Aristotelinone and serratoline: New indole alkaloids from Aristotelia serrata W.R.B. Oliver

Aristotelinone and serratoline, two new Aristotelia alkaloids, are shown to have indole and indolenine structures respectively from their spectra and reduction products.     

Analysis of the lattice,strong coupling series for g0φ4 field theory in d dimensions

We analyze the renormalized strong coupling series for lattice g₀φ⁴ field theory which is a double series in x = M⁴a⁴/g₀a_4?dandy = 1/M²a², where M is the renormalized mass, a the lattice spacing, g₀ the bare coupling constant and d the dimension of space-time. We extrapolate to large y for fixed x by using a Padé-like extrapolation technique. We study the dimensionless renormalized coupling constant G/M^4?d and find that as we approach the continuum(x → 0, y → ∞) the entire spectrum of g₀ from zero to infinity can be studied. Our results for d = 1,2,3,4 based on a series in y up to y⁵ and in x up to x³ show that for fixed lattice spacing a, G/M^4?d is a monotonic function of g₀ ranging from zero at g₀ = 0 to a maximum at g₀ = ∞. Using the high temperature expansion results, we have also derived 9 terms in y on 8 lattices of dimension 1,2,3 and 4 for the linear term in x, and studied this series to see if one can see a breakdown in this monotonic behavior of G for large y. The analysis of this latter series is inconclusive.     

Bubble pulsations between parallel plates

The dynamic response of an acoustically driven spherical bubble between parallel plates is investigated in the linear approximation. For the case of rigid plates, explicit expressions are provided for the resonance frequency and damping, and the importance of including compressibility of the liquid is discussed. For wide channels, approximate results are presented that account for finite acoustic impedance of the plates.     

Substrate-directed stereoselectivity in vicinal diamine-catalyzed synthesis of warfarin

[Structure: see text] A new mechanism involving a diimine intermediate is proposed for vicinal diamine-catalyzed synthesis of warfarin. Decreasing the NCCN dihedral angle by varying the diamine results in an increase in the enantioselectivity of warfarin synthesis.     

Structural impact of coordinating a helical 2,6-pyridyl diamide with divalent metals

[Structure: see text] The structural consequences of coordinating 2,6-bis[2-((4S)-4-methyl-4,5-dihydro-1,3-oxazol-2-yl)phenyl]carbamoylpyridines, 2, with divalent metals such as Cu(II), Ni(II), and Zn(II) are reported. Metal coordination occurs under mild conditions in a manner that preserves the helical bias of the parent ligand in the solid state and in solution. 1H NMR line-shape analysis indicates that metal coordination increases the helical interconversion barrier, thus rigidifying the dynamic helicity of 2.     

Advantages of deuterium-labelled mixed triacylglycerol in studies of intraluminal fat digestion

The (13)C-mixed triacylglcerol (MTG, 1,3-distearyl, 2-[1-(13)C]octanoyl glycerol) breath test is a non-invasive measure of intraluminal fat digestion. Recovery of (13)C in breath CO(2) is incomplete (<50%) owing to sequestration of (13)C into organic molecules via the tricarboxylic acid (TCA) cycle. In addition lack of knowledge of CO(2) production rate (VCO(2)) during the test leads to errors in the calculated percentage dose recovered (PDR). (2)H sequestration into organic molecules is low ( approximately 4%) and is not influenced by factors that affect VCO(2) such as food intake or physical activity. After oxidation of (2)H-labelled macromolecules, the label appears in body water, which can be sampled non-invasively in urine or saliva. After an overnight fast, two healthy adults consumed [(2)H]MTG (1,3-distearyl, 2-[(2)H(15)]octanoyl glycerol) and [(13)C]MTG (1,3 distearyl, 2-[1-(13)C]octanoyl glycerol) simultaneously. Total body water (TBW) was measured by (18)O dilution and also estimated from height and weight. Urine and saliva were sampled at baseline and for 10 h after consumption of the test meal. The abundance of (2)HOH and H(2) (18)O in urine and saliva was measured by continuous-flow isotope-ratio mass spectrometry. Cumulative PDR of (2)H and (18)O was calculated from the plateau enrichment, which was reached by 6 h in both saliva and urine. Recovery of (2)H calculated using measured TBW was compared with that using an estimated value of TBW. Mean recovery of (2)H in saliva was 99.3% and in urine was 96.4%. Errors introduced by estimating TBW were <5%. [(2)H]MTG could provide a simpler, more robust, indirect test of intraluminal fat digestion compared with the (13)C-breath test. Further studies are required in pancreatic insufficient patients.     

A theoretical study of the sum frequency vibrational spectroscopy of the carbon tetrachloride/water interface

Theoretical approximations to the sum frequency vibrational spectroscopy (SFVS) of the carbon tetrachloride/water interface are constructed using the quantum-corrected time correlation functions (TCF) to aid in interpretation of experimental data and to predict novel vibrational modes. Instantaneous normal mode (INM) methods are used to characterize the observed modes leading to the TCF signal, thus providing molecular resolution of the vibrational lineshapes. Detailed comparisons of the theoretical signals are made with those obtained experimentally and show excellent agreement for the spectral peaks in the O-H stretching region of water. An intermolecular mode, unique to the interface, at 848 cm(-1) is also identifiable, similar to the one seen for the water/vapor interface. INM analysis reveals the resonance is due to a wagging mode (hindered rotation) that was previously identified (Perry et al 2005 J. Chem. Phys. 123 144705) as localized on a single water molecule with both hydrogens displaced normal to the interface-generally it is found that the symmetry breaking at the interface leads to hindered translations and rotations at hydrophilic/hydrophobic interfaces that assume finite vibrational frequencies due to anchoring at the aqueous interface. Additionally, examination of the real and imaginary parts of the theoretical SFVS spectra reveal the spectroscopic species attributed the resonances and possible subspecies in the O-H region; these results are consistent with extant experimental data and associated analysis.