Tetrahedral intermediates 4. The effect of chloro-substituents on the kinetics of the breakdown of hemiorthoesters

1-Hydroxy-2-chloromethyl-1,3-dioxolane (4) and 1-hydroxy-2-dichloromethyl-1, 3-dioxolane (5) have been detected as intermediates by¹H NMR spectroscopy in the hydration of respectively 2-chloromethylene-1, 3-dioxolane and 2-dichloromethylene-1, 3-dioxolane in aqueous acetonitrile. The kinetics of the breakdown of (4) and (5) into ethylene glycol monochloroacetate and monodichloroacetate have been studied by uv spectroscopy and values ofk_H+,k_HO-, andk_H2O evaluated. It was found that the introduction of chlorosubstituents into 2-hydroxy-2-methyl-1, 3-dioxolane caused a decrease ink_H+ and increase ink_H2O- and little change ink_H2Ofor its breakdown. The mechanisms of these reactions are discussed. Present     

A laser flash photolysis and pulse radiolysis study of primary photochemical processes of flumequine

The 355 nm laser flash photolysis of argon-saturated pH 8 phosphate buffer solutions of the fluoroquinolone antibiotic flumequine produces a transient triplet state with a maximum absorbance at 575 nm where the molar absorptivity is 14,000 M(-1) cm(-1). The quantum yield of triplet formation is 0.9. The transient triplet state is quenched by various Type-1 photodynamic substrates such as tryptophan (TrpH), tyrosine, N-acetylcysteine and 2-deoxyguanosine leading to the formation of the semireduced flumequine species. This semireduced form has been readily identified by pulse radiolysis of argon-saturated pH 8 buffered aqueous solutions by reaction of the hydrated electrons and the CO2*- radicals with flumequine. The absorption maximum of the transient semireduced species is found at 570 nm with a molar absorptivity of 2,500 M(-1) cm(-1). In argon-saturated buffered solutions, the semireduced flumequine species formed by the reaction of the flumequine triplet with TrpH stoichiometrically reduces ferricytochrome C (Cyt Fe3+) under steady state irradiation with ultraviolet-A light. In the presence of oxygen, O2*- is formed but the photoreduction of Cyt Fe3+ by O2*- competes with an oxidizing pathway which involves photo-oxidation products of TrpH.     

Onset of Chiral Adenine Surface Growth

The structure and stability of adenine crystals and thin layers has been studied by using scanning tunneling microscopy, X‐ray diffraction, and density functional theory calculations. We have found that adenine crystals can be grown in two phases that are energetically quasi‐degenerate, the structure of which can be described as a pile‐up of 2D adenine planes. In each plane, the structure can be described as an aggregation of adenine dimers. Under certain conditions, kinetic effects can favor the growth of the less stable phase. These results have been used to understand the growth of adenine thin films on gold under ultra‐high vacuum conditions. We have found that the grown phase corresponds to the α‐phase, which is composed of stacked prochiral planes. In this way, the adenine nanocrystals exhibit a surface that is enantiopure. These results could open new insight into the applications of adenine in biological, medical, and enantioselective or pharmaceutical fields.     

Tailoring the morphology and properties of waterborne polyurethanes by the procedure of cellulose nanocrystal incorporation

Polyurethane waterborne synthesis was performed using a two-step method, commonly referred to as a prepolymer method. Nanocomposites based on waterborne polyurethane and cellulose nanocrystals were prepared by the prepolymer method by altering the mode and step in which the nanofillers were incorporated during the polyurethane formation. The morphology, structural, thermal, and mechanical properties of the resulting nanocomposite films were evaluated by Fourier transform infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and tensile tests. FTIR results indicated that the degree of interaction between the nanofillers and the WPU through hydrogen bonds could be controlled by the method of cellulose nanocrystal incorporation. Data obtained from SAXS experiments showed that the cellulose nanocrystals as well as the step of the reaction in which they are added influenced the morphology of the polyurethane. The reinforcing effect of CNCs on the nanocomposites depends on their morphology.     

Effect of viscosity of a liquid membrane containing oleyl alcohol on the pertraction of butyric acid

Solvent formulation is important in the optimization of the mass-transfer through supported liquid membranes (SLM) in pertraction and membrane extraction. Oleyl alcohol (OA) is frequently used as the solvent or diluent in the extraction of carboxylic acids. A disadvantage of OA is its relatively high viscosity of 28.32 mPa s at 25°C. This can be decreased by the application of a less viscous OA diluent, e.g. dodecane. The relationship between the ratio of the distribution coefficient of butyric acid (BA), D _F, and the viscosity of OA-dodecane solvents, µ, as extraction and transport characteristics, and the overall mass-transfer coefficient, K _p, through SLMs was analyzed. Dependence of the D _F/µ ratio on the OA concentration showed a maximum at the OA concentration of 15 mass % to 30 mass %. The OA concentration dependence of K _p for SLMs exhibited also a maximum at about 30 mass % and 20 mass % of OA at the BA concentration driving force of 0.12 kmol m^?3 and 0.3 kmol m^?3, respectively. Shifting of the maximum in K _p dependences towards lower OA concentrations by increasing the BA concentration driving force is in agreement with the D _F/µ ratio dependence. Using pure OA as the solvent or diluent is not preferable and a mixture of a low viscosity diluent with the OA concentration below 40 mass % should be used. The presented results show the potential of the D _F/µ ratio in the screening and formulation of solvents in extraction and SLM optimization.     

