Hydrogen-bonded Systems Research Articles

Signature of Proton-Hole Transfer in Hydrogen-Bonded Solids at 10 K.

Although proton transport in water ice is well understood, proton-hole transfer (PHT) involving proton abstraction by anions remains less explored. This study investigates PHT in H2S and NH3 solids at low temperatures, aiming to determine whether these solids exhibit negative charge transport similar to that in ice. In H2S and NH3 solids at 10 K, surface HS- and NH2- anions in hydrogen-bonded systems trigger negative current flow, providing a clear signature of PHT. This negative current is controlled by electron flow and 193 nm ultraviolet irradiation, which generates HS- and NH2- anions on the solid surfaces. In bilayer H2S/H2O and NH3/H2O solids, a significant negative current is observed only in the NH3/H2O solid, which is attributed to the exothermic proton abstraction by NH2- from H2O at the bilayer interface, a process not available for H2S on ice. This study is the first to demonstrate PHT-induced electrochemical behavior in hydrogen-bonded solids other than ice.

Quantum Nuclear Dynamics on a Distributed Set of Ion-Trap Quantum Computing Systems.

Quantum nuclear dynamics with wavepacket time evolution is classically intractable and viewed as a promising avenue for quantum information processing. Here, we use IonQ, Inc.'s 11-qubit trapped-ion quantum computer, Harmony, to study the quantum wavepacket dynamics of a shared-proton within a short-strong hydrogen-bonded system. We also provide the first application of distributed quantum computing for chemical dynamics problems, where a distributed set of quantum processes is constructed using a tensor network formalism. For a range of initial states, we experimentally drive the ion-trap system to emulate the quantum nuclear wavepacket as it evolves along the potential surface generated from the electronic structure. Following the experimental creation of the nuclear wavepacket, we extract measurement observables such as its time-dependent spatial projection and its characteristic vibrational frequencies to good agreement with classical results. Vibrational eigenenergies obtained from quantum computation are in agreement with those obtained from classical simulations to within a fraction of a kilocalorie per mole, thus suggesting chemical accuracy. Our approach opens a new paradigm for studying the quantum chemical dynamics and vibrational spectra of molecules and also provides the first demonstration of parallel quantum computation on a distributed set of ion-trap quantum computers.

Drug-Drug Cocrystal Alloy and Nanoformulation of Cytarabine: Optimized Biopharmaceutical Property and Synergistic Antitumor Efficacy.

An integrated strategy by combining cocrystallization with nanotechnology is developed to optimize in vitro/vivo performances of marine antitumor drug cytarabine (ARA) and further obtain innovative insights into the exploitation of cocrystal alloy nanoformulation. Therein, the optimization of properties and synergistic effects of ARA mainly depends on assembling with uracil (U) and antitumor drug 5-fluorouracil (FU) into the same crystal by cocrystallization technology, while the long-term efficacy is primarily maintained by playing the superiority of nanotechnology. Along this line, the first cocrystal alloy of ARA, viz., ARA-FU-U (0.6:0.4), is successfully obtained and then transformed into a nanocrystal. Single-crystal X-ray diffraction analysis demonstrates that this cocrystal alloy consists of two isomorphic cocrystals of ARA, namely, ARA-FU and ARA-U, in 0.6:0.4 ratio. An R22(8) hydrogen-bonding cyclic system formed by a cytosine fragment of ARA with U or FU can protect and stabilize the amine group on ARA, laying the foundation for regulating its properties. The in vitro/in vivo properties of the cocrystal alloy and its nanocrystals are investigated by theoretical and experimental means. It reveals that both the alloy and nanocrystal can improve physicochemical properties and promote drug absorption, thus bringing to optimized pharmacokinetic behaviors. The nanocrystal produces superior effects than the alloy that helps to extend therapeutic time and action. Particularly, relative to the corresponding binary cocrystal, the synergistic antitumor activity of ARA and FU in the cocrystal alloy is heightened obviously. It may be that U contributes to reducing the degradation of FU, specifically increasing its concentration in tumors to enhance the synergistic effects of FU and ARA. These findings provide new thoughts for the application of cocrystal alloys in the marine drug field and break fresh ground for cocrystal alloy formulations to optimize drug properties.

