Inverse gas chromatography study on the effect of humidity on the mass transport of alcohols in an ethylene-vinyl alcohol copolymer near the glass transition temperature

Inverse gas chromatography (IGC) was used to study the effect of moisture on transport properties of three low molecular weight alcohols (methanol, ethanol, and 1-butanol) through high barrier copolymers of ethylene-vinyl alcohol with an ethylene content of 38%mol (EVOH38) at 40 degrees C. The value of the partition coefficient (K) was obtained by using two approaches: (a) the fit of the slope of sorption isotherms obtained through the method of Kiselev and Yashin; and (b) the solution to the model of Romdhane and Danner obtained by using the law of moments. The second method also allowed the estimation of the diffusion coefficient (D(p)) at the different humidity conditions. None of these two methods were applicable at low values of relative humidity. With the first method, the diffusion of the permeants through the copolymer was not fast enough to allow them to reach the core of the EVOH particles used as stationary phase resulting in sorption values unrealistically low. The fit of the chromatograms obtained by using the second method also suggested questionable values of the mass transport parameters. Although the theoretical curve perfectly described the chromatogram, the low extent of the interaction and the slow diffusion resulted in interdependent values of the coefficients K and D(p), with infinite pairs of values providing the same curve profile. As the relative humidity of the carrier gas increased, the diffusivity and the sorption of the alcohols also increased, making both methods applicable. In the case of the partition coefficient, the sorption of the biggest molecules (ethanol and 1-butanol) was the most affected, the increment of K for methanol being moderate. As regards the D(p) value, methanol was the most influenced compound and 1-butanol the least. Finally, a sharp increment of the D(p) of the three alcohols was observed between 35 and 47% RH and attributed to the plasticization of the copolymer.     

Unexpected but Easy Synthesis of a Dihydrophosphadiazaazulene

Abstract

The title compound is the main product of the 2:1 reaction of DMAD with diazaphosphinines. The supposed mechanisms with intermediates and related products will be presented.     

Laccase-Mediated Transformations of Endocrine Disrupting Chemicals Abolish Binding Affinities to Estrogen Receptors and Their Estrogenic Activity in Zebrafish

Endocrine disrupting chemicals (EDCs) are known to mainly affect aquatic organisms, producing negative effects in aquaculture. Transformation of the estrogenic compounds 17??-estradiol (E2), bisphenol-A (BPA), nonylphenol (NP), and triclosan (TCS) by laccase of Coriolopsis gallica was studied. Laccase is able to efficiently transform them into polymers. The estrogenic activity of the EDCs and their laccase transformation products was evaluated in vitro as their affinity for the human estrogen receptor alpha (hER??) and for the ligand binding domain of zebrafish (Danio rerio) estrogen receptor alpha (zfER??LBD). E2, BPA, NP, and TCS showed higher affinity for the zfER??LBD than for hER??. After laccase treatment, no affinity was found, except a marginal affinity of E2 products for the zfER??LBD. Endocrine disruption studies in vivo on zebrafish were performed using the induction of vitellogenin 1 as a biomarker (VTG1 mRNA levels). The use of enzymatic bioreactors, containing immobilized laccase, efficiently eliminates the endocrine activity of BPA and TCS, and significantly reduces the effects of E2. The potential use of enzymatic reactors to eliminate the endocrine activity of EDCs in supply water for aquaculture is discussed.     

Voltammetric determination of 17β-estradiol in human urine and buttermilk samples using a simple copper(II) oxide-modified carbon paste electrode

This paper reports the voltammetric determination of 17β-estradiol in urine and buttermilk samples using a simple detector based on a carbon paste electrode (CPE) modified with copper(II) oxide (CuO). The CuO was obtained by the Pechini method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive (EDS), Fourier transform infrared (FTIR), and Raman spectroscopies. Cyclic voltammetry (CV) and square-wave voltammetry (SWV) demonstrated that the CuO-modified carbon paste electrode (CuO/CPE detector) displayed much higher electrocatalytic activity in the 17β-estradiol oxidation reaction than the CPE without modification, exhibiting a low detection limit of 21.0 nmol L^?1 with a wide linear range from 60.0 to 800.0 nmol L^?1 (R = 0.998). Satisfactory results were obtained for the determination of 17β-estradiol in human urine and buttermilk samples. The proposed electrochemical detector offers high repeatability, stability, fast response, low cost, and potential for practical application in the quantification of this hormone.

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Graphical abstract ?

