Measurement of organochlorine pesticides in drinking water: laboratory technical proficiency testing in Mexico

Accreditation and Quality Assurance - An interlaboratory comparison exercise was performed to assess the technical proficiency of laboratories in measuring the organochlorine pesticides in drinking...     

Single Fusion Events at Polarized Liquid–Liquid Interfaces

A new electrochemical framework for tracking individual soft particles in solution and monitoring their fusion with polarized liquid–liquid interfaces is reported. The physicochemical principle lies in the interfacial transfer of an ionic probe confined in the particles dispersed in solution and that is released upon their collision and fusion with the fluid interface. As a proof-of-concept, spike-like transients of a stochastic nature are reported in the current–time response of 1,2-dichloroethane(DCE)|water(W) submilli-interfaces after injection of DCE-in-W emulsions. The sign and potential dependence of the spikes reflect the charge and lipophilicity of the ionic load of the droplets. A comparison with dynamic light scattering measurements indicates that each spike is associated with the collision of a single sub-picoliter droplet. This opens a new framework for the study of single fusion events at the micro- and nanoscale and of ion transport across biomimetic soft interfaces.     

Experimental and Theoretical Study of the Stability of the Complex Fisetin–Cu(II) and A Comparative Study of Free Ligand and Complex Interaction with Molecular Singlet Oxygen

In this work, the flavonol fisetin was selected in order to study its reactivity against Cu(II), a metal ion of interest in biological media and industry. The stoichiometry and apparent formation constant of the complex in ethanolic medium at 25°C were evaluated using spectrophotometric techniques. The resulting stoichiometry was a 1:1 ligand:metal complex, and a log K = 5.17 ± 0.12 was determined. Since two possible chelation sites can be proposed for the complex formation, quantum chemistry calculations were performed on these structures. Calculations suggest that the hydroxyl-keto site is more stable for the complex formation than the catechol site. Flavonoids could exert protection against oxidative damage caused by reactive oxygen species, and this biological activity could be affected by chelation with metal ions. This led us to perform a study on the interaction of both, free flavonoid and complex, with reactive oxygen species. Our results showed both compounds quench molecular singlet oxygen photogenerated with visible light, mainly in a physical fashion. In order to analyze a possible protective effect of flavonoid and its complex against oxidative damage in biological environments, the amino acid tryptophan was selected as a model oxidation system. Free flavonoid does not have a marked protective effect, whereas its complex showed a relevant protective effect.     

Oregano Essential Oil Interactions with Photogenerated Singlet Molecular Oxygen

Essential oils are a mixture of volatile compounds, products of the secondary metabolism of plants. Once extracted, they can be deteriorated losing their organoleptic and therapeutic properties due to various environmental factors, being light exposure in aerobic conditions the main cause. In this work, the oregano essential oil extraction and characterization from Origanum vulgare plants grown in the experimental field of the FTU-UNSL and its photodegradation in MeOH:H₂O 60:40 v/v solvent were studied. Characterization by EIMS and NIST Mass Spectrometry indicates the main compounds of oregano essential oil, quantified in the extracted oil by GC-MS, are carvacrol (7.14%) and thymol (47.37%). Degradation of essential oil and its two major components can be caused by reactive oxygen species photogenerated from endogenous sensitizers as riboflavin. Our results suggest degradation occurs involving singlet molecular oxygen. Interaction of carvacrol and thymol with singlet oxygen is mainly a physical process, while essential oil has an important reactive component, which indicates there might be other constituents which could contribute to reactive photoprotection. The effect of simultaneous presence of oregano essential oil and tryptophan amino acid—used as a photooxidizable model under riboflavin-photosensitizing conditions—was studied in order to evaluate the possible photoprotection exerted by the essential oil.     

