Interfacial supramolecular biomimetic epoxidation catalysed by cyclic dipeptides

We synthesised a library of cis- and trans-cyclic dipeptides and evaluated their efficacy as catalysts in the asymmetric Weitz-Scheffer epoxidation of trans-chalcone. A thorough investigation relying on structure-activity studies and computational studies provided insights into the mechanism of the process. Our results revealed some structural features required for efficient conversion and for introduction of chirality into the product. The cyclic dipeptide acts as a catalyst by templating a supramolecular arrangement at the aqueous-organic interface required for efficient transformations to occur. Among all cyclic dipeptides investigated, cyclo(Leu-Leu) was the most efficient supramolecular catalyst.     

Liquid chromatography-tandem mass spectrometry (LC/APCI-MS/MS) methods for the quantification of captan and folpet phthalimide metabolites in human plasma and urine

Captan and folpet are fungicides largely used in agriculture. They have similar chemical structures, except that folpet has an aromatic ring unlike captan. Their half-lives in blood are very short, given that they are readily broken down to tetrahydrophthalimide (THPI) and phthalimide (PI), respectively. Few authors measured these biomarkers in plasma or urine, and analysis was conducted either by gas chromatography coupled to mass spectrometry or liquid chromatography with UV detection. The objective of this study was thus to develop simple, sensitive and specific liquid chromatography–atmospheric pressure chemical ionization-tandem mass spectrometry (LC/APCI-MS/MS) methods to quantify both THPI and PI in human plasma and urine. Briefly, deuterated THPI was added as an internal standard and purification was performed by solid-phase extraction followed by LC/APCI-MS/MS analysis in negative ion mode for both compounds. Validation of the methods was conducted using spiked blank plasma and urine samples at concentrations ranging from 1 to 250 μg/L and 1 to 50 μg/L, respectively, along with samples of volunteers and workers exposed to captan or folpet. The methods showed a good linearity (R ² > 0.99), recovery (on average 90% for THPI and 75% for PI), intra- and inter-day precision (RSD, <15%) and accuracy (<20%), and stability. The limit of detection was 0.58 μg/L in urine and 1.47 μg/L in plasma for THPI and 1.14 and 2.17 μg/L, respectively, for PI. The described methods proved to be accurate and suitable to determine the toxicokinetics of both metabolites in human plasma and urine.     

Gas-chromatography mass-spectrometry determination of phthalic acid in human urine as a biomarker of folpet exposure

Agricultural workers are exposed to folpet, but biomonitoring data are limited. Phthalimide (PI), phthalamic acid (PAA), and phthalic acid (PA) are the ring metabolites of this fungicide according to animal studies, but they have not yet been measured in human urine as metabolites of folpet, only PA as a metabolite of phthalates. The objective of this study was thus to develop a reliable gas chromatography–tandem mass spectrometry (GC–MS) method to quantify the sum of PI, PAA, and PA ring-metabolites of folpet in human urine. Briefly, the method consisted of adding p-methylhippuric acid as an internal standard, performing an acid hydrolysis at 100 °C to convert ring-metabolites into PA, purifying samples by ethyl acetate extraction, and derivatizing with N,O-bis(trimethylsilyl)trifluoro acetamide prior to GC–MS analysis. The method had a detection limit of 60.2 nmol/L (10 ng/mL); it was found to be accurate (mean recovery, 97%), precise (inter- and intra-day percentage relative standard deviations <13%), and with a good linearity (R ² > 0.98). Validation was conducted using unexposed peoples urine spiked at concentrations ranging from 4.0 to 16.1 μmol/L, along with urine samples of volunteers dosed with folpet, and of exposed workers. The method proved to be (1) suitable and accurate to determine the kinetic profile of PA equivalents in the urine of volunteers orally and dermally administered folpet and (2) relevant for the biomonitoring of exposure in workers.     

