Convenient Synthetic Sequence for the Preparation of Indanones

A convenient and general method is reported for the synthesis of indanones from aryl ketones or aldehydes.     

Strong Short-Range Cooperativity in Hydrogen-Bond Chains

Chains of hydrogen bonds such as those found in water and proteins are often presumed to be more stable than the sum of the individual H bonds. However, the energetics of cooperativity are complicated by solvent effects and the dynamics of intermolecular interactions, meaning that information on cooperativity typically is derived from theory or indirect structural data. Herein, we present direct measurements of energetic cooperativity in an experimental system in which the geometry and the number of H bonds in a chain were systematically controlled. Strikingly, we found that adding a second H-bond donor to form a chain can almost double the strength of the terminal H bond, while further extensions have little effect. The experimental observations add weight to computations which have suggested that strong, but short-range cooperative effects may occur in H-bond chains.     

Reconciling Electrostatic and n→π* Orbital Contributions in Carbonyl Interactions

Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance‐dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short‐range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O???C=O interactions.     

Highly stereoselective reductions of alpha-alkyl-1,3-diketones and alpha-alkyl-beta-keto esters catalyzed by isolated NADPH-dependent ketoreductases

[reaction: see text] The biocatalytic reduction of alpha-alkyl-1,3-diketones and alpha-alkyl-beta-keto esters employing 1 of 20 different isolated NADPH-dependent ketoreductases proved to be a highly efficient method for the preparation of optically pure keto alcohols or hydroxy esters.     

Comparative Evaluation of Different Targeted and Untargeted Analytical Approaches to Assess Greek Extra Virgin Olive Oil Quality and Authentication

Extra virgin olive oil (EVOO) is a key component of the Mediterranean diet, with several health benefits derived from its consumption. Moreover, due to its eminent market position, EVOO has been thoroughly studied over the last several years, aiming at its authentication, but also to reveal the chemical profile inherent to its beneficial properties. In the present work, a comparative study was conducted to assess Greek EVOOs’ quality and authentication utilizing different analytical approaches, both targeted and untargeted. 173 monovarietal EVOOs from three emblematic Greek cultivars (Koroneiki, Kolovi and Adramytiani), obtained during the harvesting years of 2018–2020, were analyzed and quantified as per their fatty acids methyl esters (FAMEs) composition via the official method (EEC) No 2568/91, as well as their bioactive content through liquid chromatography coupled to high resolution mass spectrometry (LC-HRMS) methodology. In addition to FAMEs analysis, EVOO samples were also analyzed via HRMS-untargeted metabolomics and optical spectroscopy techniques (visible absorption, fluorescence and Raman). The data retrieved from all applied techniques were analyzed with Machine Learning methods for the authentication of the EVOOs’ variety. The models’ predictive performance was calculated through test samples, while for further evaluation 30 commercially available EVOO samples were also examined in terms of variety. To the best of our knowledge, this is the first study where different techniques from the fields of standard analysis, spectrometry and optical spectroscopy are applied to the same EVOO samples, providing strong insight into EVOOs chemical profile and a comparative evaluation through the different platforms.     

Experimental Design and Optimization of Recovering Bioactive Compounds from Chlorella vulgaris through Conventional Extraction

Microalgae contain an abundance of valuable bioactive compounds such as chlorophylls, carotenoids, and phenolics and, consequently, present great commercial interest. The aim of this work is the study and optimization of recovering the aforementioned components from the microalgae species Chlorella vulgaris through conventional extraction in a laboratory-scale apparatus using a “green” mixture of ethanol/water 90/10 v/v. The effect of three operational conditions—namely, temperature (30–60 °C), duration (6–24 h) and solvent-to-biomass ratio (20–90 mL_solv/g_biom), was examined regarding the extracts’ yield (gravimetrically), antioxidant activity, phenolic, chlorophyll, and carotenoid contents (spectrophotometric assays), as well as concentration in key carotenoids, i.e., astaxanthin, lutein, and β-carotene (reversed-phase–high-performance liquid chromatography (RP–HPLC)). For this purpose, a face-centered central composite design (FC-CCD) was employed. Data analysis resulted in the optimal extraction conditions of 30 °C, for 24 h with 37 mL_solv/g_biom and validation of the predicted models led to 15.39% w/w yield, 52.58 mg_extr/mg_DPPH (IC50) antioxidant activity, total phenolic, chlorophyll, and carotenoid content of 18.23, 53.47 and 9.92 mg/g_extr, respectively, and the total sum of key carotenoids equal to 4.12 mg/g_extr. The experimental data and predicted results were considered comparable, and consequently, the corresponding regression models were sufficiently reliable for prediction.     

Reductions of threshold for a mid-infrared optical parametric oscillator by an intracavity optical amplifier

We demonstrate that the threshold for a mid-IR optical parametric oscillator based on periodically poled LiNbO3 is significantly reduced by the introduction of an optical amplifier inside the cavity. Thresholds as low as 8 mW and a tuning range of 3.0-4.2 microm were attained for stable single-mode operation.     

Recent progress on terahertz generation based on difference frequency generation:from power scaling to compact and portable sources

The progress achieved on power scaling and compact and portable THz sources is reviewed.By reversely stacking the GaP plates,the photon conversion efficiency is improved from 25% to 40% which corresponds to the maximum value.When the number of the plates is increased from four to five,the output power decreases because of back conversion.The THz generation is also investigated by mixing the two frequencies generated by a single Nd:YLF solid-state laser.The average output power reaches 1 μW.The introduction of two Nd:YLF crystals significantly improves the output power to 4.5 μW.This configuration facilitates the generation of different output frequencies.