Experiments in Neutrino Mass and Mixing: Part I - New Limits on Heavy Neutrino Emission in Nuclear Beta Decay. Part II - Fast Neutron Backgrounds for the San Onofre Neutrino Detector

In Part I of this thesis, a new magnetic spectrometer experiment which measured the β spectrum of ^(35)S is described. New limits on heavy neutrino emission in nuclear β decay were set, for a heavy neutrino mass range between 12 and 22 keV. In particular, this measurement rejects the hypothesis that a 17 keV neutrino is emitted, with sin^2 θ = 0.0085, at the 6δ statistical level. In addition, an auxiliary experiment was performed, in which an artificial kink was induced in the β spectrum by means of an absorber foil which masked a fraction of the source area. In this measurement, the sensitivity of the magnetic spectrometer to the spectral features of heavy neutrino emission was demonstrated.

In Part II, a measurement of the neutron spallation yield and multiplicity by the Cosmic-ray Underground Background Experiment is described. The production of fast neutrons by muons was investigated at an underground depth of 20 meters water equivalent, with a 200 liter detector filled with 0.09% Gd-loaded liquid scintillator. We measured a neutron production yield of (3.4 ± 0.7) x 10^(-5) neutrons per muon-g/cm^2, in agreement with other experiments. A single-to-double neutron multiplicity ratio of 4:1 was observed. In addition, stopped π^+ decays to µ^+ and then e^+ were observed as was the associated production of pions and neutrons, by the muon spallation interaction. It was seen that practically all of the π^+ produced by muons were also accompanied by at least one neutron. These measurements serve as the basis for neutron background estimates for the San Onofre neutrino detector.

Structural requirements for catalysis: studies on RTEM-1 β-lactamase

β-lactamases are a group of enzymes that confer resistance to penam and cephem antibiotics by hydrolysis of the β-lactam ring, thereby inactivating the antibiotic. Crystallographic and computer modeling studies of RTEM-1 β-lactamase have indicated that Asp 132, a strictly conserved residue among the class A β-lactamases, appears to be involved in substrate binding, catalysis, or both. To study the contribution of residue 132 to β-lactamase function, site saturation mutagenesis was used to generate mutants coding for all 20 amino acids at position 132. Phenotypic screening of all mutants indicated that position 132 is very sensitive to amino acid changes, with only N132C, N132D, N132E, and N132Q showing any appreciable activity. Kinetic analysis of three of these mutants showed increases in K_M, along with substantial decreases in k_(cat). Efforts to trap a stable acyl-enzyme intermediate were unsuccessfuL These results indicate that residue 132 is involved in substrate binding, as well as catalysis, and supports the involvement of this residue in acylation as suggested by Strynadka et al.

Crystallographic and computer modeling studies of RTEM-1 β-lactamase have indicated that Lys 73 and Glu 166, two strictly conserved residues among the class A β-lactamases, appear to be involved in substrate binding, catalysis, or both. To study the contribution of these residues to β-lactamase function, site saturation mutagenesis was used to generate mutants coding for all 20 amino acids at positions 73 and 166. Then all 400 possible combinations of mutants were created by combinatorial mutagenesis. The colonies harboring the mutants were screened for growth in the presence of ampicillin. The competent colonys' DNA were sequenced, and kinetic parameters investigated. It was found that lysine is essential at position 73, and that position 166 only tolerated fairly conservative changes (Aspartic acid, Histidine, and Tyrosine). These functional mutants exhibited decreased kcat's, but K_M was close to wild-type levels. The results of the combinatorial mutagenesis experiments indicate that Lysis absolutely required for activity at position 73; no mutation at residue 166 can compensate for loss of the long side chain amine. The active mutants found--K73K/E166D, K73KIE166H, and K73KIE166Y were studied by kinetic analysis. These results reaffirmed the function of residue 166 as important in catalysis, specifically deacylation.

