H-bond Strength Research Articles

Structures of a Phosphoryl Derivative of 4-Allyl-2,4-dihydro-3H-1,2,4-triazole-3-thione: An Illustrative Example of Conformational Polymorphism

Two polymorphic forms of a conformationally flexible molecule, 5-[(Diphenylphosphoryl)methyl]-4-(prop-2-en-1-yl)-2,4-dihydro-3H-1,2,4-triazole-3-thione, were obtained by crystallization and characterized by X-ray diffraction analysis and differential scanning calorimetry. The relative stability of polymorphic forms was estimated with DFT calculations of crystal structures and isolated molecules. It turns out, that in the first more dense polymorph with higher cohesion energy and crystal lattice energy, the molecule adopts an energetically unfavorable conformation, and forms dimers with lower H-bond strength, as compared to the second polymorph. On the other hand, in the second polymorph, the molecule adopts almost the lowest-energy conformation and forms infinite chains via strong H-bonds. The first form that seems to be more thermodynamically stable at room temperature transforms into the second form via two endothermic phase transitions; the apparent irreversibility of the transition is due to high energy difference between the molecular conformations in crystals.

Identical Water Dynamics in Acrylamide Hydrogels, Polymers, and Monomers in Solution: Ultrafast IR Spectroscopy and Molecular Dynamics Simulations.

The dynamics and structure of water in polyacrylamide hydrogels (PAAm-HG), polyacrylamide, and acrylamide solutions are investigated using ultrafast infrared experiments on the OD stretch of dilute HOD/H2O and molecular dynamics simulations. The amide moiety of the monomer/polymers interacts strongly with water through hydrogen bonding (H-bonding). The FT-IR spectra of the three systems indicate that the range of H-bond strengths is relatively unchanged from bulk water. Vibrational population relaxation measurements show that the amide/water H-bonds are somewhat weaker but fall within the range of water/water H-bond strengths. A previous study of water dynamics in PAAm-HG suggested that the slowing observed was due to increasing confinement with concentration. Here, for the same concentrations of the amide moiety, the experimental results demonstrate that the reorientational dynamics (infrared pump-probe experiments) and structural dynamics (two-dimensional infrared spectroscopy) are identical in the three acrylamide systems studied. Molecular dynamics simulations of the water orientational relaxation in aqueous solutions of the acrylamide monomer, trimer, and pentamer are in good agreement with the experimental results and are essentially chain length independent. The simulations show that there is a slower, low-amplitude (<7%) decay component not accessible by the experiments. The simulations examine the dynamics and structure of water H-bonded to acrylamide, in the first solvent shell, and beyond for acrylamide monomers and short chains. The experiments and simulations show that the slowing of water dynamics in PAAm-HG is not caused by confinement in the polymer network but rather by interactions with individual acrylamide moieties.

Exploring the Role of H‐Bonding in Organic Electrochemistry – From Supramolecular Applications to Mechanistic Investigations

H-bonds can exert a substantial impact on the course of organic electrode reactions due to their ability to stabilize charged intermediates and products formed during these reactions, as well as facilitate proton-coupled electron transfer (PCET) reactions. This has fundamental implications for the mechanism of organic electrode reactions, but also practical impact in supramolecular chemistry and potentially synthetic electrochemistry. My group's main focus has been on the supramolecular applications, using electron transfer to alter the strength of H-bonds to create highly redox-responsive H-bond dimers. Initially we sought to avoid proton transfer because we feared that would lead to irreversible electrochemistry. However, inevitably proton transfer did show up, but, to our surprise, did not lead to irreversible electrochemistry. To explain this, we developed a new mechanism, the "wedge scheme", that shows how H-bonding can facilitate reversible electron and proton transfer. This insight recently led us to a new PCET-based design strategy for the creation of our most highly redox-responsive H-bond dimers yet.

