dft calculations
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2022 ◽  
Vol 375 ◽  
pp. 115835
Davis Zavickis ◽  
Guntars Zvejnieks ◽  
Andrei Chesnokov ◽  
Denis Gryaznov

2022 ◽  
Vol 161 ◽  
pp. 110404
Amir Farzaneh ◽  
Mousa Javidani ◽  
Mehdi D. Esrafili ◽  
Omer Mermer

2022 ◽  
Vol 23 (2) ◽  
pp. 838
Bahaa Jawad ◽  
Puja Adhikari ◽  
Kun Cheng ◽  
Rudolf Podgornik ◽  
Wai-Yim Ching

A rational therapeutic strategy is urgently needed for combating SARS-CoV-2 infection. Viral infection initiates when the SARS-CoV-2 receptor-binding domain (RBD) binds to the ACE2 receptor, and thus, inhibiting RBD is a promising therapeutic for blocking viral entry. In this study, the structure of lead antiviral candidate binder (LCB1), which has three alpha-helices (H1, H2, and H3), is used as a template to design and simulate several miniprotein RBD inhibitors. LCB1 undergoes two modifications: structural modification by truncation of the H3 to reduce its size, followed by single and double amino acid substitutions to enhance its binding with RBD. We use molecular dynamics (MD) simulations supported by ab initio density functional theory (DFT) calculations. Complete binding profiles of all miniproteins with RBD have been determined. The MD investigations reveal that the H3 truncation results in a small inhibitor with a −1.5 kcal/mol tighter binding to RBD than original LCB1, while the best miniprotein with higher binding affinity involves D17R or E11V + D17R mutation. DFT calculations provide atomic-scale details on the role of hydrogen bonding and partial charge distribution in stabilizing the minibinder:RBD complex. This study provides insights into general principles for designing potential therapeutics for SARS-CoV-2.

Soumitra Dinda ◽  
Koushik Sarkar ◽  
Bikash Kumar Panda ◽  
Kausikisankar Pramanik ◽  
Sanjib Ganguly

2022 ◽  
Anakuthil Anoop ◽  
Venkataraman Ganesh

The tropylium catalyzed carboxylic acid O-H insertion with diazoesters providing α-hydroxy esters was reported recently through an activated carbene as the key intermediate. We report a revised mechanism involving a unique homoaromatic intermediate with the tropylium ion and the diazoester based on the DFT calculations. Our computational model provides a clear insight into the binding of the tropylium ion with the diazoester providing the homoaromatic intermediate. The reaction profiles of four different pathways were compared. The energies of the intermediates and the transition states are reported at B97-D3(SMD)/def2TZVP//B97-D3/def2TZVP (in dichloromethane). The energy profiles were compared across a few computational methods to study the sensitivity of our model across methods.

2022 ◽  
Vol 13 (1) ◽  
Ya Lv ◽  
Guoyong Luo ◽  
Qian Liu ◽  
Zhichao Jin ◽  
Xinglong Zhang ◽  

AbstractThe applications of axially chiral benzonitriles and their derivatives remain mostly unexplored due to their synthetic difficulties. Here we disclose an unusual strategy for atroposelective access to benzonitriles via formation of the nitrile unit on biaryl scaffolds pre-installed with stereogenic axes in racemic forms. Our method starts with racemic 2-arylbenzaldehydes and sulfonamides as the substrates and N-heterocyclic carbenes as the organocatalysts to afford axially chiral benzonitriles in good to excellent yields and enantioselectivities. DFT calculations suggest that the loss of p-toluenesulfinate group is both the rate-determining and stereo-determining step. The axial chirality is controlled during the bond dissociation and CN group formation. The reaction features a dynamic kinetic resolution process modulated by both covalent and non-covalent catalytic interactions. The axially chiral benzonitriles from our method can be easily converted to a large set of functional molecules that show promising catalytic activities for chemical syntheses and anti-bacterial activities for plant protections.

2022 ◽  
Feng Shao ◽  
Liqing Zheng ◽  
Jinggang Lan ◽  
Renato Zenobi

Self-assembled monolayers (SAMs) of thiolates on metal surfaces are of key importance for engineering surfaces with tunable properties. However, it remains challenging to understand binary thiolate SAMs on metals at the nanoscale under ambient conditions. Here we employ tip-enhanced Raman spectroscopy (TERS) and density functional theory (DFT) calculations to investigate local information of binary SAMs on Au(111) coadsorbed from an equimolar mixture of p-cyanobenzenethiol (pCTP) and p-aminothiophenol (pATP), including chemical composition, coadsorption behavior, phase segregation, plasmon-induced photocatalysis, and solvation effects. We found that upon competitive adsorption of pCTP and pATP on Au(111) from a methanolic solution, the coadsorption initially occurs randomly and homogeneously; eventually, pATP is replaced by pCTP through gradual growth of pCTP nanodomains. TERS imaging also allows for visualization of the plasmon-induced coupling of pATP to p,p’-dimercaptoazobenzene (DMAB) and the solvation-induced phase segregation of the binary SAMs into nanodomains, with a spatial resolution of ~9 nm under ambient conditions. According to DFT calculations, these aromatic thiolates differing only in their functional groups, -CN versus –NH2, show different adsorption energy on Au(111) in vacuum and methanol, and thus the solvation effect on adsorption energy of these thiolates in methanol can determine the dispersion state and replacement order of the binary thiolates on Au(111).

ChemCatChem ◽  
2022 ◽  
Chadatip Rodaum ◽  
Anawat Thivasasith ◽  
Ploychanok Iadrat ◽  
Pinit Kidkhunthod ◽  
Sitthiphong Pengpanich ◽  

2022 ◽  
Christof Matt ◽  
Andreas Orthaber ◽  
Jan Streuff

A catalytic enantioselective β-O-elimination reaction is reported in the form of a zirconium-catalyzed asymmetric opening of meso-ketene acetals. Furthermore, a regiodivergent β-O-elimination is demonstrated. The reaction proceeds under mild conditions, at low catalyst loadings, and produces chiral monoprotected 1,2-diol building blocks in good yield and enantiomeric excess. The combination with a Mitsunobu reaction then gives access to all 1,2-diol stereoisomers and trans-1,2-aminoalcohols in high enantiomeric purity. A stereochemical analysis supported by DFT calculations reveals that a high selectivity in the hydrozirconation step is also important for achieving high enantioselectivity, although it does not constitute the asymmetric step. This insight is crucial for the future development of related asymmetric β-elimination reactions.

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