Single-pion production in pp collisions at 0.95 GeV/c (I)

The single-pion production reactions pp → dπ⁺, pp → npπ⁺ and pp → ppπ⁰ were measured at a beam momentum of 0.95GeV/c ( T _p ≈ 400MeV) using the short version of the COSY-TOF spectrometer. The implementation of a central calorimeter provided particle identification, energy determination and neutron detection in addition to time-of-flight and angle measurements. Thus, all pion production channels were recorded with 1-4 overconstraints. The total and differential cross-sections obtained are compared to previous data and theoretical calculations. Main emphasis is put on the discussion of the ppπ⁰ channel, where we obtain angular distributions different from previous experimental results, however, partly in good agreement with recent phenomenological and theoretical predictions. In particular, we observe very large anisotropies for the π⁰ angular distributions in the kinematical region of small relative proton momenta revealing there a dominance of proton spinflip transitions associated with π⁰ s and d partial waves and emphasizing the important role of π⁰ d-waves.     

Polymerisation du trans pentadiene-1,3 par un amorceur soluble associant le triethylaluminium et l'orthotitanate de n-butyle—III. Proposition d'un modele de centre actif

By considering our experimental results and those of other authors, we have built a model of the active centre, compatible with our experiments. The proposed bititanic model can explain the effects of parameters as various as the nature of the trialkylaluminium and the initial concentration of monomer on the catalytic activity. This model also explains observations on gaseous releases observed during the formation of the organometallic precursor and observations on the intrinsic viscosity of the living polymer. Variation of the observed microstructure ratios with several parameters (monomer concentration, reaction time, molecular weight) is discussed in connection with the various theories proposed to explain the stereoregulation mechanism. Finally, the observation of branched products allowed us to explain some observations on the molecular weight distribution.     

Correlations in M1 neutron capture as evidence for a semi-direct mechanism

Evidence is presented for correlations between M1 capture and (d, p) cross-sections. This is interpreted as arising from a semi-direct M1 capture mechanism. This picture fits the main qualitative features of the data e.g. strong correlations are confined to the mass-range A = 25?35.     

Mechanism of 2,2'6,6'-tetramethylpiperidin-N-oxyl-mediated oxidation of alcohols in ionic liquids

The mechanism of 2,2'6,6'-tetramethylpiperidin- N-oxyl (TEMPO)-mediated oxidation of alcohols to aldehydes and ketones in ionic liquids has been investigated using cyclic voltammetry and rotating disk electrode voltammetry. It is shown that the presence of bases (B) and their conjugate acids (BH (+)), as well as their p K as, strongly influences the rate of reaction. Data indicated that the first step in the oxidation is the formation of the alcoholate species via acid-base equlibrium with B. The alcoholate subsequently reacts with the active form of TEMPO (T (+), i.e., the one-electron oxidized form) forming an intermediate that further reacts with T (+) and B returning TEMPO catalytically, BH (+), and the carbonyl product. A kinetic model incorporating this pre-equilibrium step has been derived, which accounts for the experimentally observed reaction kinetics. Overall, the rate of reaction is controlled by the equilibrium constant for the pre-equilibrium step; as such, strong bases are required for more kinetically efficient transformations using this redox catalyst.     

Bacterial suspensions under flow

Fluids laden with motile bacteria enter in the category of active matter, a new field currently developing at the convergence of biology, hydrodynamics and statistical physics. Such suspensions were shown recently to exhibit singular macroscopic transport properties. In this paper we review some recent results, either theoretical or experimental, on the active fluid rheology. We focus principally on bacteria suspensions and the objective is to provide the basis for understanding the emergence of the singular constitutive relations characterizing the macroscopic transport properties of such an active fluid under flow.     

Synthesis and characterization of divalent metal complexes with bipyridylamide ligands

Reaction of N-(4-pyridyl)picolinamide (4-ppa), N-(4-pyridyl)nicotinamide (4-pna), N-(4-pyridyl)isonicotinamide (4-pina), and N-(2-pyridyl)isonicotinamide (2-pina) with divalent metal salts led to the formation of six new coordination complexes. The X-ray structure of [Zn(4-ppa)₂Cl₂] (1) shows a mononuclear structure with interesting intermolecular hydrogen bonding interactions. [Zn(4-pna)(OAc)₂]_n (2), Cu(4-pna)(OTf)₂(DMF)₂]_n (3), {[Zn(4-pina)(DMF)₄](OTf)₂}_n (4), {[Fe(4-pina)(DMF)₄](OTf)₂}_n (5), and [Cu(2-pina)(OTf)₂(DMF)₂]_n (6) are one-dimensional coordination polymers with conformational differences caused by the coordination donor disposition, which demonstrates the flexibility of the pyridylamide ligands in polymeric structures. Reflectance UV-visible spectra and thermal properties of the coordination polymers are also reported.     