Systematic studies on the dynamics, intermolecular interactions and local structure in the alkyl and phenyl substituted butanol isomers

In this paper, we have studied local structure, interactions scheme and molecular dynamics of series of aliphatic butanol (AB) isomers: n-butanol, iso-butanol, sec-butanol, and their phenyl counterparts (PhB): 4-phenyl-1-butanol, 2-methyl-3-phenyl-1-propanol, and 4-phenyl-2-butanol by means of X-ray diffraction (XRD), Fourier transform infrared (FTIR), and broadband dielectric spectroscopy (BDS) methods. XRD demonstrated that aside from the main peak related to the nearest-neighbour intermolecular correlations, there is a strong pre-peak at low scattering vector range for ABs, while for PhBs, this diffraction feature was weakly visible or not detected at all. At first sight, it suggests that molecules in aliphatic alcohols tend to associate and form medium-range order, while PhBs can be considered as disordered, simple liquids. However, further thorough FTIR and BDS spectroscopy investigations have shown that the phenyl moiety affects only slightly the degree of association and does not influence the strength of H-bonds in aromatic alcohols. What is more, PhBs are characterized by a similar Kirkwood factor (gk ≫ 1) to the ABs. 4-phenyl-2-butanol is characterized by the greatest gk ~ 3.7 among all studied herein alcohols, indicating a strong correlation between dipole moments and the formation of nanoassociates of chain-like topology in its structure. Combining results obtained from different experimental techniques, we pointed out that there are clear differences in dynamic and static properties between primary and secondary alcohols, including medium- and short-range order, variation in the strength of H-bonds and distribution of these types of interactions, the enthalpy of dissociation process, the glass transition temperature, and Kirkwood factor, irrespective of the presence of steric hindrance posed by the phenyl moiety. Results discussed in this paper clearly demonstrated that a superficial analysis of standard diffraction patterns, which are often the first step to probe the structure of materials, may lead to wrong conclusions. That is why complementary techniques must be applied together to understand the structure and behavior of assembling liquids.

Correlation between Kinetics and Thermodynamics for Excited-State Intramolecular Proton Transfer Reactions.

Finding the relation between thermodynamics and kinetics for a reaction is of fundamental importance. Here, the thermodynamics and kinetics correlation of excited-state intramolecular proton transfer (ESIPT) was investigated by the TD-DFT calculation under the CAM-B3LYP/6-311+G** level. We choose the family 2-(2'-aminophyenyl)benzothiazole and its amino derivatives as paradigms, which all possess the NH-type intramolecular hydrogen bond (H-bond), and investigate the corresponding ESIPT reaction. The H-bond strength can be systematically tuned, so both activation energy ΔG‡ and free energy difference between proton transfer tautomer (T*, product) and normal species (N*, reactant) ΔGT*-N* can be varied. To minimize the environmental interference such as solvent external H-bond and polarity perturbation, a nonpolar solvent such as cyclohexane is chosen as a bath with a polarizable continuum solvation model for the calculation. As a result, the comprehensive computational approach reveals a linear relationship between ΔGT*-N* and ΔG‡, which can be expressed as ΔG‡ = ΔG0 + αΔGT*-N*. The fundamental insight is reminiscent of the Bell-Evans-Polanyi (BEP) principle where α represents the character of the position of the transition state along the proton motion coordinate. In other words, the more exergonic the ESIPT reaction is, the faster the proton transfer rate can be observed. To verify that such a correlation is not a sporadic event, another ESIPT family with an -OH proton, 1-hydroxy-11H-benzo[b]fluoren-11-one and its derivatives, was also investigated and proved to follow the BEP principle as well. Unlike the quantum mechanics description of proton transfer where either proton tunneling is dominant or solute/solvent is coupled in ESIPT, this work demonstrates that reaction kinetics and thermodynamics are strongly correlated within the same class of ESIPT molecules with an intrinsic barrier free from solvent perturbation, being faster with the more exergonic reaction.

