Frequent hypercyclicity,chaos, and unconditional Schauder decompositions

We prove that if X is any complex separable infinite-dimensional Banach space with an unconditional Schauder decomposition, X supports an operator T which is chaotic and frequently hypercyclic. In contrast with the complex case, we observe that there are real Banach spaces with an unconditional basis which support no chaotic operator.     

Lipase from Carica papaya latex presents high enantioselectivity toward the resolution of prodrug (R,S)-2-bromophenylacetic acid octyl ester

Besides the well-known papain, lipolytic activity is another interesting enzymatic activity present in latex from Carica papaya. This lipolytic activity is strongly attached to the latex solid phase, resulting in a naturally immobilized biocatalyst. In this work we describe the kinetic resolution of (R,S)-2-bromophenylacetic acid octyl ester by Carica papaya crude latex and two partially purified latex fractions. Several parameters, such as substrate concentration and solvent effects were studied. The best results were obtained using decane as solvent with 50 mM of substrate and 50 mg/mL enzyme/reaction medium; under these conditions, a high enantioselectivity (E >200) was obtained with crude latex. A twofold increase of the initial rate maintaining E >200 was obtained using purified fractions without protease and without esterase. Lipase from Carica papaya latex is the most enantioselective wild-type enzyme ever described for the studied reaction.     

Synthesis of azafluorenones and related compounds using deprotocupration–aroylation followed by intramolecular direct arylation

The efficiency of the deprotocupration–aroylation of 2-chloropyridine using lithiocuprates prepared from CuX (X=Cl, Br) and LiTMP (TMP=2,2,6,6-tetramethylpiperidido, 2 equiv) was investigated. CuCl was identified as a more suitable copper source than CuBr for this purpose. Different diaryl ketones bearing a halogen at the 2 position of one of the aryl groups were synthesized in this way from azines and thiophenes. These were then involved in palladium-catalyzed ring closure: substrates underwent expected CH-activation-type arylation to afford fluorenone-type compounds, and were also subjected to cyclization reactions leading to xanthones, notably in the presence of oxygen-containing substituents or reagents.     

Guanine-thymine intrastrand cross-linked lesion containing oligonucleotides: from chemical synthesis to in vitro enzymatic replication

An intrastrand cross-link lesion, in which two neighboring nucleobases are covalently tethered, has been site-specifically synthesized into defined sequence oligonucleotides in order to perform in vitro replication studies using either bacterial replicative or translesional synthesis polymerases. The investigated tandem base lesion that involves a cross-link between the methylene group of thymine and the C8 of an adjacent guanine residue has been prepared by UV-photolysis under anaerobic condition of the photolabile precursor 5-(phenylthiomethyl)-2'-deoxyuridine that has been site-specifically incorporated into a 9-mer oligonucleotide. After ligation, the lesion-containing modified oligonucleotide was used as a DNA template in primer extension reactions catalyzed by several DNA polymerases including the fragment Klenow exo-(Kf-) of E. coli polymerase I, the Thermus aquaticus polymerase (Taq pol) and the E. coli translesional DNA polymerase Pol IV (dinB). It was found that the primer extension reaction was stopped after the incorporation of the correct nucleotide dAMP opposite the 3'-thymine residue of guanine(C8-CH2) thymine lesion by Kf- and Pol IV; however it was noted that the efficiency of the nucleotide incorporation was reduced. In contrast, the Taq polymerase was totally blocked at the nucleotide preceding the tandem lesion. These results are strongly suggestive that the present intrastrand cross-link lesion, if not repaired, would constitute a blocking lesion for prokaryotic DNA polymerases, being likely lethal for the cell.     

Bis(tetraphenylphosphonium) (hexasulfido‐2κ2S1,S6)di‐μ‐sulfido‐disulfido‐1κ2S‐tungsten(VI)zinc(II) acetone solvate

The title complex, (C₂₄H₂₀P)₂[WZnS₄(S₆)]·C₃H₆O or (Ph₄P)₂[WS₂(μ‐S)₂{Zn(S₆)}]·Me₂CO, was unexpectedly obtained on attempted recrystallization of a mixed tungten–zinc complex of a tris(pyrazolato)borate ligand. The two metal centres of the anion have distorted tetrahedral coordination and the two tetrahedra share one S...S edge; tungsten is additionally coordinated by two terminal sulfide ligands and zinc by a chelating S₆²⁻ ligand, which has one central S—S bond significantly longer than the other four, a pattern found to be consistent for this ligand. This is the first reported example of a tetrahedral zinc centre bridging an edge of a single tetrathiotungstate(VI) or tetrathiomolybdate(VI) anion, although there are many previous examples with other metals.     

Sliding behavior of liquid droplets on tilted Langmuir-Blodgett surfaces

The sliding behavior of liquid droplets on inclined Langmuir-Blodgett surfaces was investigated. The critical sliding angle defined as the tilt angle of the surface at which the drop slides down as well as the advancing and receding contact angles was measured for five different liquids on five surfaces. In addition, the contact line geometry was analyzed at critical sliding angle. The experimental relationship between the surface tension forces resulting from contact angle hysteresis and the weight of the drop was compared to theoretical predictions. Even though the shape of the drop bases was found as skewed ellipses, a model assuming parallel-sided elongated drops is shown to describe reasonably the experimental values. This result probably indicates the main influence of the capillary forces at the rear and front edges of the drop with respect to that exerted on the lateral sides.     

A preventive maintenance policy for a continuously monitored system with correlated wear indicators

A continuously monitored system is considered, that gradually and stochastically deteriorates according to a bivariate non-decreasing Lévy process. The system is considered as failed as soon as its bivariate deterioration level enters a failure zone, assumed to be an upper set. A preventive maintenance policy is proposed, which involves a delayed replacement, triggered by the reaching of some preventive zone for the system deterioration level. The preventive maintenance policy is assessed through a cost function on an infinite horizon time. The cost function is provided in full form, and tools are provided for its numerical computation. The influence of different parameters on the cost function is studied, both from a theoretical and/or numerical point of view.