Stereostructure assignment of flexible five-membered rings by GIAO 13C NMR calculations: prediction of the stereochemistry of elatenyne

The stereochemistry of conformationally mobile five-membered rings is often hard to assign from NMR data, and [2,2']bifuranyl systems are even more challenging. GIAO (13)C NMR chemical shifts have been calculated for a series of [2,2']bifuranyl and pyranopyran species, taking into account their conformational flexibility using weighted averages of the data for all low energy conformers. We show that calculation of (13)C NMR chemical shifts using the geometries obtained using molecular mechanics greatly reduces the computational expense without a significant loss of accuracy, even in this demanding system. The results were sufficiently accurate to distinguish not only the pyran and furanyl isomers but also between all the diastereoisomeric forms. As a result of this validation, we predict the stereochemistry for the recently proposed revised structure of the natural product elatenyne, which contains a [2,2']bifuranyl core.     

Electron delocalization in the metallabenzenes: a computational analysis of ring currents

Many metallabenzene complexes appear to exhibit an enhanced thermodynamic stability which has been attributed to the concept of aromaticity. Analysis of the ring currents induced by a magnetic field, either by direct visualization or by considering nuclear or nucleus-independent chemical shielding values (NMR or NICS), have become useful theoretical tools to characterize the aromaticity of many molecules involving the main group elements. We have analyzed 21 metallabenzenes using variations of these techniques, which take account of the large core and metal orbital contributions which often lead to transition-metal-containing systems exhibiting anomalous shielding values. Analysis of individual orbital contributions to both the ring currents and chemical shielding values based upon the ipsocentric and CSGT (continuous set of gauge transformations) methods has shown that complexes such as the 18 electron Ir or Rh(C 5H 5)(PH 3) 2Cl 2 molecules should be classed as aromatic, whereas the 16 electron complexes such as Os or Ru(C 5H 5)(PH 3) 2Cl 2 should not, despite having the same occupancy of pi-MOs. The differences can be directly attributed to the HOMO/LUMO b 2 in-plane (d xy ) molecular orbital, which, when unoccupied, is available to disrupt the delocalized currents typical of aromatic systems. A range of Pd and Pt metallabenzenes with cyclopentadienyl and phosphine ligands is also discussed as having aromatic and nonaromatic character, respectively.     

The binding of nitric oxide at the Cu(i) site of copper nitrite reductase and of inorganic models: DFT calculations of the energetics and EPR parameters of side-on and end-on structures

Density functional theory calculations have been used to probe the end-on and side-on bonding motifs of nitric oxide at the Cu(i) centre in the enzyme copper nitrite reductase and in three inorganic model systems. We find that irrespective of a range of functionals used, the end-on structure is preferred by up to 40 kJ mol(-1), although this preference is smaller for the enzyme than for the inorganic model systems. We have calculated the g-tensor and atomic hyperfine coupling constants for these structures. When compared to available experimental data, for one model compound the calculated EPR parameters definitely favour an end-on structure, although this preference is somewhat less for the enzyme. Our prediction of NO end-on binding in the enzyme is at variance with structural data.     

A study of piperidinium structure-directing agents in the synthesis of silica molecular sieves under fluoride-based conditions

This study is a continuation of our efforts to understand the interplay in the self-assembly chemistry for formation of molecular sieves from guest organocations and inorganic silicon oxide. In this particular study we focus on the competitive interplay of the organocations and the synthesis cofactor fluoride anion. The anions play a key role in structure determination, as a function of net solution concentration. They compete with the role for the space-filling organocation in determining which molecular sieve host structure will be specified. In this study we look at this competition in the synthesis for a series of 33 different organocations derived from the piperidine ring system. Derivatives were prepared which both fixed substituents on the carbon and nitrogen centers on the ring. Results were discussed in terms of product selectivity from synthesis as a function of solution concentration for the reactants. A total of 17 different host topologies were found in this series, and a correlation was seen for (a) open-framework lattices (low framework densities) under the most concentrated reaction conditions and then (b) high framework density products once the conditions were more dilute. Some surprising synthesis differences are seen in comparing the performance of these structure directing agents (SDAs) in fluoride media vs hydroxide media (the more conventional environment for zeolite/molecular sieve syntheses involving silicate chemistry). Finally molecular modeling was used to understand some of the trends in product selectivity for closely related guest (SDA) candidates.     

