Strong Hydrogen-bonding Interactions Research Articles

Highly Enantioselective 6π Photoelectrocyclizations Engineered by Hydrogen Bonding.

Photochemical electrocyclization reactions are valued for both their ability to produce structurally complex molecules and their central role in elucidating fundamental mechanistic principles of photochemistry. We present herein a highly enantioselective 6π photoelectrocyclization catalyzed by a chiral Ir(III) photosensitizer. This transformation was successfully realized by engineering a strong hydrogen-bonding interaction between a pyrazole moiety on the catalyst and a basic imidazolyl ketone on the substrate. To shed light on the origin of stereoinduction, we conducted a comprehensive investigation combining experimental and computational mechanistic studies. Results from density functional theory calculations underscore the crucial role played by the prochirality and the torquoselectivity in the electrocyclization process as well as the steric demand in the subsequent [1,4]-H shift step. Our findings not only offer valuable guidance for developing chiral photocatalysts but also serve as a significant reference for achieving high levels of enantioselectivity in the 6π photoelectrocyclization reaction.

Constructing a novel humidity sensor using acrylic acid/bagasse cellulose porous hydrogel combining graphene oxide and citral for antibacterial and intelligent fruit preservation

A novel hydrogel humidity sensor was developed using acrylic acid/bagasse cellulose (AA/BC) porous hydrogel triggered by cold plasma (CP) combining graphene oxide (GO) and embedding citral for antibacterial and intelligent fruit preservation. Results showed that both GO and citral were loaded in AA/BC and had strong hydrogen bond interaction with hydrogel. Acrylic acid/bagasse cellulose/graphene oxide (AA/BC/GO) showed the highest humidity response when the compound concentration of GO was 1.0 mg/mL and the test frequency was 1 kHz, and exhibited high electrical conductivity (−2.6 mS/cm). In addition, in continuous and cyclic relative humidity (RH) tests, the response time of AA/BC/GO from 33.70 % RH to 75.30 % RH was about 177.4 s and the recovery time was about 150.6 s, with excellent sensitivity and durability. The sensors also revealed remarkable antibacterial properties against Escherichia coli and Staphylococcus aureus, among which acrylic acid/bagasse cellulose/graphene oxide-citral (AA/BC/GO-C) was the most prominent, and could extend the shelf life of mangoes for about 8 days. By intuitively judging the appearances and total color difference (TCD) of the hydrogel sensors, it could play the role of intelligent preservation by connecting their water absorption and the release of citral. Therefore, this work provided innovative strategies for the application of hydrogel sensors in food preservation.

Achieving color-tunable persistent afterglow from ultralong polyacrylamide-based room-temperature phosphorescence materials through phosphorescence Förster resonance energy transfer

Polymer-based pure organic room-temperature phosphorescence (RTP) materials have received widespread attention due to their great application prospects in many fields. However, the reports about polymer-based multicolor RTP materials were still rare. Herein, a series of monochromatic PAM-based RTP materials are constructed by facilely doping boric acid derivatives into polyacrylamide (PAM) matrices. Due to the strong intermolecular hydrogen-bonding interaction, 4-carboxyphenylboronic acid (CPBA) doped system PAM/CPBA achieves an ultralong RTP lifetime of 753 ms with a naked-eye visible blue afterglow up to 12 s. Significantly, PAM/CPBA as energy donor and the commercial fluorescent dye fluorescein (FL) or rhodamine B (RhB) as energy acceptor are used to fabricated ternary doping systems to achieve multicolor afterglow emission through phosphorescence Förster resonance energy transfer (FRET). The afterglow colors of PAM/CPBA/FL and PAM/CPBA/RhB can be easily adjusted from blue to yellow or purple by changing the doping content of FL or RhB. Inspiringly, a nearly white afterglow emission from the quaternary doping system PAM/CPBA/RhB/FL is achieved by varying the amount of FL content. Furthermore, the prepared PAM-based binary and ternary doping RTP materials can be applied in the field of information encryption.

