Effect of the Number of Methyl Groups on the Cation Affinity of Oxygen, Nitrogen, and Phosphorus Sites of Lewis Bases

2016 ◽  
Vol 120 (45) ◽  
pp. 9109-9116 ◽  
Author(s):  
Younes Valadbeigi ◽  
Jean-François Gal
2012 ◽  
Vol 8 ◽  
pp. 1406-1442 ◽  
Author(s):  
Christoph Lindner ◽  
Raman Tandon ◽  
Boris Maryasin ◽  
Evgeny Larionov ◽  
Hendrik Zipse

Using selected theoretical methods the affinity of a large range of Lewis bases towards model cations has been quantified. The range of model cations includes the methyl cation as the smallest carbon-centered electrophile, the benzhydryl and trityl cations as models for electrophilic substrates encountered in Lewis base-catalyzed synthetic procedures, and the acetyl cation as a substrate model for acyl-transfer reactions. Affinities towards these cationic electrophiles are complemented by data for Lewis-base addition to Michael acceptors as prototypical neutral electrophiles.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Oliver Loveday ◽  
Jorge Echeverría

AbstractIt is well known that, under certain conditions, C(sp3) atoms behave, via their σ-hole, as Lewis acids in tetrel bonding. Here, we show that methyl groups, when bound to atoms less electronegative than carbon, can counterintuitively participate in noncovalent interactions as electron density donors. Thousands of experimental structures are found in which methyl groups behave as Lewis bases to establish alkaline, alkaline earth, triel, tetrel, pnictogen, chalcogen and halogen bonds. Theoretical calculations confirm the high directionality and significant strength of the interactions that arise from a common pattern based on the electron density holes model. Moreover, despite the absence of lone pairs, methyl groups are able to transfer charge from σ bonding orbitals into empty orbitals of the electrophile to reinforce the attractive interaction.


2020 ◽  
Vol 85 ◽  
pp. 47-58
Author(s):  
Y Jiang ◽  
Y Liu

Various studies have observed that increased nutrient supply promotes the growth of bloom-forming cyanobacteria, but only a limited number of studies have investigated the influence of increased nutrient supply on bloom-forming cyanobacteria at the proteomic level. We investigated the cellular and proteomic responses of Microcystis aeruginosa to elevated nitrogen and phosphorus supply. Increased supply of both nutrients significantly promoted the growth of M. aeruginosa and the synthesis of chlorophyll a, protein, and microcystins. The release of microcystins and the synthesis of polysaccharides negatively correlated with the growth of M. aeruginosa under high nutrient levels. Overexpressed proteins related to photosynthesis, and amino acid synthesis, were responsible for the stimulatory effects of increased nutrient supply in M. aeruginosa. Increased nitrogen supply directly promoted cyanobacterial growth by inducing the overexpression of the cell division regulatory protein FtsZ. NtcA, that regulates gene transcription related to both nitrogen assimilation and microcystin synthesis, was overexpressed under the high nitrogen condition, which consequently induced overexpression of 2 microcystin synthetases (McyC and McyF) and promoted microcystin synthesis. Elevated nitrogen supply induced the overexpression of proteins involved in gas vesicle organization (GvpC and GvpW), which may increase the buoyancy of M. aeruginosa. Increased phosphorus level indirectly affected growth and the synthesis of cellular substances in M. aeruginosa through the mediation of differentially expressed proteins related to carbon and phosphorus metabolism. This study provides a comprehensive description of changes in the proteome of M. aeruginosa in response to an increased supply of 2 key nutrients.


Author(s):  
Valeriy G. Yakubenko ◽  
Anna L. Chultsova

Identification of water masses in areas with complex water dynamics is a complex task, which is usually solved by the method of expert assessments. In this paper, it is proposed to use a formal procedure based on the application of the method of optimal multiparametric analysis (OMP analysis). The data of field measurements obtained in the 68th cruise of the R/V “Academician Mstislav Keldysh” in the summer of 2017 in the Barents Sea on the distribution of temperature, salinity, oxygen, silicates, nitrogen, and phosphorus concentration are used as a data for research. A comparison of the results with data on the distribution of water masses in literature based on expert assessments (Oziel et al., 2017), allows us to conclude about their close structural similarity. Some differences are related to spatial and temporal shifts of measurements. This indicates the feasibility of using the OMP analysis technique in oceanological studies to obtain quantitative data on the spatial distribution of different water masses.


2019 ◽  
Vol 55 (3) ◽  
pp. 29-43 ◽  
Author(s):  
P. D. Klochenko ◽  
T. F. Shevchenko ◽  
I. N. Nezbrytskaya ◽  
Ye. P. Belous ◽  
Z. N. Gorbunova ◽  
...  

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