Hydration of the Zwitterionic and Protonated Forms of Glycine Betaine Probed by Soft X-ray Emission Spectroscopy Coupled with Chemometrics

Ohsawa, Seiji; Tokushima, Takashi; Okada, Kazumasa

doi:10.1021/acs.jpcb.0c10712

Cited by 5 publications

(4 citation statements)

References 40 publications

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“…It is evident from Figures and S6 that the self-interaction between the betaine molecules accounts for ∼65% of the total DR dynamics, while the contributions from urea–urea and water–water are strikingly small (∼7% and ∼1%, respectively). It reflects a highly dipolar character of betaine, which maintains its zwitterionic form in solutions , with a positive charge on the amide nitrogen (N) atom and a negative charge on the carboxylic oxygen (O) atom. The interaction of betaine with urea and water molecules accounts, respectively, for ∼21% and ∼5% of the total DR, highlighting the dominant role for betaine in the DR of this DES.…”

Section: Resultsmentioning

confidence: 99%

Temperature-Dependent Dielectric Relaxation Measurements of (Betaine + Urea + Water) Deep Eutectic Solvent in Hz-GHz Frequency Window: Microscopic Insights into Constituent Contributions and Relaxation Mechanisms

Mondal,

Maji,

Mitra

et al. 2024

J. Phys. Chem. B

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A combined experimental and simulation study of dielectric relaxation (DR) of a deep eutectic solvent (DES) composed of betaine, urea, and water with the composition [Betaine:Urea:Water = 11.7:12:1 (weight ratio) and 9:18:5 (molar ratio)] was performed to explore and understand the interaction and dynamics of this system. Temperature-dependent (303 ≤ T/K ≤ 343) measurements were performed over 9 decades of frequency, combining three different measurement setups. Measured DR, comprising four distinct steps with relaxation times spreading over a few picoseconds to several nanoseconds, was found to agree well with simulations. The simulated total DR spectra, upon dissection into three self (intraspecies) and three cross (interspecies) interaction contributions, revealed that the betaine− betaine self-term dominated (∼65%) the relaxation, while the urea−urea and water−water interactions contributed only ∼7% and ∼1%, respectively. The cross-terms (betaine−urea, betaine−water, and urea−water) together accounted for <30% of the total DR. The slowest DR component with a time constant of ∼1−10 ns derived dominant contribution from betaine−betaine interactions, where betaine−water and urea−water interactions also contributed. The subnanosecond (0.1−0.6 ns) time scale originated from all interactions except betaine−water interaction. An extensive interaction of water with betaine and urea severely reduced the average number of water−water H-bonds (∼0.7) and heavily decreased the static dielectric constant of water in this DES (ε s ∼ 2). Furthermore, simulated first rank collective single particle reorientational relaxations (C 1 (t)) and the structural H-bond fluctuation dynamics (C HB (t)) exhibited multiexponential kinetics with time scales that corresponded well with those found both in the simulated and measured DR.

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Section: Resultsmentioning

confidence: 99%

Temperature-Dependent Dielectric Relaxation Measurements of (Betaine + Urea + Water) Deep Eutectic Solvent in Hz-GHz Frequency Window: Microscopic Insights into Constituent Contributions and Relaxation Mechanisms

Mondal,

Maji,

Mitra

et al. 2024

J. Phys. Chem. B

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“…Amino acids are the most abundant organic components in living cells for the formation, nitrogen balance, expansion, reproduction, and well-being of organisms of both humans and animals . Glycine, with the chemical formula NH 2 CH 2 COOH, is an α-amino acid (AA) that exists in the form of a zwitterion as + NH 3 CH 2 COO – . This simplest AA has the lowest molecular weight with protein forming.…”

Section: Introductionmentioning

confidence: 99%

“… 1 Glycine, with the chemical formula NH 2 CH 2 COOH, is an α-amino acid (AA) that exists in the form of a zwitterion as + NH 3 CH 2 COO – . 2 This simplest AA has the lowest molecular weight with protein forming. Also, it is the only amino acid that does not have an asymmetrical carbon atom, causing it to be nonoptical and without any l or d configuration.…”