Enhancing interfacial bonding between the copper foil and poly-ether-ether-ketone film via dual modification using UV/ozone and silane coupling

In this study, copper foil and poly-ether-ether-ketone (PEEK) film were directly bonded using nanosecond lasers. To strengthen the interfacial bonding between the copper foil and PEEK, ultraviolet/ozone (UV/ozone) and silane coupling treatment (APTMS) methods were proposed to modify the surface of the copper foil. The UV/ozone treatment led to the oxidation of the surface of the copper foil to Cu2O. The bonding interface and fracture were characterized and analyzed via optical digital microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The Cu/PEEK joints demonstrated a 95 % improvement in peel strength following UV/ozone + silane coupling treatments. Additionally, the red shift of the typical functional group wavenumbers demonstrated a strong hydrogen bond interaction between the copper foil treated with UV/ozone + silane coupling and the PEEK film. The mechanism behind the superior peel strength of UV/ozone + ATPMS-Cu/PEEK joints was subsequently validated through the density functional theory (DFT) analysis. Moreover, DFT was utilized to calculate the differential charge transfer and binding energies of Cu/silanol and Cu2O/silanol. As per the results, the bonding of Cu2O to silanol was more stable than that of Cu to silanol.

GO enhanced Gel Polymer Electrolyte for Aqueous Zinc Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) assembled with gel polymer electrolyte (GPE) have gained great popularity due to their low cost and safety. Nevertheless, the extensive utilization of GPE based AZIBs is hindered by various challenges, such as inadequate conductivity, limited mechanical strength, and unstable electrochemical properties. Herein, through the multiple cross-linking reaction of sodium alginate (SA), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) and graphene oxide (GO), a GPE with high conductivity and excellent mechanical property was prepared. GO formed strong hydrogen-bonding interaction with polymers to build a three-dimensional network structure for ion migration and improved the mechanical property of GPE. The prepared GPE showed high ionic conductivity of 2.89×10-3 S cm-1 and excellent tensile strength of 900 kPa. In addition, the assembled Zn-Li hybrid batteryprovided a discharge specificcapacity retention rate of 67.6% and a Coulombic efficiency (CE) of approximate 100% after 1000 cycles at 1 C.

Reconstruction of Cellulose Intermolecular Interactions from Hydrogen Bonds to Dynamic Covalent Networks Enables a Thermo-processable Cellulosic Plastic with Tunable Strength and Toughness.

Its excellent renewability and biodegradability make cellulose an attractive resource to prepare fossil-based plastic alternatives. However, cellulose itself exhibits strong intermolecular hydrogen bond (H-bond) interactions, significantly restricting the mobility of cellulose chains, thus leading to poor thermo-processing performance. Here, we reconstructed the intermolecular interactions of cellulose chains via replacing the original H-bonds with dynamic covalent bonds. By this, cellulose can be easily thermo-processed into a cellulosic plastic under mild conditions (70 °C). Through adjusting the chemical structure of dynamic covalent networks, the cellulosic plastic shows tunable mechanical strength (3.0-33.5 MPa) and toughness (43-321 kJ m-2). The cellulosic plastic also exhibits excellent resistance to water, organic solvent, acid solution, alkali solution, and high temperature (>400 °C). Moreover, it owns good chemical and biological degradability and recyclability. This work provides an effective method to develop high-performance cellulosic plastics for fossil-based plastic substitution.

Enhancing gel behavior of yellow croaker surimi by fruit extracts: Physicochemical properties and molecular mechanism.