Prediction of multiferroicity in the layered hydrogen-bonded system α-CrOOH: Proton transfer ferroelectricity and strain-tunable magnetic transition

Ferroelectric materials with vertical polarization could provide ground-breaking device applications, compatible with electric-field switching even in the presence of a surface-depolarizing field. Herein, we present theoretical evidence that rhombohedral chromium oxide hydroxide α-CrOOH, which has been synthesized experimentally, is a type-Ⅰ multiferroic. First-principles calculations plus Monte Carlo simulations indicate that α-CrOOH is a room temperature proton transfer ferroelectricity semiconductor with robust electric polarization as large as 24.6 μC/cm2. Moreover, the system exhibits an anti-ferromagnetism ground state with a Neel temperature of 340 K, where strain can modulate the transition from antiferromagnetic to ferromagnetic. Finally, a two-dimensional (2D) heterostructure model was designed, composed of monolayer α-CrOOH and functional MXene, for various applications such as non-volatile memory (NVM). The remarkable properties may enable the system to hold great potential for the development of future multifunctional devices.

On the shape of the simulated infrared spectral density of strongly hydrogen-bonded systems: Mapping and identification of Hadži ABC structure in phosphonic acid dimers in gas phase

Herein, we explore the origin of three-peaked structure, referred to as the Hadži ABC structure, illustrated within the absorption bands in infrared (IR) spectra of strongly H-bonded systems. The exploration is particularly elucidated for two phosphinic acid dimers (R2POOH) in gas phase, namely bis-(iodomethyl)-phosphinic acid dimer (i.e., R = CH2I) at 465 K and dibutyl-phosphinic acid dimer (i.e., R = C4H9O) at 425 K. A direct theoretical illustration of this spectral signature, related predominantly to very strongly hydrogen bonded complexes, is proposed. The spectral density, υSO−H,is determined by the aid of an approach describing the high-frequency O − H stretching modes by harmonic potentials. The intermolecular potential modes (O…O) are assumed to be of anharmonic nature. The approach is founded on the strong anharmonic coupling approximation, which prescribes a linear dependency of the O − H frequency on the O…O stretching coordinate as rationalized by the fundamental model of Maréchal and Witkowski. Both direct relaxation of the O − H vibrational mode and its homolog, indirect one, affecting the O…O stretching mode are taken into consideration. The model also considers Davydov coupling, which describes the mutual interaction that takes place in the centrosymmetric dimer between the two existent hydrogen bonds as well as Fermi resonances, which occur between the bending modes arising in- and out-of-plane of the dimer and the fundamental O − H stretching mode. Interestingly, we illustrate how the (A, B, and C) triplet detected in the IR absorption band of phosphonic acids can be generated and discuss how the ABC structure can be numerically simulated. The approach provides a direct explanation of the emergence of this unusual feature and mainly reveals that the A peak is due to the Davydov coupling mechanism, whereas the BC diad is found to be generated by Fermi resonances. This was elucidated in a distinctly different approach, rationalized by Sheppard and Claydon, affirming that the provenance of the BC diad is exclusively due to Fermi resonances mechanism. Altogether, our results highlight the congregated effects of both Fermi resonance mechanism and Davydov coupling for the formation of the ABC structure. The model paves the way for a deeper understanding of the ABC structure, characteristic of very toxic strongly hydrogen-bonded dimers. This is of capital importance as it allows one to develop a solid understanding of nerve agents, such as phosphonic acids, from theory alone, so as to avoid difficult and dangerous experiments since they are extremely toxic.

Molecular Filter Net Synergy with Regulation in Ion Percolation for High-Performance Zn Metal Batteries.

