenvinphos and bromacil. Nanostructures have been characterized by FESEM and Raman spectroscopy. Photoelectrochemical degradation tests have been carried out both for individual pesticide solutions and for a mixture solution, and the concentration evolution with time has been followed by UV-Vis spectrophotometry. For individual pesticides, pseudo-first order kinetic coefficients of 0.402h-1 and 0.324h-1 have been obtained for chlorfenvinphos and bromacil, respectively, while for the mixture solution, these kinetic coefficients have been 0.162h-1 and 0.408h-1. The change in behavior towards pesticide degradation depending on whether individual or mixture solutions were used might be indicative of a competitive process between the two pesticide molecules when interacting with the WO3 nanostructures surface or when approaching the semiconductor/electrolyte interface.

A porous Ru nanomaterial as an efficient electrocatalyst for the hydrogen evolution reaction under acidic and neutral conditions.

A porous Ru nanomaterial exhibits high electrocatalytic performance and excellent durability for the hydrogen evolution reaction (HER) under both acidic and neutral conditions. It displays a low overpotential of 83 mV at a current density of 10 mA cm-2 and an excellent durability up to 12 h in 0.5 M H2SO4.

Kinetic study of alpha-chymotrypsin-catalyzed synthesis of kyotorphin.

A kinetic analysis of reaction-rate data obtained during a series of optimization experiments of the alpha-chymotrypsin-catalyzed synthesis of kyotorphin has been performed. The kinetic data have been fitted to a model equation derived from a proposed sequential mechanism, which has been further simplified to a first-order equation as a function of the substrate consumption. Statistical tests performed validate the model, since the fitted constants were statistically significant. In addition, the activation energy of the process has been calculated and resulted to be 32.5 +/- 2.3 kJ/mol which is within the range of other enzymatic reactions.

New anti-RNS and -RCS products for cosmetic treatment.

Oxidants and free radicals are known to be a very important factor in skin aging, taking an active part in lipidic peroxidation, breakage of proteins and DNA, etc. The most well-known are reactive oxygen species (ROS), for example, superoxide radical anion, or more commonly called, superoxide (O), hydroxyl radical (OH(*)) or hydrogen peroxide (H(2)O(2)). Both free radicals and other oxidants can be generated by metabolic activity within the cell and by other environmental challenges,. In addition, other dangerous species are known such as reactive nitrogen species (RNS) and reactive carbonyl species (RCS). Some of the most important RNS are peroxynitrite (ONOO(-)), nitrogen dioxide radical ((*)NO(2)) and the nitronium ion (NO). For RCS, some of the most important are 4-hydroxynonenal (HNE), acrolein (ACR), malondialdehyde (MDA) or glyoxal (GXL). Both compounds (RNS and RCS) are thought to play an important role in many diseases and in skin aging, for example, collagen cross-linking, DNA damage, protein tyrosine nitration, etc. This work investigates two new specific chemicals: Lipochroman-6((R))- an anti-RNS which shows good results in inhibiting the nitration of tyrosine by peroxynitrite, and Aldenine((R))- a tripeptide anti-RCS which protects cells from reactive carbonyl compounds such as HNE or ACR; it also shows the ability to prevent glycation of proteins, specifically by superoxide dismutase (SOD).

Antinociceptive activity of glycosidic enkephalin analogues.

The antinociceptive activity of two new enkephalin analogues: N1.5-(beta-D-glucopyranosyl)[D-Met2, Pro5]enkephalinamide and N1.5-(beta-D-galactopyranosyl)[D-Met2, Pro5]enkephalinamide was assessed using the tail immersion and paw pressure behavioural tests. Both enkephalin analogues appear to be more active than morphine when injected either into the fourth ventricle or intrathecally; the galactose analogue is more than 5000 times more active than morphine when injected into the fourth ventricle. The analgesic effects produced by the analogues are partially reversed by SC naloxone (0.1 mg/kg) and totally reversed when the dose of naloxone used was 1 mg/kg, suggesting that the analogues act upon more than one type of opiate receptor (mu/delta).

Biological activity of Leu-enkephalin containing hydrophobic moieties.