The identity of the residue responsible for enhancing the active site serine (Ser 70) in RTEM-1 β-lactamase has been disputed for some time. Recently, analysis of a crystal structure of RTEM-1 β-lactamase with covalently bound intermediate was published, and it was suggested that Lys 73, a strictly conserved residue among the class A β-lactamases, was acting as a general base, activating Ser 70. For this to be possible, the pK_a of Lys 73 would have to be depressed significantly. In an attempt to assay the pK_a of Lys 73, the mutation K73C was made. This mutant protein can be reacted with 2-bromoethylamine, and activity is restored to near wild type levels. ^(15)N-2-bromoethylamine hydrobromide and ^(13)C-2-bromoethylamine hydrobromide were synthesized. Reacting these compounds with the K73C mutant gives stable isotopic enrichment at residue 73 in the form of aminoethylcysteine, a lysine homologue. The pK_a of an amine can be determined by NMR titration, following the change in chemical shift of either the ^(15)N-amine nuclei or adjacent Be nuclei as pH is changed. Unfortunately, low protein solubility, along with probable label scrambling in the Be experiment, did not permit direct observation of either the ^(15)N or ^(13)C signals. Indirect detection experiments were used to observe the protons bonded directly to the ^(13)C atoms. Two NMR signals were seen, and their chemical shift change with pH variation was noted. The peak which was determined to correspond to the aminoethylcysteine residue shifted from 3.2 ppm down to 2.8 ppm over a pH range of 6.6 to 12.5. The pK_a of the amine at position 73 was determined to be ~10. This indicates that residue 73 does not function as a general base in the acylation step of the reaction. However the experimental measurement takes place in the absence of substrate. Since the enzyme undergoes conformational changes upon substrate binding, the measured pK_a of the free enzyme may not correspond to the pK_a of the enzyme substrate complex.

Beta-Hydroxyimino Phosphorus Derivatives. An Efficient Tool in Organic Synthesis

[EN] The purpose of this review article is to illustrate synthetic aspects of functionalized phosphorus derivatives containing an oximo moiety at the beta-position. First section will be focused on the synthesis of phosphine oxides, phosphonates or phosphonium salts containing an oxime group. The synthesis of these derivatives comprises the carbon–phosphorus single bond construction by reaction of haloximes with phosphorus derivatives, nucleophilic addition of phosphorus reagents to carbonyl compounds, or nucleophilic addition of phosphorus reagents to nitro olefins. This section will also concentrate on the most practical routes for the synthesis of the target compounds, through carbon–nitrogen double bond formation, which are as follows: condensation processes of carbonyl compounds and hydroxylamine derivatives or addition of hydroxylamines to allenes or alkynes. The preparative use of beta-oximo phosphorus derivatives as synthetic intermediates will be discussed in a second section, comprising olefination reaction, oxidation of oximes to nitrile oxides by reaction at the C-N double bond of the oxime moiety, oxidation of these substrates to nitrosoalkenes, reduction to the corresponding hydroxylamines and some reactions at the hydroxyl group of the hydroxyimino moiety.

A high pressure xenon time projection chamber for double beta decay

This thesis describes the design, construction and performance of a high-pressure, xenon, gas time projection chamber (TPC) for the study of double beta decay in ^(136) Xe. The TPC when operating at 5 atm can accommodate 28 moles of 60% enriched ^(136) Xe. The TPC has operated as a detector at Caltech since 1986. It is capable of reconstructing a charged particle trajectory and can easily distinguish between different kinds of charged particles. A gas purification and xenon gas recovery system were developed. The electronics for the 338 channels of readout was developed along with a data acquistion system. Currently, the detector is being prepared at the University of Neuchatel for installation in the low background laboratory situated in the St. Gotthard tunnel, Switzerland. In one year of runtime the detector should be sensitive to a 0ν lifetime of the order of 10^(24) y, which corresponds to a neutrino mass in the range 0.3 to 3.3 eV.