The uncontrollable dendrite growth and complex parasitic reactions of Zn metal anodes cause short cycle lives and low Coulombic efficiency, which seriously affect their applications. To address these issues, this research proposes an efficient ion percolating interface constituted by a hydrogen-bonded organic framework (HND) for a highly stable and reversible Zn anode. The hydrogen-bonded skeleton acts as a molecular filter net, capturing water molecules by forming targeted hydrogen-bonding systems with them, sufficiently inhibiting parasitic reactions. Additionally, the interaction of the rich-N and -O electrochemically active sites with Zn2+ effectively regulates its percolation, which greatly enhances the diffusion kinetics of Zn2+, thus facilitating rapid and uniform migration of Zn2+ at the anode surface. Through the above synergistic effect, dendrite-free anodes with highly reversible Zn plating/stripping behaviors can be achieved. Hence, the modified Zn anode (HND@Zn) performs a steady cycling time of more than 1700 h at 1 mA cm-2. Moreover, the HND@Cu||Zn asymmetric cell exhibits a stable charge/discharge process of over 1600 cycles with an average Coulombic efficiency of up to 99.6% at 5 mA cm-2. This work provides some conceptions for the evolution and application of high-performance Zn metal batteries.

Resource Optimization for Quantum Dynamics with Tensor Networks: Quantum and Classical Algorithms.

The exponential scaling of the quantum degrees of freedom with the size of the system is one of the biggest challenges in computational chemistry and particularly in quantum dynamics. We present a tensor network approach for the time-evolution of the nuclear degrees of freedom of multiconfigurational chemical systems at a reduced storage and computational complexity. We also present quantum algorithms for the resultant dynamics. To preserve the compression advantage achieved via tensor network decompositions, we present an adaptive algorithm for the regularization of nonphysical bond dimensions, preventing the potentially exponential growth of these with time. While applicable to any quantum dynamical problem, our method is particularly valuable for dynamical simulations of nuclear chemical systems. Our algorithm is demonstrated using ab initio potentials obtained for a symmetric hydrogen-bonded system, namely, the protonated 2,2'-bipyridine, and compared to exact diagonalization numerical results.

Calculation of the formation enthalpies of charge-transfer complexes with iodine from the binding constants at 298.15 K

There is a continuing interest in charge-transfer complex chemistry, particularly in their formation thermodynamics. Nowadays, the binding constants and Gibbs energies of formation are available for many complexes. However, the experimental determination of the complexation enthalpies is a more difficult procedure, as it usually requires the establishment of the temperature dependence of the binding constant. Our recent studies of the compensation relationship in the thermodynamics of solvation in hydrogen-bonded systems opened the way to the calculation of the enthalpies of specific (i.e., localized donor-acceptor) interactions (Δint(sp)H) directly from the Gibbs energies at 298.15 K (Δint(sp)G). The calculation procedure is based on the following equation: Δint(sp)G/(kJ·mol−1) = 0.66·Δint(sp)H/(kJ·mol−1) + 2.5n (n corresponds to the coordination number of a solute).In the present work, we checked whether the above relation can be applied to the complex formation between halogens (primarily iodine) and organic electron donors. For 152 complexes with aromatics, nitrogen, oxygen, sulfur, selenium, and phosphor-containing compounds, the formation enthalpies were estimated using the data on equilibrium constants at 298.15 K. In most cases, agreement with the experimental binding enthalpies within the expected measurement error was observed (RMS = 1.4 kJ·mol−1, AD = –0.4 kJ·mol−1).

Synthesis, mol-ecular and crystal structure of [(NH2)2CSSC(NH2)2]2[RuBr6]Br2·3H2O.

The title compound, bis-[di-thio-bis-(formamidinium)] hexa-bromido-ruthenium dibromide trihydrate, [(NH2)2CSSC(NH2)2]2[RuBr6]Br2·3H2O, crystallizes in the ortho-rhom-bic system, space group Cmcm, Z = 4. The [RuBr6]2- anionic complex has an octa-hedral structure. The Ru-Br distances fall in the range 2.4779 (4)-2.4890 (4) Å. The S-S and C-S distances are 2.0282 (12) and 1.783 (2) Å, respectively. The H2O mol-ecules, Br- ions, and NH2 groups of the cation are linked by hydrogen bonds. The conformation of the cation is consolidated by intra-molecular O-H⋯Br, O-H⋯O, N-H⋯Br and N-H⋯O hydrogen bonds. The [(NH2)2CSSC(NH2)2]2+ cations form a hydrogen-bonded system involving the Br - ions and the water mol-ecules. Two Br - anions form four hydrogen bonds, each with the NH2 groups of two cations, thus linking the cations into a ring. The rings are connected by water mol-ecules, forming N-H⋯O-H⋯Br hydrogen bonds.