A series of enkephalin analogues (Tyr-Gly-Gly-Phe-Leu-C-NH-R;R=C6,C8,C10,C12 and C14; C=CH2 groups) with increasing hydrophobic character have been tested behaviourally in the analgesic hot plate and tail flick tests. The analogues were administered intraperitoneally and were found to possess anti-nociceptive activity. The results indicate that apparently there is not a direct relationship between increasing hydrophobicity and activity of the enkephalin-alkyl-amide analogues. The enkephalin analogues were found to behave in the same way as the enkephalins in producing tolerance.

New glycosylpeptides with high antinociceptive activity.

The antinociceptive activity of two new synthetic glucoside and galactoside enkephalinamide analogues was studied. The effects produced by the new analogues were compared with those obtained with [D-Met2,Hyp5]enkephalinamide and with morphine. The analogues were injected into the fourth ventricle and intrathecally. Tail immersion and paw pressure behavioural tests were used to assess antinociception. One of the analogues studied, O1,5-[beta-D-galactopyranosyl] [D-Met2,Hyp5]enkephalinamide appears to be 57,000 times more potent than morphine.

A synthetic glycopeptide of substance P analogue (SP6-11) with enhanced NK-1 receptor specificity.

A new glycopeptide analogue of substance P (6-11) (SP6-11), namely, N1,6 (beta-D-glucopyranosyl) [Glu6, Pro9]SP6-11, has been synthesized and found to be water soluble. The in vitro biological activity of this glycopeptide was determined for spasmogenic activity in the guinea pig ileum and for potentiation of electrically evoked contractions in the rat vas deferens. Thus, activities on NK-1, NK-2, and NK-3 receptor types have been differentiated by two assays and, in the case of NK-1 and NK-3, receptors in guinea pig ileum (GPI) were assayed using specific pharmacological procedures. The ED50 values for the analogue and reference peptides substance P (SP), neurokinin A(NKA), and neurokinin B (NKB) were determined and potencies relative to SP were calculated. The analogue is three times more potent than the potent NK-1 agonist SP on NK-1 receptors. Moreover, this glycopeptide proved to be as selective for the NK-1 receptor as the specific agonist SPOMe (the methyl ester of substance P).

In vitro activity and selectivity of glucosidic SP(6-11) analogues.

The relative potencies of a series of substance P (6-11) analogues have been determined for spasmogenic activity in the guinea pig ileum in vitro and for potentiation of electrically evoked contractions in the rat vas deferens in vitro. ED50 values were determined for the new analogues. Substance P and its methyl ester were used as standard agonists. Substitution of Gly9 by Pro on [Glu6]SP(6-11) increased four times the activity on the NK-1 receptor. The glycosilation of [Glu6]SP(6-11) by the incorporation of a beta-D-glucopyranosyl amide residue on the gamma-carboxyl group of Glu6 reduced both the activity and selectivity. The simultaneous substitution of Gly9 by Pro and the incorporation of a monosaccharide moiety on the gamma-carboxyl of Glu6 on [Glu6]SP(6-11) yielded an analogue with 60-fold enhanced selectivity relative to substance P for the NK-1 receptor. These results may indicate that the critical factor providing potency to SP(6-11) analogues is mostly related to conformational rather than hydrophilicity aspects of the molecular structure.

Evaluation of free and liposome-encapsulated gentamycin for intramuscular sustained release in rabbits.

Gentamycin sulphate (GS) and gentamycin oleate (GO) were encapsulated in liposomes composed of phosphatidylcholine (HPC) and cholesterol (CHOL) (molar ratio 7:7:2 and 5:5:1, respectively), and were administered via intramuscular injection to rabbits, to evaluate their potential use as sustained release formulations. Five groups of five animals each were used for the pharmacokinetic study, and treatments were established as follows: 3 mg kg(-1) of GS i.v., 3 mg kg(-1) of GS i.m., 3 mg kg(-1) of liposome-containing gentamycin sulphate (LGS) i.m., 3 mg kg(-1) of GO i.m., and 3 mg kg(-1) of liposome-containing gentamycin oleate (LGO) i.m. Gentamycin plasma concentrations after i.m. administration of LGS were extremely low compared with those obtained after the i.m. administration of GS; the peak plasma concentration (Cmax) showed an eight-fold decrease with LGS, and the area under the concentration-time curve (AUC) was four-fold lower for the liposomal form. The apparent elimination half-life estimated after administration of LGS showed a three-fold increase compared with values calculated for free GS. After the administration of the same dose of LGO, Cmax obtained showed a 2.5-fold decrease in relation to peak concentrations of free GO, and the apparent beta-half life of encapsulated GO showed a three-fold increase compared with i.m. GO. Large-size liposomes containing gentamycin administered i.m. to rabbits gave sustained drug release from the injection site, providing prolonged plasma concentrations of the drug in the body.

