Comments on the evolution of strongly degenerate neutrinos in the early universe

We reconsider the evolution of strongly degenerate neutrinos in the early universe. Our chief concern is the validity of the entropy conservation after the neutrino annihilation process has frozen out (so that the establishment of chemical equilibrium is not trivial). We argue that the entropy indeed conserves because elastic scattering keeps the neutrino and antineutrino distribution functions in the equilibrium form and the sum of their chemical potential keeps zero even after the neutrino annihilation freeze-out. We also simulate the evolution of the degenerate neutrino spectrum to support the argument. We conclude that the change in the neutrino degeneracy parameter when the relativistic degrees of freedom in the universe decreases is calculated using the entropy conservation and the lepton number conservation without worrying about at what temperature the neutrino annihilation process freezes out.     

Letter: Note on Invariants of the Weyl Tensor

Algebraically special gravitational fields are described using algebraic and differential invariants of the Weyl tensor. A type III invariant is also given and calculated for Robinson-Trautman spaces.     

Working group report: Flavor physics and model building

This is the report of flavor physics and model building working group at WHEPP-9. While activites in flavor physics have been mainly focused on B-physics, those in model building have been primarily devoted to neutrino physics. We present summary of working group discussions carried out during the workshop in the above fields, and also briefly review the progress made in some projects subsequently.     

Chiral amplification in macromolecular helicity assisted by noncovalent interaction with achiral amines and memory of the helical chirality

Poly[(4-carboxyphenyl)acetylene] (poly-1) exhibits an intense induced circular dichroism (ICD) in the UV-visible region upon complexation with excess (R)-1-(1-naphthyl)ethylamine ((R)-2), owing to the formation of a predominantly single-handed helical conformation of the polymer backbone. In the presence of a small amount of (R)-2, poly-1 showed a very weak ICD due to the lack of a single-handed helical conformation. However, we have found that the co-addition of the excess bulky, achiral 1-naphthylmethylamine (5) with a small amount of (R)-2 caused a dramatic increase in the ICD magnitude, comparable to the full ICD induced by excess (R)-2. This indicates that an almost single-handed helix can be induced on poly-1 upon complexation with a small amount of (R)-2 assisted by achiral 5. Furthermore, the induced single-handed helical poly-1 could be successfully memorized by the replacement of (R)-2 and 5 with achiral 2-aminoethanol or n-butylamine.     

On-line preconcentration using dual mini-columns for the speciation of chromium(III) and chromium(VI) and its application to water samples as studied by inductively coupled plasma-atomic emission spectrometry

On-line preconcentration system for the selective, sensitive and simultaneous determination of chromium species was investigated. Dual mini-columns containing chelating resin were utilized for the speciation and preconcentration of Cr(III) and Cr(VI) in water samples. In this system, Cr(III) was collected on first column packed with iminodiacetate resin. Cr(VI) in the effluent from the first column was reduced to Cr(III), which was collected on the second column packed with iminodiacetate resin. Hydroxyammonium chloride was examined as a potential reducing agent for Cr(VI) to Cr(III).The effects of pH, sample flow rate, column length, and interfering ions on the recoveries of Cr(III) were carefully studied. Five millilitres of a sample solution was introduced into the system. The collected species were then sequentially washed by 1 M ammonium acetate, eluted by 2 M nitric acid and measured by ICP-AES. The detection limit for Cr(III) and Cr(VI) was 0.08 and 0.15 μg l⁻¹, respectively. The total analysis time was about 9.4 min.The developed method was successfully applied to the speciation of chromium in river, tap water and wastewater samples with satisfied results.     

Effect of intramolecular pi-pi and CH-pi interactions between ligands on structure, electrochemical and spectroscopic properties of fac-[Re(bpy)(CO)3(PR3)]+(bpy = 2,2'-bipyridine; PR3= trialkyl or triarylphosphines)

Intramolecular pi-pi and CH-pi interactions between the bpy and PR3 ligands of fac-[Re(bpy)(CO)3(PR3)]+ affect their structure, and electrochemical and spectroscopic properties. Intramolecular CH-pi interaction was observed between the alkyl groups on the phosphine ligand (R =nBu, Et) and the bpy ligand, and intramolecular pi-pi and CH-pi interactions were both observed between the aryl group(s) on the phosphorus ligand (R =p-MeOPh, p-MePh, Ph, p-FPh, OPh) and the bpy ligand, while no such interactions were found in the trialkylphosphite complexes (R = OiPr, OEt, OMe). The intramolecular interactions distort the pyridine rings of the bpy ligand as long as 3.7 x 10(-2)A in crystals. Molecular orbital calculations of the bpy ligand suggest that this distortion decreases the energy gap between its pi and pi* orbitals. An absorption band attributed to the pi-pi*(bpy) transition of the distorted rhenium complexes, measured in a KBr pellet, was red-shifted by 1-5 nm compared to the complexes without the distorted bpy ligand. Even in solution, similar red shifts of the pi-pi*(bpy) absorption were observed. The redox potential E1/2(bpy/bpy*-) of the complexes with the trialkylphosphine and triarylphosphine ligand are shifted positively by 110-120 mV and 60-80 mV respectively, compared with those derived from the electron-attracting property of the phosphorus ligand. In contrast with these properties, three nu(CO) IR bands, which are sensitive to the electron density on the central rhenium because of pi-back bonding, were shifted to higher energy, and a Re(I/II)-based oxidation wave was observed at a more positive potential according to the electron-attracting property of the phosphorus ligand.     