Dynamics of proton tunneling in Hydrogen-Bonded systems through Green's function formalism

This study proposes a new theoretical model based on Green's function formalism for studying proton tunneling via hydrogen bonding. This approach allows calculating the tunneling probability and the tunneling energy that proton transfer occurs along a given path inferred a priori. The method is extended to multiple protons tunneling, characterizing the behaviour of some biological molecules. Specifically, the cases of the proton transfer in the Fujicurin A molecule and the double proton tunneling in the Guanine-Cytosine base-pair are investigated. The new approach is an alternative to those present in the literature. It allows straightforwardly predicting the mechanisms of intramolecular and intermolecular proton transfers involving the rearrangement of conjugated electrons.

Impact of Nuclear Quantum Effects on the Structural Properties of Protonated Water Clusters.

Nuclear quantum effects (NQEs) play a crucial role in hydrogen-bonded systems due to quantum tunneling and proton fluctuation. Our understanding of how NQEs affect microstructures mainly focuses on bulk phases of liquids and solids but remains deficient for water clusters, including their hydrogen nuclei, hydrogen-bonded configurations, and temperature dependence. Here, we conducted ab initio molecular dynamics (MD) and path integral MD simulations to investigate the influence of NQEs on the structural properties of protonated water clusters H+(H2O)n (n = 3, 6, 9, 12). The results reveal that the NQEs become less evident as the cluster size increases due to the competition between NQEs and electrostatic interactions. Simulations of several H+(H2O)6 isomers at different temperatures indicate that the effect of elevated temperature on proton transfer is related to the initial structure. Interestingly, the process of proton transfer also involves the interconversion between Zundel-type and Eigen-type isomers. These findings significantly deepen our understanding of ion-water and water-water interactions, opening new avenues for the study of hydrated ion clusters and related systems.

Regular relations of the composition, structure and properties of crystals of hydrogen-containing compounds

Research subject. Crystals of hydrogen-containing compounds belonging to the superprotonic family. Aim. To obtain knowledge about regular relations between composition, atomic structure, real structure and physical properties of materials, with the purpose of elucidating processes occurring in condensed state and forming the basis for modification of known or obtaining new compounds. Materials and methods. Experimental data were obtained using a set of complementary physical methods, including structural analysis using X-rays, synchrotron radiation and neutrons, optical microscopy, and atomic force microscopy. Results. Experimental data on the atomic structure, real structure, and physical properties of superprotonic crystals, including systems of hydrogen bonds and their changes, were obtained. Conclusions. The physical properties of superprotonic crystals are significantly affected by hydrogen bonding systems and their changes, primarily by the formation of dynamically disordered hydrogen bonds with energetically equivalent positions of hydrogen atoms. When carrying out diagnostics of crystalline samples, account should be taken of their real structure, including the structure of surface layers and the presence of crystallization water. These factors may affect the measured physical parameters, the boundaries of existence of phases, the formation of a multiphase state under variations in temperature.

The Stability of Hydrogen-Bonded Ion-Pair Complex Unexpectedly Increases with Increasing Solvent Polarity.

The generally observed decrease of the electrostatic energy in the complex with increasing solvent polarity has led to the assumption that the stability of the complexes with ion-pair hydrogen bonds decreases with increasing solvent polarity. Besides, the smaller solvent-accessible surface area (SASA) of the complex in comparison with the isolated subsystems results in a smaller solvation energy of the latter, leading to a destabilization of the complex in the solvent compared to the gas phase. In our study, which combines Nuclear Magnetic Resonance, Infrared Spectroscopy experiments, quantum chemical calculations, and molecular dynamics (MD) simulations, we question the general validity of this statement. We demonstrate that the binding free energy of the ion-pair hydrogen-bonded complex between 2-fluoropropionic acid and n-butylamine (CH3CHFCOO-…NH3But+) increases with increased solvent polarity. This phenomenon is rationalized by a substantial charge transfer between the subsystems that constitute the ion-pair hydrogen-bonded complex. This unexpected finding introduces a new perspective to our understanding of solvation dynamics, emphasizing the interplay between solvent polarity and molecular stability within hydrogen-bonded systems.

