240 research outputs found
The Four-electron Oxidation of meso-Octaethylporphirinogen via a Metal-mediated Dealkylation Process: Formation of [RuL(PhCN)2] [H2L = 5,15-dihydro-5,5,10,15,20-hexaethylporphyrin].
Local chiral interactions and magnetic structure of few-nucleon systems
The magnetic form factors of H, H, and He, deuteron
photodisintegration cross sections at low energies, and deuteron threshold
electrodisintegration cross sections at backward angles in a wide range of
momentum transfers, are calculated with the chiral two-nucleon (and
three-nucleon) interactions including intermediate states that have
recently been constructed in configuration space. The =3 wave
functions are obtained from hyperspherical-harmonics solutions of the
Schr\"odinger equation. The electromagnetic current includes one- and two-body
terms, the latter induced by one- and two-pion exchange (OPE and TPE,
respectively) mechanisms and contact interactions. The contributions associated
with intermediate states are only retained at the OPE level, and are
neglected in TPE loop (tree-level) corrections to two-body (three-body) current
operators. Expressions for these currents are derived and regularized in
configuration space for consistency with the interactions. The low-energy
constants that enter the contact few-nucleon systems. The predicted form
factors and deuteron electrodisintegration cross section are in excellent
agreement with experiment for momentum transfers up to 2--3 fm. However,
the experimental values for the deuteron photodisintegration cross section are
consistently underestimated by theory, unless use is made of the Siegert form
of the electric dipole transition operator. A complete analysis of the results
is provided, including the clarification of the origin of the aforementioned
discrepancy.Comment: 24 pages, 13 figure
Metallohosts Derived from the Assembly of Sugars Around Transition Metals - The Complexation of Alkali Metal Cations.
Muon capture on deuteron and 3He
The muon capture reactions 2H(\mu^-,\nu_\mu)nn and 3He(\mu^-,\nu_\mu)3H are
studied with conventional or chiral realistic potentials and consistent weak
currents. The initial and final A=2 and 3 nuclear wave functions are obtained
from the Argonne v18 or chiral N3LO two-nucleon potential, in combination with,
respectively, the Urbana IX or chiral N2LO three-nucleon potential in the case
of A=3. The weak current consists of polar- and axial-vector components. The
former are related to the isovector piece of the electromagnetic current via
the conserved-vector-current hypothesis. These and the axial currents are
derived either in a meson-exchange or in a chiral effective field theory
(chiEFT) framework. There is one parameter (either the N-to-\Delta axial
coupling constant in the meson-exchange model, or the strength of a contact
term in the chiEFT model) which is fixed by reproducing the Gamow-Teller matrix
element in tritium beta-decay. The model dependence relative to the adopted
interactions and currents (and cutoff sensitivity in the chiEFT currents) is
weak, resulting in total rates of 392.0 +/- 2.3 Hz for A=2, and 1484 +/- 13 Hz
for A=3, where the spread accounts for this model dependence.Comment: 15 pages, 1 figure, submitted to Phys. Rev.
