Magnetic Circular Dichroism Study of Analogues of the DNA Binding Ligands Netropsin and Distamycin A

UV absorption and MCD data of a complete series of netropsin-like oligopeptides containing between one and five N-methyl-pyrrole residues are reported. The presence of three MCD bands in the region between 220 and 350 nm can be related to the resonance of the peptide groups with the methylpyrrole systems of the oligopeptides. The longest wavelength absorption bands of all netropsin-like compounds investigated are ascribed to two electronic transitions of the resonance methypyrrole-carboxamide units. - Complex formation with DNA affects these MCD bands and hence modifies the transitions. This is explained by hypercon-jugation in the chromophoric system as a result of specific hydrogen bonding of peptide groups with dA·dT pairs of double stranded DNA.     

Click Chemistry in Ultra-high Vacuum – Tetrazine Coupling with Methyl Enol Ether Covalently Linked to Si(001)

The additive-free tetrazine/enol ether click reaction was performed in ultra-high vacuum (UHV) with an enol ether group covalently linked to a silicon surface: Dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate molecules were coupled to the enol ether group of a functionalized cyclooctyne which was adsorbed on the silicon (001) surface via the strained triple bond of cyclooctyne. The reaction was observed at a substrate temperature of 380 K by means of X-ray photoelectron spectroscopy (XPS). A moderate energy barrier was deduced for this click reaction in vacuum by means of density functional theory based calculations, in good agreement with the experimental results. This UHV-compatible click reaction thus opens a new, flexible route for synthesizing covalently bound organic architectures.     

Cellular resolution optical coherence microscopy with high acquisition speed for in-vivo human skin volumetric imaging

In this Letter, we report for the first time (to our knowledge) in-vivo volumetric optical coherence microscopy images of skin epidermal cells. We achieved micrometer-class resolution, 2 μm laterally and axially, with an acquisition speed of 23 K A-scans/s and over 90 dB sensitivity to a depth of 1 mm by employing a custom, liquid-lens-based, dynamic-focusing objective, a broadband light source, and a custom, astigmatism-corrected Czerny-Turner spectrometer with a high-speed complementary metal-oxide-semiconductor camera.     

Ionic liquids: structuration agents in a fluorinated matrix

The use of ionic liquids as functional building blocks based on pyridinium, imidazolium and phosphonium cations to achieve materials combining a structuration at nanoscale with the dramatic mechanical properties of the resulting ionomers has been successfully demonstrated for the first time in a fluorinated matrix.     

Bessel beam spectral-domain high-resolution optical coherence tomography with micro-optic axicon providing extended focusing range

Endoscopic imaging in tubular structures, such as the tracheobronchial tree, could benefit from imaging optics with an extended depth of focus (DOF) to accommodate the varying sizes of tubular structures across patients and along the tree within the same patient. Yet the extended DOF needs to be accomplished without sacrificing resolution while maintaining sufficient sensitivity and speed of imaging. In this Letter, we report on the measured resolution and sensitivity achieved with a custom-made micro-optic axicon lens designed to theoretically achieve an 8 mm DOF. A measured invariant resolution of approximately 8 microm is demonstrated across a 4 mm measured DOF using the micro-optic axicon while achieving an invariant sensitivity of approximately 80 dB with a 25 mW input power. Double-pass Bessel beam spectral-domain optical coherence tomography with an axicon micro-optic lens (i.e., <1 mm in diameter) is, for the first time to our knowledge, demonstrated in a biological sample demonstrating invariant resolution and signal-to-noise ratio across a 4 mm measured DOF, which is compared to Gaussian beam imaging.     

In situ generation of high aspect ratio silica particles in polypropylene

Polypropylene/silica microcomposites with high aspect ratio silica fillers were in situ generated into a molten polypropylene (PP) matrix. The synthesis of the inorganic domains are based on hydrolysis-condensation reactions of both alkoxysilanes precursors, the tetraethoxysilane (TEOS) and the Dynasil^? 40 (composed of TEOS and partially condensed TEOS with residual ethoxy groups) respectively. The sol?Cgel reactions kinetics studied at room temperature into an acid hydroalcoholic medium for several conditions of pH associated to the processing conditions were the keys factors to control the deformability of the inorganic droplets. Thanks to a shearing hot stage coupled with an optical microscope, silica needles were obtained with a Dynasil^? 40 solution treated 120?min at pH?=?3 in presence of 4?g of ethanol and then placed between two slices of PP in the stage. The deformation of the droplets were then observed once the material was molten and a shearing applied. On the contrary, no deformation was possible with TEOS precursors solutions. The results transposed to the microextruder process equipped at the die with a drawing line allowed to obtain a well pronounced elongated shape of the silica particles dispersed in the polypropylene matrix.     

N‐Heterocyclic Olefin–Carbon Dioxide and –Sulfur Dioxide Adducts: Structures and Interesting Reactivity Patterns

Depending on the amount of methanol present in solution, CO₂ adducts of N‐heterocyclic carbenes (NHCs) and N‐heterocyclic olefins (NHOs) have been found to be in fully reversible equilibrium with the corresponding methyl carbonate salts [EMIm][OCO₂Me] and [EMMIm][OCO₂Me]. The reactivity pattern of representative 1‐ethyl‐3‐methyl‐NHO–CO₂ adduct 4 has been investigated and compared with the corresponding NHC–CO₂ zwitterion: The protonation of 4 with HX led to the imidazolium salts [NHO–CO₂H][X], which underwent decarboxylation to [EMMIm][X] in the presence of nucleophilic catalysts. NHO–CO₂ zwitterion 4 can act as an efficient carboxylating agent towards CH acids such as acetonitrile. The [EMMIm] cyanoacetate and [EMMIm]₂ cyanomalonate salts formed exemplify the first C?C bond‐forming carboxylation reactions with NHO‐activated CO₂. The reaction of the free NHO with dimethyl carbonate selectively led to methoxycarbonylated NHO, which is a perfect precursor for the synthesis of functionalized ILs [NHO–CO₂Me][X]. The first NHO‐SO₂ adduct was synthesized and structurally characterized; it showed a similar reactivity pattern, which allowed the synthesis of imidazolium methyl sulfites upon reaction with methanol.