Comparison of Yarrowia lipolytica and Pichia pastoris Cellular Response to Different Agents of Oxidative Stress

Yeast cells exposed to adverse conditions employ a number of defense mechanisms in order to respond effectively to the stress effects of reactive oxygen species. In this work, the cellular response of Yarrowia lipolytica and Pichia pastoris to the exposure to the ROS-inducing agents’ paraquat, hydrogen peroxide, and increased air pressure was analyzed. Yeast cells at exponential phase were exposed for 3 h to 1 mM paraquat, to 50 mM H₂O₂, or to increased air pressure of 3 or 5 bar. For both strains, the cellular viability loss and lipid peroxidation was lower for the cells exposed to increased air pressure than for those exposed to chemical oxidants. The glutathione induction occurred only in Y. lipolytica strain and reached the highest level as a response to PQ exposure. In general, antioxidant enzymes were more expressed in Y. lipolytica than in P. pastoris. The enzyme superoxide dismutase was induced in both strains under all the oxidant conditions but was dependent on the cellular growth phase, being undetectable in non-growing cells, whereas glutathione reductase was more induced in those conditions. Hydrogen peroxide was the most efficient inducer of catalase. Both yeast cultures underwent no cellular growth inhibition with increased air pressure, indicating that these yeast species were able to adapt to the oxidative stressful environment.     

Lipid nanotube formation from streptavidin-membrane binding

A novel transformation of giant lipid vesicles to produce nanotubular structures was observed upon the binding of streptavidin to biotinylated membranes. Unlike membrane budding and tubulation processes caused by proteins involved with endocytosis and vesicle fusion, streptavidin is known to crystallize at near the isoelectric point (pI 5 to 6) into planar sheets against biotinylated films. We have found, however, that at neutral pH membranes of low bending rigidity (<10kT), such as 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), spontaneously produce tubular structures with widths ranging from micrometers to below the diffraction limit (<250 nm) and lengths spanning up to hundreds of micrometers. The nanotubes were typically held taut between surface-bound vesicles suggesting high membrane tension, yet the lipid nanotubes exhibited a fluidic nature that enabled the transport of entrained vesicles. Confocal microscopy confirmed the uniform coating of streptavidin over the vesicles and nanotubes. Giant vesicles composed of lipid membranes of higher bending energy exhibited only aggregation in the presence of streptavidin. Routes toward the development of these highly curved membrane structures are discussed in terms of general protein-membrane interactions.     

Non-isothermal depolymerisation kinetics of poly(ethylene oxide)

The depolymerisation of low molecular weight poly(ethylene oxide) (PEO) under mild conditions was studied using a linear temperature ramped non-isothermal technique and the results compared with those obtained from a conventional isothermal technique. The analysis of the non-isothermal kinetic (NIK) data was performed using an original computer program incorporating an algorithm that systematically minimizes the sum of the squares of the residuals between the experimental data and the calculated theoretical kinetic profile in order to extract the kinetic parameters. The results revealed that the depolymerisation of PEO proceeds in accordance with the Ekenstam model and follows the Arrhenius equation over the temperature range of ca. 40-130 °C. The NIK analysis resulted in a two-dimensional convergence to produce a unique solution set for the kinetic parameters of E_a = 89.4 kJ mol⁻¹ and A = 9.6 × 10⁶ h⁻¹. These data are consistent with the results obtained from the isothermal experiments. It is proposed that NIK analysis is a quick and reliable means of obtaining kinetic parameters relevant to lifetime predictions in polymers whose degradation behaviour can be considered to be close to ideal.     

Synthesis, spectroscopic characterization, and conformational properties of trichloromethanesulfenyl acetate, CCl3SOC(O)CH3

Trichloromethanesulfenyl acetate, CCl 3SOC(O)CH 3, belongs to the family of sulfenic esters. This molecule has been characterized by vibrational spectroscopy. The conformational and geometrical properties of this species have been determined by IR and Raman spectroscopy, X-ray diffraction, and quantum chemical calculations. Geometry optimizations of the most stable forms were performed with ab initio (HF, MP2) and density functional theory (B3LYP) methods. According to our data, this compound results in a gauche-syn conformer with C 1 symmetry (gauche orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the most stable geometry, and trans-syn conformer with C s symmetry (trans orientation around the S-O bond and syn orientation of the CO double bond with respect to the S-O single bond) for the second stable conformer (1.1 and 0.53 kcal/mol higher in energy than the most stable C 1 form according to the matrix FTIR spectroscopy and MP2/6-31G* level of the theory, respectively). The crystalline solid (monoclinic, P2 1/ n, a = 8.0152(17) A, b = 5.7922(13) A, c = 17.429(4) A, alpha = gamma = 90 degrees , beta = 100.341(3) degrees ) consists exclusively of the main form. The geometrical parameters (X-ray diffraction) are d C-Cl = 1.767(19) A, d C-S = 1.797(2) A, d S-O = 1.663(14) A, d CO = 1.189(2) A, d O-C = 1.389(3) A, d C-C = 1.483(3) A, angles Cl-C-Cl = 110.3(11) degrees , Cl-C-S = 111.8(12) degrees , C-S-O = 97.4(8) degrees , S-O-C = 116.7(11) degrees , O-CO = 122.8(19) degrees , OC-C = 127.1(2) degrees , and the main torsion angles are delta(CSOC) = 105.9(15) degrees and delta(SOC(O)) = 7.6(3) degrees . The geometrical data calculated with B3LYP/6-31G++(3df,3pd), B3LYP/6-311G++(3df,3pd), B3LYP/aug-cc-pVTZ, and MP2/6-31G* are in good agreement with diffraction data.     