Controlling H-Bond Strength Via Proton-Coupled Electron Transfer

An important goal in supramolecular chemistry is the development of stimuli-responsive systems in which supramolecular assembly is controlled by external signals. One way to do this is to use electron transfer to perturb the strength of H-bonds. The principle is straightforward: reduction that increases negative charge on a H-acceptor (A) or oxidation that increases positive charge on a H-donor (D) will increase the strength of a H-bond. However, oxidation or reduction can also lead to full proton transfer, resulting in an increase in unfavorable secondary interactions that counteracts the effect of the initial electron transfer. But, with proper design, proton transfer can lead to an increase in favorable secondary interactions, enhancing the effect of the initial electron transfer. The success of the latter strategy is demonstrated with the 3 H-bond DAD array, 1, that contains a N-methyl-4,4'-bipyridinium redox couple.1 In CH2Cl2, 1 forms a three H-bond dimer with ADA array, 2, with a modest Kb of 500 M−1 due to the unfavorable secondary interactions. Initial CV studies show that two electron reduction of the bipyridinium increases the binding strength by 2×105 giving a very strong Kb of ~108 M−1. This value is consistent with expectations for a DDD-AAA H-bond complex, strongly suggesting that electron transfer not only creates an ionic H-bond but also leads to proton transfer and conversion of the secondary interactions from unfavorable to favorable. In this presentation, the results of a full investigation of this system will be reported, including UV-vis spectroelectrochemical studies that support proton transfer and NMR studies of possible 1-1 and 2-2 homodimerization. Furthermore, theoretical CV’s that include, if needed, homodimerization will be fit to the experimental CV’s to provide a more exact measure of the binding enhancement in this system. 1H. Choi, K. Baek, S. Toenjes, J. L. Gustafson, and D. K. Smith, J. Am. Chem. Soc. 2020, 142, 17271-17276. DOI: 10.1021/jacs.0c07841 Figure 1

Disentangling Chromophore States in a Reversibly Switchable Green Fluorescent Protein: Mechanistic Insights from NMR Spectroscopy.

The photophysical properties of fluorescent proteins, including phototransformable variants used in advanced microscopy applications, are influenced by the environmental conditions in which they are expressed and used. Rational design of improved fluorescent protein markers requires a better understanding of these environmental effects. We demonstrate here that solution NMR spectroscopy can detect subtle changes in the chemical structure, conformation, and dynamics of the photoactive chromophore moiety with atomic resolution, providing such mechanistic information. Studying rsFolder, a reversibly switchable green fluorescent protein, we have identified four distinct configurations of its p-HBI chromophore, corresponding to the cis and trans isomers, with each one either protonated (neutral) or deprotonated (anionic) at the benzylidene ring. The relative populations and interconversion kinetics of these chromophore species depend on sample pH and buffer composition that alter in a complex way the strength of H-bonds that contribute in stabilizing the chromophore within the protein scaffold. We show in particular the important role of histidine-149 in stabilizing the neutral trans chromophore at intermediate pH values, leading to ground-state cis-trans isomerization with a peculiar pH dependence. We discuss the potential implications of our findings on the pH dependence of the photoswitching contrast, a critical parameter in nanoscopy applications.

Investigating the property and strength of intermolecular interaction in saturated and unsaturated cyclic cations constructed ionic liquids

In this work, we have investigated the intermolecular interaction and hydrogen bond (H-bond) strength of unsaturated and saturated cations of ionic liquids (ILs) ([EMIM]+, [Epy]+, [Epr]+, and [Epp]+) with Cl-, [BF4]-, [DCA]-, and [OAC]- anions, for the aim of determining how is the influence of the unsaturated and saturated cations on the ion binding. Via molecular dynamic simulations and density functional theory calculations, it is found that saturated [Epr]+ and [Epp]+ manifest the strongest binding energies with Cl- and [OAC]-, where electrostatics effect overwhelms the induction and dispersion effects, as the dominant factor determining ion binding. On the other hand, the resolution of H-bond strength in ion-pair implies that it is stronger in [Epr]+ and [Epp]+ based ILs, especially the strongest when they pair with Cl-. Our results verify that saturated heterocycle-based cations serve as stronger anion binding sites and stronger H-bond donors than unsaturated ones, and that such ILs can be potentially applied in areas with specific demanding with strong ion binding.

O-H stretching frequency red shifts do not correlate with the dissociation energies in the dimethylether and dimethylsulfide complexes of phenol derivatives.

