Hydrogen Bond Strength Research Articles

Exploring the excited state multi-proton transfer path and the associated photophysical properties of P-TNS molecule by DFT and TDDFT theory

Recently, Chen et al. designed and synthesized a new multi-purpose dye probe P-TNS with bifunctional groups, which has an ultra-fast excited state intramolecular proton transfer characteristic (ESIPT) (Spectrochim Acta A Mol Biomol Spectrosc., 2021, 262: 120084.). The P-TNS molecules are very sensitive to hydrazine (N2H4) and cyanide (CN-), which makes it have a good practical application prospect in the field of probe detection. However, the corresponding optical properties and the related mechanisms have not been systematically investigated in experiments. In the present work, the proton transfer pathways as well as the photophysical properties changes in the transfer path of P-TNS with three intramolecular hydrogen bonds (HB1, HB2 and HB3) are revealed for the first time. First, the analysis of potential energy surface and potential energy curve determined the stable conformation of P-TNS molecule and its isomer structure, and clarified the reaction mechanism of ESIPT process. Subsequently, the analysis of the frontier molecular orbitals reveal that the charge difference is the driving force required for the proton transfer process from the microscopic level, which led to the determination that the HB1 structure without the charge difference could not complete the ESIPT process. Finally, the variation of hydrogen bond strength and the path of proton transfer are demonstrated from several perspectives of hydrogen bond parameters, hydrogen bond energy, infrared vibrational frequency (IR) and reduced density gradient (RDG) surface. This study essentially explains the photophysical properties and proton transfer pathways of a new multipurpose dye probes for organic luminescence with bifunctional groups, which are important for the fields of spectroscopy and measurement technology, and also provides ideas for the design and synthesis of new fluorescent probes.

Structure-property relationships in alkoxy substituted benzoates from experimental and computational thermochemistry

The energetics of formation and the phase transitions for isomeric methyl and ethyl methoxy‑benzoates were studied. The vapour pressures of methyl 2‑methoxy-benzoate and methyl 4‑methoxy-benzoate were measured by transpiration method. The high-precision combustion calorimetry was used to derive the liquid-phase enthalpy of formation of methyl 2‑methoxy-benzoate. The new results and the data available in the literature were critically evaluated using the structure-property correlations. Reliable correlations were established between the vaporisation enthalpies and the normal boiling temperatures as well as with the Kovats indices. Moreover, the validity of vaporisation enthalpies of alkyl methoxy‑benzoates was proved using structure-property relationships within families of structurally similar molecules. Mutual validation of the experimental and theoretical gas phase enthalpies of formation was performed using high-level quantum-chemical methods. The enthalpic contributions to the enthalpy of formation in the gas phase, resulting from the nearest and non-nearest neighbour interactions of the substituents in the benzene ring, were developed and used to quantify the intra-molecular hydrogen bond strength in the ortho-substituted species.

Non‐Innocent π Linkers Affect Cooperativity in Hydrogen‐Bonded Macrocycles

AbstractRigid, linear π‐conjugated acetylene linkers connecting a hydrogen‐bond acceptor to a hydrogen‐bond donor are established building blocks for self‐assembled hydrogen‐bonded macrocycles. Kohn‐Sham molecular orbital and Voronoi deformation density analyses reveal that the acetylene linker plays an unprecedented, non‐innocent role in the cooperativity of these hydrogen‐bonded macrocycles. The acetylene linker can abstract electron density from the hydrogen‐bond acceptor and donor, due to the linkers’ low‐lying π‐LUMO. As a result, the hydrogen‐bond acceptor becomes less negatively charged, which both hampers the cooperativity, as well as the hydrogen bond strength, in the hydrogen‐bonded macrocycles. This effect becomes more pronounced when the size of the acetylene linker increases. The findings presented in this work can act as design principles for the development of novel supramolecular macrocycles based on hydrogen bonds.

