Carbon Dioxide Activation at Metal Centers: Evolution of Charge Transfer from Mg .+ to CO2 in [MgCO2(H2O)n].+, n=0–8

We investigate activation of carbon dioxide by singly charged hydrated magnesium cations Mg ^.+(H₂O)_n, through infrared multiple photon dissociation (IRMPD) spectroscopy combined with quantum chemical calculations. The spectra of [MgCO₂(H₂O)_n]^.+ in the 1250–4000 cm^?1 region show a sharp transition from n=2 to n=3 for the position of the CO₂ antisymmetric stretching mode. This is evidence for the activation of CO₂ via charge transfer from Mg ^.+ to CO₂ for n≥3, while smaller clusters feature linear CO₂ coordinated end‐on to the metal center. Starting with n=5, we see a further conformational change, with CO₂^.? coordination to Mg²⁺ gradually shifting from bidentate to monodentate, consistent with preferential hexa‐coordination of Mg²⁺. Our results reveal in detail how hydration promotes CO₂ activation by charge transfer at metal centers.     

Betacyanins and Betaxanthins in Cultivated Varieties of Beta vulgaris L. Compared to Weed Beets

There are 11 different varieties of Beta vulgaris L. that are used in the food industry, including sugar beets, beetroots, Swiss chard, and fodder beets. The typical red coloration of their tissues is caused by the indole-derived glycosides known as betalains that were analyzed in hypocotyl extracts by UV/Vis spectrophotometry to determine the content of betacyanins (betanin) and of betaxanthins (vulgaxanthin I) as constituents of the total betalain content. Fields of beet crops use to be also infested by wild beets, hybrids related to B. vulgaris subsp. maritima or B. macrocarpa Guss., which significantly decrease the quality and quantity of sugar beet yield; additionally, these plants produce betalains at an early stage. All tested B. vulgaris varieties could be distinguished from weed beets according to betacyanins, betaxanthins or total betalain content. The highest values of betacyanins were found in beetroots ‘Monorubra’ (9.69 mg/100 mL) and ‘Libero’ (8.42 mg/100 mL). Other beet varieties contained less betacyanins: Sugar beet ‘Labonita’ 0.11 mg/100 mL; Swiss chard ‘Lucullus,’ 0.09 mg/100 mL; fodder beet ‘Monro’ 0.15 mg/100 mL. In contrast with weed beets and beetroots, these varieties have a ratio of betacyanins to betaxanthins under 1.0, but the betaxanthin content was higher in beetcrops than in wild beet and can be used as an alternative to non-red varieties. Stability tests of selected varieties showed that storage at 22 °C for 6 h, or at 7 °C for 24 h, did not significantly reduce the betalain content in the samples.     

Synthesis,experimental and in silico studies of N‐fluorenylmethoxycarbonyl‐O‐tert‐butyl‐N‐methyltyrosine,coupled with CSD data: a survey of interactions in the crystal structures of Fmoc–amino acids

Recently, fluorenylmethoxycarbonyl (Fmoc) amino acids (e.g. Fmoc–tyrosine or Fmoc–phenylalanine) have attracted growing interest in biomedical research and industry, with special emphasis directed towards the design and development of novel effective hydrogelators, biomaterials or therapeutics. With this in mind, a systematic knowledge of the structural and supramolecular features in recognition of those properties is essential. This work is the first comprehensive summary of noncovalent interactions combined with a library of supramolecular synthon patterns in all crystal structures of amino acids with the Fmoc moiety reported so far. Moreover, a new Fmoc‐protected amino acid, namely, 2‐{[(9H‐fluoren‐9‐ylmethoxy)carbonyl](methyl)amino}‐3‐{4‐[(2‐hydroxypropan‐2‐yl)oxy]phenyl}propanoic acid or N‐fluorenylmethoxycarbonyl‐O‐tert‐butyl‐N‐methyltyrosine, Fmoc‐N‐Me‐Tyr(t‐Bu)‐OH, C₂₉H₃₁NO₅, was successfully synthesized and the structure of its unsolvated form was determined by single‐crystal X‐ray diffraction. The structural, conformational and energy landscape was investigated in detail by combined experimental and in silico approaches, and further compared to N‐Fmoc‐phenylalanine [Draper et al. (2015). CrystEngComm, 42 , 8047–8057]. Geometries were optimized by the density functional theory (DFT) method either in vacuo or in solutio. The polarizable conductor calculation model was exploited for the evaluation of the hydration effect. Hirshfeld surface analysis revealed that H…H, C…H/H…C and O…H/H…O interactions constitute the major contributions to the total Hirshfeld surface area in all the investigated systems. The molecular electrostatic potentials mapped over the surfaces identified the electrostatic complementarities in the crystal packing. The prediction of weak hydrogen‐bonded patterns via Full Interaction Maps was computed. Supramolecular motifs formed via C—H…O, C—H…π, (fluorenyl)C—H…Cl(I), C—Br…π(fluorenyl) and C—I…π(fluorenyl) interactions are observed. Basic synthons, in combination with the Long‐Range Synthon Aufbau Modules, further supported by energy‐framework calculations, are discussed. Furthermore, the relevance of Fmoc‐based supramolecular hydrogen‐bonding patterns in biocomplexes are emphasized, for the first time.     

