On the localization of water-soluble porphyrins in micellar systems evaluated by static and time-resolved frequency-domain fluorescence techniques

Fluorescence quenching of meso-tetrakis-4-sulfonatophenyl (TPPS(4)) and meso-tetrakis-4-N-methylpyridil (TMPyP) porphyrins is studied in aqueous solution and upon addition of micelles of sodium dodecylsulfate (SDS), cetyltrimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and t-octylphenoxypolyethoxyethanol (Triton X-100). Potassium iodide (KI) was used as quencher. Steady-state Stern-Volmer plots were best fitted by a quadratic equation, including dynamic (K(D)) and static (K(S)) quenching. K(S) was significantly smaller than K(D). Frequency-domain fluorescence lifetimes allowed estimating bimolecular quenching constants, k(q). At 25 degrees C, in aqueous solution, TMPyP shows k(q) values a factor of 2-3 higher than the diffusional limit. TPPS(4) shows collisional quenching with pH dependent k(q) values. For TMPyP quenching results are consistent with reported binding constants: a significant reduction of quenching takes place for SDS, a moderate reduction is observed for HPS and almost no change is seen for Triton X-100. Similar data were obtained at 50 degrees C. For CTAC-TPPS(4) system an enhancement of quenching was observed as compared to pure buffer. This is probably associated to accumulation of iodide at the cationic micellar interface. The attraction between CTAC headgroups and I(-), and repulsion between SDS and I(-), enhances and reduces the fluorescence quenching, respectively, of porphyrins located at the micellar interface. The small quenching of TPPS(4) in Triton X-100 is consistent with strong binding as reported in the literature.     

Immobilized microorganisms in the reduction of ethyl benzoylacetate

The enantioselective reduction of ethyl benzoylacetate (EBA) into ethyl (S)-3-hydroxy-3-phenylpropanoate (S-HPPE) by nine yeast strains and three filamentous fungi strains is described. The conversion obtained was in the range 0-89% and the enantiomeric excess was 100% in many cases. Conversion levels were higher when the reduction was performed with microorganisms immobilized in calcium alginate and enantioselectivity remained excellent. Some reaction’s conditions of bioreduction by immobilized cells of Rhodotorula rubra were studied using a 2^5-2 fractional factorial design.     

Antifungal Effect and Inhibition of the Virulence Mechanism of D-Limonene against Candida parapsilosis

Yeasts from the Candida parapsilosis complex are clinically relevant due to their high virulence and pathogenicity potential, such as adherence to epithelial cells and emission of filamentous structures, as well as their low susceptibility to antifungals. D-limonene, a natural compound, emerges as a promising alternative with previously described antibacterial, antiparasitic, and antifungal activity; however, its mechanisms of action and antivirulence activity against C. parapsilosis complex species have not been elucidated. Therefore, in the present study, we aimed to evaluate the antifungal and antivirulence action, as well as the mechanism of action of D-limonene against isolates from this complex. D-limonene exhibited relevant antifungal activity against C. parapsilosis complex yeasts, as well as excellent antivirulence activity by inhibiting yeast morphogenesis and adherence to the human epithelium. Furthermore, the apoptotic mechanism induced by this compound, which is not induced by oxidative stress, represents an important target for the development of new antifungal drugs.     

Analytic Binding Energies for Two-Baryon Bound States in 2 + 1 Strongly Coupled Lattice QCD With Two-Flavors

We consider a lattice SU(3) QCD model in 2 + 1 dimensions, with two flavors and 2 × 2 spin matrices. An imaginary time functional integral formulation with Wilson’s action is used in the strong coupling regime, i.e. small hopping parameter ${0 < \kappa \ll 1}$ , and much smaller plaquette coupling ${\beta, 0 < \beta \ll \kappa}$ . In this regime, it is known that the low-lying energy-momentum spectrum contains isolated dispersion curves identified with baryons and mesons with asymptotic masses ${m\approx-3\ln\kappa}$ and ${m_m\approx-2\ln\kappa}$ , respectively. We prove the existence of two (labelled by ±) two-baryon bound states for each of the total isospin sectors I = 0,1 and we obtain, in each case, the exact binding energies ${\epsilon_{I\,\pm} }$ (of order ${\kappa^2}$ ) which extend to jointly analytic function in ${\kappa}$ and β. We also prove that these points are the only mass spectrum up to slightly above the bound state masses. Precisely, we show, for ${\alpha_0=\frac 14, \alpha_1=\frac 1{12}, \alpha_2=\frac12, \alpha_3=\frac 34}$ and small ${\delta >0 }$ , that the bound state masses ${2m-\epsilon_{I\,\pm}}$ are the only points in the mass spectrum in ${(0,2m-\epsilon_{I\,\pm}+\delta \alpha_I\kappa^2)}$ , for I = 0,1, and in ${(0,2m-(1+\delta)\alpha_I\kappa^2)}$ , for I = 2,3. These results are exact and validate our previous results obtained in a ladder approximation. The method employs suitable two- and four-point correlations with spectral representations and a lattice Bethe-Salpeter equation. For I = 0,1, a quark, antiquark space-range one potential of order ${\kappa^2}$ is found to be the dominant contribution to the two-baryon interaction and the interaction of the individual quark isospins of one baryon with those of the other is described by permanents. A novel spectral free decomposition (but spectral representation motivated, for real κ and β) of the two-point correlation, after performing a complex extension, is a key ingredient in showing the joint analyticity of the binding energy.     

