Search results for "CET"
showing 10 items of 6679 documents
Unveiling the high reactivity of cyclohexynes in [3 + 2] cycloaddition reactions through the molecular electron density theory
2018
[3 + 2] cycloaddition (32CA) reactions of cyclohexyne, a cyclic strained acetylene, with methyl azide and methoxycarbonyl diazomethane have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d) computational level. These 32CA reactions, which take place through a one-step mechanism involving highly asynchronous transition state structures, proceed with relatively low activation enthalpies of 6.0 and 4.3 kcal mol-1, respectively, both reactions being strongly exothermic. The reactions are initiated by the creation of a pseudoradical center at one of the two acetylenic carbons of cyclohexyne with a very low energy cost, 1.0 kcal mol-1, which promotes the eas…
Formation and trapping of the thermodynamically unfavoured inverted-hemicucurbit[6]uril
2019
Amplification of a thermodynamically unfavoured macrocyclic product through the directed shift of the equilibrium between dynamic covalent chemistry library members is difficult to achieve. We show for the first time that during condensation of formaldehyde and cis-N,N'-cyclohexa-1,2-diylurea formation of inverted-cis-cyclohexanohemicucurbit[6]uril (i-cis-cycHC[6]) can be induced at the expense of thermodynamically favoured cis-cyclohexanohemicucurbit[6]uril (cis-cycHC[6]). The formation of i-cis-cycHC[6] is enhanced in low concentration of the templating chloride anion and suppressed in excess of this template. We found that reaction selectivity is governed by the solution-based template-a…
Three Co(II) Metal-Organic Frameworks with Diverse Architectures for Selective Gas Sorption and Magnetic Studies.
2019
Three Co(II) metal–organic frameworks, namely, {[Co2(L)2(OBA)2(H2O)4]·xG}n (1), {[Co(L)0.5(OBA)]·xG}n (2), and {[Co2(L)2(OBA)2(H2O)]·DMA·xG}n (3) [where L = 2,5-bis(3-pyridyl)-3,4-diaza-2,4-hexadiene, H2OBA = 4,4′-oxybisbenzoic acid, DMF = dimethylformamide, DMA = dimethylacetamide, and G denotes disordered guest molecules], have been synthesized under diverse reaction conditions through self-assembly of a bent dicarboxylate and a linear spacer with a Co(II) ion. While 1 is crystallized at room temperature in DMF to form a 2D layer structure, 2 is formed by the assembly of similar components under solvothermal conditions with a 3D network structure. On the other hand, changing the solvent t…
Catalytic enantioselective aza-Reformatsky reaction with seven-membered cyclic imines dibenzo[b,f][1,4]oxazepines
2017
A catalytic enantioselective aza-Reformatsky reaction is reported with cyclic dibenzo[b,f][1,4]oxazepines and ethyl iodoacetate leading to the synthesis of chiral ethyl 2-(10,11-dihydrodibenzo[b,f][1,4]oxazepin-11-yl)acetate derivatives with excellent yields and high enantioselectivities (up to 98% yield and 97 : 3 er) using a readily available diaryl prolinol L4 as the chiral ligand and Me2Zn as the zinc source under an air atmosphere. Furthermore, different transformations were carried out with the corresponding chiral β-amino esters, preserving in all cases the optical purity.
Modulating the DNA cleavage ability of copper(II) Schiff bases through ternary complex formation
2018
Copper(II) complexes with the potentially tridentate Schiff bases N-[(3-ethoxy-2-hydroxyphenyl)methylidene]-N′-tosylbenzene-1,2-diamine (H2L1) and N-[(2-hydroxynaphthanyl)methylidene]-N′-tosylbenzene-1,2-diamine (H2L2) have been synthesized by electrochemical oxidation of the metal in an electrochemical cell containing a solution of the corresponding ligand in acetonitrile. Adducts of these compounds with 2,2′-bipyridine (2,2′-bpy), 4,4′-bipyridine (4,4′-bpy) or 1,10-phenanthroline (phen) were also obtained. The complexes have been characterized by microanalysis, mass spectrometry, EPR, IR and UV-Vis spectroscopies, as well as DFT calculations. The ligand H2L1 and the compounds [CuL1(H2O)]·…
Who's better at spotting? A comparison between aerial photography and observer-based methods to monitor floating marine litter and marine mega-fauna.
2020
Pollution by marine litter is raising major concerns due to its potential impact on marine biodiversity and, above all, on endangered mega-fauna species, such as cetaceans and sea turtles. The density and distribution of marine litter and mega-fauna have been traditionally monitored through observer-based methods, yet the advent of new technologies has introduced aerial photography as an alternative monitoring method. However, to integrate results produced by different monitoring techniques and consider the photographic method a viable alternative, this ‘new’ methodology must be validated. This study aims to compare observations obtained from the concurrent application of observer-based and…
Modelling circulation in an ice-covered lake
2010
In deep ice-covered lakes with temperatures below 4 °C the heat flux from the bottom sediment results in a horizontal density gradient and a consequent flow along the bottom slope. Measurements in Lake Paajarvi, Finland, show a stable temperature field where a heat gain through the bottom and a heat loss through the ice nearly balance each other. The circulation is thermal with low velocities (less than 1.5 cm s -1 ). We used the 3D hydrodynamic Princeton Ocean Model as a tool to simulate the water circulation and the temperature distribution under the ice. The model forcing was based on field temperature measurements. The model simulations suggest that in midwinter the velocity field of th…
Niche partitioning amongst northwestern Mediterranean cetaceans using stable isotopes
2021
Abstract Ten species of cetaceans coexist in the Mediterranean Sea, one of the richest seas in biodiversity and endemisms worldwide. The conservation status of Mediterranean cetaceans has been a concern for many years, particularly due to increasing anthropogenic threats such as global warming and overfishing. We established the stable isotopic niches of carbon, nitrogen, and sulphur for five species of cetaceans inhabiting the northwestern Mediterranean Sea to elucidate the mechanisms of coexistence. The fin whale exploited epipelagic habitats with a low trophic level; the bottlenose dolphin was mostly neritic and had a high trophic level; the Risso’s dolphin was oceanic and fed bathypelag…
Effects of acclimation time and epigenetic mechanisms on growth of Neurospora in fluctuating environments
2017
AbstractReaction norms or tolerance curves have often been used to predict how organisms deal with fluctuating environments. A potential drawback is that reaction norms measured in different constant environments may not capture all aspects of organismal responses to fluctuating environments. We examined growth of the filamentous fungusNeurospora crassain fluctuating temperatures and tested if growth in fluctuating temperatures can be explained simply by growth in different constant temperatures or if more complex models are needed. In addition, as previous studies on fluctuating environments have revealed that past temperatures that organisms have experienced can affect their response to c…
Anhydrobiosis in yeasts: Glutathione synthesis by yeast Ogataea (Hansenula) polymorpha cells after their dehydration-rehydration.
2019
The possibility of using active dry microbial preparations in biotechnological processes is essential for the development of new modern industrial technologies. In this study, we show the possibility of obtaining such preparations of the genetically engineered yeast strain Ogataea (Hansenula) polymorpha with glutathione overproduction. Special pre-treatment involving the gradual rehydration of dry cells in water vapour led to the restoration/reactivation of almost 100% of dehydrated cells. Furthermore, dry cells do not lose their viability during storage at room temperatures. Application of dry cells as the inoculum provides the same levels of glutathione synthesis as that of a native yeast…