An unexpected formation of a 14-membered Cyclodepsipeptide

The treatment of diluted solutions of the hydroxy diamides 6a and 6b in toluene with HCl gas at 100° gave the dimeric, 14-membered cyclodepsipeptide 10 in up to 72% yield (Scheme 3). The same product was formed from the linear dimer of 6b, the depsipeptide 11, under the same conditions (cf. Scheme 4). All attempts to prepare the cyclic seven-membered monomer 9, starting with different precursors and using different lactonization methods failed, and 10 was the only product which was isolated (cf. Scheme 6). For example, the reaction of the ester 20 with NaH in toluene at 80° led exclusively to the cyclodimer 10. On the other hand, the base-catalyzed cyclization of the hydroxy diester 22, which is the 'O-analogue' of 20, yielded neither the seven- membered dilactone, nor the 14-membered tetralactone, but only the known trimer 23 and tetramer 24 of 2,2- dimethylpropano-3-lactone (cf. Scheme 7)

Electrochemical CO2 conversion in Ionic Liquid-based electrolytes

The exponential increase in the concentration of greenhouse gasses in the atmosphere is considered one of the most important reasons for climate change. Carbon Dioxide is the most significant anthropogenic gas that contributes to global warming. CO2 capture and storage (CCS) has been proposed as one of the most important invention to mitigate CO2 emissions. Moreover, conversion of carbon dioxide into energy-rich chemicals is a viable approach to reducing the global carbon footprint. The most common techniques to remove CO2 from gas streams are the chemical and physical adsorption by liquid solvents. Traditionally, aqueous amine solutions have been used as chemical solvents because of their high selectivity, high reactivity and low price. Unfortunately, they present also many disadvantages associated with the high energy demand required for the solvent regeneration, corrosion issues and loss of solvent because of their high volatility. Hence, in the need to find more efficient solvents for CO2 capture and conversion, Ionic Liquids (ILs) have been highlighted as very good alternatives to common amine solution.[1] Within this field lies this research, which in turn is part of a much broader European project called SunCoChem. For this project we are testing the stability and performance of various ionic liquids, provided by Iolitec, Ionic Liquids Technologies GmbH, and in particular their ability to capture and electrochemically convert a pure CO2 stream to CO with high efficiencies. The ionic liquids were tested in a two-compartment H-type electrochemical cell. In the anodic chamber a nickel mesh electrode was immersed in a solution of potassium hydroxide and in the cathodic one a silver foil cathode was employed in a solution of acetonitrile and ionic liquid. An organic solvent was used to favor the dissolution of the ionic liquid and the homogenization of the solution. Other organic solvents such as propylene carbonate, ethylene glycol and 1-butanol were also tested with the aim of finding the best compromise between low viscosity, good conductivity and high electrochemical stability window. The Ionic Liquids (ILs) tested so far have a cationic part based on imidazole, which is expected to stabilize and lower the activation energy for the reduction of CO2. During Linear Sweep Voltammetry (LSV) tests this trend was confirmed by a shift to more positive potentials of the onset (~ 0.5V) for the CO2 reduction reaction in the presence of these Ionic Liquid and interesting value of current density were reached. Throughout the Chronopotentiometry (CP) studies, some ILs evidenced a decrease in the applied potential indicating the increase of the electrolyte conductivity. Our results evidence relevant current density values, a good stability during chronopotentiometry (CP) tests and a high selectivity towards the target product: CO, which however change depending on the used IL. AKCNOWLEDGMENT: The research leading to these results has received funding from the European Union’s Horizon 2020 Research and Innovation Action programme under the SunCoChem project (Grant Agreement No 862192). REFERENCES: [1] Shokat Sarmad et al, Carbon Dioxide Capture with Ionic Liquids and Deep Eutectic Solvents: A New Generation of Sorbents, 2016, https://doi.org/10.1002/cssc.20160098