In this perspective, we present a comprehensive report on the spectroscopic and computational investigations of the hydrogen bonded (H-bonded) complexes of Me2O and Me2S with seven para-substituted H-bond donor phenols. The salient finding was that although the dissociation energies, D0, of the Me2O complexes were consistently higher than those of the analogous Me2S complexes, the red-shifts in phenolic O-H frequencies, Δν(O-H), showed the exactly opposite trend. This is in contravention of the general perception that the red shift in the X-H stretching frequency in the X-HY hydrogen bonded complexes is a reliable indicator of H-bond strength (D0), a concept popularly known as the Badger-Bauer rule. This is also in contrast to the trend reported for the H-bonded complexes of H2S/H2O with several para substituted phenols of different pKa values wherein the oxygen centered hydrogen bonded (OCHB) complexes consistently showed higher Δν(O-H) and D0 compared to those of the analogous sulfur centered hydrogen bonded (SCHB) complexes. Our effort was to understand these intriguing observations based on the spectroscopic investigations of 1 : 1 complexes in combination with a variety of high level quantum chemical calculations. Ab initio calculations at the MP2 level and the DFT calculations using various dispersion corrected density functionals (including DFT-D3) were performed on counterpoise corrected surfaces to compute the dissociation energy, D0, of the H-bonded complexes. The importance of anharmonic frequency computations is underscored as they were able to correctly reproduce the observed trend in the relative OH frequency shifts unlike the harmonic frequency computations. We have attempted to find a unified correlation that would globally fit the observed red shifts in the O-H frequency with the H-bonding strength for the four bases, namely, H2S, H2O, Me2O, and Me2S, in this set of H-bond donors. It was found that the proton affinity normalized Δν(O-H) values scale very well with the H-bond strength.

N-H⋯X interactions stabilize intra-residue C5 hydrogen bonded conformations in heterocyclic α-amino acid derivatives.

Nature makes extensive and elaborate use of hydrogen bonding to assemble and stabilize biomolecular structures. The shapes of peptides and proteins rely significantly on N–H⋯O Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> C interactions, which are the linchpins of turns, sheets and helices. The C5 H-bond, in which a single residue provides both donor and acceptor, is generally considered too weak to force the backbone to adopt extended structures. Exploiting the synergy between gas phase (experimental and quantum chemistry) and solution spectroscopies to decipher IR spectroscopic data, this work demonstrates that the extended C5-based conformation in 4-membered ring heterocyclic α-amino acid derivatives is significantly stabilized by the formation of an N–H⋯X H-bond. In this synergic system the strength of the C5 interaction remains constant while the N–H⋯X H-bond strength, and thereby the support provided by it, varies with the heteroatom.

Selective separation of lactic, malic, and tartaric acids based on the hydrophobic deep eutectic solvents of terpenes and amides

The selective separation of lactic, malic and tartaric acids coexisting in broth can be improved by effectively regulating the H-bond strength and H-bond competition based on hydrophobic eutectic solvents composed of terpenes and amides.

Electrochemically-Controlled Dimerization in Ferrocene-Containing Ureidopyrimidones: Effect of Ferrocene Position

Ureidopyrimidones (UPy’s) are well-known to dimerize in weakly polar solvents via the formation of four strong, linear H-bonds. Application of heat or mechanical stress can be used to break these bonds, which has led to their use as a linker in self-healing supramolecular polymers. On-going research in our lab is focused on further increasing the versatility of the UPy system by creating electroactive UPy’s in which dimerization strength can also be controlled through oxidation and reduction. Previously, we have shown that dimers based on the ferrocene-UPy derivative, 1, break apart upon oxidation of the ferrocene to the ferrocenium form at mM concentrations in CH2Cl2. This could be due both to the creation of electrostatic repulsion and a decrease in H-bond strength due to the reduced H-donor ability of the O and N on the pyrimidone side. In this project, another Fc-UPy has been prepared, 2, in which the ferrocene is attached to the urea side of the molecule. In contrast to 1, oxidation of 2 shows a single reversible ferrocene CV wave in CH2Cl2 at mM concentrations. Under these conditions, 1H NMR indicates that 2 is fully dimerized, thus, it appears that, unlike with 1, oxidation has no significant effect on dimerization of 2. In both cases, oxidation would increase electrostatic repulsion. However, unlike in 1, oxidation of 2 should actually increase H-bond strength by making the urea NH a stronger H-donor. Therefore, it appears that the effect of oxidation on the H-donating or accepting ability is a more crucial factor for dimerization control than electrostatics in these systems. Figure 1

Novel Poly Deep Eutectic Solvents Based Supported Liquid Membranes for CO2 Capture

