Solvent Relaxation in Phospholipid Bilayers: Principles and Recent Applications

Although there exist a number of methods, such as NMR, X-ray, e.g., which explore the hydration of phospholipid bilayers, the solvent relaxation (SR) method has the advantage of simple instrumentation, easy data treatment and possibility of measuring fully hydrated samples. The main information gained from SR by the analysis of recorded “time-resolved emission spectra” (TRES) is micro-viscosity and micro-polarity of the dye microenvironment. Based on these parameters, one can draw conclusions about water structure in the bilayer. In this review, we focus on physical background of this method, on all the procedures that are needed in order to obtain relevant parameters, and on the requirements on the fluorescence dyes. Furthermore, a few recent applications (the effect of curvature, binding of antibacterial peptides and phase transition) illustrating the versatility of this method are mentioned. Moreover, limitations and potential problems are discussed.     

Long-term retention of ice-nucleating active Pseudomonas fluorescens by overwintering colorado potato beetles

Ice nucleating-active Pseudomonas fluorescens F264C was fed to Colorado potato beetles to determine bacterial retentioin in the beetle gut and its effect on the cold hardiness of this insect pest. The bacrterium was present in beetles recovered after overwintering in the field, seven months after their exposure to P. fluorescens. Retention was evident not only in the detection of the P. fluorescens ice nucleating gene, inaW, in bacterial cultures from beetle guts but also in the elevated supercooling points of some treated beetles.     

Low-lying (K π = 0+) states of gadolinium isotopes

The sd-interacting boson approximation (sd-IBA) and the df-interacting boson approximation (df-IBA) can be related to each other and the states of the interacting boson approximation model can be identified with the fully symmetric states in the sdf interacting boson approximation model. A systematic study of the sdf-IBA model showed that the constructed Hamiltonian can successfully describe the strong octupole correlations in the deformed nuclei. We showed that the interacting boson approximation may account for many of these K ^π ?=?0⁺ states. It was found that the calculated energy spectra of the gadolinium isotopes agree quite well with the experimental data. The observed B(E2) values were also calculated and compared with the experimental data.     

Magnetism and Raman spectroscopy of the dimeric lanthanide iodates Ln(IO3)3 (Ln=Gd, Er) and magnetism of Yb(IO3)3

Colorless single crystals of Gd(IO₃)₃ or pale pink single crystals of Er(IO₃)₃ have been formed from the reaction of Gd metal with H₅IO₆ or Er metal with H₅IO₆ under hydrothermal reaction conditions at 180 °C. The structures of both materials adopt the Bi(IO₃)₃ structure type. Crystallographic data are (MoKα, λ=0.71073 Å): Gd(IO₃)₃, monoclinic, space group P2₁/n, a=8.7615(3) Å, b=5.9081(2) Å, c=15.1232(6) Å, β=96.980(1)°, V=777.03(5) Z=4, R(F)=1.68% for 119 parameters with 1930 reflections with I>2σ(I); Er(IO₃)₃, monoclinic, space group P2₁/n, a=8.6885(7) Å, b=5.9538(5) Å, c=14.9664(12) Å, β=97.054(1)°, V=768.4(1) Z=4, R(F)=2.26% for 119 parameters with 1894 reflections with I>2σ(I). In addition to structural studies, Gd(IO₃)₃, Er(IO₃)₃, and the isostructural Yb(IO₃)₃ were also characterized by Raman spectroscopy and magnetic property measurements. The results of the Raman studies indicated that the vibrational profiles are adequately sensitive to distinguish between the structures of the iodates reported here and other lanthanide iodate systems. The magnetic measurements indicate that only in Gd(IO₃)₃ did the 3+ lanthanide ion exhibit its full 7.9 μ_B Hund's rule moment; Er³⁺ and Yb³⁺ exhibited ground state moments and gap energy scales of 8.3 μ_B/70 K and 3.8 μ_B/160 K, respectively. Er(IO₃)₃ exhibited extremely weak ferromagnetic correlations (+0.4 K), while the magnetic ions in Gd(IO₃)₃ and Yb(IO₃)₃ were fully non-interacting within the resolution of our measurements (∼0.2 K).     

Enzyme Shielding in an Enzyme‐thin and Soft Organosilica Layer

The fragile nature of most enzymes is a major hindrance to their use in industrial processes. Herein, we describe a synthetic chemical strategy to produce hybrid organic/inorganic nanobiocatalysts; it exploits the self‐assembly of silane building blocks at the surface of enzymes to grow an organosilica layer, of controlled thickness, that fully shields the enzyme. Remarkably, the enzyme triggers a rearrangement of this organosilica layer into a significantly soft structure. We demonstrate that this change in stiffness correlates with the biocatalytic turnover rate, and that the organosilica layer shields the enzyme in a soft environment with a markedly enhanced resistance to denaturing stresses.     

First Structural Determination of a Trivalent Californium Compound with Oxygen Coordination.

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PHOTOREACTIVITY OF 5-GERANOXYPSORALEN AND LACK OF PHOTOREACTION WITH DNA

5-Geranoxypsoralen, commonly called bergamottin, a major furocoumarin contained in bergamot oil, is reported in vitro as a highly photoreactive psoralen. In ethanol, it exhibits quite a high triplet state quantum yield (approximately 0.37). The triplet state is involved in subsequent photochemistry which depends on the initial concentration and on the presence of oxygen. In contrast to most psoralens, absorption and fluorescence data suggest that 5-geranoxypsoralen does not interact with DNA in the dark. No UVA-induced interstrand cross-links in DNA were shown.     

Synthesis and Characterization of a Helicene‐Based Imidazolium Salt and Its Application in Organic Molecular Electronics

Herein we demonstrate the synthesis of a helicene‐based imidazolium salt. The salt was prepared by starting from racemic 2‐methyl[6]helicene, which undergoes radical bromination to yield 2‐(bromomethyl)[6]helicene. Subsequent treatment with 1‐butylimidazole leads to the corresponding salt 1‐butyl‐3‐(2‐methyl[6]helicenyl)‐imidazolium bromide. The prepared salt was subsequently characterized by using NMR spectroscopy and X‐ray analysis, various optical spectrometric techniques, and computational chemistry tools. Finally, the imidazolium salt was immobilized onto a SiO₂ substrate as a crystalline or amorphous deposit. The deposited layers were used for the development of organic molecular semiconductor devices and the construction of a fully reversible humidity sensor.