Experimental and theoretical comparison of the vibrational and NMR spectra of novel 6-6’-(1E-1’E)-(Propane-1,3Diylbis (Azanylyidene)) Bis (Phenylmethylylidene)) Bis (3-Octyloxy) Phenol), NBO and molecular docking studies

The characterization study of the synthesized novel compound 6-6’-(1E-1’E)-(Propane-1,3Diylbis(Azanylyidene))Bis(Phenylmethylylidene))Bis(3-Octyloxy)Phenol) (C45H58N2O4) was done by FT-IR, Raman and NMR spectra. Vibrational analysis was realized with normal coordinate treatment, and vibrational modes were assigned in the mid-IR region. The 13C and 1H -NMR spectra of the title compound were measured in DMSO and chloroform, and the corresponding chemical shifts were calculated in the different basis sets (6-31++G(d,p), 6-311G(2d,p), 6-311++G(2d,p), TZVPP) of DFT-B3LYP with continuum models. The vibrational and NMR spectroscopies show that the existence of the intramolecular resonance-assisted hydrogen bonds(O-H...N) results in the redshift of OH vibrational modes and its high proton chemical shifts (ca. 16 ppm), as confirmed by X-ray crystal structure and NRT studies.13C NMR chemical shifts of the Schiff base bond are determined as ca. 174 ppm. The calculations indicate that both the intramolecular hydrogen bond strength and the OH-proton chemical shift increase with increasing solvent polarity. The molecular docking studies reveal that the title ligand has the potency of inhibition against the VIM-2 and NDM-1 active sites of metallo-β-lactamase receptor.

Polyol-dependent adhesion mechanism of XDI- and H6XDI-based polyurethanes

Polyurethanes (PUs) consisting of m-xylylene diisocyanate (XDI) exhibit excellent thermal stability and optical properties. To further enhance the optical properties, 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI) is considered a potential isocyanate for optically clear adhesives; however, a detailed analysis of the adhesion mechanism has not been investigated. Herein, we synthesized PUs using diisocyanates (XDI, H6XDI) and polyols [polypropylene glycol (PPG), polycaprolactone diol (PCL), and polycarbonate diol (PCD)]. To investigate the adhesion mechanism, the interaction between each PUs and functionalized self-assembled monolayers was analyzed using a Surface Forces Apparatus at the nanoscale. Additionally, macroscopic surface energy measurement and probe tack testing were performed. Overall, higher hydrophobic interaction in PCD-containing PUs and predominant hydrogen bonding in PPG-containing PUs was measured. Also, hydrophobic interaction was stronger for H6XDI compared to that of XDI in all polyols. These findings clarified polyol-dependent adhesion mechanisms of XDI- and H6XDI-based PUs and could be used to design PUs with controlled strength of hydrogen bonds and hydrophobic interactions.

Thermal dependence of the hydrated proton and optimal proton transfer in the protonated water hexamer

Water is a key ingredient for life and plays a central role as solvent in many biochemical reactions. However, the intrinsically quantum nature of the hydrogen nucleus, revealing itself in a large variety of physical manifestations, including proton transfer, gives rise to unexpected phenomena whose description is still elusive. Here we study, by a combination of state-of-the-art quantum Monte Carlo methods and path-integral molecular dynamics, the structure and hydrogen-bond dynamics of the protonated water hexamer, the fundamental unit for the hydrated proton. We report a remarkably low thermal expansion of the hydrogen bond from zero temperature up to 300 K, owing to the presence of short-Zundel configurations, characterised by proton delocalisation and favoured by the synergy of nuclear quantum effects and thermal activation. The hydrogen bond strength progressively weakens above 300 K, when localised Eigen-like configurations become relevant. Our analysis, supported by the instanton statistics of shuttling protons, reveals that the near-room-temperature range from 250 K to 300 K is optimal for proton transfer in the protonated water hexamer.

Spectroscopic investigations and electronic transitions, topology studies, and biological assay of a potent antimicrobial compound: 2-amino-pyrimidine benzoic acid

The derivatives of benzoic acid, a claimed anti-fungal agent, are physiologically active components of vitamin B-complex. Signals in a heavily deshielded area is found using nuclear magnetic resonance analysis. In optimized geometry, the result reveals that nitrogen and oxygen are responsible for transfer of charge within the ring system wherein increases the bond length. Broadening and red shifting, which result from vibrational assignments, show the strength of intermolecular hydrogen bonds. Topological analysis like atoms in molecules, reduced density gradient graph that demonstrates favorable findings The electron localized function and localized orbital locator analysis are helpful when a site displays a strong distribution of electrons as a result of having the presence of a covalent bond, a lone pair of electrons, or a nuclear shell there. Findings of in vitro tests for antimicrobial activity clearly show that all two strains’ activity and inhibition both rise as compound concentrations climb. The title chemical may be verified to block antimicrobial activity and be a pesticide using molecular docking, in vitro antimicrobial activity, and qualities of a drug’s resemblance.

High-Performance and Stability Electrochromic Devices with a Water Isotopologue.

