Search results for "combinatorial"
showing 10 items of 1208 documents
Cut-off method for endogeny of recursive tree processes
2016
Given a solution to a recursive distributional equation, a natural (and non-trivial) question is whether the corresponding recursive tree process is endogenous. That is, whether the random environment almost surely defines the tree process. We propose a new method of proving endogeny, which applies to various processes. As explicit examples, we establish endogeny of the random metrics on non-pivotal hierarchical graphs defined by multiplicative cascades and of mean-field optimization problems as the mean-field matching and travelling salesman problems in pseudo-dimension q>1.
A Push-Pull Mechanism Helps Design Highly Competent G-Quadruplex-DNA Catalysts
2021
International audience; Massive efforts are currently being invested to improve the performance, versatility, and scope of applications of nucleic acid catalysts. G-quadruplex (G4)/hemin DNAzymes are of particular interest owing to their structural programmability and chemical robustness. However, optimized catalytic efficiency is still bottleneck and the activation mechanism is unclear. Herein, we have designed a series of parallel G4s with different proximal cytosine (dC) derivatives to fine-tune the hemin-binding pocket for G4-DNAzymes. Combining theoretical and experimental methods, we have assessed the dependence of catalytic enhancement on the electronic properties of proximal dCs and…
The noncovalent dimerization of a G-quadruplex/hemin DNAzyme improves its biocatalytic properties.
2020
While many protein enzymes exert their functions through multimerization, which improves both selectivity and activity, this has not yet been demonstrated for other naturally occurring catalysts. Here, we report a multimerization effect applied to catalytic DNAs (or DNAzymes) and demonstrate that the enzymatic efficiency of G-quadruplexes (GQs) in interaction with the hemin cofactor is remarkably enhanced by homodimerization. The resulting non-covalent dimeric GQ–DNAzyme system provides hemin with a structurally defined active site in which both the cofactor (hemin) and the oxidant (H2O2) are activated. This new biocatalytic system efficiently performs peroxidase- and peroxygenase-type biot…
Biotechnological applications of the sepiolite interactions with bacteria: Bacterial transformation and DNA extraction
2020
International audience; Among the various clay minerals, sepiolite, which is a natural nanofibrous silicate that exhibit a poor cell toxicity, is a potential promising nanocarrier for the non-viral and stable transfer of plasmid DNA into bacteria, mammalian and human cells. We first show here that sepiolite binds to bacteria, which can be useful in decontamination protocols. In a previous research we have shown that is possible to modulate the efficiency of the absorption of different types of DNA molecules onto sepiolite, and that the DNA previously adsorbed could be recovered preserving the DNA structure and biological activity. Taking advantage of both, the sepiolite/bacteria and sepioli…
Di-tert-butyl Phosphonate Route to the Antiviral Drug Tenofovir
2021
Di-tert-butyl oxymethyl phosphonates were investigated regarding their suitability for preparing the active pharmaceutical ingredient tenofovir (PMPA). First, an efficient and simple access to the crystalline di-tert-butyl(hydroxymethyl)phosphonate was developed. O-Mesylation gave high yields of the active phosphonomethylation reagent. For the synthesis of tenofovir, a two-step sequence was developed using Mg(OtBu)2 as the base for the alkylation of (R)-9-(2-hydroxypropyl)adenine. Subsequent deprotection could be achieved with aqueous acids. (Di-tert-butoxyphosphoryl)methyl methanesulfonate showed to be the most efficient electrophile tested, affording PMPA in 72% yield on a 5 g scale. The …
Tuning the Basicity of Synergic Bimetallic Reagents: Switching the Regioselectivity of the Direct Dimetalation of Toluene from 2,5‐ to 3,5‐Positions
2008
Meta-meta metalation: Remarkably, toluene can be directly dimanganated or dimagnesiated at the 3,5-positions using bimetallic bases with active Me3SiCH2 ligands (see scheme, blue). In contrast, n-butyl ligands lead to 2,5-metalation (red). tmp=2,2,6,6-tetramethylpiperidide.
Dipeptides of S-Substituted Dehydrocysteine as Artzyme Building Blocks: Synthesis, Complexing Abilities and Antiproliferative Properties †
2021
Background: Dehydropeptides are analogs of peptides containing at least one conjugate double bond between α,β-carbon atoms. Its presence provides unique structural properties and reaction centre for chemical modification. In this study, the series of new class of dipeptides containing S-substituted dehydrocysteine with variety of heterocyclic moieties was prepared. The compounds were designed as the building blocks for the construction of artificial metalloenzymes (artzymes). Therefore, the complexing properties of representative compounds were also evaluated. Furthermore, the acknowledged biological activity of natural dehydropeptides was the reason to extend the study for antiproliferativ…
Polycationic Monomeric and Homodimeric Asymmetric Monomethine Cyanine Dyes with Hydroxypropyl Functionality—Strong Affinity Nucleic Acids Binders
2021
New analogs of the commercial asymmetric monomethine cyanine dyes thiazole orange (TO) and thiazole orange homodimer (TOTO) with hydroxypropyl functionality were synthesized and their properties in the presence of different nucleic acids were studied. The novel compounds showed strong, micromolar and submicromolar affinities to all examined DNA ds-polynucleotides and poly rA–poly rU. The compounds studied showed selectivity towards GC-DNA base pairs over AT-DNA, which included both binding affinity and a strong fluorescence response. CD titrations showed aggregation along the polynucleotide with well-defined supramolecular chirality. The single dipyridinium-bridged dimer showed intercalatio…
Asymmetric synthesis of functionalized tetrahydrofluorenones via an NHC-catalyzed homoenolate Michael addition
2018
The first example of an N-heterocyclic carbene-catalyzed asymmetric desymmetrization of enal-tethered cyclohexadienones via an intramolecular homoenolate Michael addition/esterification reaction is described. This new protocol offers a direct entry to various functionalized tetrahydrofluorenones with three contiguous stereocenters in high yields, good diastereoselectivities and excellent enantioselectivities.
Asymmetric Organocatalytic Wittig [2,3]-Rearrangement of Oxindoles
2016
A highly enantioselective organocatalytic [2,3]-rearrangement of oxindole derivatives is presented. The reaction was catalyzed by squaramide, and this provides access to 3-hydroxy 3-substituted oxindoles in high enantiomeric purities.