Coding for locality in reconstructing permutations

The problem of storing permutations in a distributed manner arises in several common scenarios, such as efficient updates of a large, encrypted, or compressed data set. This problem may be addressed in either a combinatorial or a coding approach. The former approach boils down to presenting large sets of permutations with locality, that is, any symbol of the permutation can be computed from a small set of other symbols. In the latter approach, a permutation may be coded in order to achieve locality. Both approaches must present low query complexity to allow the user to find an element efficiently. We discuss both approaches, and give a particular focus to the combinatorial one. In the combinatorial approach, we provide upper and lower bounds for the maximal size of a set of permutations with locality, and provide several simple constructions which attain the upper bound. In cases where the upper bound is not attained, we provide alternative constructions using a variety of tools, such as Reed-Solomon codes, permutation polynomials, and multi-permutations. In addition, several low-rate constructions of particular interest are discussed. In the coding approach we discuss an alternative representation of permutations, present a paradigm for supporting arbitrary powers of the stored permutation, and conclude with a proof of concept that permutations may be stored more efficiently than ordinary strings over the same alphabet.     

The Impact of X-Ray Radiation on Chemical and Optical Properties of Triple-Cation Lead Halide Perovskite: from the Surface to the Bulk

Understanding the effects of X-rays on halide perovskite thin films is critical for accurate and reliable characterization of this class of materials, as well as their use in detection systems. In this study, advanced optical imaging techniques are employed, both spectrally and temporally resolved, coupled with chemical characterizations to obtain a comprehensive picture of the degradation mechanism occurring in the material during photoemission spectroscopy measurements. Two main degradation pathways are identified through the use of local correlative physico-chemical analysis. The first one, at low X-Ray fluence, shows minor changes of the surface chemistry and composition associated with the formation of electronic defects. Moreover, a second degradation route occurring at higher fluence leads to the evaporation of the organic cations and the formation of an iodine-poor perovskite. Based on the local variation of the optoelectronic properties, a kinetic model describing the different mechanisms is proposed. These findings provide valuable insight on the impact of X-rays on the perovskite layers during investigations using X-ray based techniques. More generally, a deep understanding of the interaction mechanism of X-rays with perovskite thin films is essential for the development of perovskite-based X-ray detectors and solar for space applications.     

Chiral Anthranyl Trifluoromethyl Alcohols: Structures,Oxidative Dearomatization and Chiroptical Properties

Chiral trifluoromethyl alcohol groups were introduced at the hindered ortho positions of 9,10-diphenylanthracenes to investigate their effects on the physical properties and reactivity towards oxidative dearomatization. In such compact structures, the position in different quadrants and the preferred orientation of the −CH(OH)CF₃ groups were determined by the relative and absolute configurations of each stereoisomer, respectively. As a consequence, the stereochemistry governs the organization of the H-bonded molecules in single crystals (homochiral dimers vs ribbon), whereas in chlorinated solvents, they all behave as discrete compounds. Concerning their reactivity, the stereospecific dearomative oxidation of these molecules leads to 9,10-bis-spiro-isobenzofuran-anthracenes, when using organic single-electron transfer oxidants. The chiroptical properties of the alcohols and the corresponding dearomatized products were compared and showed an important modulation of the intensity.     

Potential cancer chemopreventive agents from Arbutus unedo

A phytochemical study of the petroleum ether and ethyl acetate extracts of the entire plant of Arbutus unedo led to the isolation of a new sterol, 7beta-hydroxystigmast-4-en-3-one (1), and nine known compounds of the flavan, steroid, and terpenoid types. The structure of 1 was determined by spectroscopic data interpretation in combination with molecular modeling calculations. The absolute stereochemistry of C-7 was assigned as S for compound 1 based on the obtained CD spectral data. Activity in the JB6 cell transformation assay was found for pomolic acid 3-acetate (4). All isolates obtained were evaluated in a cyclooxygenase-2 (COX-2) inhibition assay.     

NMR and theoretical calculations: a unified view of the cis/trans isomerization of 2-substituted thiazolidines containing peptides

The cis/trans isomerization of peptides containing the pseudoproline (4R)-thiazolidine-4-carboxylic acid Cys(Psi (R1,R2) pro) is investigated from both an experimental and a theoretical point of view by NMR and DFT calculations. A series of Ac-Cys(Psi(R1,R2) pro)-OCH3 and Ac-Cys(Psi(R1,R2) pro)-NHCH3 peptides were prepared to assess the influence of the substitution at the C2 position as well as of the amide following the thiazolidine residue. For each compound, the cis/trans ratio along with free energy, the puckering of the thiazolidine ring and the free rotational energy barrier are reported and discussed. We observe there is a pronounced effect of the C2 substituents and of the chirality upon the cis/trans ratio with the population of the cis content in the order (2R)-Cys(Psi(CH3,H) pro)<(2S)-Cys(Psi(H,CH3) pro)相似文献   

Tautomerism and 1H, 13C and 15N NMR spectral assignments of some nitro derivatives of malonic acid diamide

Because of its reactivity, malonic acid diamide (1) was initially identified as an alternative precursor for the development of a new class of high-density insensitive energetic materials possessing low sensitivity to thermal decomposition and detonation by impact. Nitration of 1 was studied under different conditions and led to three different tautomeric forms (2-4) of nitromalonic acid diamine. Using stronger oxidation conditions the oxadiazole 5 was generated in one step. We report the full 1H, 13C and 15N NMR structural characterization of these compounds in DMSO together with thermal, infrared, mass spectrometric and x-ray analysis. Experimental data obtained for 4 are compatible with an enol-imine form. Our interpretation is consistent with calculated 1H and 13C NMR spectra (ACD).     

Preparation of functionalized aryl- and heteroarylpyridazines by nickel-catalyzed electrochemical cross-coupling reactions

A general efficient electrochemical method for the preparation of aryl- and heteroarylpyridazines in a nickel-catalyzed cross-coupling reaction of 3-chloro-6-methoxypyridazine and 3-chloro-6-methylpyridazine with a range of functionalized aryl or heteroaryl halides is reported.