Time-resolved fluorescence spectra using time-correlated photon counting: Picosecond fluorescence in aqueous solutions of Cr(III) complexes at room temperature

A new procedure for measuring time-resolved emission spectra has been implemented. This technique has subnanosecond time resolution combined with the sensitivity and dynamic range needed to cope with extremely weak luminescence. Using this method the emissions of Cr(NH₃)₂ (NCS)₄^? and Cr(NCS)₆^3- in aqueous solution at room temperature have each been analyzed into two components. The fast component has a broad spectrum and is assigned to prompt fluorescence with lifetime below 100 ps. The slow component is dominated by phosphorescence but may include some delayed fluorescence. The phosphorescence lifetime is 5.5 ± 0.5 ns in Cr(NH₃)₂ (NCS)₄^? and 1.65 ± 0.1 ns in Cr(NCS)₆^3-. Order of magnitude estimates have been derived for other photophysical parameters.     

Computational studies of Cu(II)/Met and Cu(I)/Met binding motifs relevant for the chemistry of Alzheimer's disease

A systematic study of the binding motifs of Cu(II) and Cu(I) to a methionine model peptide, namely, N-formylmethioninamide 1, has been carried out by quantum chemical computations. Geometries of the coordination modes obtained at the B3LYP/6-31G(d) level of theory are discussed in the context of copper coordination by the peptide backbone and the S atom of a methionine residue in peptides with special emphasis on Met35 of the amyloid-beta peptide (Abeta) of Alzheimer's disease. The relative binding free energies in the gas phase, DeltaG(g), are calculated at the B3LYP/6-311+G(2df,2p)//B3LYP/6-31G(d) level of theory, and the solvation affects are included by means of the COSMO model to obtain the relative binding energies in solution, DeltaG(aq). A free energy of binding, DeltaG(aq) = -19.4 kJ mol(-1), relative to aqueous Cu(II) and the free peptide is found for the most stable Cu(II)/Met complex, 12. The most stable Cu(I)/Met complex, 23, is bound by -15.6 kJ mol(-1) relative to the separated species. The reduction potential relative to the standard hydrogen electrode is estimated to be E degrees (12/23) = 0.41 V. On the basis of these results, the participation of Met35 as a low affinity binding site of Cu(II) in Abeta, and its role in the redox chemistry underlying Alzheimer's disease is discussed.     

Cobalt(II) and cobalt(III) dipicolinate complexes: solid state,solution, and in vivo insulin-like properties

The synthesis and characterization of Co(II) and Co(III) 2,6-pyridinedicarboxylate (dipic(2-)) complexes are reported. Solid-state X-ray characterizations were performed on [Co(H(2)dipic)(dipic)].3H(2)O and [Co(dipic)(mu-dipic)Co(H(2)O)(5)].2H(2)O. Two coordination modes not previously observed in dipicolinate transition metal complexes were observed in these complexes; one involves metal coordination to the short C-O (C=O) bond, and the other involves metal coordination to a protonated oxygen atom. Solution studies, including paramagnetic NMR and UV-vis spectroscopy, were done showing the high stability and low lability of the Co(III) complex, whereas the Co(II) complexes exhibited ligand exchange in the presence of excess ligand. The [Co(dipic)(2)](2-) complex has pH dependent lability and in this regard is most similar to the [VO(2)dipic](-) complex. The [Co(dipic)(2)](2-) was found to be effective in reducing the hyperlipidemia of diabetes using oral administration in drinking water in rats with STZ-induced diabetes. Oral administration of VOSO(4) was used as a positive control for metal efficacy against diabetes. In addition to providing a framework to evaluate structure-function relationships of various transition metal complexes in alleviating the symptoms of diabetes, this work describes novel aspects of structural and solution cobalt chemistry.     

Methods for the determination of the number of polytetrahydrofuran branches in neoprene-g-polytetrahydrofuran

Methods for the determination of the number of the number of polytetrahydrofuran branches in neoprene-g-polytetrahydrofuran were examined. Only two suitable methods were found; namely, termination of oxonium ions by triphenylphosphine followed by ³¹P-NMR and termination with NH₄OH? NH₄Cl buffer and reaction with fluorescamine followed by fluorescence spectroscopy. Both methods led to the conclusion that Neoprene W has 9 ± 1 active halogens per mole that can be used to initiate tetrahydrofuran polymerization when silver salts are added. Among the methods examined in this study the fluorescence method was the most reliable, most reproducible, fastest, and simplest.     

Chain folding in polyamides: A study on Nylons 66, 610, and 612 as crystallized from solution

The present paper, dealing with nylons 66, 610, and 612, is part of a study on a series of polyamides as crystallized from solution. The lath-shaped crystallization products, aggregated in the form of sheaves, possess the characteristics of chain-folded single crystals. In particular, they can be collected in the form of oriented mats which display arced X-ray reflections both in the wide- and low-angle regions. This enables the fold surfaces to be indexed as 00l. In a given polymer the long spacing has a characteristic value and for different polymers it varies in the ratio of the monomer lengths. The measured layer thickness corresponds closely to four-unit cell lengths. The fact that this holds for all three polymers implies that the fold length is determined by the number of hydrogen bonds between the stems. In view of the small value of this figure (due to the large identity period) the long period can only be apportioned between straight stems and folds in a limited number of ways which enables some concrete suggestions to be made on the possible constitution of the fold itself. On annealing, the fold length increases preferentially by factors of 2. A mechanism with general implications for the refolding behavior of polymers is proposed.     