In this report, an ammonium metatungstate (AMT) and ferrous chloride [Fe(II)Cl2] electrochromic liquid (ECL) was synthesized using a hydrothermal method, with D2O used as the solvent instead of H2O. The results show that the use of D2O can improve the stability and performance of ECLs. The hydrogen evolution process in electrochromic devices (ECDs) filled with ECL becomes more difficult, while the material exchange process becomes easier. The ECD exhibits a color modulation amplitude of 58%@680 nm at 2 V. After 500 cycles, the device's performance remains above 95% at a current density of 1.5 mA/cm2. Hydrogen bonds in D2O solutions are expected to exhibit stronger forces compared to those in regular H2O solutions. Therefore, we hypothesize that enhancing the strength of hydrogen bonds in H2O solutions is an effective approach for improving the performance and stability of electrochromic solutions.

Atomic electronegativity-dependent intramolecular hydrogen bond and fluorescence characteristics of novel scaffold-based fluorophore: a TD-DFT study.

In this work, fluorescent properties and excited-state intramolecular proton transfer (ESIPT) processes of 2,5-bis(benzo[d]thiazol-2-yl)phenol (BTP) and its derivatives (BOP and BSeP) with different heteroatom atoms (O and Se) have been systematically explored by the density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The calculated absorption and fluorescence emission peaks agree well with the experimental values in acetonitrile. From the data of structures, topological parameters, reduced density gradient analyses, and infrared (IR) vibrational frequencies, the intramolecular hydrogen bonds (IHBs) of BTP and its derivatives are enhanced upon light-excitation. The potential energy curves show that the ESIPT process occurs in BTP and its derivatives after surmounting 0.167-0.306eV energy barrier. The strength of intramolecular hydrogen bond, HOMO-LUMO energy gap, and red-shifted value of absorption and fluorescence emission wavelengths are dependent on the electron-withdrawing ability of heteroatom from O to S and Se. We believe that this work can pave the way for developing a new ESIPT-based fluorophore with better luminescent properties.

Investigation of 3D printing of toddler foods with special shape and function based on fenugreek gum and flaxseed protein

The practicability of using corn and flaxseed protein as printing inks for manufacture of printed products specifically designed for toddlers as a dysphagia diet with high precision and special shapes with addition of fenugreek gum (FGG) was investigated. 3D printing was used to process grains and dysphagia-compatible food (corn) into a dietary product with attractive appearance which was also easy to swallow. Rheological measurements shown that appropriate amount of flaxseed protein (FP, 0–10 %) can reduce the stickiness and yield strength of printing material. Based on FTIR measurements, FP weakened the hydrogen bond strength of inks, but it was still an important gradient for the formation of the ink suitable for precision 3D printing. The TPA results shown that the addition of FP (0–10 %) remarkably reduced both the stickiness and hardness of the ink. These results shown that compared with the control group, materials with FGG additions possessed higher printing accuracy and self-supporting ability. Ink with 5 % FP content exhibited the best printability and swallowability, while ink with 10 % FP content had the lowest viscosity and hardness, but it was not suitable for 3D printing. 3D printing of objects printed using Ink-C (5%FP and 0.8 %FGG) showed high support characteristic and attractive appearance. According to the international IDDSI testing standards, Ink-C (5%FP and 0.8 %FGG), Ink-E (15%FP and 0.8 %FGG), and Ink-F (20%FP and 0.8 %FGG) were defined as level 5-minced and moist foods.

Leveraging the relative strengths of hydrogen and halogen bonds to control nanostructures

Halogen bonds (XBs) and hydrogen bonds (HBs) present a straightforward yet effective strategy for controlling nanostructure morphology. The self-assembled nanopattern, modulated by the relative strengths of XBs and HBs, has rarely been studied using analogous molecules. This research systematically evaluates the relationship between the strengths of Br···O hetero-XBs and N···H HBs in directing the formation of 2D supramolecular co-assembled structures. In this work, tetracarboxylic acid (PEDA), featuring four carboxyl substitutions, forms a stable hydrogen-bonded Rosette network that can function as a template for trapping guest molecules of complementary shape and size. The star-shaped bromine-substituted 1,3,5-tris(3,5-dibromophenyl)benzene (TDB) and 2,4,6-tri(4-pyridyl)-1,3,5-triazine (TPT) serve as XB donor and HB acceptor respectively, thus capable of acting as guest molecules co-assembly with the PEDA at the heptanoic acid/HOPG interface. Bimolecular co-assembly patterns resulting from these combinations were investigated using scanning tunneling microscopy (STM) and supported by density functional theory (DFT) calculations. The findings indicate that TDB molecules can be accommodated within the triangular cavities of the Rosette network due to the weaker Br···O hetero-XB. Concurrently, the similar star-shaped TPT can co-assemble with PEDA to form an acid–pyridine–acid Ladder-like network based on stronger N···H HBs. Therefore, Br···O hetero-XBs seemingly play no decisive role in the coassembly process of PEDA and TDB. Conversely, N···H HBs hold evident significance in the coassembly of PEDA and TPT. This work potentially holds substantial value for the future design and customization of devices employing the interplay of XBs and HBs.

