scholarly journals Quantitative Assessment of Tetrel Bonding Utilizing Vibrational Spectroscopy

Molecules ◽  
2018 ◽  
Vol 23 (11) ◽  
pp. 2763 ◽  
Author(s):  
Daniel Sethio ◽  
Vytor Oliveira ◽  
Elfi Kraka
Keyword(s):  
Vibrational Spectroscopy ◽  
Quantitative Assessment ◽  
Positive Charge ◽  
Lone Pair ◽  
Electron Delocalization ◽  
Exchange Repulsion ◽  
First Time ◽  
Tetrel Bonds ◽  
Incomplete Picture ◽  
Positively Charged

A set of 35 representative neutral and charged tetrel complexes was investigated with the objective of finding the factors that influence the strength of tetrel bonding involving single bonded C, Si, and Ge donors and double bonded C or Si donors. For the first time, we introduced an intrinsic bond strength measure for tetrel bonding, derived from calculated vibrational spectroscopy data obtained at the CCSD(T)/aug-cc-pVTZ level of theory and used this measure to rationalize and order the tetrel bonds. Our study revealed that the strength of tetrel bonds is affected by several factors, such as the magnitude of the σ-hole in the tetrel atom, the negative electrostatic potential at the lone pair of the tetrel-acceptor, the positive charge at the peripheral hydrogen of the tetrel-donor, the exchange-repulsion between the lone pair orbitals of the peripheral atoms of the tetrel-donor and the heteroatom of the tetrel-acceptor, and the stabilization brought about by electron delocalization. Thus, focusing on just one or two of these factors, in particular, the σ-hole description can only lead to an incomplete picture. Tetrel bonding covers a range of −1.4 to −26 kcal/mol, which can be strengthened by substituting the peripheral ligands with electron-withdrawing substituents and by positively charged tetrel-donors or negatively charged tetrel-acceptors.

Positive charge modifications alter the ability of XIP to inhibit the plasma membrane calcium pump

1996 ◽  
Vol 271 (3) ◽  
pp. C736-C741 ◽  
Author(s):  
W. Xu ◽  
C. Gatto ◽  
M. A. Milanick
Keyword(s):  
Plasma Membrane ◽  
Positive Charge ◽  
Calcium Pump ◽  
Inhibitory Peptide ◽  
Ca Pump ◽  
Contact Points ◽  
Plasma Membrane Calcium Pump ◽  
Peptide Analogues ◽  
Positively Charged

Exchange inhibitory peptide (XIP; RRLLFYKYVYKRYRAGKQRG) is the shortest peptide that inhibits the plasma membrane Ca pump at high Ca (A. Enyedi, T. Vorherr, P. James, D. J. McCormick, A. G. Filoteo, E. Carafoli, and J. T. Penniston, J. Biol. Chem. 264: 12313-12321, 1989). Sulfosuccinimidyl acetate (SNA)-modified XIP does not inhibit the Ca pump; SNA neutralizes the positive charge on Lys at positions 7, 11, and 17. Peptide 2CK-XIP (RRLLFYRYVYRCYCAGRQKG) inhibits the pump, but the iodoacetamido-modified peptide does not inhibit. Three peptide analogues, in which 7, 11, and 17 were Ala, Cys, or Lys, inhibited about as well as XIP. SNA modification of these analogues (each with 1 Lys) did not inhibit. SNA modification of 2CK-XIP results in a peptide that does not inhibit; thus position 19 is important. Our results suggest that it is critical that position 19 be positively charged, that positions 7, 11, and 17 are important contact points between XIP and the Ca pump (with at least one positively charged), and that, whereas it is not essential that residues 12 and 14 be positive, they cannot be negative.

Anomalous stabilizing and destabilizing effects in some cyclic π-electron systems

1993 ◽  
Vol 71 (8) ◽  
pp. 1123-1127 ◽  
Author(s):  
Peter Politzer ◽  
M. Edward Grice ◽  
Jane S. Murray ◽  
Jorge M. Seminario
Keyword(s):  
Ab Initio ◽  
Lone Pair ◽  
Electrostatic Potentials ◽  
Electron Delocalization ◽  
Isodesmic Reaction ◽  
Computational Studies ◽  
Electron Systems ◽  
Molecular Electrostatic Potentials ◽  
Lone Pairs

Ab initio computational studies have been carried out for three molecules that are commonly classed as antiaromatic: cyclobutadiene (1), 1,3-diazacyclobutadiene (7), and 1,4-dihydropyrazine (6). Their dinitro and diamino derivatives were also investigated. Stabilizing or destabilizing energetic effects were quantified by means of the isodesmic reaction procedure at the MP2/6-31G*//HF/3-21G level, and calculated molecular electrostatic potentials (HF/STO-5G//HF/3-21G) were used as a probe of electron delocalization. Our results do not show extensive delocalization in the π systems of any one of the three parent molecules. The destabilization found for 1 and 7 is attributed primarily to strain and to repulsion between the localized π electrons in the C=C and C=N bonds, respectively. However, 6 is significantly stabilized, presumably due to limited delocalization of the nitrogen lone pairs. NH2 groups are highly stabilizing, apparently because of lone pair delocalization. NO2 is neither uniformly stabilizing nor destabilizing.