Optical properties of transparent alkali gallium silicate glass-ceramics containing Ni2+-doped beta-Ga2O3 nanocrystals

Broadband near-infrared (IR) luminescence in transparent alkali gallium silicate glass-ceramics containing N2+-doped beta-Ga2O3 nanocrystals was observed. This broadband emission could be attributed to the T-3(2g) (F-3) -> (3)A(2g) (F-3) transition of octahedral Ni2+ ions in glass-ceramics. The full width at half-maximum (FWHM) of the near-IR luminescence and fluorescent lifetime of the glass-ceramic doped with 0.10 mol% NiO were 260 nm and similar to 1220 mu s, respectively. It is expected that transparent Ni2+-doped beta-Ga2O3 glass-ceramics with this broad near-IR emission and long fluorescent lifetime have potential applications as super-broadband optical amplification media.

Broadband infrared luminescence from transparent glass-ceramics containing Ni2+-doped beta-Ga2O3 nanocrystals

Transparent Ni2+-doped beta-Ga2O3 glass-ceramics were synthesized. The nanocrystal phase in the glass-ceramics was identified to be beta-Ga2O3 and its size was about 3.6 nm. It was confirmed from the absorption spectra that the ligand environment of Ni2+ ions changed from the trigonal bi-pyramid fivefold sites in the as-cast glass to the octahedral sites in the glass-ceramics. The broadband infrared emission centering at 1270 nm with full width at half maximum (FWHM) of more than 250 nm was observed. The fluorescence lifetime was about 1.1 mu s at room temperature. The observed infrared emission could be attributed to the T-3 (2g) (F-3) -> (3)A (2g) (F-3) transition of octahedral Ni2+ ions. It is suggested that the Ni2+-doped transparent beta-Ga2O3 glass-ceramics with broad bandwidth and long lifetime have a potential as a broadband amplification medium.

Reaction of glucose catalyzed by framework and extraframework tin sites in zeolite beta

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup, and is now being considered as an intermediate step in the possible route of biomass conversion into fuels and chemicals. Recently, it has been shown that a hydrophobic, large pore, silica molecular sieve having the zeolite beta structure and containing framework Sn⁴⁺ (Sn-Beta) is able to isomerize glucose into fructose in aqueous media. Here, I have investigated how this catalyst converts glucose to fructose and show that it is analogous to that achieved with metalloenzymes. Specifically, glucose partitions into the molecular sieve in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center (framework Sn⁴⁺), isomerizes into the acyclic form of fructose and finally ring closes to yield the furanose product. Akin to the metalloenzyme, the isomerization step proceeds by intramolecular hydride transfer from C2 to C1. Extraframework tin oxides located within hydrophobic channels of the molecular sieve that exclude liquid water can also isomerize glucose to fructose in aqueous media, but do so through a base-catalyzed proton abstraction mechanism. Extraframework tin oxide particles located at the external surface of the molecular sieve crystals or on amorphous silica supports are not active in aqueous media but are able to perform the isomerization in methanol by a base-catalyzed proton abstraction mechanism. Post-synthetic exchange of Na⁺ with Sn-Beta alters the glucose reaction pathway from the 1,2 intramolecular hydrogen shift (isomerization) to produce fructose towards the 1,2 intramolecular carbon shift (epimerization) that forms mannose. Na⁺ remains exchanged onto silanol groups during reaction in methanol solvent, leading to a near complete shift in selectivity towards glucose epimerization to mannose. In contrast, decationation occurs during reaction in aqueous solutions and gradually increases the reaction selectivity to isomerization at the expense of epimerization. Decationation and concomitant changes in selectivity can be eliminated by addition of NaCl to the aqueous reaction solution. Thus, framework tin sites with a proximal silanol group are the active sites for the 1, 2 intramolecular hydride shift in the isomerization of glucose to fructose, while these sites with Na-exchanged silanol group are the active sites for the 1, 2 intramolecular carbon shift in epimerization of glucose to mannose.