A Chemical Probe for the ATAD2 Bromodomain

ATAD2 is a cancer‐associated protein whose bromodomain has been described as among the least druggable of that target class. Starting from a potent lead, permeability and selectivity were improved through a dual approach: 1) using CF₂ as a sulfone bio‐isostere to exploit the unique properties of fluorine, and 2) using 1,3‐interactions to control the conformation of a piperidine ring. This resulted in the first reported low‐nanomolar, selective and cell permeable chemical probe for ATAD2.     

Site-specific insertion of 3-aminotyrosine into subunit alpha2 of E. coli ribonucleotide reductase: direct evidence for involvement of Y730 and Y731 in radical propagation

E. coli ribonucleotide reductase (RNR) catalyzes the production of deoxynucleotides using complex radical chemistry. Active RNR is composed of a 1:1 complex of two subunits: alpha2 and beta2. Alpha2 binds nucleoside diphosphate substrates and deoxynucleotide/ATP allosteric effectors and is the site of nucleotide reduction. Beta2 contains the stable diiron tyrosyl radical (Y122.) cofactor that initiates deoxynucleotide formation. This process is proposed to involve reversible radical transfer over >35 A between the Y122 in beta2 and C439 in the active site of alpha2. A docking model of alpha2beta2, based on structures of the individual subunits, suggests that radical initiation involves a pathway of transient, aromatic amino acid radical intermediates, including Y730 and Y731 in alpha2. In this study the function of residues Y730 and Y731 is investigated by their site-specific replacement with 3-aminotyrosine (NH2Y). Using the in vivo suppressor tRNA/aminoacyl-tRNA synthetase method, Y730NH2Y-alpha2 and Y731NH2Y-alpha2 have been generated with high fidelity in yields of 4-6 mg/g of cell paste. These mutants have been examined by stopped flow UV-vis and EPR spectroscopies in the presence of beta2, CDP, and ATP. The results reveal formation of an NH2Y radical (NH2Y730. or NH2Y731.) in a kinetically competent fashion. Activity assays demonstrate that both NH2Y-alpha2s make deoxynucleotides. These results show that the NH2Y. can oxidize C439 suggesting a hydrogen atom transfer mechanism for the radical propagation pathway within alpha2. The observed NH2Y. may constitute the first detection of an amino acid radical intermediate in the proposed radical propagation pathway during turnover.     

Experimental evidence for the curve crossing mechanism for collisional excitation in keV N2+*/He collisions by emission spectroscopy

Collision-induced emission (CIE) experiments were carried out by coupling a spectrograph and charge-coupled device detector (CCD) to a commercial analytical mass spectrometer. An Einzel lens and a deceleration-reacceleration lens assembly as described in the current article were installed in the mass spectrometer to allow for the deceleration of the ions before collision. Collision-induced emission spectra of N2+*/He collisions at lab frame collision energies from 2 to 8 keV were obtained from 190-1020 nm. The emissions were assigned to the Deltav=+2, +1, 0, -1, -2 vibrational transition progression in the N2+* B 2Sigmau+-->X 2Sigmag+ electronic transition as well as some atomic lines from the fragments N+, N* and the target gas He. N2+* A 2u-->X 2Sigmag+ emission was also observed but was very weak due to the long lifetime of the A 2u state. The relative intensities of the N2+*, N, and N+ emissions are independent of the ion translational energy within the studied energy range. This observation supports the curve-crossing mechanism for collisional excitation, suggesting that a complicated sequence of curve-crossings takes place upon collisional activation.     

Cryopreservation of peach palm zygotic embryos

Cryopreservation is a safe and cost-effective option for long-term germplasm conservation of non-orthodox seed species, such as peach palm (Bactris gasipaes). The objective of the present study was to establish a cryopreservation protocol for peach palm zygotic embryos based on the encapsulation-dehydration technique. After excision, zygotic embryos were encapsulated with 3 percent sodium alginate plus 2 M glycerol and 0.4 M sucrose, and pre-treated or not with 1 M sucrose during 24 h, followed by air-drying. Fresh weight water contents of beads decreased from 83 percent and 87 percent to 18 percent and 20 percent for pre-treated or non-pretreated beads, respectively, after 4 h of dehydration. Sucrose pre-treatment at 1 M caused lower zygotic embryo germination and plantlet height in contrast to non-treated beads. All the variables were statistically influenced by dehydration time. Optimal conditions for recovery of cryopreserved zygotic embryos include encapsulation and dehydration for 4 h in a forced air cabinet to 20 percent water content, followed by rapid freezing in liquid nitrogen (-196 degree C) and rapid thawing at 45 degree C. In these conditions 29 percent of the zygotic embryos germinated in vitro. However, plantlets obtained from dehydrated zygotic embryos had stunted haustoria and lower heights. Histological analysis showed that haustorium cells were large, vacuolated, with few protein bodies. In contrast, small cells with high nucleus:cytoplasm ratio formed the shoot apical meristem of the embryos, which were the cell types with favorable characteristics for survival after exposure to liquid nitrogen. Plantlets were successfully acclimatized and showed 41+/-9 percent and 88+/-4 percent survival levels after 12 weeks of acclimatization from cryopreserved and non-cryopreserved treatments, respectively.