Beamforming for directional sources: additional estimator and evaluation of performance under different acoustic scenarios

Beamforming is done with an array of sensors to achieve a directional or spatially-specific response by using a model of the arriving wavefront. Conventionally, a plane wave or point source model is used and this can cause decreased array gain or even total breakdown of beamforming when the source is directional. To avoid this, the authors proposed in recent work an alternative beamforming method which defines a set of "sub-beamformers," each designed to respond to a different spatial mode of the source. The outputs of the individual sub-beamformers are combined in a weighted sum to give an overall output of better quality than that of a monopole beamformer. This paper extends the previous work by introducing an additional estimator for the weighted sum and by presenting simulation results to demonstrate the relative performance of the proposed method and the different estimators for a directional source in the presence of diffuse noise, reverberation, and an interfering source. Gain optimization subject to a constraint on the white-noise gain with the proposed beamforming method is also introduced. Generally, when beamforming on directional sources, the proposed method outperforms beamforming with a point source model when the input signal-to-noise ratio (SNR) is 0 dB or higher.     

Explicit characterization of the super-replication strategy in financial markets with partial transaction costs

We consider a continuous time multivariate financial market with proportional transaction costs and study the problem of finding the minimal initial capital needed to hedge, without risk, European-type contingent claims. The model is similar to the one considered in Bouchard and Touzi [B. Bouchard, N. Touzi, Explicit solution of the multivariate super-replication problem under transaction costs, The Annals of Applied Probability 10 (3) (2000) 685–708] except that some of the assets can be exchanged freely, i.e. without paying transaction costs. In this context, we generalize the result of the above paper and prove that the super-replication price is given by the cost of the cheapest hedging strategy in which the number of non-freely exchangeable assets is kept constant over time. Our proof relies on the introduction of a new auxiliary control problem whose value function can be interpreted as the super-hedging price in a model with unbounded stochastic volatility (in the directions where transaction costs are non-zero). In particular, it confirms the usual intuition that transaction costs play a similar role to stochastic volatility.     

Hyperpolarization of amino acid derivatives in water for biological applications

We report on the successful synthesis and hyperpolarization of N-unprotected α-amino acid ethyl propionate esters and extensively, on an alanine derivative hyperpolarized by PHIP (4.4 ± 1.0% ¹³C-polarization), meeting required levels for in vivo detection. Using water as solvent increases biocompatibility and the absence of N-protection is expected to maintain biological activity.     

Ueber das Argon.

Ohne Zusammenfassung     

A Generalized Topological Recursion for Arbitrary Ramification

The Eynard–Orantin topological recursion relies on the geometry of a Riemann surface S and two meromorphic functions x and y on S. To formulate the recursion, one must assume that x has only simple ramification points. In this paper, we propose a generalized topological recursion that is valid for x with arbitrary ramification. We justify our proposal by studying degenerations of Riemann surfaces. We check in various examples that our generalized recursion is compatible with invariance of the free energies under the transformation ${(x, y) \mapsto (y, x)}$ , where either x or y (or both) have higher order ramification, and that it satisfies some of the most important properties of the original recursion. Along the way, we show that invariance under ${(x, y) \mapsto (y, x)}$ is in fact more subtle than expected; we show that there exists a number of counterexamples, already in the case of the original Eynard–Orantin recursion, that deserve further study.     

Multiple-quantum vector field imaging by magnetic resonance

We introduce a method for non-invasively mapping fiber orientation in materials and biological tissues using intermolecular multiple-quantum coherences. The nuclear magnetic dipole field of water molecules is configured by a CRAZED sequence to encode spatial distributions of material heterogeneities. At any given point r in space, we obtain the spherical coordinates of fiber orientation (theta,phi) with respect to the external field by comparing three signals ||G(X)||, ||(Y)||, and ||G(Z)|| (modulus), acquired with linear gradients applied along the X, Y, and Z axes, respectively. For homogeneous isotropic materials, a subtraction ||G(Z)|| - ||G(X)|| - ||G(Y)|| gives zero. With anisotropic materials, we find an empirical relationship relating ||G(Z)|| - ||G(X)|| - ||G(Y)||/(||G(X)|| + ||G(Y)|| + ||G(Z)||) to the polar angle theta, while ||G(X|| - ||G(Y)||/(||G(X)|| + ||G(Y)|| + ||G(Z)||) is related to the azimuthal angle phi. Experiments in structured media confirm the structural sensitivity. This technique can probe length scales not accessible by conventional MRI and diffusion tensor imaging.