Alloxazines and isoalloxazines. Mass spectrometric analysis of riboflavin and related compounds

The positive ion electron-impact mass spectra of a series of alloxazines, iso-alloxazines and some derivatives have been examined. The compounds employed were lumichrome (7,8-dimethylalloxazine), 1,3-dimethyllumichrome, lumiflavin (7,8,10-trimethyl-iso-alloxazine), 3-methyllumiflavin, riboflavin [7,8-dimethyl-10-(D-1′-ribityl)-iso-alloxazine], riboflavin tetraacetate, 3-methylriboflavin tetraacetate and riboflavin tetrapropionate. By using exact mass measurements, metastable ion defocusing and the mass/composition shifts occurring with derivatives, it has been possible to arrive at detailed interpretations of the mass spectra of all compounds. With lumichrome and lumiflavin, fragmentation commences by elimination of HNCO from the pyrimidine ring. With riboflavin and its derivatives the ribityl chain cleaves off first, followed by decomposition of the iso-alloxazine ring. Application of these methods and findings to the structural analysis of chemically interesting modified flavins is predicted to be rewarding.     

Finding jets and summing soft gluons: a new algorithm

We examine a new algorithm for finding jets ine ⁺ e ^– annihilation, using a jet measure based on relative transverse momentum. We perform an analytic calculation of the three-jet fraction at lowest order, and compare our result with the standard jet-finding algorithm. For soft gluons in an abelian theory it is shown that the leading double logarithms exponentiate, unlike the situation for the commonly used algorithm based on invariant mass. In QCD we find that there are leading non-abelian logarithms, and we calculate these explicitly atO( _s ² ). We discuss the modifications to the algorithm which are needed when the mass of a parton cluster is taken into account. The hope is that the new algorithm will allow an improved theoretical analysis at smaller values of the resolution parametery _T , and hence an improved fit to the experimental data.Nick Brown was tragically killed on 13th June, 1991. This paper is dedicated to his memory     

Hard form factors for meson-baryon strong couplings as derived from deep inelastic lepton scattering

As stimulated by earlier attempts for obtaining theNN andN form factors from the deep inelastic lepton scattering data, we extend the analysis by taking into account effects of additional mesons including, , ,K, andK ^*, with the coupling constants fixed by the lowenergy nucleon-nucleon and hyperon-nucleon scattering data. Contrary to an earlier claim that the NN andN form factor must be very soft (e.g., with the cutoff mass less than 500 MeV in the monopole form), we find, for example, that with all form factors parametrized in the dipole form, a universal cutoff mass of 1150 MeV in the/N sector and 1400 MeV in the/ sector yields predictions in excellent agreement with recently published neutrino data on the momentum fractions carried by thes, , and¯d quarks, as well as consistent with the sea-to-valence ratio extracted from the CDHS data and the Femilab E615 experiment. Similar results can also be obtained by using exponential cutoffs for all couplings, or by using monopole forms for some vertices while retaining dipole forms for the rest. The success of the mesonexchange picture in generating the strangeness content in a proton suggests an alternative understanding of the origin of sea quarks in the proton.We wish to thank G. Garvey, K. Holinde, L.-C. Liu, M. B. Johnson, M. Strikman, A. W. Thomas and Jochen Wambach for helpful conversations. W-Y. P. Hwang wishes to acknowledge the Alexander von Humboldt Foundation for a fellowship to visit Jülich for conducting research. His research works was also supported in part by the National Science Council of the Republic of China. The work of G. E. Brown is supported in part by a Humboldt award, in part by NATO Grant RG85/0093, and in part by the U.S. Department of Energy.     

Functionalized enamines—XXII : Annelation of enamines of polycyclic α,β-unsaturated ketones; a facile partial synthesis of furano- indolo- and benzsteroids. Total synthesis of 3-oxa-A-norsteroid

Reaction of dienamine 4a with substituted phenacyl bromides gave steroidal[3,4-b] furans 5a–g. The same principle reaction was utilized for the total synthesis of (±) 2 - (p - chlorophenyl) - 3 - oxa - A - nor - estra - 1,5(10), 9(11) - triene - 17 - acetate 12a. Treatment of 4a, b with benzenediazonium salts, in DMF, followed by a Fischer-indole cyclization yielded steroidal[6, 7-b] indoles 8a–k. Dienamine 4b could be annelated to benz[4, 5, 6] steroids 9a and 9b by reaction with methyl vinyl ketone and crotonaldehyde, respectively.     

