Modification of Guanine with Photolabile N‐Hydroxypyridine‐2(1H)‐thione: Monomer Synthesis,Oligonucleotide Elaboration,and Photochemical Studies

The photochemistry of N‐hydroxypyridine‐2(1H)‐thione (NHPT), inserted as a photolabile modifier at the 6‐position of 2′‐deoxyguanosine or guanosine, has been evaluated. In particular, 6‐[(1‐oxidopyridin‐2‐yl)sulfanyl]‐ ( 1a ) and 6‐[(pyridin‐2‐yl)sulfanyl]‐2′,6‐dideoxyguanosine ( 2a ), novel photolabile derivatives of the natural nucleosides, were synthesized and characterized. The observed photolysis products of 1a in organic solvents could only be rationalized by assuming a rapid equilibrium with the corresponding 6‐[(2‐thioxopyridin‐1(2H)‐yl)oxy] analogue 3a (Scheme 5). Transient spectroscopy of 1a indicated a strong triplet‐excited state suitable for triplet → triplet energy transfer or singlet‐oxygen generation. The NHPT function was stable enough for (slightly modified) automated solid‐phase oligonucleotide synthesis. The utility of the above compounds is discussed, as well as their potential use in photosensitization of reactive oxygen species in DNA.     

A standard protocol for single nucleotide primer extension in the human genome using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Analysis of single nucleotide polymorphisms (SNPs) has become an increasingly important area of research, with numerous applications in medical genetics, population genetics, forensic science, and agricultural biotechnology. Large-scale SNP analyses require the development of methodologies that are economical, flexible, accurate and capable of automation. Primer extension in conjunction with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is currently emerging as a potential method for high-throughput SNP genotyping. We have evaluated a number of published primer extension methods and refined a simple and robust protocol to analyze human autosomal disease-causing mutations and population genetic markers on the Y-chromosome. Twelve different variant sites were examined, and homozygotes, heterozygotes and hemizygotes were accurately typed. A 100% concordance was observed between SNP genotypes obtained using the MALDI-TOFMS technique and alternative genotyping methods, such as restriction fragment length polymorphism (RFLP) assays and denaturing high-performance liquid chromatography (DHPLC). Since multiple polymorphisms can be detected in single reactions, the method provides a cost-effective approach for SNP analysis. The protocol is also extremely flexible (able to accommodate new markers) and can be adapted to a number of platforms without the use of commercial kits.     

Er as marker for order–disorder determination in the PbTiO3 system

Er³⁺ ions were added to the PbTiO₃ network using the polymeric precursor method to characterize the order–disorder transformation found in this material by means of experimental and theoretical approach. The disordered and ordered material structures were studied by photoluminescence measurements, X-ray diffraction (XRD) and UV–visible spectroscopy. The Er³⁺ ions served as a marker to identify the structural short-range order beginning in the PbTiO₃ matrix. From photoluminescence results it was concluded that disordered PbTiO₃ powders have a certain short range order in the network that are undetected by XRD measurements. The electronic structures were calculated by the ab initio periodic method in DFT level with the non-local B3LYP hybrid approximation for the Ti atom site interpretation using density of states (DOS) results. This analysis enabled understanding that Ti atom sphere coordination can create possible states for radioactive return and trap of electron–holes pair.     

Modelling of ceramide interactions with porous graphite carbon in non-aqueous liquid chromatography

Interactions of solutes on porous graphitic carbon (PGC) with non-aqueous mobile phases are studied by the linear solvation energy relationship (LSER). Studies have been carried out with eight binary mixtures composed of a weak solvent (acetonitrile or methanol) and a strong solvent (tetrahydrofuran, n-butanol, CH2Cl2, 1,1,2-trichloro-2,2,1-trifluoroethane). The systematic analysis of a set of test compounds was performed for each solvent mixture in isocratic mode (50:50). The results were compared to those obtained on PGC with hydro-organic liquids and supercritical fluids. They were then correlated with the observed retention behaviour of lipid compounds, more particularly ceramides.     

Optimized interferometry with Gaussian states

We revisit Mach—Zehnder interferometry using a suitable phase-space analysis and present a rigorous optimization of the sensitivity in realistic condition, i.e., for Gaussian input states, and taking into account nonunit quantum efficiency in the detection stage. The working regime of the interferometer is optimized at fixed input energy versus the squeezing phases and amplitudes as well as the distribution of squeezing in the two input signals. For ideal detection we find the known result that the squeezing resource allows to beat the shot-noise limit. For nonunit detection efficiency, we show that for fixed input energy one can always optimize the squeezing fraction in order to enhance the sensitivity with respect to the case of no squeezing, even in cases when one cannot go beyond the shot-noise limit. The text was submitted by the authors in English.     

Preparation of γ-trimethylsilylallyldibutylstannane grafted on solid support: a clean and easily recyclable reagent for the synthesis of 2,6-disubstituted dihydropyrans

The synthesis of the γ-trimethylsilyldibutylallylstannane grafted on an insoluble macroporous polymer is reported. This bimetallic reagent was treated with aldehydes in the presence of indium trichloride to afford in good yields both symmetrical and unsymmetrical cis-2,6-disubstituted dihydropyrans, practically uncontaminated with organotin residues (less than 20 ppm). The potential for regeneration and reuse of this supported bimetallic reagent is pointed out.     

A two-step MaxLik-MaxEnt strategy to infer photon distribution from <Emphasis Type="Italic">on/off</Emphasis> measurement at low quantum efficiency

A method based on Maximum-Entropy (ME) principle to infer photon distribution from on/off measurements performed with few and low values of quantum efficiency is addressed. The method consists of two steps: at first some moments of the photon distribution are retrieved from on/off statistics using Maximum-Likelihood estimation, then ME principle is applied to infer the quantum state and, in turn, the photon distribution. Results from simulated experiments on coherent and number states are presented.     

Direct observation of nanocrystallite buckling in carbon fibers under bending load

Single carbon fibers are deformed in bending by forming loops with varying radius. Position-resolved x-ray diffraction patterns from the bent fibers are collected from the tension to the compression region with a synchrotron radiation nanobeam of 100 nm size from a waveguide structure. A strain redistribution with a shift of the neutral axis is observed. A significant increase of the misorientation of the graphene sheets in the compression region shows that intense buckling of the nanosized carbon crystallites is the physical origin of different tensile and compressive properties.     

Variational Monte Carlo study of pentaquark states

Accurate numerical solution of the five-body Schr?dinger equation is effected via variational Monte Carlo calculations. The spectrum is assumed to exhibit a narrow resonance with strangeness S = +1. A fully antisymmetrized and pair-correlated five-quark wave function is obtained for the assumed nonrelativistic Hamiltonian, which has spin, isospin, and color dependent pair interactions and many-body confining terms, which are fixed by the nonexotic spectra. Gauge field dynamics are modeled via flux-tube exchange factors. The energy determined for the ground states with J(pi) = (1/2)- ((1/2)+) is 2.22 (2.50) GeV. A lower energy negative parity state is consistent with recent lattice results. The short-range structure of the state is analyzed via its diquark content.