Kinetically controlled enzyme-catalyzed synthesis of kyotorphin. An optimization study.

Regarding the alpha-chymotrypsin-catalyzed synthesis of Z-Tyr-Arg-NH2, the effect on the reaction yield of the following experimental factors is discussed: DMF/buffer proportions, reaction temperature, and donor/nucleophile ratios. The experimental design shows that relatively better yields are obtained by increasing the reaction temperature and lowering the cosolvent proportion while maintaining a slight excess of nucleophile. The ascensional line reaches an optimal response surface very flat voided of a well-defined maximum.

Pharmacokinetics of enrofloxacin after intravenous and intramuscular injection in rabbits.

The pharmacokinetics and bioavailability of enrofloxacin were determined after IV and IM administration of 5 mg/kg of body weight to 6 healthy adult rabbits. Using nonlinear least-squares regression methods, data obtained were best described by a 2-compartment open model. After IV administration, a rapid distribution phase was followed by a slower elimination phase, with a half-life of 131.5 +/- 17.6 minutes. The mean body clearance rate was 22.8 +/- 6.8 ml/min/kg, and the mean volume of distribution was 3.4 +/- 0.9 L/kg. This large volume of distribution and the K12/K21 ratio close to 1, indicated that enrofloxacin was widely distributed in the body, but not retained in tissues. After a brief lag period (6.2 +/- 2.86 min), IM absorption was rapid (4.1 +/- 1.3 min) and almost complete. The mean extent of IM absorption was 92 +/- 11%, and maximal plasma concentration of 3.04 +/- 0.34 micrograms/ml was detected approximately 10 minutes after administration.

Effect of pH and chloride concentration on the removal of hexavalent chromium in a batch electrocoagulation reactor.

In this work, the effect of pH and chloride ions concentration on the removal of Cr(VI) from wastewater by batch electrocoagulation using iron plate electrodes has been investigated. The initial solution pH was adjusted with different concentrations of H(2)SO(4). The presence of chloride ions enhances the anode dissolution due to pitting corrosion. Fe(2+) ions formed during the anode dissolution cause the reduction of Cr(VI) to form Cr(III), which are co-precipitated with Fe(3+) ions at relatively low pH. The reduction degree of Cr(VI) to Cr(III) and the solubility of metal hydroxide species (both chromic and iron hydroxides) depend on pH. At higher concentrations of H(2)SO(4), the reduction of Cr(VI) to Cr(III) by Fe(2+) ions is preferred, but the coagulation of Fe(3+) and Cr(III) is favoured at the lower H(2)SO(4) concentrations.

[D-Met2,Pro5] enkephalin [N1.5-beta-D-glucopyranosyl] amide: a glycosylpeptide with high antinociceptive activity.

Different synthetic strategies have been attempted for the synthesis of a glycosylpeptide resulting from the covalent bonding of a sugar residue to the C-terminal carboxyl group of an enkephalin related pentapeptide. The final structure is: Tyr-D-Met-Gly-Phe-Pro [N1.5-beta-D-glucopyranosyl] amide. The in vitro potency on the GPI test of this analogue was IC50 = 64.0 nM. However, its antinociceptive activity by tail immersion tests, after intraperitoneal administration, was 2000 and 200 times higher than morphine in rats and mice, respectively.

Synthesis and biological activity of substance P analogues.

The synthesis of the hexapeptide [Glu6]SP6-11 and its glycosylated analogue at the Glu6 gamma-carboxyl position by solution procedures according to several strategies is discussed. The biological activity of SP, [Glu6]SP6-11 (VI) and [Glu(beta-D-Glcp)6]SP6-11 (VIII) have been determined and compared to SP by the GPI and RVD assays. The introduction of a beta-D-glucopyranosyl moiety at the sixth position of the [Glu6]SP6-11 did not affect to a great extent the in vitro activity pattern of the parent hexapeptide.