Aerosol lenses propagation model

We propose a model based on the properties of cascading lenses modulation transfer function (MTF) to reproduce the irradiance of a screen illuminated through a dense aerosol cloud. In this model, the aerosol cloud is broken into multiple thin layers considered as individual lenses. The screen irradiance generated by these individual layers is equivalent to the point-spread function (PSF) of each aerosol lens. Taking the Fourier transform of the PSF as a MTF, we cascade the lenses MTF to find the cloud MTF. The screen irradiance is found with the Fourier transform of this MTF. We show the derivation of the model and we compare the results with the Undique Monte Carlo simulator for four aerosols at three optical depths. The model is in agreement with the Monte Carlo for all the cases tested.     

Exploring the Chemistry of Non-sticky Sugars: Synthesis of Polyfluorinated Carbohydrate Analogues of d-Allopyranose

There is a growing interest in the preparation of polyfluorinated carbohydrates. A limited number of fluorohexopyranosides have been used in biological investigations because of the synthetic challenge they present. Hence, we report the synthesis of fluorinated homodimer, fluorodisaccharides, C-terminal fluoroglycopeptides, lipoic acid fluoroglycoconjugate and trifluoroallopyranoside derivatives functionalized at C-6. Our strategy uses levoglucosan as inexpensive starting material and facilitates an approach to complex carbohydrate analogues with multiple C−F bonds. The challenge of our synthetic route centered around an efficient preparation of crucial 1,6-anhydro-2,4-dideoxy-difluoroglucopyranose and focused on achieving a difficult glycosylation of the trifluoroallopyranose donor. The results clearly highlight challenges related to the preparation of polyhalogenated complex organic molecules and pave the way to access novel medically relevant tools.     

A luminescent sensor for tyrosine phosphorylation

We have developed a luminogenic probe for tyrosine phosphorylation based on a short peptide sequence containing an iminodiacetate moiety near the site of phosphorylation. In response to kinase activity, the probe provides a strong luminescence enhancement, resulting from the increased ability of the probe to bind and sensitize Tb3+ and Eu3+ ions upon phosphorylation.     

Total synthesis of iejimalide A-D and assessment of the remarkable actin-depolymerizing capacity of these polyene macrolides

A concise and convergent total synthesis of the highly cytotoxic marine natural products iejimalide A-D (1-4) is reported, which relies on an effective ring-closing metathesis (RCM) reaction of a cyclization precursor containing no less than 10 double bonds. Because of the exceptional sensitivity of this polyunsaturated intermediate and its immediate precursors toward acid, base, and even gentle warming, the assembly process hinged upon the judicious choice of protecting groups and the careful optimization of all individual transformations. As a consequence, particularly mild protocols for Stille as well as Suzuki reactions of elaborate coupling partners have been developed that hold considerable promise for applications in other complex settings. Moreover, a series of non-natural "iejimalide-like" compounds has been prepared, differing from the natural lead in the polar head groups linked to the macrolide's N-terminus. With the aid of these compounds it was possible to uncover the hitherto unknown effect of iejimalide and analogues on the actin cytoskeleton. Their capacity to depolymerize this microfilament network rivals that of the latrunculins which constitute the standard in the field. Structural modifications of the peptidic terminus in 2 are thereby well accommodated, without compromising the biological effects. The iejimalides hence constitute an important new class of probe molecules for chemical biology in addition to their role as promising lead structures for the development of novel anticancer agents.     

Oxidation of 2'-deoxycytidine to four interconverting diastereomers of N1-carbamoyl-4,5-dihydroxy-2-oxoimidazolidine nucleosides

Modification of 2'-deoxycytidine (dCyd) by hydroxyl radicals and direct ionization leads to the formation of various oxidation products, including dCyd 5,6-glycols, 5-hydroxy-2'-deoxycytidine, and ring fragmentation products. The mechanism of oxidation is complex and poorly understood. In the present work, we have prepared four cis- and trans-diastereomers of N1-(2-deoxy-beta-D-erythro-pentofuranosyl)-1-carbamoyl-2-oxo-4,5-dihydroxyimidazolidine by bromination of dCyd followed by peroxidation of the resulting dCyd bromohydrins. The structure and stereochemistry of each product were determined by 1H NMR, 13C NMR, and 2D NOE analyses. The formation of imidazolidine products involves rearrangement of initial 5(6)-hydroxy-6(5)-hydroperoxides to C6-C2 endoperoxides, which subsequently decompose by a concerted pathway to imidazolidine products. A remarkable feature of the four diastereomers was their ability to interconvert via single and successive cycles of ring-chain tautomerism at N1-C5 and N3-C4, leading to epimerization of C5 and C4, respectively. The rate of isomerization was greater for cis-diastereomers compared to trans-diastereomers, and the rate sharply increased with pH (pH 9.0>7.0>5.5).     

Preparation, structural analysis and dielectric properties of Bi x La1−x FeO3 perovskite

Rare earth element substituted bismuth ferrites (BiFeO₃) are of enormous importance as magnetoelectric materials. The polycrystalline samples of Bi _x La_1−x FeO₃ (x=0, 0.2, 0.4, 0.6, 0.8) were prepared by solid-state reaction using standard ceramic method. The single-phase formation of these compounds was confirmed by X-ray diffraction (XRD) studies. The samples with x=0, 0.2, 0.4, 0.6 are found to be orthorhombic while the sample with x=0.8 is triclinic. The dielectric constant (ε′) and dissipation factor (tan δ) were measured in the frequency range 100 Hz to 1 MHz at room temperature and as a function of temperature at certain fixed frequencies (1 kHz, 10 kHz, 100 kHz, 1 MHz). All the samples showed dielectric dispersion. The dielectric constant with temperature shows a broad peak; the peak temperature shifts with frequency which reflects the relaxor-type behavior. The peak above 600 K in the measured temperature range corresponds to antiferromagnetic ordering temperature (Néel temperature). The broadness of the peak changes with composition. The ac conductivity as well as ε′ are found to be maximum for the sample x=0.2 at room temperature.     

Bicomplex Quantum Mechanics: I. The Generalized Schrödinger Equation

We introduce the set of bicomplex numbers which is a commutative ring with zero divisors defined by where We present the conjugates and the moduli associated with the bicomplex numbers. Then we study the bicomplex Schr?dinger equation and found the continuity equations. The discrete symmetries of the system of equations describing the bicomplex Schr?dinger equation are obtained. Finally, we study the bicomplex Born formulas under the discrete symmetries. We obtain the standard Born’s formula for the class of bicomplex wave functions having a null hyperbolic angle.