Recent advances and applications of iridium-catalysed asymmetric allylic substitution

Since their discovery in 1997, iridium-catalysed asymmetric allylic substitutions have been developed into a broadly applicable tool for the synthesis of chiral building blocks via C-C and C-heteroatom bond formation. The remarkable generality of these reactions and the high levels of regio- and enantioselectivity that are usually obtained in favour of the branched products have been made possible by a thorough investigation of the catalyst system and its mode of action. Therefore, today the Ir-catalysed asymmetric allylic substitution is a powerful reaction in the organic chemist's repertoire and has been used extensively for several applications. This article aims to provide an overview of the development of iridium catalysts derived from an Ir salt and a chiral phosphoramidite and their application to the enantioselective synthesis of natural products and biologically relevant compounds.     

Amplification of the linear and nonlinear optical response of a chiral molecular crystal

We have observed large second-order nonlinear optical and vibrational circular dichroism (VCD) responses in a charge-transfer-type L-Histidinium salt. Using X-ray Diffraction, VCD spectroscopy, and time-dependent density functional theory to characterize the compound, we employ a two-level model to explain and quantify the strongly enhanced optical signals. We find that both linear and nonlinear optical responses are greatly enhanced by a single low-lying charge-transfer state.     

Development of an organo- and enzyme-catalysed one-pot,sequential three-component reaction

A one-pot, three-component process is described which involves both organo- and enzyme-catalysed carbon–carbon bond-forming steps. In the first step, an organocatalyst catalyses the aldol reaction between acetaldehyde and a glyoxylamide. After dilution with additional aqueous buffer, and addition of pyruvate and an aldolase enzyme variant, a second aldol reaction occurs to yield a final product. Crucially, it was possible to develop a reaction in which both the organo- and enzyme-catalysed reactions could be performed in the same aqueous buffer system. The reaction described is the first example of a one-pot, three-component reaction in which the two carbon–carbon bond-forming processes are catalysed using the combination of an organocatalyst and an enzyme.     

Data-dependent neutral gain MS<Superscript>3</Superscript>: Toward automated identification of the N-Oxide functional group in drug metabolites

We report here an automated method for the identification of N-oxide functional groups in drug metabolites by using the combination of liquid chromatography/tandem mass spectrometry (LC/MS ⁿ ) based on ion-molecule reactions and collision-activated dissociation (CAD). Data-dependent acquisition, which has been readily utilized for metabolite characterization using CAD-based methods, is adapted for use with ion-molecule reaction-based tandem mass spectrometry by careful choice of select experimental parameters. Two different experiments utilizing ion-molecule reactions are demonstrated, data-dependent neutral gain MS³ and data-dependent neutral gain pseudo-MS³, both of which generate functional group selective mass spectral data in a single experiment and facilitate increased throughput in structural elucidation of unknown mixture components. Initial results have been generated by using an LC/MS ⁿ method based on ion-molecule reactions developed earlier for the identification of the N-oxide functional group in pharmaceutical samples, a notoriously difficult functional group to identify via CAD alone. Since commercial software and straightforward, external instrument modification are used, these experiments are readily adaptable to the industrial pharmaceutical laboratory.     

Self-assembled films from WO3: Electrochromism and lithium ion diffusion

WO₃/chitosan and WO₃/chitosan/poly(ethylene oxide) (PEO) films were prepared by the layer-by-layer method. The presence of chitosan enabled PEO to be carried into the self-assembled structure, contributing to an increase in the Li⁺ diffusion rate. On the basis of the galvanostatic intermittent titration technique (GITT) and the quadratic logistic equation (QLE), a spectroelectrochemical method was used for determination of the “optical” diffusion coefficient (D_op), enabling analysis of the Li⁺ diffusion rate and, consequently, the coloration front rate in these host matrices. The D_op values within the WO₃/chitosan/PEO film were significantly higher than those within the WO₃/chitosan film, mainly for higher values of injected charge. The presence of PEO also ensured larger accessibility to the electroactive sites, in accordance with the method employed here. Hence, this spectroelectrochemical method allowed us to separate the contribution of the diffusion process from the number of accessible electroactive sites in the materials, thereby aiding a better understanding of the useful electrochemical and electrochromic properties of these films for use in electrochromic devices.     