The azeotropy eliminating mechanism of ethyl acetate-acetonitrile system via ionic liquid entrainer: A combination of FTIR and DFT study

Ionic liquids (ILs) are good candidates for azeotropy separation. Knowledge of the microstructure properties of azeotrope − IL mixtures is important because they could reveal the molecular intrinsic cause of the elimination of azeotropy and represent the basis for the practical process. In this work, the microstructures of ethyl acetate-acetonitrile azeotrope mixtures and a representative IL, 1‑butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N], which could eliminate the azeotropy of the ethyl acetate-acetonitrile system, were studied by Fourier transform infrared spectroscopy with the assistance of quantum chemical calculations and excess spectra. The C≡N stretching vibrational region of acetonitrile was closely examined. The interaction complexes of ethyl acetate-acetonitrile and ion cluster/ion pair/ion − acetonitrile were identified. Weak strength hydrogen-bonds with electrostatically dominant and closed-shell interaction properties were found in these complexes. The interactions between [BMIM][Tf2N] and acetonitrile were stronger than those between ethyl acetate and acetonitrile, which caused the addition of IL to easily destroy the ethyl acetate-acetonitrile interaction complex. The interactions between [BMIM][Tf2N] and acetonitrile were stronger than those between [BMIM][Tf2N] and ethyl acetate, which would influence the relative volatility of ethyl acetate and acetonitrile in the azeotrope system. When x(IL) was larger than 0.027, all the interaction complexes between acetonitrile and ethyl acetate were completely broken apart, and the azeotrope was eliminated.

Elucidation of hydrogen bond strength of benzylalcohol with alkyl Acetoacetates: The confirmation study by excess thermodynamic Properties, FTIR and DFT analysis

In this study, density of pure liquids and their binary mixtures of benzylalcohol (BA) with methyl acetoacetate (MAA), ethyl acetoacetate (EAA) and allyl acetoacetate (AAA) were measured experimentally at T=(298.15–313.15) K and P = 0.1 MPa by using Rudolph Research Analytical digital densitometer. Experimental data was correlate by applying Jouyban–Acree theoretical equation. Furthermore, the speed of sound of all studied pure and their binary solutions were measured at T= (298.15 and 308.15) K at atmospheric pressure at 2 MHz. The experimental density and speed of sound data further were used to calculate the excess molar volume (VmE), isentropic compressibility (κs), excess isentropic compressibility (κsE) and excess speed of sound (uE) at all compositions and temperature ranges. The calculated VmE, κsE, uE and experimental speed of sound were compared with theoretical models such as Redlich-Kister, Hwang, CFT and FLT equations. The obtained data were analyzed in terms of intermolecular interactions such as hydrogen bond formation between two atoms of benzylalcohol and acetoacetates. Among all the three systems, BA + MAA showed highest negative excess molar volume magnitude due to the change of molecular geometry through the keto-enol tautomerism. The negative magnitude of VmE data confirms the formation of H-bond between the –OH---O- groups of component molecules. Similarly, BA + EAA system showed highest negative magnitude of κSE owing to the more compressible than resultant ideal solutions. The deviation in κSE magnitude in binary systems due to the geometrical fitting and specific interactions in atoms of the benzylalcohol and acetoacetates. Furthermore, the existence of hydrogen bond and its strength in binary mixtures were confirmed by experimental FTIR spectroscopy and theoretical density functional theory (DFT) calculations.