VIBRATIONAL SPECTROSCOPY OF CO/Cu(211) WITH A CO TERMINATED TIP

1999 ◽  
Vol 13 (20) ◽  
pp. 709-715 ◽  
Author(s):  
FRANCESCA MORESCO ◽  
GERHARD MEYER ◽  
KARL HEINZ RIEDER
Keyword(s):  
Vibrational Spectroscopy ◽  
Scanning Tunneling Microscope ◽  
Scanning Tunneling ◽  
Rotational Mode ◽  
Tunneling Microscope ◽  
Vibrational Excitations ◽  
Translational Mode ◽  
Inelastic Tunneling ◽  
Open Question ◽  
First Time

Vibrational excitations of an isolated CO molecule adsorbed on a Cu(211) surface have been, for the first time, observed with a CO terminated scanning tunneling microscope tip. Both the frustrated translational and rotational modes were observed, and in agreement with the case of a metallic tip. The presence of a CO molecule on the tip, transferred by controlled vertical manipulation, strongly influences the frustrated translational mode of the CO molecule, while it does not affect the frustrated rotational mode. The present work demonstrates that scanning tunneling vibrational spectroscopy is also possible with a molecule at the end of the tip, opening new interesting fields of research and putting some more light on the still open question of inelastic tunneling and its selection rules.

Wallach rearrangement of azoxypyridines and azoxypyridine N-oxides — Charge distributions and dramatic reactivity differences

2008 ◽  
Vol 86 (4) ◽  
pp. 298-304 ◽  
Author(s):  
Erwin Buncel ◽  
Sam-Rok Keum ◽  
Srinivasan Rajagopal ◽  
Eric Kiepek ◽  
Robin A Cox
Keyword(s):  
Sulfuric Acid ◽  
Positive Charge ◽  
Theoretical Calculations ◽  
Medium Effect ◽  
Mulliken Charge ◽  
Reaction Intermediates ◽  
Charge Distributions ◽  
First Time ◽  
Acid Region

Extension of our studies of the generic Wallach rearrangement (of azoxybenzene to 4-hydroxyazobenzene) to the heteroaromatic series (azoxypyridines and axoxypyridine N-oxides) has revealed some dramatic reactivity differences, particularly for the α and β compounds. We have studied the 3-isomers and the 4-isomers in each series, each with α and β forms, eight compounds in all, in the 100 wt% sulfuric acid region of acidity. In those cases in which a product could be observed, the α and β isomers both give the same one, the corresponding 4′-hydroxyazo compounds. All the compounds react much more slowly than does azoxybenzene itself, presumably because of the extra positive charge present in the substrates, but the β isomers have half-lives of seconds and the α isomers half-lives of hundreds of hours in the 100 wt% H2SO4 acidity region. The α compounds have measurable pKBH+ values, but the β compounds do not, exhibiting only a medium effect in the acidity region in which the α compounds protonate. This means that for the β compounds, the protonated intermediates must be much less stable and the postulated reaction intermediates must be much more stable than for the α compounds. To clarify this, we have obtained Mulliken charge distributions for the various species concerned, calculating the charge carried by each half of the molecule, larger charge separations being taken to indicate lesser stability. As far as we can establish, this is the first time that this technique has been used to indicate the stabilities of carbocationic species.Key words: azoxypyridines, azoxypyridine N-oxides, Wallach rearrangement, excess acidity, basicities, theoretical calculations, charge distributions, reactivities.