Computational Design of Photosensitive Polymer Templates To Drive Molecular Nanofabrication.

Molecular electronics promises the ultimate level of miniaturization of computers and other machines as organic molecules are the smallest known physical objects with nontrivial structure and function. But despite the plethora of molecular switches, memories, and motors developed during the almost 50-years long history of molecular electronics, mass production of molecular computers is still an elusive goal. This is mostly due to the lack of scalable nanofabrication methods capable of rapidly producing complex structures (similar to silicon chips or living cells) with atomic precision and a small number of defects. Living nature solves this problem by using linear polymer templates encoding large volumes of structural information into sequence of hydrogen bonded end groups which can be efficiently replicated and which can drive assembly of other molecular components into complex supramolecular structures. In this paper, we propose a nanofabrication method based on a class of photosensitive polymers inspired by these natural principles, which can operate in concert with UV photolithography used for fabrication of current microelectronic processors. We believe that such a method will enable a smooth transition from silicon toward molecular nanoelectronics and photonics. To demonstrate its feasibility, we performed a computational screening of candidate molecules that can selectively bind and therefore allow the deterministic assembly of molecular components. In the process, we unearthed trends and design principles applicable beyond the immediate scope of our proposed nanofabrication method, e.g., to biologically relevant DNA analogues and molecular recognition within hydrogen-bonded systems.

Trans-cinnamaldehyde fumigation inhibits Escherichia coli by affecting the mechanism of intracellular biological macromolecules

This study aimed to determine the antibacterial mechanism of cinnamaldehyde fumigation in Escherichia coli (E. coli). Through vapour fumigation, cinnamaldehyde was confirmed to exhibit effective antibacterial activity against E. coli. The minimum inhibitory concentration (MIC) and minimum bacterial concentration (MBC) were 0.25 μL/mL and 0.5 μL/mL, respectively. Based on transmission electron microscopy, the wrinkled bacterial cells observed after fumigation could be related to the leakage of intracellular substances. Laser tweezers Raman spectroscopy revealed changes in the main chain of proteins, the hydrogen bond system and spatial structure, and single- and double-stranded DNA breaks. In addition, breakage of the fatty acyl chain backbone was found to affect the vertical order degree of the lipid bilayer and cell membrane fluidity, thereby inhibiting the growth of E. coli. Overall, our findings indicate that cinnamaldehyde fumigation inhibits E. coli growth by inducing changes in intracellular biological macromolecules.

Reaction Pathways of Water Dimer Following Single Ionization.

Water dimer (H2O)2─a vital component of the earth's atmosphere─is an important prototypical hydrogen-bonded system. It provides direct insights into fundamental chemical and biochemical processes, e.g., proton transfer and ionic supramolecular dynamics, occurring in astro- and atmospheric chemistry. Exploiting a purified molecular beam of water dimer and multimass ion imaging, we report the simultaneous detection of all generated ion products of (H2O)2+ fragmentation following single ionization. Detailed information about ion yields and reaction energetics of 13 ion-radical pathways, 6 of which are new, of (H2O)2+ are presented, including strong 18O-isotope effects.

The local state of hydrogen atoms and proton transfer in the crystal structure of natural berborite, Be2(BO3)(OH)‧H2O: Low-temperature single crystal X-ray analysis, IR and 1H NMR spectroscopy, and crystal chemistry and structural complexity of beryllium borates

Beryllium borates are mostly water-free, with the natural mineral berborite, Be2(BO3)(OH)‧H2O, being the only known exception. A sample of berborite from the Vevja quarry, Tvedalen, Larvik, Norway was studied by single-crystal X-ray diffraction, variable temperature 1H nuclear magnetic resonance (NMR), and infrared (IR) spectroscopy. The crystal structure is the trigonal 1T-polytype with space group P321 and is based on electroneutral [BeØ2(BΔO3)]-layers formed by BeO3Ø-tetrahedra and BΔO3-triangles. Due to statistical occupancy of the Ø-ligand by hydroxyl groups (50%) and water molecules (50%), berborite-1T and its related polytypes are characterized by complex systems of hydrogen bonds. Accurate analysis shows that in the structure of berborite there are two independent systems of hydrogen bonds involving mobile protons. Lowering of temperature results in the complete stabilization of protons at the critical “freezing-point” of 243 K. The crystal chemistry and complexity of layered beryllium borates are discussed. Despite the broad structural diversity of these compounds, their crystal structures are classified as simple (20–100 bits per unit cell) or intermediately complex (100–500 bits per unit cell). The complexity of berborite polytypes increases in accordance with the quantity of layers from 29.038 (1T) to 78.077 (2H), which is in good agreement with the negative contribution of complexity to the configurational entropy.