The effects of acceleration in jets: kinematics of the near field vortices

Direct and large-eddy simulations (DNS/LES) of accelerating round jets are used to analyze the effects of acceleration on the kinematics of vortex rings in the near field of the jet (x/D < 12). The acceleration is obtained by increasing the nozzle jet velocity with time, in a previously established (steady) jet, and ends once the inlet jet velocity is equal to twice its initial value. Several acceleration rates (α = 0.02–0.6) and Reynolds numbers (Re _D = 500–20000) were simulated. Acceleration maps were used to make a detailed study of the kinematics of vortex rings in accelerating jets. One of the effects of the acceleration is to cause a number of new primary and secondary vortex merging events that are absent from steady jets. As the acceleration rate α increases, both the number of primary merging events between rings and the axial position where these take place decreases. The statistics for the speed of the starting ring that forms at the start of the acceleration phase for each simulation, agree well with the statistics for the “front” speed observed by Zhang and Johari (Phys Fluids 8:2185–2195, 1996). Acceleration maps and flow visualizations show that during the acceleration phase the near field coherent vortices become smaller and are formed at an higher frequency than in the steady jet, and their (mean) shedding frequency increases linearly with the acceleration rate. Finally, it was observed that the acceleration decreases the spreading rate of the jet, in agreement with previous experimental works.      

Network modeling of chromatography by stochastic phenomena of adsorption,diffusion and convection

The limitation of macroscopic models to represent structural parameters, such as topology and morphology, as well as population effects, i.e. multi-molecules movement, in the modeling of chromatography systems has implications on the understanding of the phenomenological aspects that contribute to the separation mechanisms in porous media. The representation of the porous structure of chromatographic columns by a three-dimensional cubic network of interconnected sites allows a better analysis of the structural characteristics of the porous column and its connection with the phenomena of adsorption, diffusion and convection. In the present work the application of an interconnected cubic network model associated with a stochastic modeling of the adsorption, diffusion and convection phenomena leads to the proper representation of the dynamic aspects of the breakthrough curves related to separation processes in chromatographic columns. Therefore, it is possible to study the dynamics of solute retention from the molecules distribution in the separation processes throughout the column. Among the mass transfer mechanisms investigated, the convection showed to be closely related to the separation dynamics of chromatography, with the diffusion having little effects. The adsorption influenced both the separation dynamics and solute retention.     

Surface characterization by XPS, contact angle measurements and ToF-SIMS of cellulose fibers partially esterified with fatty acids

The topochemistry of the controlled heterogeneous esterification of cellulose fibers with fatty acid chlorides of different chain length, both in swelling and non-swelling media, was assessed by X-ray Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and contact angle measurements. On the one hand, the results provided by the combined use of these three powerful techniques showed unambiguously the occurrence of the reaction at the fibers' surface and, on the other hand, the XPS results showed that the surface coverage with the fatty acid moieties increased with their chain length, but was only modestly affected by the degree of substitution (DS), suggesting that when the esterification yield was increased (higher DS values), an in-depth reaction also occurred, particularly when DMF was used as a cellulose swelling medium, involving the OH groups buried below the fibers' surface.     

Strong surjectivity of maps from 2-complexes into the 2-sphere

Given a model 2-complex K _P of a group presentation P, we associate to it an integer matrix Δ _P and we prove that a cellular map f: K _P → S ² is root free (is not strongly surjective) if and only if the diophantine linear system Δ _P Y = $ \overrightarrow {deg} $ \overrightarrow {deg} (f) has an integer solution, here $ \overrightarrow {deg} $ \overrightarrow {deg} (f)is the so-called vector-degree of f