An Effective Synthesis of N,N-Diphenyl Carbazolium Salts

Synlett ◽  
2017 ◽  
Vol 29 (10) ◽  
pp. 1314-1318 ◽  
Author(s):  
Charles Diesendruck ◽  
Sinai Aharonovich ◽  
Nansi Gjineci ◽  
Dario Dekel
Keyword(s):  
Positive Charge ◽  
Quaternary Ammonium Salts ◽  
Simple Approach ◽  
Ammonium Salts ◽  
State Structure ◽  
Pi Systems ◽  
Effective Synthesis ◽  
Short Time ◽  
First Time ◽  
General Method

Tetraaryl ammonium salts are a synthetic challenge, since there is no general method for the arylation of triaryl amines. Contrary to other quaternary ammonium salts, tetraaryl ammonium salts should be very chemically stable. The ipso carbons are not very electrophilic, since the positive charge is distributed throughout the pi systems and they have no acidic β hydrogens. Here we demonstrate a simple approach to N,N-diphenyl carbazolium salts using only three synthetic steps, allowing for an easy production of these salts in large amounts and in a relatively short time. In addition, we study the Cu(I) catalyzed multi-arylation of 2,2’-diaminobiphenyl, focusing on the regioselectivity of each step. Finally, we characterize, for the first time, the solid state structure of a tetraaryl ammonium salt.

scholarly journals The growth of interest for astronomical X-ray polarimetry

2018 ◽  
Author(s):  
Frédéric Marin
Keyword(s):  
Quantitative Assessment ◽  
Supernova Remnant ◽  
Scientific Literature ◽  
High Energy ◽  
X Ray ◽  
Highly Sensitive ◽  
In The Beginning ◽  
First Time

Astronomical X-ray polarimetry was first explored in the end of the 60's by pioneering rocket instruments. The craze arising from the first discoveries on stellar and supernova remnant X-ray polarization led to the addition of X-ray polarimeters on-board of early satellites. Unfortunately, the inadequacy of the diffraction and scattering technologies required to measure polarization with respect to the constraints driven by X-ray mirrors and detectors, coupled to long integration times, slowed down the field for almost 40 years. Thanks to the development of new, highly sensitive, compact X-ray polarimeters in the beginning of the 2000's, the possibility to observe astronomical X-ray polarization is rising again and scientists are now ready to explore the high energy sky thanks to modern X-ray polarimeters. In the forthcoming years, several X-ray missions (both rockets, balloons and satellites) will open a new observational windows. A wind of renewal blows over the area of X-ray polarimetry and this paper presents for the first time a quantitative assessment, all based on scientific literature, of the growth of interest for astronomical X-ray polarimetry.

Role of S4 positively charged residues in the regulation of Kv4.3 inactivation and recovery

2007 ◽  
Vol 293 (3) ◽  
pp. C906-C914 ◽  
Author(s):  
Matthew R. Skerritt ◽  
Donald L. Campbell
Keyword(s):  
Positive Charge ◽  
Voltage Sensitivity ◽  
Shaker Channels ◽  
Recovery From Inactivation ◽  
Kv4 Channels ◽  
Charged Residues ◽  
Arginine Residues ◽  
Voltage Sensing Domain ◽  
Positively Charged

The molecular and biophysical mechanisms by which voltage-sensitive K+ (Kv)4 channels inactivate and recover from inactivation are presently unresolved. There is a general consensus, however, that Shaker-like N- and P/C-type mechanisms are likely not involved. Kv4 channels also display prominent inactivation from preactivated closed states [closed-state inactivation (CSI)], a process that appears to be absent in Shaker channels. As in Shaker channels, voltage sensitivity in Kv4 channels is thought to be conferred by positively charged residues localized to the fourth transmembrane segment (S4) of the voltage-sensing domain. To investigate the role of S4 positive charge in Kv4.3 gating transitions, we analyzed the effects of charge elimination at each positively charged arginine (R) residue by mutation to the uncharged residue alanine (A). We first demonstrated that R290A, R293A, R296A, and R302A mutants each alter basic activation characteristics consistent with positive charge removal. We then found strong evidence that recovery from inactivation is coupled to deactivation, showed that the precise location of the arginine residues within S4 plays an important role in the degree of development of CSI and recovery from CSI, and demonstrated that the development of CSI can be sequentially uncoupled from activation by R296A, specifically. Taken together, these results extend our current understanding of Kv4.3 gating transitions.

Study of adsorption of the SARS-CoV-2 virus spike protein by vibrational spectroscopy using terahertz metamaterials

2022 ◽  
Vol 52 (1) ◽  
pp. 2-12
Author(s):  
M R Konnikova ◽  
O P Cherkasova ◽  
T A Geints ◽  
E S Dizer ◽  
A A Man'kova ◽  
...  
Keyword(s):  
Vibrational Spectroscopy ◽  
Receptor Binding ◽  
Quantitative Assessment ◽  
Binding Domain ◽  
Spike Protein ◽  
Receptor Binding Domain ◽  
Protein Films ◽  
Original Technique ◽  
Terahertz Metamaterials

Abstract Adhesion of the spike protein of the SARS-CoV-2 virus is studied by vibrational spectroscopy using terahertz metamaterials. The features of metastructure absorption upon the deposition of histidine, albumin, and the receptor-binding domain of the spike protein films are investigated. An original technique for quantitative assessment of the efficiency of virus adhesion on the metamaterial surfaces are proposed and experimentally tested.