Speaker Recognition Using Constrained Convolutional Neural Networks in Emotional Speech

Speaker recognition is an important classification task, which can be solved using several approaches. Although building a speaker recognition model on a closed set of speakers under neutral speaking conditions is a well-researched task and there are solutions that provide excellent performance, the classification accuracy of developed models significantly decreases when applying them to emotional speech or in the presence of interference. Furthermore, deep models may require a large number of parameters, so constrained solutions are desirable in order to implement them on edge devices in the Internet of Things systems for real-time detection. The aim of this paper is to propose a simple and constrained convolutional neural network for speaker recognition tasks and to examine its robustness for recognition in emotional speech conditions. We examine three quantization methods for developing a constrained network: floating-point eight format, ternary scalar quantization, and binary scalar quantization. The results are demonstrated on the recently recorded SEAC dataset.     

Biofortification—A Frontier Novel Approach to Enrich Micronutrients in Field Crops to Encounter the Nutritional Security

Globally, many developing countries are facing silent epidemics of nutritional deficiencies in human beings and animals. The lack of diversity in diet, i.e., cereal-based crops deficient in mineral nutrients is an additional threat to nutritional quality. The present review accounts for the significance of biofortification as a process to enhance the productivity of crops and also an agricultural solution to address the issues of nutritional security. In this endeavor, different innovative and specific biofortification approaches have been discussed for nutrient enrichment of field crops including cereals, pulses, oilseeds and fodder crops. The agronomic approach increases the micronutrient density in crops with soil and foliar application of fertilizers including amendments. The biofortification through conventional breeding approach includes the selection of efficient genotypes, practicing crossing of plants with desirable nutritional traits without sacrificing agricultural and economic productivity. However, the transgenic/biotechnological approach involves the synthesis of transgenes for micronutrient re-translocation between tissues to enhance their bioavailability. Soil microorganisms enhance nutrient content in the rhizosphere through diverse mechanisms such as synthesis, mobilization, transformations and siderophore production which accumulate more minerals in plants. Different sources of micronutrients viz. mineral solutions, chelates and nanoparticles play a pivotal role in the process of biofortification as it regulates the absorption rates and mechanisms in plants. Apart from the quality parameters, biofortification also improved the crop yield to alleviate hidden hunger thus proving to be a sustainable and cost-effective approach. Thus, this review article conveys a message for researchers about the adequate potential of biofortification to increase crop productivity and nourish the crop with additional nutrient content to provide food security and nutritional quality to humans and livestock.     

Characterisation of fire retardant poly(phenylene ether) high impact polystyrene in the UL-94 test

The distribution of the temperature and the morphology of the charred material formed in the combustion of blends of poly(phenylene ether) (PPE) with high impact polystyrene (HIPS), carried out in the UL94 test, were examined. The effect of the fire retardant triphenyl phosphate is shown to be the decrease of time of burning, of temperature of the specimen and of zone involved in combustion, without apparent modification of the char structure. Hypothesis on gas and condensed phase fire retardant mechanisms are discussed.     

The electrodeless discharge lamp: a prospective tool for photochemistry: Part 3. The microwave photochemistry reactor

A simple and original microwave photochemical reactor is described in detail. It consists of an electrodeless discharge lamp placed into the reaction vessel in a modified domestic microwave oven. The microwave field generates ultraviolet radiation by the lamp at the same time when it interacts with the reaction mixture. The construction, experimental set-ups, applications, and safety precautions are discussed.     

Synthesis of novel azanorbornylpurine derivatives

Azanorbornylpurine derivatives were prepared by Mitsunobu reaction of appropriate hydroxyazanorbornane derivative with 6-chloropurine or construction of purine base at azanorbornylamines. The prepared target compounds were evaluated for antiviral activity and effect on neuronal and muscle nicotinic acetylcholine receptors.     

Magnetic fluid poly(ethylene glycol) with moderate anticancer activity

Poly(ethylene glycol) (PEG)-containing magnetic fluids - magnetite (Fe₃O₄) stabilized by sodium oleate - were prepared. Magnetic measurements confirmed superparamagnetic behaviour at room temperature. The structure of that kind of magnetic fluid was characterized using different techniques, including electron microscopy, photon cross correlation spectroscopy and small-angle neutron scattering, while the adsorption of PEG on magnetic particles was analyzed by differential scanning calorimetry and Fourier transform infrared spectroscopy. From the in vitro toxicity tests it was found that a magnetic fluid containing PEG (MFPEG) partially inhibited the growth of cancerous B16 cells at the highest tested dose (2.1 mg/ml of Fe₃O₄ in MFPEG).     

Computing determinantal representation of generalized inverses

We investigate implementation of the determinantal representation of generalized inverses for complex and rational matrices in the symbolic package MATHEMATICA. We also introduce an implementation which is applicable to sparse matrices.