The Self-Association of the KRAS4b Protein is Altered by Lipid-Bilayer Composition and Electrostatics

KRAS is a peripheral membrane protein that regulates multiple signaling pathways, and is mutated in ≈30 % of cancers. Transient self-association of KRAS is essential for activation of the downstream effector RAF and oncogenicity. The presence of anionic phosphatidylserine (PS) lipids in the membrane was shown to promote KRAS self-assembly, however, the structural mechanisms remain elusive. Here, we employed nanodisc bilayers of defined lipid compositions, and probed the impact of PS concentration on KRAS self-association. Paramagnetic NMR experiments demonstrated the existence of two transient dimer conformations involving alternate electrostatic contacts between R135 and either D153 or E168 on the “α4/5-α4/5” interface, and revealed that lipid composition and salt modulate their dynamic equilibrium. These dimer interfaces were validated by charge-reversal mutants. This plasticity demonstrates how the dynamic KRAS dimerization interface responds to the environment, and likely extends to the assembly of other signaling complexes on the membrane.     

Unexpected acceleration of Ultrasonic-Assisted iodide dosimetry in the catalytic presence of ionic liquids

This study investigates the potential of using small amounts of ionic liquids (IL) to enhance ultrasound-assisted extraction of lipids content from green microalgae. Three imidazolium-based ILs (butyl, octyl and dodecyl), each of them with two anions (bromide and acetate) were tested as additives. Viscosity and surface tension of the ILs aqueous mixtures were analyzed to determine the influence of ILs’ anions and alkyl chain length, whereas KI dosimetry experiments were used as an indicator of radicals formation. A key finding suggests that the small addition of ILs improves the ultrasonication either by enhancing the viscosity and reducing the water surface tension, leading to a more powerful acoustic cavitation process or by increasing HO° production likely to oxidize the microalgae cells membranes, and consequently disrupting them on a more efficient manner. KI dosimetry also revealed that long ILs alkyl chain is detrimental. This experimental observation is confirmed thus strengthened as the yield of extracted lipids from green microalgae has shown an incremental trend when the IL concentration also increased. These hypotheses are currently under investigation to spot detailed impact of ILs on cavitation process.     

Contribution of Supercritical Fluid Chromatography coupled to High Resolution Mass Spectrometry and UV detections for the analysis of a complex vegetable oil – Application for characterization of a Kniphofia uvaria extract

Lipids are an important and diverse group of naturally occurring organic compounds present in all biological entities. They play many essential roles in the survival of the organisms. Analysis of lipids is extremely complex due to their large variety of chemistries. In this work, we describe an innovative method for the characterization of the lipid composition in a complex and unknown vegetable oil: an extract of Kniphofia uvaria seeds; using Supercritical Fluid Chromatography (SFC) coupled to Atmospheric Pressure Chemical Ionization (APCI), High-Resolution Mass Spectrometry (HRMS) and UV detections. Thanks to the properties of supercritical CO₂ allowing the use of a large number of chromatographic columns, an effective separation for this complex matrix was obtained.     

EPR Spectroscopic Studies of Lipoxygenases

Polyunsaturated fatty acids are sources of diverse natural, and chemically designed products. The enzyme lipoxygenase selectively oxidizes fatty acid acyl chains using controlled free radical chemistry; the products are regio‐ and stereo‐chemically unique hydroperoxides. A conserved structural fold of ≈600 amino acids harbors a long and narrow substrate channel and a well‐shielded catalytic iron. Oxygen, a co‐substrate, is blocked from the active site until a hydrogen atom is abstracted from substrate bis‐allylic carbon, in a non‐heme iron redox cycle. EPR spectroscopy of ferric intermediates in lipoxygenase catalysis reveals changes in the metal coordination and leads to a proposal on the nature of the reactive intermediate. Remarkably, free radicals are so well controlled in lipoxygenase chemistry that spin label technology can be applied as well. The current level of understanding of steps in lipoxygenase catalysis, from the EPR perspective, will be reviewed.     