Far-infrared laser magnetic resonance spectrum of NHD

Far-infrared laser magnetic resonance spectra of NHD (X ²A′') (0,0,0) have been observed. Data are presented for the rotational transitions 3₁₃ ← 2₀₂ and 4₁₃ ← 3₂₂ observed at wavelengths of 211.3 and 374.1 μm respectively. Theoretical values of the transition magnetic field strengths have been calculated using the best available molecular constants. The agreement between theory and experiment confirms our spectroscopic assignments, but indicates that with further experimental data, considerable refinement of the molecular constants will be obtained.     

Use of a Dual-Marker Form of Analysis to Estimate Binding Constants Between Receptors and Ligands by Affinity Capillary Electrophoresis

This work describes the use of a dual-standard analysis approach termed the time-average ratio (TAR) in affinity capillary electrophoresis (ACE) to estimate binding constants of receptors to ligands. In this form of analysis the TAR is the migration time of the receptor divided by the average of the sum of the migration times of two non-interacting standards. This change in TAR as a function of the concentration of ligand yields a value for the binding constant. This concept is demonstrated using three model systems: carbonic anhydrase B (CAB, EC 4.2.1.1) and arylsulfonamides, vancomycin (Van) and ristocetin (Rist) from Streptomyces orientalis and Nocardia lurida, respectively, and d-Ala- d-Ala terminus peptides. Three ACE techniques are used to examine the three systems: standard ACE, flow-through partial-filling ACE (FTPFACE), and on-column derivatization coupled to ACE. The findings described here demonstrate that ACE data analyzed using the TAR form of analysis yield binding constants between receptors and ligands comparable to those estimated using other ACE forms of analysis. A comparison to three other forms of analysis is described.     

Validation of the CALUX bioassay for the screening of PCDD/Fs and dioxin-like PCBs in retail fish

The chemical-activated luciferase expression (CALUX) assay is a reporter gene assay that detects dioxin-like compounds based on their ability to activate the aryl hydrocarbon receptor (AhR) and thus expression of the reporter gene. In this paper, the CALUX assay was examined for its application in the screening of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dioxin-like PCBs) in retail fish. The sample extracts were cleaned up on a sulfuric acid-silica gel column followed by an activated carbon column, and the AhR activity of the separated PCDD/F and dioxin-like PCB fractions was determined using the assay. The quantitative limit for 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.98 pg ml(-1) (0.19 pg assay(-1) in the standard curve, corresponding to 0.16 pg g(-1) of CALUX-based toxic equivalency (2,3,7,8-TCDD equivalents) in the tested sample. Recovery tests in which dioxins were added to fish samples resulted in acceptable recoveries (77-117%). The CALUX assay performed well in the analysis of dioxins in fish samples and a comparative study revealed a strong correlation between the CALUX assay and high-resolution gas chromatography-high-resolution mass spectrometry analysis for the determination of PCDD/Fs (r = 0.89) and dioxin-like PCBs (r = 0.91) in retail fish (n = 22). These data revealed that the CALUX assay would be a useful screening method for PCDD/Fs and dioxin-like PCBs in retail fish.     

Chemometric Analysis of Urinary Volatile Organic Compounds to Monitor the Efficacy of Pitavastatin Treatments on Mammary Tumor Progression over Time

Volatile organic compounds (VOCs) in urine are potential biomarkers of breast cancer. Previously, our group has investigated breast cancer through analysis of VOCs in mouse urine and identified a panel of VOCs with the ability to monitor tumor progression. However, an unanswered question is whether VOCs can be exploited similarly to monitor the efficacy of antitumor treatments over time. Herein, subsets of tumor-bearing mice were treated with pitavastatin at high (8 mg/kg) and low (4 mg/kg) concentrations, and urine was analyzed through solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS). Previous investigations using X-ray and micro-CT analysis indicated pitavastatin administered at 8 mg/kg had a protective effect against mammary tumors, whereas 4 mg/kg treatments did not inhibit tumor-induced damage. VOCs from mice treated with pitavastatin were compared to the previously analyzed healthy controls and tumor-bearing mice using chemometric analyses, which revealed that mice treated with pitavastatin at high concentrations were significantly different than tumor-bearing untreated mice in the direction of healthy controls. Mice treated with low concentrations demonstrated significant differences relative to healthy controls and were reflective of tumor-bearing untreated mice. These results show that urinary VOCs can accurately and noninvasively predict the efficacy of pitavastatin treatments over time.