A critical evaluation of a long pathlength cell for flow-based spectrophotometric measurements

Coupling of a flow cell based on a liquid core waveguide (LCW) to flow systems for spectrophotometric measurements was critically evaluated. Flow-based systems with and without chemical reactions were exploited to estimate the increase in analytical signal in comparison to those obtained with a conventional 1-cm cell under different experimental conditions. The Schlieren effect associated to intense concentration gradients in the sample zone was investigated with model solutions that do not absorb visible electromagnetic radiation. The effect of radiation scattering was lower than the expected by considering the increase in the optical path, being the magnitude of the perturbation up to 40% higher for the 100-cm LCW cell. Several alternatives for compensation of the Schlieren effect were experimentally investigated. The potentiality of the LCW for turbidimetric measurements and coupling to monosegmented flow analysis was also evaluated.     

Infrared spectroscopy of discrete uranyl anion complexes

The Free-Electron Laser for Infrared Experiments (FELIX) was used to study the wavelength-resolved multiple photon photodissociation of discrete, gas-phase uranyl (UO22+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands and are comparable to solution-phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm(-1) higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity.     

Theoretical study of the gas-phase chemiionization reactions La + O and La + O2

The La + O and La + O 2 chemiionization reactions have been investigated with quantum chemical methods. For La + O 2(X (3)Sigma g) and La + O 2(a (1)Delta g), the chemiionization reaction La + O 2 --> LaO 2 (+) + e (-) has been shown to be endothermic and does not contribute to the experimental chemielectron spectra. For the La + O 2(X (3)Sigma g) reaction conditions, chemielectrons are produced by La + O 2 --> LaO + O, followed by La + O --> LaO (+) + e (-). This is supported by the same chemielectron band, arising from La + O --> LaO (+) + e (-), being observed from both the La + O( (3)P) and La + O 2(X (3)Sigma g) reaction conditions. For La + O 2(a (1)Delta g), a chemielectron band with higher electron kinetic energy than that obtained from La + O 2(X (3)Sigma g) is observed. This is attributed to production of O( (1)D) from the reaction La + O 2(a (1)Delta g) --> LaO + O( (1)D), followed by chemiionization via the reaction La + O( (1)D) --> LaO (+) + e (-). Potential energy curves are computed for a number of states of LaO, LaO* and LaO (+) to establish mechanisms for the observed La + O --> LaO (+) + e (-) chemiionization reactions.     

Kinetics of the anionic homopolymerizations of ß–myrcene and 4–methylstyrene in cyclohexane initiated by n–butyllithium

The kinetics of isothermal anionic homopolymerization of ß–myrcene (MYR) and 4–methylstyrene (4MS) in cyclohexane, initiated by n–butyllithium was studied at different temperatures (55, 63, and 71 ° C). The kinetic information obtained from the homopolymerizations was used to estimate the parameters of the Eyring equation, ΔH^?= 84080 J/mol and ΔS^?= ?21.9 J/mol·K for the MYR, and ΔH^?= 51250 J/mol and ΔS^?= ?116.8 J/mol·K for the 4MS, to calculate the apparent propagation coefficients $k_p^{\mathrm{app}}$ as a function of temperature. Finally, the parameters obtained for the Eyring equation were validated by applying them in a mathematical model representing the kinetics of nonisothermal (quasi‐adiabatic) polymerization experiments of MYR and 4MS. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2157–2165     

pH-Sensitive surfactants from lysine: assessment of their cytotoxicity and environmental behavior