Non-aqueous calcium-based dual-ion batteries with an organic electrode of high-rate performance

Calcium-based batteries are considered a promising candidate for the sustainable energy storage system of the next generation because of the abundance of Ca. However, the development of Ca-based batteries is hindered by the incompatibility between metallic Ca and common electrolytes as well as the absence of calcium-ion-hosted materials with good performance and cycling stability. Herein, we firstly investigate a small molecular organic material, 3,4,9,10-perylenetetracarboxylic diimide (PTCDI), as the calcium-ion host for calcium-ion batteries (CIBs) in the non-aqueous electrolyte. Spectroscopic, structural, and computational studies reveal that PTCDI with an enhanced Ca2+-storage degree can increase the solubility of reduced PTCDI due to the reduced π-π interaction, suppressed by the saturated electrolyte owing to the high redeposition rate to form a PTCDI film with strengthened hydrogen bonds, which facilitates a fast enolization reaction for Ca2+ storage. A cell assembled with the PTCDI negative electrode and carbon-based positive electrode exhibits a high-power density >3000 W kg−1, a high energy density of ∼150 Wh kg−1, and superior reversible capacity of 80 mAh g−1 at 5 A g−1. The assembled CIB even demonstrates the high-rate performance (90 mAh g−1 at 1 A g−1) and ultra-stable cyclability over 4000 cycles with negligible decay at -10 °C, suggesting the promising future as low-temperature batteries.

D2O as an Imperfect Replacement for H2O: Problem or Opportunity for Protein Research?

D2O is commonly used as a solvent instead of H2O in spectroscopic studies of proteins, in particular, in infrared and nuclear-magnetic-resonance spectroscopy. D2O is chemically equivalent to H2O, and the differences, particularly in hydrogen-bond strength, are often ignored. However, replacing solvent water with D2O can affect not only the kinetics but also the structure and stability of biomolecules. Recent experiments have shown that even the mesoscopic structures and the elastic properties of biomolecular assemblies, such as amyloids and protein networks, can be very different in D2O and H2O. We discuss these findings, which probably are just the tip of the iceberg, and which seem to call for obtaining a better understanding of the H2O/D2O-isotope effect on water-water and water-protein interactions. Such improved understanding may change the differences between H2O and D2O as biomolecular solvents from an elephant in the room to an opportunity for protein research.

Dynamic Role of the Intramolecular Hydrogen Bonding in the S1 State Relaxation Dynamics Revealed by the Direct Measurement of the Mode-Dependent Internal Conversion Rate of 2-Chlorophenol and 2-Chlorothiophenol.

The dynamic role of the intramolecular hydrogen bond in the S1 relaxation of cis-2-chlorophenol (2-CP) or cis-2-chlorothiophenol (2-CTP) has been investigated in a state-specific manner. Whereas ultrafast internal conversion is dominant for 2-CP, the H-tunneling competes with internal conversion for 2-CTP even at the S1 origin. The S0-S1 internal conversion rate of 2-CTP could be directly measured from the S1 lifetimes of 2-CTP-d1 (Cl-C6H4-SD) as the D-tunneling is kinetically blocked, allowing distinct estimations of tunneling and internal conversion rates with increasing the energy. The internal conversion rate of 2-CTP increases by two times at the out-of-plane torsional mode excitation, suggesting that the internal conversion is facilitated at the nonplanar geometry. It then sharply increases at ∼600 cm-1, indicating that the S1/S0 conical intersection is readily accessible at the extended C-Cl bond length. The strength of the intramolecular hydrogen bond should be responsible for the distinct dynamic behaviors of 2-CP and 2-CTP.

Inductive Effects on Intramolecular Hydrogen Bond Strength: An Investigation of the Effect of an Electron-Withdrawing CF3 Group Adjacent to an Alcohol Hydrogen Bond Donor.

This combined experimental and theoretical study seeks to determine the role that inductive effects have on hydrogen bonds by an investigation into the change in intramolecular hydrogen bond strength in 2-amino-1-trifluoromethylethanol (2ATFME) relative to that in 2-aminoethanol (2AE). Toward this end, the rotational spectra of the normal, 13C, and 15N isotopologues have been measured using Fourier transform microwave spectroscopy and fit to the rotational, quadrupole coupling, and centrifugal distortion constants of the Watson A-reduction Hamiltonian. Structural parameters used to characterize the strength of the intramolecular hydrogen bond have been determined from the experimental structures of both 2ATFME and 2AE as well as from MP2/6-311++G(d,p) calculations. A comparison of these parameters in 2ATFME with those of 2AE indicates that the electron-withdrawing trifluoromethyl CF3 group strengthens the hydrogen bond. These include a 4% decrease in the distance between the donor and acceptor heavy atoms of the hydrogen bond, a 6% increase toward linearity of the OH···N angle, and a 23% decrease of the COH···N torsional angle toward planarity in 2ATFME relative to 2AE. This trend toward increased intramolecular hydrogen bond strength in 2ATFME is also observed within the ab initio structures.