The poly deep eutectic solvents (PDESs), a potential substituent to ionic liquids, have emerged as relatively new material and have been successfully applied in catalysis, nanotechnology, and, more importantly, in gas separation. Herein, the PDESs were incorporated for the first time in the CO2 capturing membranes to exploit their inherent advantages in acid gas capture. The PDESs were synthesized by mixing choline chloride (hydrogen bond acceptor-HBA) and two hydrogen bond donors-HBDs (polyacrylic acid &amp; polyacrylamide) separately in different molar ratios. The physical changes of the resulting homogeneous mixture along with the FTIR confirmed the successful synthesis of the PDESs. Afterward, these PDESs were impregnated into microporous polyvinylidene fluoride (PVDF) membrane support to fabricate supported liquid membranes (SLMs). The gas performance of the prepared PDES-SLMs was tested under pure and mixed-gas conditions for CO2, CH4, and N2. The factors affecting the practical application of SLMs, such as the effect of composition of the PDESs, temperature, and volume fraction of the CO2 in the feed gas, were investigated systematically. The prepared PDES-SLMs showed significant CO2 permeabilities up to 27 Barrer as well as remarkably high CO2/CH4 and CO2/N2 selectivities of the order of 55.5 and 60, respectively. It was observed that by increasing the choline content and the temperature, the activation energy required for CO2 capture decreased, which enhanced the membrane performance (permeability and selectivity). This can be ascribed to the basicity, molar free volume, and the H-bonding strength of the synthesized PDESs. The green potential, low cost, and the significant gas separation performance make theses PDESs a favorable alternative to the competing PILs in capturing the greenhouse acid gases.

Reversible multicolor chromism in layered formamidinium metal halide perovskites

Metal halide perovskites feature crystalline-like electronic band structures and liquid-like physical properties. The crystal–liquid duality enables optoelectronic devices with unprecedented performance and a unique opportunity to chemically manipulate the structure with low energy input. In this work, we leverage the low formation energy of metal halide perovskites to demonstrate multicolor reversible chromism. We synthesized layered Ruddlesden-Popper FAn+1PbnX3n+1 (FA = formamidinium, X = I, Br; n = number of layers = 1, 2, 3 … ∞) and reversibly tune the dimensionality (n) by modulating the strength and number of H-bonds in the system. H-bonding was controlled by exposure to solvent vapor (solvatochromism) or temperature change (thermochromism), which shuttles FAX salt pairs between the FAn+1PbnX3n+1 domains and adjacent FAX “reservoir” domains. Unlike traditional chromic materials that only offer a single-color transition, FAn+1PbnX3n+1 films reversibly switch between multiple colors including yellow, orange, red, brown, and white/colorless. Each colored phase exhibits distinct optoelectronic properties characteristic of 2D superlattice materials with tunable quantum well thickness.

Effect of hydrogen-bond strength on photoresponsive properties of polymer-azobenzene complexes

Supramolecular complexation between photoresponsive azobenzene chromophores and a photopassive polymer host offers synthetic and design advantages compared with conventional covalent azo-containing polymers. In this context, it is important to understand the impact of the strength of the supramolecular interaction on the optical response. Herein, we study the effect of hydrogen-bonding strength between a photopassive polymer host [poly(4-vinylpyridine), or P4VP] and three azobenzene analogues capable of forming weaker (hydroxyl), stronger (carboxylic acid), or no H-bonding with P4VP. The hydroxyl-functionalized azo forms complete H-bonding complexation up to equimolar ratio with VP, whereas the COOH-functionalized azo reaches only up to 30% H-bond complexation due to competing acid dimerization that leads to partial phase separation and azo crystallization. We show that the stronger azo-polymer H-bonding nevertheless provides higher photoinduced orientation and better performance during optical surface patterning, in terms of grating depth and diffraction efficiency, when phase separation is either avoided altogether or is limited by using relatively low azo contents. These results demonstrate the importance of the H-bonding strength on the photoresponse of azopolymer complexes, as well as the need to consider the interplay between different intermolecular interactions that can affect complexation.

Ultrafast Dynamics at Lipid-Water Interfaces.