On the Reactivity of Metal and Organometallic Halides and Pseudohalides Towards Stannosiloxane (Ph3Sn-O-SiPh3)

Abstract

Interactions of HgX₂ (X = Cl, Br, I, SCN, CN, NCO), SbCl₃, TeCl₄, and PhTeCl₃ with Ph₃Sn-O-SiPh₃ at room temperature have been found to proceed with the simultaneous cleavage of Sn-O and Si-O bonds, invariably yielding Ph₂SnO, Ph₃SiX, and the corresponding organo-mercury, -antimony, and -tellurium derivatives. The course of the reactions suggests the instability of the Sn-O-M (M = Hg, Sb, Te) system.

GRAPHICAL ABSTRACT      

Precessional frequency of ferromagnetic elements: Influence of magnetic domain width

A model is presented that semi-quantitatively describes the dependence of precessional frequency on magnetic domain width in ferromagnetic thin film elements. With decreasing domain width an increase of precessional frequency at zero-bias field by a factor of about 1.5 is found experimentally and from the calculations. The modelled value of change of precessional frequency is in agreement with the experimental results. The simple model offers the opportunity to relate the drastic effects of domain structure on the dynamic magnetic properties of soft-magnetic thin films by a straightforward approach.     

Debye series expansion of shaped beam scattering by GI-POF

We derive Debye series expansion (DSE) for infinitely long multilayered cylinders normally incident by shaped beam. Typically the interaction between multilayered cylinders and Gaussian beam is derived in detail, and localized approximation is introduced to calculate the beam shaped coefficients. Finally DSE is employed to the study of rainbow scattering by graded-index polymer optical fiber (GI-POF).     

The structural and optical properties of ZnO/Si thin films by RTA treatments

ZnO/Si thin films were prepared by rf magnetron sputtering method and some of the samples were treated by rapid thermal annealing (RTA) process at different temperatures ranging from 400 to 800 °C. The effects of RTA treatment on the structural properties were studied by using X-ray diffraction and atomic force microscopy while optical properties were studied by the photoluminescence measurements. It is observed that the ZnO film annealed at 600 °C reveals the strongest UV emission intensity and narrowest full width at half maximum among the temperature ranges studied. The enhanced UV emission from the film annealed at 600 °C is attributed to the improved crystalline quality of ZnO film due to the effective relaxation of residual compressive stress and achieving maximum grain size.     

Phase transformation in BN films by nitrogen-protected annealing at atmospheric pressure

Two groups of RF-sputtered BN films (pure hexagonal phase and approximately 27.5% cubic content, respectively) were annealed at 600 to 1000 °C under nitrogen at atmospheric pressure after deposition. FTIR spectroscopy indicates a reversible transformation from hexagonal phase to cubic phase, and again hexagonal phase. The most effective temperature for h-BN converting to cubic zincblende (c-BN) is 900 °C. Further, the indirectly stepwise transformation from hexagonal (h-BN) to explosive BN (E-BN) and then to c-BN employing metastable E-BN as an intermedium was observed. In addition, we tentatively put forward that the existence of defective h-BN and the N defects plays a key role on h-BN to c-BN transformation.     

Minority Carrier Lifetime in As-Grown Germanium Doped Czochralski Silicon

The minority carrier lifetime of as-grown germanium-doped Czochralski （GCZ） silicon wafers doped with germanium concentrations [Ge]=10^16-10^18 cm^-3 is investigated in comparison with conventional CZ silicon samples. It is found that the lifetime distribution along the ingot changes with the variation of[Ge]. There is a critical value of [Ge] = 10^16 cm^-3 beyond which Ge can obviously influence the lifetime of as-grown ingots. This phenomenon is considered to be associated with the competition or combination between the oxygen related thermal donors （TDs） and electrically active Ge-related complexes. The related formation mechanisms and distributions are also discussed.