The toxicity and environmental behavior of new pH-sensitive surfactants from lysine are presented. Three different chemical structures are studied: surfactants with one amino acid and one alkyl chain, surfactants with two amino acids on the polar head and one alkyl chain, and gemini surfactants. The pH sensitivity of these compounds can be tuned by modifying their chemical structures. Cytotoxicity has been evaluated using erythrocytes and fibroblast cells. The toxic effects against these cells depend on the hydrophobicity of the molecules as well as their cationic charge density. The effect of hydrophobicity and cationic charge density on toxicity is different for each type of cells. For erythrocytes, the toxicity increases as hydrophobicity and charge density increases. Nevertheless, for fibroblasts cationic charge density affects cytotoxicity in the opposite way: the higher charge density, the lower the toxicity. The effect of the pH on hemolysis has been evaluated in detail. The aquatic toxicity was established using Daphnia magna . All surfactants yielded EC(50) values considerably higher than that reported for cationic surfactants based on quaternary ammonium groups. Finally, their biodegradability was evaluated using the CO(2) headspace test (ISO 14593). These lysine derivatives showed high levels of biodegradation under aerobic conditions and can be classified as "readily biodegradable compounds".     

Development of a sequential injection–square wave voltammetry method for determination of paraquat in water samples employing the hanging mercury drop electrode

This work describes the development and optimization of a sequential injection method to automate the determination of paraquat by square-wave voltammetry employing a hanging mercury drop electrode. Automation by sequential injection enhanced the sampling throughput, improving the sensitivity and precision of the measurements as a consequence of the highly reproducible and efficient conditions of mass transport of the analyte toward the electrode surface. For instance, 212 analyses can be made per hour if the sample/standard solution is prepared off-line and the sequential injection system is used just to inject the solution towards the flow cell. In-line sample conditioning reduces the sampling frequency to 44 h⁻¹. Experiments were performed in 0.10 M NaCl, which was the carrier solution, using a frequency of 200 Hz, a pulse height of 25 mV, a potential step of 2 mV, and a flow rate of 100 μL s⁻¹. For a concentration range between 0.010 and 0.25 mg L⁻¹, the current (i _p, μA) read at the potential corresponding to the peak maximum fitted the following linear equation with the paraquat concentration (mg L⁻¹): i _p = (−20.5 ± 0.3)C _paraquat − (0.02 ± 0.03). The limits of detection and quantification were 2.0 and 7.0 μg L⁻¹, respectively. The accuracy of the method was evaluated by recovery studies using spiked water samples that were also analyzed by molecular absorption spectrophotometry after reduction of paraquat with sodium dithionite in an alkaline medium. No evidence of statistically significant differences between the two methods was observed at the 95% confidence level.     

Highly homogeneous stereocontrolled construction of quaternary hydroxyesters by addition of dimethylzinc to α-ketoesters promoted by chiral perhydrobenzoxazines and B(OEt)3

A highly efficient enantioselective addition of Me(2)Zn to α-ketoesters, assisted by a chiral perhydro-1,3-benzoxazine ligand, is described. This novel catalytic system offers homogeneous elevated enantioselectivities in the preparation of α-hydroxyesters that bear a quaternary stereocenter, with a minor dependence on electronic and steric effects when aromatic, heteroaromatic, or aliphatic α-ketoesters are employed. The catalyst can be recovered and reused without loss of activity.     

Strain dependence of polarization and piezoelectric response in epitaxial BiFeO3 thin films

Epitaxial strain has recently emerged as a powerful means to engineer the properties of ferroelectric thin films, for instance to enhance the ferroelectric Curie temperature (T(C)) in BaTiO(3). However, in multiferroic BiFeO(3) thin films an unanticipated strain-driven decrease of T(C) was reported and ascribed to the peculiar competition between polar and antiferrodistortive instabilities. Here, we report a systematic characterization of the room-temperature ferroelectric and piezoelectric properties for strain levels ranging between -2.5% and +1%. We find that polarization and the piezoelectric coefficient increase by about 20% and 250%, respectively, in this strain range. These trends are well reproduced by first-principles-based techniques.     

Unexpected trends in halogen-bond based noncovalent adducts

Unexpected trends in the strengths of halogen-bond based adducts of CY(3)I (Y = F, Cl, Br, I) with two typical Lewis bases (chloride and trimethylamine) show that the halogen-bond donor strength (Lewis acidity) of a compound R-X is not necessarily increased with higher electronegativity of the (carbon-based) group R.