Lipid membranes are more than just barriers between cell compartments; they provide molecular environments with a finely tuned balance between hydrophilic and hydrophobic interactions that enable proteins to dynamically fold and self-assemble to regulate biological function. Characterizing dynamics at the lipid-water interface is essential to understanding molecular complexities from the thermodynamics of liquid-liquid phase separation down to picosecond-scale reorganization of interfacial hydrogen-bond networks.Ultrafast vibrational spectroscopy, including two-dimensional infrared (2D IR) and vibrational sum-frequency generation (VSFG) spectroscopies, is a powerful tool to examine picosecond interfacial dynamics. Two-dimensional IR spectroscopy provides a bond-centered view of dynamics with subpicosecond time resolutions, as vibrational frequencies are highly sensitive to the local environment. Recently, 2D IR spectroscopy has been applied to carbonyl and phosphate vibrations intrinsically located at the lipid-water interface. Interface-specific VSFG spectroscopy probes the water vibrational modes directly, accessing H-bond strength and water organization at lipid headgroup positions. Signals in VSFG arise from the interfacial dipole contributions, directly probing headgroup ordering and water orientation to provide a structural view of the interface.In this Account we discuss novel applications of ultrafast spectroscopy to lipid membranes, a field that has experienced significant growth over the past decade. In particular, ultrafast experiments now offer a molecular perspective on increasingly complex membranes. The powerful combination of ultrafast, interface-selective spectroscopy and simulations opens up new routes to understanding multicomponent membranes and their function. This Account highlights key prevailing views that have emerged from recent experiments: (1) Water dynamics at the lipid-water interface are slow compared to those of bulk water as a result of disrupted H-bond networks near the headgroups. (2) Peptides, ions, osmolytes, and cosolvents perturb interfacial dynamics, indicating that dynamics at the interface are affected by bulk solvent dynamics and vice versa. (3) The interfacial environment is generally dictated by the headgroup structure and orientation, but hydrophobic interactions within the acyl chains also modulate interfacial dynamics. Ultrafast spectroscopy has been essential to characterizing the biophysical chemistry of the lipid-water interface; however, challenges remain in interpreting congested spectra as well as designing appropriate model systems to capture the complexity of a membrane environment.

The effect of hydrogen bonding on diffusion and permeability in UV-cured Polyacrylate-based networks for controlled release

Polyacrylates are important polymers widely used in pharmaceutical industry such as drug coatings due to their low cost, processability and ease of functionalisation. Chemical functionalities (e.g. H-bonding) can be easily included to modulate the transport of low molecular weight drug-like entities through the network. Understanding how such microscopic structural modifications determine macroscopic diffusion is critical for designing next generation responsive polymers. In this study pulsed field gradient (PFG) 1H NMR measurements of the self-diffusion of a dye molecule (Eosin Y) in a series of polyacrylate networks with differing H-bonding strength were undertaken; it was found that the diffusion of Eosin Y is significantly reduced in networks with H-bonding. Detailed analyses by 1H NMR relaxometry and double quantum (DQ) NMR show that H-bonding can also reduce polymer chain mobility. Furthermore, DSC thermoporometry showed a significant increase in the average network mesh size potentially due to the pre-organization of H-bonding containing monomer during network curing. By introducing the H-bonding disrupter, LiClO4, it was found that the diffusivity of solute becomes positively correlated to the average mesh size across the series of networks. Hence, a modified diffusion model based on hydrodynamic theory is proposed to separate the direct (solute-network) H-bonding contribution to solute diffusion from the indirect contribution arising from monomer pre-ordering induced mesh size reduction. Finally, it is shown that the same direct and indirect contributions to microscopic diffusivity, arising from the H-bond strength of the co-monomers, also contribute significantly to the macroscopic membrane permeability which is similarly subject to H-bond disruption.

Direct and Reliable Method for Estimating the Hydrogen Bond Energies and Cooperativity in Water Clusters, Wn, n = 3 to 8.

No direct method for estimating the individual O-H···O hydrogen bond (H-bond) energies in water clusters (Wn) exists in the literature. In this work, we propose such a direct method based on the molecular tailoring approach, which also enables the estimation of the cooperativity contributions. The calculated H-bond energies at MP2(full)/aug-cc-pVTZ and CCSD(T)/aug-cc-pVDZ levels for Wn, n = 3 to 8, agree well with one another and fall between 0.3 and 11.6 kcal mol-1 with the cooperativity contributions in the range of -1.2 and 7.0 kcal mol-1. For gauging the accuracy of our H-bond energies for a cluster, the H-bond energy sum is added to the sum of monomer energies, and the results are compared with the respective total energy. These two values agree with each other to within 8.3 mH (∼5 kcal mol-1), testifying the accuracy of our estimated H-bond energies. Further, these H-bond strengths show a good correlation with the respective O-H stretching frequencies and the molecular electron density values at the (3, -1) O-H···O H-bond critical point.

The Prodigious Hydrogen Bonds with Sulfur and Selenium in Molecular Assemblies, Structural Biology, and Functional Materials.