Variational multirate integration in multi-body dynamics

For systems that contain slow and fast dynamics, variational multirate integration schemes are used. These schemes split the system into parts which are simulated using two time grids consisting of micro and macro nodes. This formulation can be extended for multi-body systems. The rigid multi-body system is described by the so called director formulation and constraints describing the joints connecting the bodies. With the Lagrange multiplier method, the constraints are introduced into the equations of motion. A way to implement the null space method into the variational multirate framework is shown and the influence on the number of unknowns is investigated. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of Benzofurans by the Action of Copper on Terminal Alkynes and O-Halophenols

Cuprous acetylides react with aryl halides to yield aryl acetylenes and with o-halophenols to give benzofurans.^1,2 The broad scope of this latter reaction for the synthesis of benzofuran natural products is shown by application inter alia to norlignans,³ euparinoids,⁴ phytoalexins,⁵ furanocoumarins,⁶ fomannoxin,⁷ isotubaic acid⁸ and machicendiol.     

Novel Methods to Manipulate Autolysis in Sparkling Wine: Effects on Yeast

Sparkling wine made by the traditional method (Méthode Traditionelle) develops a distinct and desirable flavour and aroma profile attributed to proteolytic processes during prolonged ageing on lees. Microwave, ultrasound and addition of β-glucanase enzymes were applied to accelerate the disruption of Saccharomyces cerevisiae, and added to the tirage solution for secondary fermentation in traditional sparkling winemaking. Scanning electron microscopy and flow cytometry analyses were used to observe and describe yeast whole-cell anatomy, and cell integrity and structure via propidium iodide (PI) permeability after 6-, 12- and 18-months post-tirage. Treatments applied produced features on lees that were distinct from that of the untreated control yeast. Whilst control yeast displayed budding cells (growth features) with smooth, cavitated and flat external cell appearances; microwave treated yeast cells exhibited modifications like ‘doughnut’ shapes immediately after treatment (time 0). Similar ‘doughnut’-shaped and ‘pitted/porous’ cell features were observed on progressively older lees from the control. Flow cytometry was used to discriminate yeast populations; features consistent with cell disruption were observed in the microwave, ultrasound and enzyme treatments, as evidenced by up to 4-fold increase in PI signal in the microwave treatment. Forward and side scatter signals reflected changes in size and structure of yeast cells, in all treatments applied. When flow cytometry was interpreted alongside the scanning electron microscopy images, bimodal populations of yeast cells with low and high PI intensities were revealed and distinctive ‘doughnut’-shaped cell features observed in association with the microwave treatment only at tirage, that were not observed until 12 months wine ageing in older lees from the control. This work offers both a rapid approach to visualise alterations to yeast cell surfaces and a better understanding of the mechanisms of yeast lysis. Microwave, ultrasound or β-glucanase enzymes are tools that could potentially initiate the release of yeast cell compounds into wine. Further investigation into the impact of such treatments on the flavour and aroma profiles of the wines through sensory evaluation is warranted.     

Psychophysical recovery from pulse-train forward masking in electric hearing

Psychophysical pulse-train forward-masking (PTFM) recovery functions were measured in fifteen subjects with the Nucleus mini-22 cochlear implant and six subjects with the Clarion cochlear implant. Masker and probe stimuli were 500-Hz trains of 200- or 77-micros/phase biphasic current pulses. Electrode configurations were bipolar for Nucleus subjects and monopolar for Clarion subjects. Masker duration was 320 ms. Probe duration was either 10 ms or 30 ms. Recovery functions were measured for a high-level masker on a middle electrode in all 21 subjects, on apical and basal electrodes in 7 of the Nucleus and 3 of the Clarion subjects, and for multiple masker levels on the middle electrode in 8 Nucleus subjects and 6 Clarion subjects. Recovery functions were described by an exponential process in which threshold shift (in microA) decreased exponentially with increasing time delay between the offset of the masker pulse train and the offset of the probe pulse train. All but 3 of the 21 subjects demonstrated recovery time constants on a middle electrode that were less than 95 ms. The mean time constant for these 18 subjects was 54 ms (s.d. 17 ms). Three other subjects tested on three electrodes exhibited time constants larger than 95 ms from an apical electrode only. Growth-of-masking slopes depended upon time delay, as expected from an exponential recovery process, i.e., progressively shallower slopes were observed at time delays of 10 ms and 50 ms. Recovery of threshold shift (in microA) for PTFM in electrical hearing behaves inthe same way as recovery of threshold shift (in dB) for pure-tone forward masking in acoustic hearing. This supports the concept that linear microamps are the electrical equivalent of acoustic decibels. Recovery from PTFM was not related to speech recognition in a simple manner. Three subjects with prolonged PTFM recovery demonstrated poor speech scores. The remaining subjects with apparently normal PTFM recovery demonstrated speech scores ranging from poor to excellent. Findings suggest that normal PTFM recovery is only one of several factors associated with good speech recognition in cochlear-implant listeners. Comparisons of recovery curves for 10- and 30-ms probe durations in two subjects showed little or no temporal integration at time delays less than 95 ms where recovery functions have steep slopes. The same subjects exhibited large amounts of temporal integration at longer time delays where recovery slopes are more gradual. This suggests that probe detection depends primarily on detection of the final pulses in the probe stimulus and supports the use of offset-to-offset time delays for characterizing PTFM recovery in electric hearing.