Host-Guest Technique for Designing Highly Energetic Compounds with the Nitroamino Group.

A new energetic material, 2-azido-4,7-nitroamino-1H-imidazo[4,5-d]pyridazine (ANIP) with a highly sensitive azido group and its host-guest compounds (ANIP/H2O and ANIP/H2O2), and energetic salts were obtained. With the guest and protons in host molecules, an abundant hydrogen bond system can be formed. This results in high crystal density and good sensitivity, which suggests that the host-guest strategy is a promising way to balance the contradiction between energy and sensitivity and provides a new path to obtain a new generation of high energetic materials.

Diffusion Monte Carlo method for barrier heights of multiple proton exchanges and complexation energies in small water, ammonia, and hydrogen fluoride clusters.

Proton exchange reactions are of key importance in many processes in water. However, it is nontrivial to achieve reliable barrier heights for multiple proton exchanges and complexation energies in hydrogen-bonded systems theoretically. Performance of the fixed-node diffusion quantum Monte Carlo (FN-DMC) with the single-Slater-Jastrow trial wavefunction on total energies, barrier heights of multiple proton exchanges, and complexation energies of small water, ammonia, and hydrogen fluoride clusters is investigated in this study. Effects of basis sets and those of locality approximation (LA), T-move approximation (T-move), and determinant localization approximation (DLA) schemes in dealing with the nonlocal part of pseudopotentials on FN-DMC results are evaluated. According to our results, diffuse basis functions are important in achieving reliable barrier heights and complexation energies with FN-DMC, although the cardinal number of the basis set is more important than diffuse basis functions on total energies of these systems. Our results also show that the time step bias with DLA and LA is smaller than T-move; however, the time step bias of DMC energies with respect to time steps using the T-move is roughly linear up to 0.06a.u., while this is not the case with LA and DLA. Barrier heights and complexation energies with FN-DMC using these three schemes are always within chemical accuracy. Taking into account the fact that T-move and DLA are typically more stable than LA, FN-DMC calculations with the T-move or DLA scheme and basis sets containing diffuse basis functions are suggested for barrier heights of multiple proton exchanges and complexation energies of hydrogen-bonded clusters.

Composition and structure of tungsten antimony acid

Tungsten antimony acids (TAA) with the composition H(2)Sb(2)WXO6·nH2O (0 < x ≤ 1.45; 0 < n ≤ 2.0) have been synthesized by hydrolysis of antimony trichloride pre-oxidized with nitric acid in the presence of varying amounts of Na2WO4. To obtain TAA protonated forms, the samples were kept in a 96% solution of sulphuric acid, the precipitate was washed until reaction became neutral and dried in air. The amount of tungsten, antimony, and silver ions in TAA was determined using energy dispersive analysis. Changes in structural parameters upon doping of AA with tungsten ions were studied using a Bruker D8 ADVANCE X-ray diffractometer (CuKa1-radiation). The number of oxonium ions in TAA was determined by the substitutionof these ions by silver ions in equivalent amounts (Ag+-TAA forms). All obtained TAA samples and Ag+ TAA forms had a pyrochlore-type structure, space group symmetry Fd3m. Refinement of the arrangement of atoms in the structure using the Rietveld method showed that tungsten ions replace antimony ions and are statistically located in 16c, oxygen anions in 48f, and oxonium ions and water molecules in 16d and 8b positions, respectively. When tungsten ions were introduced into samples, the structural parameters of the resulting phases changed. There was a decrease in the unit cell parameter and the distance between antimony ions and oxygen anions, while an increase in the distance between oxonium ions and oxygen anions located in 48f positions was observed. This allowed the removal of a proton from oxonium molecules and its transport via a system of hydrogen bonds formed by water molecules