Hydrogen bonds (H-bonds) play important roles in imparting functionality to the basic molecules of life by stabilizing their structures and directing their interactions. Numerous studies have been devoted to understanding H-bonds involving highly electronegative atoms like nitrogen, oxygen, and halogens and consequences of those H-bonds in chemical reactions, catalysis, and structure and function of biomolecules; but the involvement of less electronegative atoms like sulfur and selenium in H-bond formation establishes the concept of noncanonical H-bonds. Initially belittled for the "weak" nature of their interactions, these perceptions have gradually evolved over time through dedicated efforts by several research groups. This has been facilitated by advancements in experimental methods for their detection through gas-phase laser spectroscopy and solution NMR spectroscopy, as well as through theoretical predictions from high level quantum chemical calculations.In this Account, we present insights into the versatility of the sulfur and selenium centered H-bonds (S/SeCHBs) by highlighting their multifarious applications in various fields from chemical reactions to optoelectronic properties to structural biology. Our group has highlighted the significance and strength of such H-bonds in natural and modified biomolecules. Here, we have reviewed several molecular assemblies, biomolecules, and functional materials, where the role of these H-bonds is pivotal in influencing biological functions. It is worth mentioning here that the precise experimental data obtained from gas-phase laser spectroscopy have contributed considerably to changing the existing perceptions toward S/SeCHBs. Thus, molecular beam experiments, though difficult to perform on smaller model thio- or seleno-substituted Molecules, etc. (amides, nucleobases, drug molecules), are inevitable to gather elementary knowledge and convincing concepts on S/SeCHBs that can be extended from a small four-atom sulfanyl dimer to a large 14 kDa iron-sulfur protein, ferredoxin. These H-bonds can also tailor a fascinating array of molecular frameworks and design supramolecular assemblies by inter- and intralinking of individual "molecular Lego-like" units.The discussion is indeed intriguing when it turns to the usage of S/SeCHBs in facile synthetic strategies like tuning regioselectivity in reactions, as well as invoking phenomena like dual phosphorescence and chemiluminescence. This is in addition to our investigations of the dispersive nature of the hydrogen bond between metal hydrides and sulfur or selenium as acceptor, which we anticipate would lead to progress in the areas of proton and hydride transfer, as well as force-field design. This Account demonstrates how ease of fabrication, enhanced efficiency, and alteration of physicochemical properties of several functional materials is facilitated owing to the presence of S/SeCHBs. Our efforts have been instrumental in the evaluation of various S/SeCHBs in flue gas capture, as well as design of organic energy harvesting materials, where dipole moment and polarizability have important roles to play. We hope this Account invokes newer perspectives with regard to how H-bonds with sulfur and selenium can be adequately adopted for crystal engineering, for more photo- and biophysical studies with different spectroscopic methods, and for developing next-generation field-effect transistors, batteries, superconductors, and organic thin-film transistors, among many other multifunctional materials for the future.

The effects of amino acid sequence and solvent polarity on the self-assembling of cyclic peptide nanotubes and molecular channel formation inside the lipid bilayer

In this article, the effects of amino acid sequence and solvent polarity on the self-assembling process of cyclic peptides (CPs) were investigated by employing molecular dynamic (MD) simulations and quantum chemistry calculations. As a result, CP dimers are not stable in water, because of hydrogen bond (H-bond) lost between the CP units, while chloroform increases the stability of the CP dimers. MM-PBSA and MM-GBSA calculations confirmed that solvent polarity has an important effect on the stability of the CP dimers. Dynamical behavior of the cyclic peptide nanotubes (CPNTs) in chloroform indicates that CPNTs composed of leucine and phenylalanine are better molecular containers than that of isoleucine. At the next step, the ability of these CPNTs in molecular channel formation inside a fully hydrated DMPC (dimyristoylphosphatidylcholine) bilayer was investigated during 50 ns MD simulations. The obtained results show that only CPNT composed of isoleucine can form a molecular channel inside the DMPC membrane because isoleucine has a greater hydrophobicity than leucine and phenylalanine. This property increases the interactions between the CPNT and lipid residues, which elevates the stability of the CPNT inside the DMPC bilayer. Quantum chemistry calculations and non-covalent interactions analysis indicate that the solvent changes the stability and dynamical behavior of the CPNTs through the change in the H-bond strength. Finally, according to the different analyses, it can be concluded that the amino acid sequence in the CP units has an important role in designing specific nanostructures.