The aim of this study was to investigate the effects of grape seed extract (GSE), acerola cherry extract (ACE), and blueberry extract (BBE) on the physicochemical properties and structure of the yellow croaker surimi gel. In addition, molecular docking and molecular dynamics (MD) simulation were utilized to study the binding mechanism of yellow croaker's fibrillin and fruit extracts. Surimi gel with 1.5% GSE, ACE, and BBE had the highest water holding capacity, hardness, chewability, cohesion, breaking force, breaking distance, gel strength, and densest 3D network structure, according to the experiment's findings. Nevertheless, the cross-linking of proteins in surimi was blocked with the further increase of fruit extract (1.5%-2.0%), and the existing network of surimi was weakened or even destroyed. Three fruit extracts had little effect on the secondary structure of the surimi gel. Besides, hydrophobic and disulfide bonds are the main chemical bonds of croaker surimi. Molecular docking showed that B-type procyanidine (BP) interacted with ASN-183, SER-571, ASP-525, ARG-350, LYS-188, GLU-349, CYS-353, and other active amino acids in croaker protein. Moreover, it can form strong hydrogen bond interaction with ASN-183, SER-571, ASP-525, and ARG-350 at the active sites of protein. The BP-Larimichthys crocea protein system's MD simulation was carried out, and calculations for the simulation's root mean square deviation, root mean square fluctuation, radius of gyration, solvent accessible surface area, and hydrogen bonds were made. It was found that these indices can demonstrate that the BP binding contributes to the stability of the yellow croaker structure.

Interaction between ultrasound-modified pectin and icaritin.

Pectin can improve the bioaccessibility of icaritin as a nanocarrier, and ultrasound can modify the pectin structure. However, the interaction between ultrasound-modified pectin (UMP) and icaritin remains unclearly. In this work, the effects of UMP on the physiochemical properties of icaritin/pectin micelles (IPMs) were investigated. The IPMs prepared with UMP (UMP-IPMs) showed lower encapsulation efficiencies and loading capacities, comparing with native IPMs. UMP-IPMs had smaller particle sizes (325-399nm) than native IPMs (551nm). The Mw, viscosity, G' and G" of pectin were determined. NMR spectra indicated that the repeating unit in pectins remained consistently before and after ultrasound treatment, and 7-OH of icaritin was involved in hydrogen bond formation with pectin. The larger chemical shift movement of 6-H and 7-OH for U3-IPMs than P0-IPMs suggested that stronger hydrogen bond interaction between icaritin and pectin. UMP-IPMs exhibited stronger anti-proliferation activities against HepG2 cells than native IPMs.

A strong, biodegradable, and closed-loop recyclable bamboo-based plastic substitute enabled by polyimine covalent adaptable networks

Environmental pollution caused by nondegradable fossil-based plastics is one of the biggest global concerns. Bamboo, which is a renewable and biodegradable biomass resource, is a promising material for developing green plastic substitutes. However, the processing (e.g., thermal processing) of bamboo into plastic substitutes remains a considerable challenge because bamboo is a stable multicomponent structure crosslinked via strong hydrogen bond (H-bond) and covalent-bond interactions, which results in its non-thermoplastic characteristic. Herein, bamboo powders (BPs) were integrated into polyimine (PI) covalent adaptable networks (CANs) using a simple heat-pressing approach, which helped us successfully fabricate a thermally processable composite film (BP/PI). The heat-driven dynamic network exchange characteristic of PI also provides BP/PI with excellent reshaping, rehealing, and remolding capabilities. The multiple H-bond interactions between BPs and PI provide BP/PI with excellent tensile strength (45.2 MPa) and flexural strength (121.9 MPa). BP/PI also exhibits remarkable water and organic solvent resistance, chemical degradability, closed-loop recyclability, and biodegradability. This attractive BP/PI material represents a high-performance and ecofriendly plastic substitute.

Crystal structure and supramolecular features of a bis-urea-functionalized pillar[5]arene

The crystal structure of a bis-urea derivative based on A1/A2-functionalized pillar[5]arene (DUP) that encapsulates dimethyl formamide (DMF) inside the macrocyclic cavity is reported. The crystal structure of DUP·DMF, C63H70N4O12·C3H7NO, reveals that out of two urea functionalized spacers, one arm is oriented above the macrocyclic cavity with strong hydrogen-bonding interactions between the urea H atoms and DMF guest, whereas, the other arm is positioned away from the macrocycle, leading to intermolecular hydrogen-bonding interactions between the urea H atoms of two adjacent pillar[5]arene macrocycles, resulting in the formation of a supramolecular dimer.