Measurement of the neutron beta decay asymmetry using ultracold neutrons

The free neutron beta decay correlation A₀ between neutron polarization and electron emission direction provides the strongest constraint on the ratio λ = g_A/g_V of the Axial-vector to Vector coupling constants in Weak decay. In conjunction with the CKM Matrix element V_ud and the neutron lifetime τ_n, λ provides a test of Standard Model assumptions for the Weak interaction. Leading high-precision measurements of A₀ and τ_n in the 1995-2005 time period showed discrepancies with prior measurements and Standard Model predictions for the relationship between λ, τ_n, and V_ud. The UCNA experiment was developed to measure A₀ from decay of polarized ultracold neutrons (UCN), providing a complementary determination of λ with different systematic uncertainties from prior cold neutron beam experiments. This dissertation describes analysis of the dataset collected by UCNA in 2010, with emphasis on detector response calibrations and systematics. The UCNA measurement is placed in the context of the most recent τ_n results and cold neutron A₀ experiments.

Modulation of the effectiveness of 17-alpha-hydroxy-20-beta-dihydroprogesterone or of a gonadotrophic extract on the in vitro intrafollicular maturation of oocytes of the rainbow trout Salmo gairdnerii by various non-maturing steroids [Translation from: Compte Rendu Hebdomadaire des Seances de l'Academie des Sciences, Paris, Series D 281, 811-814, 1975]

The effectiveness of 17 α-hydroxy-20 β-dihydroprogesterone (17 α-20 β Pg) or of a trout hypophyseal gonadotrophic extract on the in vitro intrafollicular maturation of trout oocytes can be modulated by steroids which do not have a direct maturing effect; the effectiveness of the gonadotrophic extract is lowered by oestradiol and oestrone and increased by testosterone. As these steroids have no significant effect on maturation induced by 17 α-20 β Pg, the site of their activity is probably in the follicular envelopes. Corticosteroids, and Cortisol and cortisone in particular increase the effectiveness of the gonadotrophic extract, but increase the effectiveness of 17 α-20 β Pg even more strongly, suggesting that this 'progestagen' has a direct effect on oocyte sensitivity.

Beta and gamma vibrational bands in deformed nuclei

Energies and relative intensities of gamma transitions in ¹⁵²Sm, ¹⁵²Gd, ¹⁵⁴Gd, ¹⁶⁶Er, and ²³²U following radioactive decay have been measured with a Ge(Li) spectrometer. A peak fitting program has been developed to determine gamma ray energies and relative intensities with precision sufficient to give a meaningful test of nuclear models. Several previously unobserved gamma rays were placed in the nuclear level schemes. Particular attention has been paid to transitions from the beta and gamma vibrational bands, since the gamma ray branching ratios are sensitive tests of configuration mixing in the nuclear levels. As the reduced branching ratios depend on the multipolarity of the gamma transitions, experiments were performed to measure multipole mixing ratios for transitions from the gamma vibrational band. In ¹⁵⁴Gd, angular correlation experiments showed that transitions from the gamma band to the ground state band were predominantly electric quadrupole, in agreement with the rotational model. In ²³²U, the internal conversion spectrum has been studied with a Si(Li) spectrometer constructed for electron spectroscopy. The strength of electric monopole transitions and the multipolarity of some gamma transitions have been determined from the measured relative electron intensities.

The results of the experiments have been compared with the rotational model and several microscopic models. Relative B(E2) strengths for transitions from the gamma band in ²³²U and ¹⁶⁶Er are in good agreement with a single parameter band mixing model, with values of z₂= 0.025(10) and 0.046(2), respectively. Neither the beta nor the gamma band transition strengths in ¹⁵²Sm and ¹⁵⁴Gd can be accounted for by a single parameter theory, nor can agreement be found by considering the large mixing found between the beta and gamma bands. The relative B(E2) strength for transitions from the gamma band to the beta band in ²³²U is found to be five times greater than the strength to the ground state band, indicating collective transitions with strength approximately 15 single particle units.

Electrical and optical investigations of beta-gallium oxide

An experimental investigation of the optical properties of β–gallium oxide has been carried out, covering the wavelength range 220-2500 nm.

The refractive index and birefringence have been determined to about ± 1% accuracy over the range 270-2500 nm, by the use of a technique based on the occurrence of fringes in the transmission of a thin sample due to multiple internal reflections in the sample (ie., the "channelled spectrum" of the sample.)