Antiprotozoal and Antibacterial Activity of Ravenelin,a Xanthone Isolated from the Endophytic Fungus Exserohilum rostratum

The natural compound ravenelin was isolated from the biomass extracts of Exserohilum rostratum fungus, and its antimicrobial, antiplasmodial, and trypanocidal activities were evaluated. Ravenelin was isolated by column chromatography and HPLC and identified by NMR and MS. The susceptibility of Gram-positive and Gram-negative bacteria strains to ravenelin was determined by microbroth dilution assay. Cytotoxicity was evaluated in hepatocarcinoma cells (HepG2) and BALB/c peritoneal macrophages by using MTT. SYBR Green I-based assay was used in the asexual stages of Plasmodium falciparum. Trypanocidal activity was tested against the epimastigote and intracellular amastigote forms of Trypanosoma cruzi. Ravenelin was active against Gram-positive bacteria strains, with emphasis on Bacillus subtilis (MIC value of 7.5 µM). Ravenelin’s antiparasitic activities were assessed against both the epimastigote (IC₅₀ value of 5 ± 1 µM) and the intracellular amastigote forms of T. cruzi (IC₅₀ value of 9 ± 2 µM), as well as against P. falciparum (IC₅₀ value of 3.4 ± 0.4 µM). Ravenelin showed low cytotoxic effects on both HepG2 (CC₅₀ > 50 µM) and peritoneal macrophage (CC₅₀ = 185 ± 1 µM) cells with attractive selectivity for the parasites (SI values > 15). These findings indicate that ravenelin is a natural compound with both antibacterial and antiparasitic activities, and considerable selectivity indexes. Therefore, ravenelin is an attractive candidate for hit-to-lead development.     

Immobilization of Eversa® Transform via CLEA Technology Converts It in a Suitable Biocatalyst for Biolubricant Production Using Waste Cooking Oil

The performance of the previously optimized magnetic cross-linked enzyme aggregate of Eversa (Eversa-mCLEA) in the enzymatic synthesis of biolubricants by transesterification of waste cooking oil (WCO) with different alcohols has been evaluated. Eversa-mCLEA showed good activities using these alcohols, reaching a transesterification activity with isoamyl alcohol around 10-fold higher than with methanol. Yields of isoamyl fatty acid ester synthesis were similar using WCO or refined oil, confirming that this biocatalyst could be utilized to transform this residue into a valuable product. The effects of WCO/isoamyl alcohol molar ratio and enzyme load on the synthesis of biolubricant were also investigated. A maximum yield of around 90 wt.% was reached after 72 h of reaction using an enzyme load of 12 esterification units/g oil and a WCO/alcohol molar ratio of 1:6 in a solvent-free system. At the same conditions, the liquid Eversa yielded a maximum ester yield of only 34%. This study demonstrated the great changes in the enzyme properties that can be derived from a proper immobilization system. Moreover, it also shows the potential of WCO as a feedstock for the production of isoamyl fatty acid esters, which are potential candidates as biolubricants.     

Intra- and Inter-molecular Sulf- hydryl Hydrogen Bonding: Facilitating Proton Transfer Events for Determination of pH in Sea Water

This work presents the electrochemical response of a 2-(methylthio)phenol glassy carbon based electrode for a promising voltammetric pH sensor in both buffered and low-buffered solutions. Electropolymerization of the redox species was performed with the resulting polymer presenting a Nernstian response in buffered media, with a sensitivity of 51 mV/pH unit. The effectiveness of the sulfhydryl bond to facilitate proton transfer from the bulk solution to the phenol molecules has been confirmed, providing an accurate pH measurement of 8.28 in sea water media, compared to that measured with a calibrated glass pH probe of 8.30.     

Confined ferrofluid droplet in crossed magnetic fields

When a ferrofluid drop is trapped in a horizontal Hele-Shaw cell and subjected to a vertical magnetic field, a fingering instability results in the droplet evolving into a complex branched structure. This fingering instability depends on the magnetic field ramp rate but also depends critically on the initial state of the droplet. Small perturbations in the initial droplet can have a large influence on the resulting final pattern. By simultaneously applying a stabilizing (horizontal) azimuthal magnetic field, we gain more control over the mode selection mechanism. We perform a linear stability analysis that shows that any single mode can be selected by appropriately adjusting the strengths of the applied fields. This offers a unique and accurate mode selection mechanism for this confined magnetic fluid system. We present the results of numerical simulations that demonstrate that this mode selection mechanism is quite robust and “overpowers” any initial perturbations on the droplet. This provides a predictable way to obtain patterns with any desired number of fingers.     

An Analytical Model for Flow of Seawater Adjacent to an Igneous Wall

Transport in Porous Media - We develop an analytical model describing the flow of NaCl– $$\hbox {H}_2\hbox {O}$$ in a saturated porous medium adjacent to a hot vertical wall and apply the...