Human Hair as a Natural Sun Protection Agent: A Quantitative Study

The rising incidence of skin cancers attributable to excessive sun exposure has become a major health concern worldwide. While numerous studies have analyzed the sun protective effect of sunscreens, clothing and antioxidants, none to date have measured the photoprotective effect of hair, despite clinical evidence that individuals with balding or thinning hair are at greater risk of skin lesions that can progress to cancer, hence the recommendation to use hats or umbrellas. We analyzed the level of protection offered by hair according to hair density, thickness and color using the spectral transmittance and corrected for relative erythema effectiveness. Our results show that hair provides a barrier against both UVB and UVA radiation which is significantly increased with respect to the hair density, thickness and the presence of melanins. This is the first study to quantify sun protection factor offered by hair, namely hair ultraviolet protection factor (HUPF). We believe that hair should be recognized as an important natural sun barrier in the prevention of UV‐induced skin cancers.     

Hollow‐fiber solvent bar microextraction with gas chromatography and electron capture detection determination of disinfection byproducts in water samples

A liquid‐phase microextraction method that uses a hollow‐fiber solvent bar microextraction technique was developed by combining gas chromatography with electron capture detection for the analysis of four trihalomethanes (chloroform, dichlorobromomethane, chlorodibromomethane, and bromoform) in drinking water. In the microextraction process, 1‐octanol was used as the solvent. The technique operates in a two‐phase mode with a 5 min extraction time, a 700 rpm stirring speed, a 30°C extraction temperature, and NaCl concentration of 20%. After microextraction, one edge of the membrane was cut, and 1 μL of solvent was collected from the membrane using a 10 μL syringe. The solvent sample was directly injected into the gas chromatograph. The analytical characteristics of the developed method were as follows: detection limits, 0.017–0.037 ng mL⁻¹; linear working range, 10–900 ng mL⁻¹; recovery, 74 ± 9–91 ± 2; relative standard deviation, 5.7–10.3; and enrichment factor, 330–455. A simple, fast, economic, selective, and efficient method with big possibilities for automation was developed with a potential use to apply with other matrices and analytes.     

Determination of the axial force on stay cables accounting for their bending stiffness and rotational end restraints by free vibration tests

Determination of the axial force in terms of its natural frequencies may be significantly influenced by the bending stiffness of the cable and the rotational elastic restraints at the ends, depending on the geometrical and mechanical parameters of the cable and its supports and restraints, particularly in cement-grouted parallel-bundle wire cables. The paper presents an explicit analytical expression for the natural frequencies taking into account both the bending stiffness of the cable and the rotational restraint at the ends that may be used to determine the axial force. While the bending stiffness of the cable and the axial force are selected as variables to attain an optimal match between analytical and experimental data, the rotational stiffness at the ends is treated as a known parameter in that process. The degree of rotational restraint at the ends cannot be accurately inferred from the sequence of the experimentally determined natural frequencies, since this parameter does not appreciably affect the progression of their values. Techniques are discussed that allow approximate determination of the rotational stiffness at the ends for the most common arrangements of anchors and cables with, and without, intermediate supports provided by deviators located near the ends. The axial force and the bending stiffness of the cable are both simultaneously adjusted by matching the natural frequencies of the analytical model with the experimental values. The proposed approach leads to a reduction of the error in the estimation of the axial force for short cables with relatively high bending stiffness such as those typical of cement-grouted parallel-bundle wire cables often used as cable stays for bridges until the early 1990s.     

Enantioselective addition of terminal alkynes to N-(diphenylphosphinoyl)imines catalyzed by Zn–BINOL complexes

Chiral nonracemic N-(diphenylphosphinoyl)-protected propargylic amines have been prepared by addition of terminal alkynes to N-(diphenylphosphinoyl)aldimines in the presence of dimethylzinc and 3,3′-dibromo-BINOL as catalyst. The reaction works with a variety of aromatic and heteroaromatic aldimines and with different alkynes, providing the expected products in generally good yields and enantiomeric excesses (up to 96%).