The optical absorption coefficient has been determined over the range 220 - 300 nm, which range spans the fundamental absorption edge of β – Ga₂O₃. Two techniques were used in the absorption coefficient determination: measurement of transmission of a thin sample, and measurement of photocurrent from a Schottky barrier formed on the surface of a sample. Absorption coefficient was measured over a range from 10 to greater than 10⁵, to an accuracy of better than ± 20%. The absorption edge was found to be strongly polarization-dependent.

Detailed analyses are presented of all three experimental techniques used. Experimentally determined values of the optical constants are presented in graphical form.

Synthesis of nickel(II) complexes of alpha-isoxazolylazo-beta-diketones and their absorption of spin-coating films and thermal properties for HD-DVD-R

Three kinds of new nickel(II) complexes of alpha-isoxazolylazo-beta-diketones with blue-violet light absorption were synthesized. Their structures were postulated based on elemental analysis, MS and FT-IR spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. The absorption properties and thermal stability of these complexes were discussed. The static optical recording test for high density digital versatile disc-recordable (HD-DVD-R) system was also studied. (c) 2005 Elsevier B.V. All rights reserved.

Rare earth doped beta-diketone complexes as promising high-density optical recording materials for blue optoelectronics

Some kinds of rare earth beta-diketone complexes with blue-violet light absorption edge were synthesized using the ligands of thenoyltrifluoroacctone (HTTA), 2, 2'-dipyridyl (BIPY) and different metal ions (Gd3+, Sm3+ and La3+). Their contents, structures and optoelectronic parameters were monitored by elemental analysis, MS, IR and UV spectra. The solubility of rare earth beta-diketone complexes in 2, 2, 3, 3-tetrafluoro-1-propanol (TFP) and absorption properties of their films in the region 300-800 nm were measured. The influence on the difference of absorption maximum from rare earth beta-diketone complexes to beta-diketone ligand by different metal ions was studied. In addition, the thermal stability of rare earth beta-diketone complexes was also reported. (C) 2005 Elsevier B.V. All rights reserved.

Spectroscopic and thermal properties of short wavelength metal (II) complexes containing alpha-isoxazolylazo-beta-diketones as co-ligands

Two new azo dyes of alpha-isoxazolylazo-beta-dilcetones and their Ni(II) and Cu(II) complexes with blue-violet light wavelength were synthesized using a coupling component, different diazo components and metal (II) ions (Ni2+ and Cu2+). Based on the elemental analysis, MS spectra and FT-IR spectral analyses, azo dyes were unequivocally shown to exist as hydrazoketo and azoenol forms which were respectively obtained from the solution forms and from the solid forms. The action of sodium methoxide (NaOMe) on azo dyes in solutions converts hydrazoketo form into azoenol form, so azo dyes are coordinated with metal (II) ions as co-ligands in the azoenol forms. The solubility of all the compounds in common organic solvents such as 2,2,3,3-tetrafluoro-1-propanol (TFP) or chloroform (CHCl3) and absorption properties of spin-coating thin films were measured. The difference of absorption maxima from the complexes to their ligands was discussed. In addition, the TG analysis of the complexes was also determined, and their thermal stability was evaluated. It is found that these new metal (II) complexes had potential application for high-density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra in blue-violet light region and high thermal stability. (c) 2004 Elsevier B.V. All rights reserved.

Synthesis, spectral, and thermal characterizations of Ni(II) and Cu(II) beta-diketone complexes with thenoyltrifluoroacetone ligand

Two kinds of nickel(II) and copper(II) P-diketone complexes derived from thenoyltrifluoroacetone ligand with blue-violet light absorption were synthesized by reacting free ligand and different metal(II) ions in sodium methoxide solution. Their structures were postulated based on elemental analysis, ESI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. Their solubility in organic solvents, absorption properties of thin film and thermal stability of these complexes were evaluated. (c) 2006 Elsevier B.V. All rights reserved.