Elucidating the hydrotropism behaviour of aqueous caffeine and sodium benzoate solution through NMR and neutron total scattering analysis

Hydrotropism is a convenient way to increase the solubility of drugs by up to several orders of magnitude, and even though it has been researched for decades with both experimental and simulation methods, its mechanism is still unknown. Here, we use caffeine/sodium benzoate (CAF-SB) as model system to explore the behaviour of caffeine solubility enhancement in water through NMR spectroscopy and neutron total scattering. 1H NMR shows strong interaction between caffeine and sodium benzoate in water. Neutron total scattering combined with empirical potential structure refinement, a systematic method to study the solution structure, reveals π-stacking between caffeine and the benzoate anion as well as Coulombic interactions with the sodium cation. The strongest hydrogen bond interaction in the system is between benzoate and water, which help dissolve CAF-SB complex and increase the solubility of CAF in water. Besides, the stronger interaction between CAF and water and the distortion of water structure are further mechanisms of the CAF solubility enhancement. It is likely that the variety of mechanisms for hydrotropism shown in this system can be found for other hydrotropes, and NMR spectroscopy and neutron total scattering can be used as complementary techniques to generate a holistic picture of hydrotropic solutions.

Understanding the influence of ethylene glycol on the microscopic behavior of imidazolium-based monocationic and dicationic ionic liquid

In the present work, the influence of a molecular co-solvent, ethylene glycol (EG) on the microscopic behaviour of an imidazolium-based dicationic ionic liquid (DIL) is analysed by employing time-resolved fluorescence anisotropy (TRFA) and nuclear magnetic resonance (NMR) spectroscopic techniques. In order to have a clear understanding of the specific role of DIL, a mono-cationic ionic liquid (MIL) containing an alkyl side chain unit, same as the alkyl spacer chain length of DIL, has also been investigated. The rotational diffusion of two fluorescent probes 9-PA and R110 have been carried out in both neat MIL and DIL and their mixtures with various fractions of EG. The analysis of the results has demonstrated that, within the studied concentration range, the microstructure of MIL encompassing both polar and nonpolar domains gets disrupted as the mole fraction of EG increases. However, a similar investigation in DIL has revealed that the micro-structure of DIL gets affected slightly when similar proportions of EG are added to DIL. This behaviour of DIL is attributed to the enhanced rigidity of the DIL structure due to its folded structural arrangements. Furthermore, NMR studies have provided additional insights into the interactions between the components of ILs and the added solvent. It has been observed that EG can form strong hydrogen-bonding interactions with the imidazolium-ring and alkyl chain protons of MIL. However, such interaction has not been observed in DIL. Moreover, the translational diffusion coefficient (Dt) value for the cationic moiety of both MIL and DIL, measured through NMR, has depicted that in the presence of EG, the change in Dtvalue is much higher for MIL than that for DIL. Overall, the outcome of the combined fluorescence and NMR studies have pointed out that the behaviour of DIL and MIL in the presence of a co-solvent is very different from one another and thus the individual mixture (IL+solvent) can be used for various targeted industrial applications.

Achiral Sm(III)-Based Metal-Organic Framework as a Luminescence Sensor for Enantiodiscrimination of Quinine and Quinidine.