Nucleophilic Aromatic Substitution on Pentafluorophenyl‐Substituted Dipyrranes and Tetrapyrroles as a Route to Multifunctionalized Chromophores for Potential Application in Photodynamic Therapy

The application of porphyrinoids in biomedical fields, such as photodynamic therapy (PDT), requires the introduction of functional groups to tune their solubility for the biological environment and to allow a coupling to other active moieties or carrier systems. A valuable motif in this regard is the pentafluorophenyl (PFP) substituent, which can easily undergo a regiospecific nucleophilic replacement (S_NAr) of its para‐fluorine atom by a number of nucleophiles. Here, it is shown that, instead of amino‐substitution on the final porphyrinoid or BODIPY (boron dipyrromethene), the precursor 5‐(PFP)‐dipyrrane can be modified with amines (or alcohols). These dipyrranes were transformed into amino‐substituted BODIPYs. Condensation of these dipyrranes with aldehydes gave access to trans‐A₂B₂‐porphyrins and trans‐A₂B‐corroles. By using pentafluorobenzaldehyde, it was possible to introduce another para‐fluorine atom, which enabled the synthesis of multifunctionalized tetrapyrroles. Furthermore, alkoxy‐ and amino‐substituted dipyrranes were applied to the synthesis of A₃B₃‐hexaphyrins. The polar porphyrins that were prepared by using this method exhibited in vitro PDT activity against several tumor cell lines.     

Use of Magnetic Resonance Imaging as a Tool for the Study of Foamy Oil Behavior for an Extra‐Heavy Crude Oil. T2 /Viscosity Correlation with Respect to Pressure

The purpose of this work is to present the results of the phase behavior study for a live heavy oil during a pressure depletion process using magnetic resonance imaging (MRI) as a tool to characterize foamy oil phenomena. The experiments were carried out in the pressure range of 13.1 to 1.4MPa. Signal intensity images were obtained at each pressure and with respect to time, that is, approximately for a total time of 3h after each pressure change. It is possible to see a variation in intensity across the sample. These changes can be associated with changes in mobility as well as segregation of the oil. It was also possible to observe that what we trust is the formation of gas channels at the last two pressure values, as it comes out of solution. A correlation between the transverse relaxation time T2 and temperature was established with the aim of producing one between T2 and viscosity. In this way viscosity maps for the live oil were obtained as a function of pressure and time. It was observed that above the bubble point, the viscosity maps varied from low to high to low with respect to time for the same pressure. Below the bubble point the situation is reverse. The viscosity map changes from high to low to high with respect to time for the same pressure. The study shows the potential use of MRI to follow viscosity changes during pressure depletion test in a PVT MRI cell.     

Analysis of the piezoelectric properties of tangentially polarized, stripe-electroded cylinders

The electromechanical properties of thin tangentially polarized, stripe-electroded piezoceramic elements are considered. Theoretical analysis is made based on a piecewise linear approximation of the actual nonuniform electric field in the volume of the stripe-electroded cylinder design. Analytical expressions are derived for the electromechanical properties (including the effective coupling coefficient) of the tangentially polarized elements as a function of the geometry and electrode configuration (i.e., electrode width and spacing). The properties of stripe-electroded cylinders are calculated and compared with the ideal case of a uniform circumferential electric field, which may be realized in practice with segmented cylinders comprised of 33-polarized bar elements. The reasons for the reduction in the effective coupling coefficient of tangentially polarized stripe-electroded cylinders compared to the ideal coupling coefficient k(33) achievable with the segmented cylinder designs are discussed. The results of calculations of the electromechanical properties are in good agreement with experimentally obtained data on a variety of samples.     

Experimental investigation of effects of variation in heating rate,temperature and heat flux on fire properties of a non-charring polymer

Journal of Thermal Analysis and Calorimetry - Differential scanning calorimetry (DSC) technique is used to study the solid reactions in the 2024 Al–Cu–Mg and 2014...