Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C₃ symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis.     

New Penta(tetrathiafulvalenyl)[60]fullerenes for Supramolecular Materials

New penta(organo)fullerenes donor–acceptor systems bearing five tetrathiafulvalene recognition units have been synthesized to promote self‐assemblies similar in appearance to shuttlecocks nested into each other thanks to the conical host cavity created around the fullerene together with the π–π and electronic interactions.     

Generating Artificial Reverberation via Genetic Algorithms for Real-Time Applications

We introduce a Virtual Studio Technology (VST) 2 audio effect plugin that performs convolution reverb using synthetic Room Impulse Responses (RIRs) generated via a Genetic Algorithm (GA). The parameters of the plugin include some of those defined under the ISO 3382-1 standard (e.g., reverberation time, early decay time, and clarity), which are used to determine the fitness values of potential RIRs so that the user has some control over the shape of the resulting RIRs. In the GA, these RIRs are initially generated via a custom Gaussian noise method, and then evolve via truncation selection, random weighted average crossover, and mutation via Gaussian multiplication in order to produce RIRs that resemble real-world, recorded ones. Binaural Room Impulse Responses (BRIRs) can also be generated by assigning two different RIRs to the left and right stereo channels. With the proposed audio effect, new RIRs that represent virtual rooms, some of which may even be impossible to replicate in the physical world, can be generated and stored. Objective evaluation of the GA shows that contradictory combinations of parameter values will produce RIRs with low fitness. Additionally, through subjective evaluation, it was determined that RIRs generated by the GA were still perceptually distinguishable from similar real-world RIRs, but the perceptual differences were reduced when longer execution times were used for generating the RIRs or the unprocessed audio signals were comprised of only speech.     

Antiphytopathogenic activity of Psoralea glandulosa (Fabaceae) against Botrytis cinerea and Phytophthora cinnamomi

The resinous exudate, three meroterpenes, namely bakuchiol (1), 3-hydroxybakuchiol (2), 12-hydroxyisobakuchiol (3), and one furanocoumarin, psoralen (4), were isolated from the leaves of culen (Psoralea glandulosa). In addition to these, two semi-synthetic derivatives, bakuchiol acetate (5) and bakuchiol methyl eter (6), were obtained from 1, and were subsequently evaluated in vitro for the inhibitory effect of resin and compounds on the mycelial growth of Botrytis cinerea Pers.: Fr. and Phytophthora cinnamomi Rands. The resinous exudate inhibited the mycelial growth of both the pathogens, while bakuchiol (1) exhibited an inhibitory effect on the mycelial growth of B. cinerea up to 94% at a concentration of 150 mg/L and psoralen (4) reduced the mycelial growth of P. cinnamomi up to 80% at a concentration of 150 mg/L. These compounds have the ability of blocking the development of mycelial growth and may be used as a potential biopesticide in the agricultural sector once the in vivo test results have been validated.     

The Keto–Enol Tautomerism of Biliverdin in Bacteriophytochrome: Could it Explain the Bathochromic Shift in the Pfr Form?†

Phytochromes are ubiquitous photoreceptors found in plants, eukaryotic algae, bacteria and fungi. Particularly, when bacteriophytochrome is irradiated with light, a Z‐to‐E (photo)isomerization takes place in the biliverdin chromophore as part of the Pr‐to‐Pfr conversion. This photoisomerization is concomitant with a bathochromic shift in the Q‐band. Based on experimental evidence, we studied a possible keto–enol tautomerization of BV, as an alternative reaction channel after its photoisomerization. In this contribution, the noncatalyzed and water‐assisted reaction pathways for the lactam–lactim interconversion through consecutive keto–enol tautomerization of a model BV species were studied deeply. It was found that in the absence of water molecules, the proton transfer reaction is unable to take place at normal conditions, due to large activation energies, and the endothermic formation of lactim derivatives prevents its occurrence. However, when a water molecule assists the process by catalyzing the proton transfer reaction, the activation free energy lowers considerably. The drastic lowering in the activation energy for the keto–enol tautomerism is due to the stabilization of the water moiety through hydrogen bonds along the reaction coordinate. The absorption spectra were computed for all tautomers. It was found that the UV–visible absorption bands are in reasonable agreement with the experimental data. Our results suggest that although the keto–enol equilibrium is likely favoring the lactam tautomer, the equilibrium could eventually be shifted in favor of the lactim, as it has been reported to occur in the dark reversion mechanism of bathy phytochromes.     

Automated DBS Extraction Prior to Hilic/RP LC–MS/MS Target Screening of Drugs

This article describes a rapid LC–MS/MS target screening method based on an automated extraction of 5 μL dried blood spots (DBS), two 5 min chromatographic runs on orthogonal phase columns (RP and Hilic) and a data dependent acquisition (DDA) of product ions spectra for the reliable identification of the detected compounds. The extraction step was performed in 2 min by using the LC autosampler itself in 96-well plates. This procedure was evaluated using 22 model compounds frequently encountered in forensic investigations, i.e., cocaine, benzodiazepines, amphetamines, opioids, antidepressants and antipsychotics. These investigations showed that even if the extraction step was reduced to a minimum, the extraction recoveries were satisfactory (median value of 40 %) and allowed for the detection of the model compounds in their therapeutic ranges, with the exception of morphine. Moreover, the use of two different chromatographic columns broadened the number of screening targets to those that behaved poorly under RP conditions, such as amphetamines or glucuronides, while keeping chromatographic gradients very short. This procedure was applied to 34 authentic post-mortem cases. It allowed the detection of 89 % of the compounds that were quantified in the routine procedures and the formal identification of 77 % of the compounds using their product ions spectra. These results were considered more than satisfactory compared to routine screening alone (GC–MS and LC-DAD, 55 % compound identification). The method described in this article is therefore a powerful approach for a fast, reliable and efficient target screening of drugs in forensic and clinical investigations.     

Evaluation of unsteady pressure fields and forces in rotating airfoils from time-resolved PIV

The final stages of transitional phenomena in laminar separation bubbles play a key role in their reattachment process, and they condition the boundary layer properties and flow structure after reattachment. In this experimental study, the evolution of the perturbation velocity spectra found in this zone is first presented, showing the nonlinear growth of instabilities in their path to develop fully turbulent spectra. The study of the average flow field allows the scaling of the reattachment region, both in its extension and in the characterization of the integral boundary layer magnitudes. Experimental laws are proposed for the evolution of the momentum thickness and of the shape factor. In addition, a universal, wake-like mean velocity profile is found shortly after the reattachment station. The phase-locked characterization technique allows measurements conditioned to the presence of a fluid event. This technique is used to track the evolution of large-scale structures, whose dynamics is seen to dominate the fluid behavior in the reattachment zone. The simultaneous existence of two vortex blobs is found to characterize this flow region, with the longest lived one being convected toward the wall and stretched. This process results in the fast breakdown of the large-scale vorticity structure and the sudden formation of 3-D, small scales that promote the rapid flow evolution toward a fully developed turbulent state.