Section: Introductionmentioning

confidence: 99%

Green Synthesis and Bioactivity of Aliphatic N-Substituted Glycine Derivatives

2023

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Standard amino acids have an asymmetric α-carbon atom to which −COOH, −NH 2 , −H, and −R groups are bonded. Among them, glycine is the simplest (R = −H) with no asymmetric carbon, and other natural amino acids are C-substituted of glycine. Here, we have designed and made a green synthesis of some new N-substituted glycine derivatives with R−(NH)CH 2 −COOH formula, where R is flexible and hydrophobic with different chain lengths and benches of the type propyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, 2aminoheptyl, and octyl. These glycine derivatives were characterized by recording their melting points and FT-IR, mass, 1 H NMR, and 13 C NMR spectra. DFT studies revealed that 2-aminoheptyl glycine had the highest electronegativity value and can thus act as a good bidentate ligand for the metal centers. ADME comparative results and bioavailability radars indicated that both octyl-and 2-aminoheptyl glycine had the most lipophilicity, making them good agents in cell passing. Furthermore, lipophilicity determination showed that octyl glycine was the best and propylgly was more soluble than others. Based on solubility, lipophilicity, and dipole moment values, propyl-and 2aminoheptyl-glycine were considered for bio-macromolecular interaction studies. Thus, the interaction of these two agents with DNA and HSA was studied using absorption spectroscopy and circular dichroism techniques. Due to the presence of the R-amine group, they can interact with the DNA by H-binding and hydrophobicity, while electrostatic mode could not be ruled out. Meanwhile, molecular docking studies revealed that octyl-and 2-aminoheptyl glycine had the highest negative docking energy, which reflects their higher tendency to interact with DNA. The DNA binding affinity of two candidate AAs was determined by viscosity measurement and fluorescence emission recording, which confirms that groove binding occurs. Also, the toxicity of these synthesized amino acid derivates was tested against the human foreskin fibroblast (HFF) cell line. They showed IC 50 values within the range of 127−344 μM after 48 h with the highest toxicity for 2-aminoheptyl glycine.

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“…In recent years, much attention has been paid to the study of the interaction between trimethylglycine (glycine betaine, GB) and water in order to understand the structure–performance relationships for chemical, biological and pharmaceutical applications [ 1 , 2 ]. Experimental and theoretical investigations [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ] have provided valuable insights into the solvent effects on the zwitterionic GB. In contrast to the solvation of aliphatic amino acid zwitterions [ 11 , 12 , 13 , 14 ], where the hydration shells of the amino group (NH 3 + ), carboxylate group (COO − ) and methylene group (CH 2 ) should be considered [ 15 , 16 ], it is necessary to focus on the interaction of COO − with water in GB.…”

Section: Introductionmentioning

confidence: 99%

Specific Proton-Donor Properties of Glycine Betaine. Metric Parameters and Enthalpy of Noncovalent Interactions in its Dimer, Water Complexes and Crystalline Hydrate

Frolov,

Shishkina,

Vener

2023

IJMS

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Trimethylglycine (glycine betaine, GB) is an important organic osmolyte that accumulates in various plant species in response to environmental stresses and has significant potential as a bioactive agent with low environmental impact. It is assumed that the hydration of GB is playing an important role in the protective mechanism. The hydration and aggregation properties of GB have not yet been studied in detail at the atomistic level. In this work, noncovalent interactions in the GB dimer and its complexes with water and crystalline monohydrate are studied. Depending on the object, periodic and non-periodic DFT calculations are used. Particular attention is paid to the metric parameters and enthalpies of intermolecular hydrogen bonds. The identification of noncovalent interactions is carried out by means of the Bader analysis of periodic or non-periodic electron density. The enthalpy of hydrogen bonds is estimated using the Rosenberg formula (PCCP 2 (2000) 2699). The specific proton donor properties of glycine betaine are due to its ability to form intermolecular C–H∙∙∙O bonds with the oxygen atom of a water molecule or the carboxylate group of a neighboring GB. The enthalpy of these bonds can be significantly greater than 10 kJ/mol. The water molecule that forms a hydrogen bond with the carboxylate group of GB also interacts with its CH groups through lone pairs of electrons. The C–H∙∙∙O bonds contribute up to 40% of the total entropy of the GB–water interaction, which is about 45 kJ/mol. The possibility of identifying C–H∙∙∙O bonds by the proton nuclear magnetic resonance method is discussed.

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Hydration of the Zwitterionic and Protonated Forms of Glycine Betaine Probed by Soft X-ray Emission Spectroscopy Coupled with Chemometrics

Cited by 5 publications

References 40 publications

Temperature-Dependent Dielectric Relaxation Measurements of (Betaine + Urea + Water) Deep Eutectic Solvent in Hz-GHz Frequency Window: Microscopic Insights into Constituent Contributions and Relaxation Mechanisms

Temperature-Dependent Dielectric Relaxation Measurements of (Betaine + Urea + Water) Deep Eutectic Solvent in Hz-GHz Frequency Window: Microscopic Insights into Constituent Contributions and Relaxation Mechanisms

Green Synthesis and Bioactivity of Aliphatic N-Substituted Glycine Derivatives

Specific Proton-Donor Properties of Glycine Betaine. Metric Parameters and Enthalpy of Noncovalent Interactions in its Dimer, Water Complexes and Crystalline Hydrate

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