Mechanically strong, soft yet tough, tear-resistant and room-temperature healable elastomers via dynamic biphasic hard segment strategy for flame retardant application

Due to the inherent weak molecular chain migration ability of hard polymer materials, leads to their inability to recover after damage. Hence, a novel approach as the “dynamic biphasic hard segment” strategy is proposed. This strategy involves introducing hard segments with both hard and soft phase structures into the molecular chain to balance high mechanical strength with self-healing properties. The essential features of dynamic biphasic hard segments include: (Ⅰ) asymmetric continuous loose structure, (Ⅱ) controllable binding energy strength, (III) sequential dissociation and recombination of multiple hydrogen bonds. To synthesize supramolecular polyurethane elastomers (PUMI-A3D7) based on this dynamic biphasic hard segment strategy. PUMI-A3D7 exhibits high mechanical strength, toughness, notch insensitivity and room temperature self-healing ability. Specifically, the mechanical tensile strength of PUMI-A3D7 is 26.59 MPa, and 96.54% of its original mechanical properties can be restored within 24 h after a fracture. Using the superior properties of PUMI-A3D7 as the matrix, a flexible room temperature repairable flame-retardant composite (PUMI-A3D7/Al(OH)3/GP) is developed. PUMI-A3D7/Al(OH)3/GP possesses both room temperature self-healing function and flame-retardant properties. Notably, few studies have been conducted on repairable flexible flame-retardant materials. The combination of self-healing and flame-retardant properties provides valuable guidance for the development of multi-functional materials in the future.

Polymorphism and Multi-Component Crystal Formation of GABA and Gabapentin.

This study exploits the polymorphism and multi-component crystal formation of γ-amino butanoic acid (GABA) and its pharmaceutically active derivative, gabapentin. Two polymorphs of GABA and both polymorphs of gabapentin are structurally revisited, together with gabapentin monohydrate. Hereby, GABA form II is only accessible under special conditions using additives, whereas gabapentin converts to the monohydrate even in the presence of trace amounts of water. Different accessibilities and phase stabilities of these phases are still not fully clarified. Thus, indicators of phase stability are discussed involving intermolecular interactions, molecular conformations, and crystallization environment. Calculated lattice energy differences for polymorphs reveal their similar stability. Quantification of the hydrogen bond strengths with the atoms-in-molecules (AIM) model in conjunction with non-covalent interaction (NCI) plots also shows similar hydrogen bond binding energy values for all polymorphs. We demonstrate that differences in the interacting modes, in an interplay with the intermolecular repulsion, allow the formation of the desired phase under different crystallization environments. Salts and co-crystals of GABA and gabapentin with fumaric as well as succinic acid further serve as models to highlight how strongly HBs act as the motif-directing force in the solid-phase GABA-analogs. Six novel multi-component entities were synthesized, and structural and computational analysis was performed: GABA fumarate (2:1); two gabapentin fumarates (2:1) and (1:1); two GABA succinates (2:1) and (1:1); and a gabapentin:succinic acid co-crystal. Energetically highly attractive carboxyl/carboxylate interaction overcomes other factors and dominates the multi-component phase formation. Decisive commonalities in the crystallization behavior of zwitterionic GABA-derivatives are discussed, which show how they can and should be understood as a whole for possible related future products.

Electron density analysis of the ionized states of Watson-Crick GC base pair: A novel approach to investigate the cause of altered base pairing

Using electron density analysis, we present a model study to investigate the effect of ionization on the structure of the guanine-cytosine (GC) base pair. The structures of G, C, GC, GC–, and GC+ were optimized using DFT. NBO analysis were made to compare the interaction energies and the H-bond strengths in GC, GC–, and GC+. Electron difference density map (EDDM) of GC, GC–, and GC+ were plotted in the hydrogen bonding plane of GC. EDDM map shows the electronic density redistribution upon ionization which locate the important regions that controls the strength of hydrogen bonds in GC base pair. EDDM along with the optimized structures of G, C and GC confirms the localization of positive charge on G and negative charge on C in GC+ and GC–, respectively. Using this novel approach, it has been shown pictorially the cause of induced instability on hydrogen bonding interaction upon ionization. This deviates the linearity and planarity of the structure, providing an opportunity to alter the base pairing.