Controlled ventilation during NMR spectroscopic studies: hemodynamic and biochemical consequences

The effects of different ventilation methods on cardiac output measured by the indicator-dilution method, liver blood flow measured by a deuterium washout technique using 2H nuclear magnetic resonance (NMR) and liver concentrations of ATP and intracellular pH determined with 31P NMR were compared in anesthetized rats. No differences in mean arterial blood pressure were demonstrable with the different modes of ventilation. However, significant drops in cardiac output were observed between freely breathing and animals ventilated with positive pressure but not the high frequency oscillatory method (407 +/- 46 and 520 +/- 88 vs. 633 +/- 86 ml/min/kg, p less than 0.05 and p = NS, respectively). Moreover, liver blood flow was significantly reduced during positive pressure but not high frequency oscillatory ventilation compared with free breathing rats (32 +/- 4 and 43 +/- 10 vs. 46 +/- 8 ml/100 g, p less than 0.05 and p = NS, respectively). 31P NMR spectroscopy revealed no effects of either ventilation method on tissue ATP or intracellular pH as estimated by the chemical shift of inorganic phosphate. These data suggest that controlled ventilation in normal rats accomplished with standard positive pressure methods is associated with major decreases in cardiac output and liver blood flow despite maintenance of normal blood pressure. High frequency oscillatory ventilation appears to effect less compromise of cardiac output and hepatic perfusion than positive pressure ventilation and may, therefore, be preferable for some biological studies.     

Hydrogen bonding incis-2,3-epoxycyclooctanol

Hydrogen bonding and the electron-withdrawing or electron-donating characteristics of substituent groups that are neighboring to epoxide groups can affect the reactivity of the epoxide ring. The crystal structure ofcis-2,3-epoxycyclooctanol has been determined as a saturated eight-membered ring compound in which a hydroxyl group is attached to the C(1) atom that is adjacent to a 2,3-fused epoxy ring. The findings are that the longer epoxide C-O bond (and hence the one expected to be more readily broken) is the one farther from the hydroxyl group [1.462(1) å versus 1.447(1) å] and that the optimal hydrogen bonding is to an adjacent molecule radier than within the molecule. The shortest C-C bond is that of the epoxide group; the bond adjacent to it (on the side farther from the hydroxyl group) is the next shortest.     

Studies of hydrogen bonding: Part XXIX. An experimental and theoretical approach to the structure of nitriles and of hydrogen-bonded complexes with phenol

Dipole moments, μ_a, of four nitriles, have been determined experimentally and calculated by the CNDO/2 method. The results obtained can be accounted for in terms of a planar trimer parallel-antiparallel model held together in clusters. Experimental and CNDO/2 calculated dipole moments of hydrogen-bonded complexes between nitriles and phenol indicate strongly that the O-H proton in phenol is located perpendicular to the triple bond.     

Microwave assisted fluorination: an improved method for side chain fluorination of substituted 1-arylethanones

A two-step, one-pot microwave (MW) assisted fluorination of 1-arylethanones to their corresponding 1-aryl-2-fluoroethanones has been developed. The first step utilises Selectfluor™ as a fluorinating agent in methanol forming 1-aryl-2-fluoroethanones and their corresponding dimethyl acetals. In the second step, water is added and Selectfluor™ acts as a Lewis acid in the hydrolytic cleavage of the dimethyl acetals. Compared to the thermal synthesis, the MW assisted method leads to a reduction in reaction time both in the fluorination and for the dimethyl acetal cleavage. Moreover, the one-pot procedure reduces reagent and solvent consumption. The method is best suited for the preparation of 1-aryl-2-fluoroethanones containing substituents that deactivates electrophilic aromatic substitution, however highly electron deficient ketones such as 1-(3,5-dinitrophenyl)ethanone reacts more slowly. Reactions using electron rich aromatic ketones had a low regioselectivity, and also produced fluoroaromatic products.     

Assignments of the Pfr-Pr FTIR difference spectrum of cyanobacterial phytochrome Cph1 using 15N and 13C isotopically labeled phycocyanobilin chromophore