Muon capture on deuteron using local chiral potentials
The muon capture reaction in the
doublet hyperfine state is studied using nuclear potentials and consistent
currents derived in chiral effective field theory, which are local and
expressed in coordinate-space (the so-called Norfolk models). Only the largest
contribution due to the scattering state is considered. Particular
attention is given to the estimate of the theoretical uncertainty, for which
four sources have been identified: (i) the model dependence, (ii) the chiral
order convergence for the weak nuclear current, (iii) the uncertainty in the
single-nucleon axial form factor, and (iv) the numerical technique adopted to
solve the bound and scattering systems. This last source of uncertainty
has turned out essentially negligible. The doublet muon capture rate
has been found to be
s, where the three errors come from the first three sources of
uncertainty. The value for obtained within this local chiral
framework is compared with previous calculations and found in very good
agreement.Comment: 33 pages, 3 figure
Solid-phase synthesis of peptides containing reverse-turn mimetic bicyclic lactams
The solid-phase synthesis and characterization of a series of peptides (4-15) containing reverse-turn mimetic bicyclic lactams is reported. The bicyclic lactams (1a, 1b) possess high structural similarity to the two central residues of a Pturn. Amino acid conjugates of these bicyclic lactams were synthesized on solid supports following a g-fluorenylmethoxycarbonyl (FMOC) protection strategy on WangMerrifield resin. Coupling between amino acids was accomplished by means of diisopropylcarbodiimide (DIC)/ hydroxyazabenzotriazole (HOAt). Coupling between amino acids and the mimics was performed with the potent Carpino's reagent O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramelhyluronium hexafluorophosphate (HATU). The final compounds were cleaved from the resin and obtained as N-acetylated methyl esters or benzyl amides
Scaling and intermittency of brain events as a manifestation of consciousness
We discuss the critical brain hypothesis and its relationship with intermittent renewal processes displaying power-law decay in the distribution of waiting times between two consecutive renewal events. In particular, studies on complex systems in a "critical" condition show that macroscopic variables, integrating the activities of many individual functional units, undergo fluctuations with an intermittent serial structure characterized by avalanches with inverse-power-law (scale-free) distribution densities of sizes and inter-event times. This condition, which is denoted as "fractal intermittency", was found in the electroencephalograms of subjects observed during a resting state wake condition. It remained unsolved whether fractal intermittency correlates with the stream of consciousness or with a non-task-driven default mode activity, also present in non-conscious states, like deep sleep. After reviewing a method of scaling analysis of intermittent systems based of event-driven random walks, we show that during deep sleep fractal intermittency breaks down, and re-establishes during REM (Rapid Eye Movement) sleep, with essentially the same anomalous scaling of the pre-sleep wake condition. From the comparison of the pre-sleep wake, deep sleep and REM conditions we argue that the scaling features of intermittent brain events are related to the level of consciousness and, consequently, could be exploited as a possible indicator of consciousness in clinical applications
Synthesis and Conformational Studies of Peptidomimetics Containing a New Bifunctional Diketopiperazine Scaffold Acting as a \u3b2-Hairpin Inducer
A practical synthesis of a new bifunctional diketopiperazine (DKP) scaffold 1, formally derived from the cyclization of L-aspartic acid and (S)-2,3-diaminopropionic acid, is reported. DKP-1 bears a carboxylic acid and an amino functionalities in a cis relationship, which have been used to grow peptide sequences.
Tetra-, penta-, and hexapeptidomimetic sequences were prepared by solution-phase peptide synthesis (Boc strategy). Conformational analysis of these derivatives was carried out by a combination of 1H
NMR spectroscopy, IR spectroscopy, CD spectroscopy, and computer modeling, and reveals the formation of beta-hairpin mimics involving 10-membered and 18-membered H-bonded rings and a reverse turn of the
growing peptide chain
Mapping powdery mildew (Blumeria graminis f. sp. tritici) resistance inwild and cultivated tetraploid wheats
Wheat is the most widely grown crop and represents the staple food for one third of the world’s population. Wheat is attacked by a large variety of pathogens and the use of resistant cultivars is an effective and environmentally safe strategy for controlling diseases and eliminating the use of fungicides. In this study, a collection of wild and cultivated tetraploid wheats (Triticum turgidum) were evaluated for seedling resistance (SR) and adult plant resistance (APR) to powdery mildew (Blumeria graminis) and genotyped with a 90K single nucleotide polymorphism (SNP) array to identify new sources of resistance genes. The genome-wide association mapping detected 18 quantitative trait loci (QTL) for APR and 8 QTL for SR, four of which were identical or at least closely linked to four QTL for APR. Thirteen candidate genes, containing nucleotide binding sites and leucine-rich repeats, were localized in the confidence intervals of the QTL-tagging SNPs. The marker IWB6155, associated to QPm.mgb-1AS, was located within the gene TRITD1Av1G004560 coding for a disease resistance protein. While most of the identified QTL were described previously, five QTL for APR (QPm.mgb-1AS, QPm.mgb-2BS, QPm.mgb-3BL.1, QPm.mgb-4BL, QPm.mgb-7BS.1) and three QTL for SR (QPm.mgb-3BL.3, QPm.mgb-5AL.2, QPm.mgb-7BS.2) were mapped on chromosome regions where no resistance gene was reported before. The novel QTL/genes can contribute to enriching the resistance sources available to breeders
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