Rapid simultaneous determination of amines and organic acids in citrus using high-performance liquid chromatography

Rapid analytical method for the simultaneous separation and determination of amines and organic acids is a vital interest for quality control of citrus and their products. In the present study, a simultaneous high performance liquid chromatography (HPLC) method for the rapid separation of three amines and two organic acids was developed. Chromatographic separation of compounds was achieved using Xbridge C₁₈ column at ambient temperature, with an isocratic mobile phase of 3 mM phosphoric acid at a flow rate of 1.0 mL min⁻¹. A photodiode array (PDA) detector was used to monitor the eluent at 223 nm and 254 nm with a total analysis time of 10 min. Extraction of amines and organic acids from citrus juice was optimized. The method was validated by tests of linearity, recovery, precision and ruggedness. The limit of detection (LOD) and limit of quantification (LOQ) for amines and ascorbic acid were determined to be 5 ng and 9.8 ng, respectively. All calibration curves showed good linearity (R² ≥ 0.9999) within the test ranges. The recoveries of the amines and organic acids ranged between 84% and 117%. The identity of each peak was confirmed by mass spectral (MS) analysis. The developed method was successfully applied to analyze the content of amines and organic acids in six different species and two varieties of citrus. Results indicate that mandarin and Marrs sweet orange contain high level of amines, while pummelo and Rio Red grapefruit had high content of ascorbic acid (137-251 μg mL⁻¹) and citric acid (5-22 mg mL⁻¹). Synephrine was the major amine present in Clementine (114 μg mL⁻¹) and Marrs sweet orange (85 μg mL⁻¹). To the best of our knowledge, this is the first report on simultaneous separation and quantification of amines and organic acids in Marrs sweet orange, Meyer lemon, Nova tangerine, Clementine, Ugli tangelo and Wekiwa tangelo.     

A fiber optic sensor for transverse strain measurement

A fiber optic sensor capable of measuring two independent components of transverse strain is described. The sensor consists of a single Bragg grating written into high-birefringent, polarization-maintaining optical fiber. When light from a broadband source is used to illuminate the sensor, the spectra of light reflected from the Bragg grating contain two peaks corresponding to the two orthogonal polarization modes of the fiber. Two independent components of transverse strain in the core of the fiber can be computed from the changes in wavelength of the two peaks if axial strain and temperature changes in the fiber are zero or known. Experiments were performed to determine the response of the sensor by loading an uncoated sensor in diametral compression over a range of fiber orientations relative to the loading. The results of these experiments were used with a finite element model to determine a calibration matrix relating the transverse strain in the sensor to the wavelength shifts of the Bragg peaks. The performance of the sensor was then verified by measuring the transverse strains produced by loading the fiber in a V-groove fixture.     

Liquid–liquid microextraction methods based on ultrasound-assisted emulsification and single-drop coupled to gas chromatography–mass spectrometry for determining strobilurin and oxazole fungicides in juices and fruits

Two procedures are proposed based on ultrasound-assisted emulsification and single-drop liquid–liquid microextraction for the sensitive determination of seven strobilurin and six oxazole fungicides in fruits and juice samples. Both miniaturized techniques are coupled to gas chromatography with mass spectrometry in the selected ion monitoring mode, GC–MS(SIM). The procedures use low density organic solvents, and several factors influencing the emulsification, extraction and collection efficiency are optimized. The detection limits obtained at a signal-to-noise ratio of 3 are below the MRLs set by the European Commission. Enrichment factors are between 140–1140 for the first technique used and 80–1600 for the latter. The recoveries obtained for spiked samples are satisfactory for all compounds. The methods are validated according to the Commission Decision 2002/657/EC. Different fruit and juices are analyzed by the proposed method and none of the samples contained fungicide residues above the detection limits.     

Broadband terahertz ultrasonic transducer based on a laser-driven piezoelectric semiconductor superlattice

Spectral characteristics of laser-generated acoustic waves in an InGaN/GaN superlattice structure are studied at room temperature. Acoustic vibrations in the structure are excited with a femtosecond laser pulse and detected via transmission of a delayed probe pulse. Seven acoustic modes of the superlattice are detected, with frequencies spanning a range from 0.36 to 2.5 THz. Acoustic waves up to ∼2 THz in frequency are not significantly attenuated within the transducer which indicates excellent interface quality of the superlattice. The findings hold promise for broadband THz acoustic spectroscopy.     

Hub-and-spoke network design and fleet deployment for string planning of liner shipping

All shipping liner companies divide their service regions into several rotations (strings) in order to operate their container vessels. A string is the ordered set of ports at which a container vessel will call. Each port is usually called at no more than twice along one string, although a single port may be called at several times on different strings. The size of string dictates the number of vessels required to offer a given frequency of service. In order to better use their shipping capacity, groups of Liner Service Providers sometimes make a short term agreement to merge some of their service routes (in a certain region) into one main ocean going rotation and p feeder rotations. In order to minimize the weighted sum of transit time, and fixed deployment costs, this paper proposes a mixed integer linear programming model of the network design, and an allocation of proper capacity size and frequency setting for every rotation. Given that none of the existing general-purpose MIP solvers is able to solve even very small problem instances in a reasonable time, we propose a Lagrangian decomposition approach which uses a heuristic procedure and is capable of obtaining practical and high quality solutions in reasonable times. The model will be applied on a real example, and we shall present some of the results obtained by our model which show how it facilitates a better use of assets and a significant reduction in the use of fuel, therefore allowing a more environmentally friendly service.