IONIC LIQUIDS FOR CAPTURE AND ELECTROCHEMICAL CONVERSION OF CO2 - CIS 2021

The exponential increase in the concentration of greenhouse gasses in the atmosphere is considered one of the most important reasons for climate change. Carbon Dioxide is the most significant anthropogenic gas that contributes to global warming. CO2 capture and storage (CCS) has been proposed as one of the most important inventions to mitigate CO2 emissions. The most common techniques to remove CO2 from gas streams are the chemical and physical adsorption by liquid solvents. Traditionally, aqueous amine solutions have been used as chemical solvents because of their high selectivity, high reactivity and low price. Unfortunately, they present also many disadvantages associated with the high energy demand required for the solvent regeneration and corrosion. Hence, in the need to find more efficient solvents for CO2 capture and conversion, Ionic Liquids (ILs) have been highlighted as very good alternatives to common amine solution. (1) Within this field lies this research, which in turn is part of a much broader European project called SunCoChem. For this project we are testing the stability and performance of various ionic liquids, provided by Iolitec, Ionic Liquids Technologies GmbH, and in particular their ability to capture and electrochemically convert a pure CO2 stream to CO with high efficiencies. The ionic liquids were tested in a two-compartment H-type electrochemical cell. In the anodic chamber a nickel mesh electrode was immersed in a solution of potassium hydroxide and in the cathodic one a silver foil cathode was employed in a solution of CH3CN and ionic liquid. The eight Ionic Liquids (ILs) used as electrolytes have a cationic part based on imidazole, which is expected to stabilize and lower the activation energy for the reduction of CO2. Our results evidence relevant current density values, a good stability during chronopotentiometry (CP) tests and a high selectivity towards the target product: CO, which however change depending on the used IL. AKCNOWLEDGMENT: The research leading to these results has received funding from the European Union’s Horizon 2020 Research and Innovation Action programme under the SunCoChem project (Grant Agreement No 862192). References: [1] Shokat Sarmad et al2016, https://doi.org/10.1002/cssc.20160098

IONIC LIQUIDS FOR CAPTURE AND ELECTROCHEMICAL CONVERSION OF CO2 - ISE 2021

The exponential increase in the concentration of greenhouse gasses in the atmosphere is considered one of the most important reasons for climate change. Carbon Dioxide is the most significant anthropogenic gas that contributes to global warming. CO2 capture and storage (CCS) has been proposed as one of the most important invention to mitigate CO2 emissions. Moreover, conversion of carbon dioxide into energy-rich chemicals is a viable approach to reducing the global carbon footprint. The most common techniques to remove CO2 from gas streams are the chemical and physical adsorption by liquid solvents. Traditionally, aqueous amine solutions have been used as chemical solvents because of their high selectivity, high reactivity and low price. Unfortunately, they present also many disadvantages associated with the high energy demand required for the solvent regeneration, corrosion issues and loss of solvent because of their high volatility. Hence, in the need to find more efficient solvents for CO2 capture and conversion, Ionic Liquids (ILs) have been highlighted as very good alternatives to common amine solution.[1] Within this field lies this research, which in turn is part of a much broader European project called SunCoChem. For this project we are testing the stability and performance of various ionic liquids, provided by Iolitec, Ionic Liquids Technologies GmbH, and in particular their ability to capture and electrochemically convert a pure CO2 stream to CO with high efficiencies. The ionic liquids were tested in a two-compartment H-type electrochemical cell. In the anodic chamber a nickel mesh electrode was immersed in a solution of potassium hydroxide and in the cathodic one a silver foil cathode was employed in a solution of acetonitrile and ionic liquid. An organic solvent was used to favor the dissolution of the ionic liquid and the homogenization of the solution. Other organic solvents such as propylene carbonate, ethylene glycol and 1-butanol were also tested with the aim of finding the best compromise between low viscosity, good conductivity and high electrochemical stability window. The Ionic Liquids (ILs) tested so far have a cationic part based on imidazole, which is expected to stabilize and lower the activation energy for the reduction of CO2. During Linear Sweep Voltammetry (LSV) tests this trend was confirmed by a shift to more positive potentials of the onset (~ 0.5V) for the CO2 reduction reaction in the presence of these Ionic Liquid and interesting value of current density were reached. Throughout the Chronopotentiometry (CP) studies, some ILs evidenced a decrease in the applied potential indicating the increase of the electrolyte conductivity. Our results evidence relevant current density values, a good stability during chronopotentiometry (CP) tests and a high selectivity towards the target product: CO, which however change depending on the used IL. AKCNOWLEDGMENT: The research leading to these results has received funding from the European Union’s Horizon 2020 Research and Innovation Action programme under the SunCoChem project (Grant Agreement No 862192). REFERENCES: [1] Shokat Sarmad et al, Carbon Dioxide Capture with Ionic Liquids and Deep Eutectic Solvents: A New Generation of Sorbents, 2016, https://doi.org/10.1002/cssc.20160098

Understanding the role of imidazolium-based ionic liquids in the electrochemical CO2 reduction reaction

The development of efficient CO 2 capture and utilization technologies driven by renewable energy sources is mandatory to reduce the impact of climate change. Herein, seven imidazolium-based ionic liquids (ILs) with different anions and cations were tested as catholytes for the CO2 electrocatalytic reduction to CO over Ag electrode. Relevant activity and stability, but different selectivities for CO2 reduction or the side H 2 evolution were observed. Density functional theory results show that depending on the IL anions the CO 2 is captured or converted. Acetate anions (being strong Lewis bases) enhance CO2 capture and H2 evolution, while fluorinated anions (being weaker Lewis bases) favour the CO2 electroreduction. Differently from the hydrolytically unstable 1-butyl-3-methylimidazolium tetrafluoroborate, 1-Butyl-3-Methylimidazolium Triflate was the most promising IL, showing the highest Faradaic efficiency to CO (>95%), and up to 8 h of stable operation at high current rates (−20 mA & −60 mA), which opens the way for a prospective process scale-up