     

Ferromagnetic Coupling through Spin Polarization in a Dinuclear Copper(II) Metallacyclophane

No Abstract     

The reaction of β-aminoenones with substituted acetonitriles. Regiospecific synthesis of 2(1H)-pyridones

Unsymmetrically substituted β-aminoenones react with malononitrile, cyanomethylphenylsulfone, benzoyl-acetonitrile and ethyl cyanoacetate, in very mild conditions, to yield regiospecifically 3-functionalized 2(1H)-pyridones in high yields.     

Molecular dynamics simulations of surface oxide-water interactions on Pt(111) and Pt/PtCo/Pt3Co(111)

Classical molecular dynamics simulations of the interactions of water with oxidized Pt(111) and Pt/PtCo/Pt(3)Co(111) surfaces are performed by modeling water with the CF1 central force model that allows molecular dissociation and therefore the presence of other intermediates of the oxygen reduction reaction different from atomic oxygen. It is found that the water-surface oxide interactions do not affect the overall structure of the catalyst represented by an extended periodic slab. However, such interactions are affected by changes in the electrochemical potential which are simulated by higher values of the surface and atomic oxygen charges at increased oxygen coverage. Thus, electrochemical potential as well as the presence of protons and anions products of acid dissociation define the identity and the amount of oxygen reduction reaction intermediates such as OH or H(3)O. We observe agglomerations of water molecules over regions of the surface and the presence of OH and H(3)O in their vicinity. Our simulation model is able to qualitatively reproduce features of the degradation of the catalyst surface after oxidation and reduction cycles.     

Impregnated ruthenium on magnetite as a recyclable catalyst for the N-alkylation of amines, sulfonamides, sulfinamides, and nitroarenes using alcohols as electrophiles by a hydrogen autotransfer process

Various impregnated metallic salts on magnetite have been prepared, including cobalt, nickel, copper, ruthenium, and palladium salts, as well as a bimetallic palladium-copper derivative. Impregnated ruthenium catalyst is a versatile, inexpensive, and simple system for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines, sulfonamides, sulfinamides, and nitroarenes, using in all cases alcohols as the initial source of the electrophile, through a hydrogen autotransfer process. In the case of sulfinamides, this is the first time that these amino compounds have been alkylated following this strategy, allowing the use of chiral sulfinamides and secondary alcohols to give the alkylated compound with a diastereomeric ratio of 92:8. In these cases, after alkylation, a simple acid deprotection gave the expected primary amines in good yields. The ruthenium catalyst is quite sensitive, and small modifications of the reaction medium can change the final product. The alkylation of amines using potassium hydroxide renders the N-monoalkylated amines, and the same protocol using sodium hydroxide yields the related imines. The catalyst can be easily removed by a simple magnet and can be reused up to ten times, showing the same activity.     

Role of sequence and conformation on the photochemistry and the photophysics of A-T DNA dimers: an experimental and computational approach

The role of base sequence and conformation on the photochemistry and photophysics of thymidylyl (3'-5')-2'-deoxyadenosine sodium salt (TpdA) and 2-deoxyadenylyl (3'-5')-thymidine ammonium salt (dApT) was studied. To this end, nanosecond transient absorption at 266 nm, steady-state irradiation at 254 nm, and quantum chemical calculations were used. The transient absorption spectra show the solvated electron broad band in the visible region for each dinucleotide. In addition, low-intensity absorption bands are observed in the UV region, which are attributed to the deprotonated and protonated neutral radicals of adenine and thymine bases. Photoionization (PI) occurs by one- and two-photon pathways; the latter accounting for approximately 70% of the net PI yield. A diffusion-limited rate constant of 2.0 x 10(10) M(-1) s(-1) was obtained for the reaction of the neutral molecule with the photoejected electron in both sequences. The photodestruction yield, measured from the chromophore loss at 260 nm, decreases in the presence of well-known electron scavengers. This suggests the participation of base radical anions as one of the photodegradation pathways, which is higher in TpdA than in dApT. The intermediacy of a radical ion pair (charge separated state) between the adjacent adenine and thymine bases is proposed in the formation of the [2 + 2] cycloadduct intermediate. The [2 + 2] cycloadduct intermediate is known to be the precursor of the thymine-adenine eight-member ring photoproduct (TA*). Conformational constrains in the radical ion pair are suggested to explain the absence of the TA* photoproduct in dApT. This hypothesis is supported by semiempirical calculations performed on all relevant reactive intermediates proposed to participate in the mechanism of formation of TA*. Altogether, the results show that sequence and conformation profoundly influence the photochemistry and the photophysics of these DNA model systems.