The reversible red and far-red light-induced transitions of cyanobacterial phytochrome Cph1 from Synechocystis PCC 6803 were investigated by Fourier transform infrared (FTIR) difference spectroscopy. High-quality light-induced Pfr-Pr difference FTIR spectra were recorded for the 58 kDa N-terminal domain of Cph1 by repetitive photochemical cycling and signal averaging. The Pfr-Pr difference spectra in H(2)O and D(2)O were very similar to those previously reported for full-length 85 kDa Cph1.(1) Published assignments were extended by analysis of the effects of (13)C and (15)N isotope substitutions at selected sites in the phycocyanobilin chromophore and by (15)N global labeling of the protein. The Pfr-Pr difference spectra were dominated by an amide I peak/trough at 1653 cm(-1)(+)/1631 cm(-1)(-) and a smaller amide II band at 1554 cm(-1). Labeling effects allowed specific chromophore assignments for the C(1)=O (1736 cm(-1)(-)/1724 cm(-1)(+)) and C(19)=O (1704 cm(-1)(-)) carbonyl vibrations, C=C vibrations at 1589 cm(-1)(+), and bands at 1537(-), 1512(+), 1491(-), 1163(+), 1151(-), 1134(+), 1109(-), and 1072(-) cm(-1) that must involve chromophore C-N bonds. A variety of additional changes were insensitive to isotope labeling of the chromophore. Effects of (15)N labeling of the protein were used to tentatively assign some of these to specific amino acid changes. Those insensitive to (15)N labeling included a protonated aspartic or glutamic acid at 1734 cm(-1)(-)/1722 cm(-1)(+) and a cysteine at 2575 cm(-1)(+)/2557 cm(-1)(-). Bands sensitive to (15)N protein labeling at 1487 cm(-1)(+)/1502 cm(-1)(-) might arise from trytophan and bands at 1261 cm(-1)(+)/1244 cm(-1)(-) and 1107 cm(-1)(-)/1095 cm(-1)(+) might arise from a histidine environment or protonation change. These assignments are discussed in light of the 15Z-E photoisomerization model of phototransformation and the associated protein conformational changes.     

STRUCTURE-ACTIVITY STUDIES OF PHOTOACTIVATED ANTIVIRAL AND CYTOTOXIC TRICYCLIC THIOPHENES

The photoactivated antiviral and cytotoxic activities of the naturally occurring thiophene, alpha-terthienyl (1), and 15 synthetic analogues were evaluated against murine cytomegalovirus and Sindbis virus, and murine mastocytoma cells. After irradiation with near UV light, alpha-terthienyl and most of its analogues had significant toxicity, with minimum inhibitory concentrations in the range of 0.02-40 microM. In the absence of near UV irradiation, only one analogue had antiviral activity and five were cytotoxic. The most active analogues were those containing carboxylic acid, hydroxyl, or cyano substituents. Quantitative structure-activity relationship analysis of thiophene phototoxicity suggested that the rate of singlet oxygen production is the primary determinant of antiviral and cytotoxic activities. For phototoxicity against murine cytomegalovirus, a significant role for hydrophobicity was also demonstrated. Tricyclic thiophenes show significant potential for photochemotherapy of viral infections and cancer, and further evaluation in animal models is recommended.     

On the Elliptic Genera of Manifolds of Spin(7) Holonomy

Superstring compactification on a manifold of Spin(7) holonomy gives rise to a 2d worldsheet conformal field theory with an extended supersymmetry algebra. The \({\mathcal{N} = 1}\) superconformal algebra is extended by additional generators of spins 2 and 5/2, and instead of just superconformal symmetry one has a c = 12 realization of the symmetry group \({\mathcal{S}W(3/2,2)}\). In this paper, we compute the characters of this supergroup and decompose the elliptic genus of a general Spin(7) compactification in terms of these characters. We find suggestive relations to various sporadic groups, which are made more precise in a companion paper.     

Evaluations of solid electrodes for use in voltammetric monitoring of heavy metals in samples from metallurgical nickel industry

Evaluation of different solid electrode systems for detection of zinc, lead, cobalt, and nickel in process water from metallurgical nickel industry with use of differential pulse stripping voltammetry has been performed. Zinc was detected by differential pulse anodic stripping voltammetry (DPASV) on a dental amalgam electrode as intermetallic Ni–Zn compound after dilution in ammonium buffer solution. The intermetallic compound was observed at –375 mV, and a linear response was found in the range 0.2–1.2 mg L^–1 (r²=0.98) for 60 s deposition time. Simultaneous detection of nickel and cobalt in the low g L^–1 range was successfully performed by use of adsorptive cathodic stripping voltammetry (AdCSV) of dimethylglyoxime complexes on a silver–bismuth alloy electrode, and a good correlation was found with corresponding AAS results (r²=0.999 for nickel and 0.965 for cobalt). Analyses of lead in the g L^–1 range in nickel-plating solution were performed with good sensitivity and stability by DPASV, using a working electrode of silver together with a glassy carbon counter electrode in samples diluted 1:3 with distilled water and acidified with H₂SO₄ to pH 2. A new commercial automatic at-line system was tested, and the results were found to be in agreement with an older mercury drop system. The stability of the solid electrode systems was found to be from one to several days without any maintenance needed.