SESAR Solution 08.01 Validation Plan (VALP) for V2 - Part I; D2.1.040

Dissemination level = CO confidentialThis validation plan describes the V2 validation activities planned for solution 1 of the PJ08 Advanced Airspace Management. The aim of the planned validation activities in Wave 1 is to complete V2 maturity level of the four Operational Improvements as foreseen in the Transition Validation Strategy [22]: • AOM-0208- B • AOM-0805 • AOM-0809A & AOM-0809-B • CM-0102- B Model based, fast time simulations and real time simulations are planned to address stakeholders’ needs and assess the KPAs. This document is part of a project that has received funding from the SESAR Joint Undertaking under grant agreement No 731796 under European Union’s Horizon 2020 research and innovation programme.SESAR Solution 08.01 Validation Plan (VALP) for V2 - Part I; D2.1.040acceptedVersio

SiNWs-based electrochemical double layer micro-supercapacitors with wide voltage window (4V) and long cycling stability using a protic ionic liquid electrolyte

The present work reports the use and application of a novel protic ionic liquid (triethylammonium bis(tri fluoromethylsulfonyl)imide; NEtH TFSI) as an electrolyte for symmetric planar micro-supercapacitors based on silicon nanowire electrodes. The excellent performance of the device has been successfully demonstrated using cyclic voltammetry, galvanostatic charge-discharge cycles and electrochemical impedance spectroscopy. The electrochemical characterization of this system exhibits a wide operative voltage of 4 V as well as an outstanding long cycling stability after millions of galvanostatic cycles at a high current density of 2 mA cm. In addition, the electrochemical double layer micro-supercapacitor was able to deliver a high power density of 4 mWcm in a very short time pulses (a few ms). Our results could be of interest to develop prospective on-chip micro-supercapacitors using protic ionic liquids as electrolytes with high performance in terms of power and energy densities

Synthesis of cyclic depsipeptides under direct amide cyclization conditions

This work describes the use of the "direct amide cyclization" (DAC) of dipeptides which contain β-, γ-, or δ-hydroxy acids, obtained by the reaction of the corresponding hydroxy acids with 3-amino-2H-azirines, the so-called "azirine/oxazolone" method. The goal of this work was to synthesize cyclic depsipeptides with potential biological activities and to establish the limits of the DAC. Several attempts to prepare a 7-membered cyclodepsipeptide via DAC are described, based on analogies with syntheses of 6- and 9-membered depsipeptides. Instead of the desired 7-membered ring, only its dimer was obtained. Variation of the concentration, temperature, reaction time, solvents and substituents led to the dimeric product exclusively, and no monomeric product was found in any of the reaction mixtures. Molecular modeling shows that the formation of the dimeric depsipeptide is indeed energetically favored over the formation of the monomer. Extending the use of the DAC on depsipeptides containing γ-hydroxy acids, which could potentially yield 8-membered cyclic depsipeptides, did not lead to the desired products, but instead to 5-membered imino lactones or chlorinated acids. A mechanism for the formation of both products has been proposed. When the DAC conditions were applied to a linear precursor, containing a δ-hydroxy acid, again none of the expected products was formed. The linear ω-chloro acid was the only product isolated. Thus, the dependence of the result of the DAC reaction on whether an α-, β-, γ-, or δ- hydroxy acid diamide is used has been confirmed and it may be concluded that the direct amide cyclization is an appropriate method for the synthesis of cyclic depsipeptides only if the terminal OH group is in α- or β-position of the hydroxy acid

MULTIPLE PERIL RISK INSURANCE OF AGRICULTURAL CROPS – A MYTH OR REALITY

The insurance of agricultural crops is a conservative type of insurance. It is quite rarely that radical organizational changes are introduced. Currently, however, conditions dictate the introduction ofthere are the necessary conditions such changes in the Republic of Bulgaria. Modern development of agricultural production is a prerequisite for changing the methodology of this type of insurance so as to adapt it to the demands of agricultural producers. This article develops the thesis that a similar change might be implemented by transforming the liability of insurance companies from a liability related to certain risks and losses to a liability referring to any risks and losses. In other words, it is possible to make the transition to the so-called multiple peril risk insurance. Multiple peril risk insurance is considered to be a novelty which has only recently been introduced in EU member-states with advanced economies. Therefore, it is the subject of large-scale discussions. The objective is to choose to introduce such an option that will best correspond to the specific features of the agricultural development and traditions in the Republic of Bulgaria and related insurance practice