THE EFFECT OF PROCOAGULANT PHOSPHOLIPID VESICLES WITH NET POSITIVE CHARGE ON THE ACTIVITY OF PROTHROMBINASE

1987 ◽  
Author(s):  
J Rosing ◽  
H Speijer ◽  
J W P Govers-Riemslag ◽  
R F A Zwaal
Keyword(s):  
Vitamin K ◽  
Negative Charge ◽  
Positive Charge ◽  
Coagulation Factor ◽  
Phospholipid Vesicles ◽  
Electrostatic Model ◽  
Acidic Phospholipid ◽  
Positively Charged ◽  
Net Positive Charge ◽  
Prothrombin Activation

It is generally thought that procoagulant phospholipid surfaces that promote the activation of vitamin K-dependent coagulation factors should have a net negative charge in order to promote calcium-dependent binding of the enzymes (FVIIa, FIXa and FXa) and substrates (prothrombin and FX) of the coagulation factor-activating complexes. Two models have been proposed to explain calcium-mediated association of vitamin K-dependent proteins with phospholipid: a) an electrostatic model, in which a positively-charged protein-calcium complex is attracted by a negatively-charged phospholipid surface and b) a chelation model in which a coordination complex is formed between calcium ions, γ-carboxyglutamic acids of the proteins and negatively-charged membrane phospholipids. To study the effect of the electrostatic potential of phospholipid vesicles on their activity in the pro-thrombinase complex the net charge of vesicles was varied by introduction of varying amounts of positively-charged stearylamine in the membrane surface. Introduction of 0-15 mole% stearylamine in phospholipid vesicles that contained 5 mole% phosphatidylseri-ne (PS) hardly affected their activity in prothrombin activation. Electrophoretic analysis showed that vesicles with > 5 mole% stearylamine had a net positive charge. The procoagulant activity of vesicles that contained phosphatidic acid, phosphatidylglyce-rol, phosphatidylinositol or phosphatidyl-glactate (PLac) as acidic phospholipid was much more effected by incorporation of stearylamine. Amounts of stearylamine that compensated the negative charge of acidic phospholipid caused considerable inhibition of the activity of the latter vesicles in prothrombin activation. The comparison of vesicles containing PS and PLac as acidic phospholipid is of special interest. PS and PLac only differ by the presence of NH+ 3-group in the serine moiety of PS. Thus, in spite of the fact that vesicles with PLac are more negatively charged than vesicles with PS, they are less procoagulant. Our results show that a) although procoagulant membranes have to contain acidic phospholipids there is no requirement for a net negative charge, b) the amino group of phosphatidylserine has an important function in the interaction of procoagulant membranes with vitamin K-dependent proteins and c) the chelation model can satisfactorily explain calcium-mediated lipid-protein association.

scholarly journals The Position of Solid Carbon Dioxide in the Triboelectric Series

2019 ◽  
Vol 72 (8) ◽  
pp. 633 ◽  
Author(s):  
Jinyang Zhang ◽  
Simone Ciampi
Keyword(s):  
Carbon Dioxide ◽  
Negative Charge ◽  
Plastic Material ◽  
Indirect Evidence ◽  
Liquid Carbon ◽  
Solid Carbon Dioxide ◽  
Dry Ice ◽  
First Time ◽  
Charge Sign ◽  
Positively Charged

The process of releasing liquid carbon dioxide from a fire extinguisher is accompanied by a strong static charging of the plastic material making up the extinguisher discharge horn. Firefighters often report an electric shock when operating CO2 extinguishers, but the origin of this electrostatic hazard is largely unknown. Here, we begin to investigate this phenomenon, and test the hypothesis of plastic samples being tribocharged on contact with rapidly flowing solid CO2. Using Faraday pail measurements, we show that non-conductive polymers gain a net static charge when brought in and out of contact with dry ice (solid CO2). These measurements of charge sign and magnitude give indirect evidence helping to place solid CO2 for the first time on the triboelectric series. Polydimethylsiloxane (PDMS), polytetrafluoroethylene (PTFE), and polyvinyl chloride (PVC) samples acquire a negative charge when rubbed against dry ice, whereas poly(methyl methacrylate) (PMMA), glass, and nylon surfaces become positively charged. Therefore, we suggest the position of dry ice in the triboelectric series to be close to that of materials with stable cations and unstable anions, possibly locating it between PMMA and PVC.

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