Biomembrane phospholipid-oxide surface interactions: crystal chemical and thermodynamic basis

Quartz has the least favored surface among many oxides for bacterial attachment and for lipid bilayer or micelle interactions. Tetrahedrally coordinated crystalline silica polymorphs are membranolytic toward liposomes, lysosomes, erythrocytes, and macrophages. Amorphous silica, the octahedral silica polymorph, (stishovite), and oxides such as Al2O3, Fe2 O3, and TiO2 are less cytotoxic. Existing theories for membrane rupture that invoke interactions between oxide surfaces and cell membrane phospholipids (PLs) do not adequately explain these differences in membranolytic potential of the oxides. The author presents a crystal chemical, thermodynamic model for the initial interaction of oxide surfaces with the quaternary ammonium component of the PL's polar head group. The model includes solvation energy changes and electrostatic forces during adsorption, represented by the dielectric constant of the solid and the charge-to-radius ratio of the adsorbing solute. The nature of oxide-solute interactions compared with oxide-water, solute-water, and water-water interactions determines the membranolytic activity of the oxide, where the solute is TMA+, the quaternary ammonium moeity. Significant membrane rupture, as on quartz, requires unfavorable adsorption entropy (DeltaS(ads,TMA+)<0) to maximize disruption of normal membrane structure and requires favorable Gibbs free energy of exchange between TMA+ and the ambient Na+ ions (DeltaG(exc,TMA+/Na+) = DeltaG(ads,TMA+)-DeltaG(ads,Na+)<0) to maximize the extent of membrane affected. For amorphous silica, DeltaS(ads,TMA+) >0, so disruption of structure is limited, even though G(exc,TMA+/Na+) is <0. Stishovite and other oxides have DeltaS(ads,TMA+) <0, but now DeltaG(exc,TMA+/Na+) is>0 at the acidic to circumneutral pHs of cellular and subcellular organelle fluids. The model predicts the correct sequence of membranolytic ability: quartz > or = amorphous SiO2 >Al2O3 >Fe2O3 >TiO2. The model thus explains the relatively poor adhesion of bacterial cells to quartz and the lack of quartz as a biomineral. It is proposed that one function of extracellular polymeric substances exuded by bacteria is to render mineral surfaces more hydrophilic.     

First total synthesis of a new sesquiterpenoid natural product, (±)-3-(2,4-dihydroxybenzoyl)-4,5-dimethyl-5-(4,8-dimethyl-3(E),7(E)-nonadien-1-yl)tetrahydro-2-furanone

An efficient and stereodefined process is described for the first preparation of a new prenyl-benzoylfuranone type sesquiterpenoid, (±)-3-(2,4-dihydroxybenzoyl)-4,5-dimethyl-5-(4,8-dimethyl-3(E),7(E)-nonadien-1-yl)tetrahydro-2-furanone. The synthetic strategy is based on nucleophilic addition of organometallic reagents to the functionalized ketoamides elaborated from dihydroxyacetone dimer for the stereoselective construction of the key quaternary carbon center in the target compound.     

The structures of macbecin I and II : New antitumor antibiotics

Macbecin I 1, C₃₀H₄₂N₂O₈, and macbecin II 2, C₃₀H₄₄N₂O₈, were shown to be 2,6-disubstituted benzoquinone and hydroquinone derivatives by an oxidation-reduction relationship, UV. ¹H and ¹³C NMR spectra. Alkaline methanolysis of 1 gave a 2-aminobenzoquinone derivative 5, suggesting an ansa-structure for 1, and acid hydrolysis of 1 gave decarbamoyl products 9,10 and 11, indicative of the location of carbamoyloxy group in allylic position. Spin decoupling studies on 1,3 and 5clarified the partial structures [A], [B], [C] and [D]. From their mutual disposition two structures 1a and 1b, were proposed out of which 1a has been selected for the structure of 1 on the basis of the structure of oxidative degradation product 12. X-Ray analysis of the bromoacetyl derivative of 1 confirmed the above proposed structure and determined the absolute stereochemistry of 1 and 2.