A priori phase prediction of zeolites: case study of the structure-directing effects in the synthesis of MTT-type zeolites

This study first uses molecular modeling to examine the structure-directing effects of small amines that are selective for the crystallization of MTT-type zeolite phases. The optimized van der Waals interactions of these small amines are compared within the one-dimensional pore zeolites with the MTT, TON, and MTW frameworks. From these results and our previous molecular modeling studies of structure-directing agents (SDA) for MTT-type zeolites, a large number of amines or quaternary ammonium molecules are successfully predicted to be selective for MTT phases. These molecules were chosen by matching the crystallographic periodicity of the pore structure with the distances between the centers of branched groups in these molecules. These molecules vary in length and in the number of branched moieties, and a few of these molecules are polymeric or oligomeric. In test cases where the distances between the branched groups are not multiples of the pore periodicity, with few exceptions these molecules usually do not produce MTT phases. Finally, we discuss the inorganic conditions necessary for crystallization of MTT phases in borosilicate preparations with some of the diamines in this investigation.     

Effects of masking noise on vowel and sibilant contrasts in normal-hearing speakers and postlingually deafened cochlear implant users

The role of auditory feedback in speech production was investigated by examining speakers' phonemic contrasts produced under increases in the noise to signal ratio (N/S). Seven cochlear implant users and seven normal-hearing controls pronounced utterances containing the vowels /i/, /u/, /e/ and /ae/ and the sibilants /s/ and /I/ while hearing their speech mixed with noise at seven equally spaced levels between their thresholds of detection and discomfort. Speakers' average vowel duration and SPL generally rose with increasing N/S. Average vowel contrast was initially flat or rising; at higher N/S levels, it fell. A contrast increase is interpreted as reflecting speakers' attempts to maintain clarity under degraded acoustic transmission conditions. As N/S increased, speakers could detect the extent of their phonemic contrasts less effectively, and the competing influence of economy of effort led to contrast decrements. The sibilant contrast was more vulnerable to noise; it decreased over the entire range of increasing N/S for controls and was variable for implant users. The results are interpreted as reflecting the combined influences of a clarity constraint, economy of effort and the effect of masking on achieving auditory phonemic goals-with implant users less able to increase contrasts in noise than controls.     

The Iowa connection

A summary of the Fluorinated Ylide Chemistry, Organometallic Chemistry, Phosphonate Chemistry, Single-Electron-Transfer Chemistry and Metal Hydride Chemistry carried out at the University of Iowa is described.     

Error-compensating algorithms in phase-shifting interferometry: a comparison by error analysis

In this paper, two families of phase-shifting algorithms with π/2 phase steps are studied. In family I, three new algorithms are derived by using the averaging technique based on the Surrel six-sample algorithm with phase shifts of π/2. Family II includes four well-known algorithms derived by the averaging technique based on the conventional four-sample algorithm with π/2 phase steps. A polynomial model of phase-shift errors used to describe general expressions for calculation of the correct object phase via the Fourier spectra analysing method as a function of the harmonic order in the fringe signal is presented. The error-compensating properties of the algorithms in families I and II are investigated by the Fourier spectra analysing method. It is found that the averaging technique, when used in any of the algorithm with π/2 phase steps, can improve the phase-shifting algorithm property: it is insensitive to phase-shift error when the fringe signal contains the first harmonic, but it can't be used to enhance the phase-shifting algorithm properties when the fringe signal contains higher order harmonics (n2). P–V (peak–valley) phase errors are calculated by the computer simulation and tables and plots are presented, from which the algorithms in families I and II are compared. It is shown that the algorithms in family I are more insensitive to phase-shift errors when the fringe signal contains the second harmonic and the algorithms in family II are more insensitive to phase-shift errors when the fringe signal is a sinusoidal waveform.     

Multi-anode detection in electrospray ionization time-of-flight mass spectrometry

An electrospray ionization ion source coupled to a time-of-flight mass analyzer incorporating a multi-anode time-to-digital converter is described. High-speed data acquisition (kHz mass spectral acquisition) rates are achieved. The four-anode detector produces a significant increase in detection/counting efficiency over that for a single-anode detector. In this work a 2.5 times increase in detection efficiency is demonstrated. The multi-anode detector is also used as a diagnostic tool to optimize transmission of the ion optics.