The effective discrimination and determination of the chiral antimalarial drugs quinine (QN) and quinidine (QD) are extremely important for human health. Herein, a 2D achiral Sm-based metal-organic framework (IMU-MOF1 = [Sm(tpba)(L)]n, where Htpba = 4-(2,2':6″,2'-terpyridin)-4'-ylbenzioc acid and H2L = 2,2'-biquinoline-4,4'-dicarboxylic acid) was successfully prepared by the solvothermal method. More importantly, IMU-MOF1 was designed as an ultrasensitive fluorescent probe for the identification of chiral enantiomer drugs. The limits of detection for QN and QD are 4.24 × 10-11 and 7.54 × 10-12 M, respectively. Furthermore, it was demonstrated that the stronger hydrogen-bonding interactions between IMU-MOF1 and quinine furnish a more efficient energy transfer to the ligands in the sensing process, resulting in a significant fluorescence enhancement of IMU-MOF1.

Supramolecular interactions in some organic hydrated 2,4,6-triaminopyrimidinium carboxylate and sulfate salts.

Four salts, namely, 2,4,6-triaminopyrimidinium 6-chloronicotinate dihydrate, C4H8N5+·C6H3ClNO2-·2H2O, (I), 2,4,6-triaminopyrimidinediium pyridine-2,6-dicarboxylate dihydrate, C4H9N52+·C7H3NO42-·2H2O, (II), 2,4,6-triaminopyrimidinediium sulfate monohydrate, C4H9N52+·SO42-·H2O, (III), and 2,4,6-triaminopyrimidinium 3,5-dinitrobenzoate dihydrate, C4H8N5+·C7H3N2O6-·2H2O, (IV), were synthesized and characterized by X-ray diffraction techniques. Proton transfer from the corresponding acid to the pyrimidine base has occurred in all four crystal structures. Of the four salts, two [(I) and (IV)] exist as monoprotonated bases and two [(II) and (III)] exist as diprotonated bases. In all four crystal structures, the acid interacts with the pyrimidine base through N-H...O hydrogen bonds, generating an R22(8) ring motif. The sulfate group mimics the role of the carboxylate anions. The water molecules present in compounds (I)-(IV) form water-mediated large ring motifs. The formation of water-mediated interactions in these crystal structures can be used as a model in the study of the hydration of nucleobases. Water molecules play an important role in building supramolecular structures. In addition to these strong hydrogen-bonding interactions, some of the crystal structures are further enriched by aromatic π-π stacking interactions [(I) and (II)].

Novel quinazoline-chromene hybrids as anticancer agents: Synthesis, biological activity, molecular docking, dynamics and ADME studies.

In this study, new quinazoline-chromene hybrid compounds were synthesized. The cytotoxic effects on cell viability of the hybrid compounds were tested against A549 human lung adenocarcinoma and BEAS-2B healthy bronchial epithelial cell lines in vitro. In addition, the ability of the active compounds to inhibit cell migration was tested. Molecular docking studies were performed to evaluate the ligand-protein interactions, and molecular dynamics simulations were performed to determine the interactions and stability of ligand-protein complexes. In silico absorption, distribution, metabolism, and excretion (ADME) studies were conducted to estimate the drug-likeness of the compounds. Compounds 4 (IC50 = 51.2 µM) and 5 (IC50 = 44.2 µM) were found to be the most active agents against A549 cells. They are found to be more selective against A549 cells than the reference drug doxorubicin. They also have the ability to significantly inhibit cell migration. They have the best docking scores against epidermal growth factor receptor (EGFR) (-11.300 and -11.226 kcal/mol) and vascular endothelial growth factor receptor 2 (VEGFR2) (-10.987 and -11.247 kcal/mol), respectively. In MD simulations, compounds 4 and 5 have strong hydrogen bond interactions above 80% of simulation times and showed a low ligand root mean square deviation (RMSD) around 2 Å. According to the ADME analysis, compounds 4 and 5 exhibit excellent drug-likeness and pharmacokinetic characteristics.

Enhanced stability and catalytic performance of laccase immobilized on magnetic graphene oxide modified with ionic liquids

Graphite oxide (GO) is an excellent laccase immobilization material. However, the electrostatic interaction between graphene leads to the accumulation of GO, as well as the interaction with the surface of enzyme molecules causing protein denaturation and deactivation, which limits its further industrial application. In this study, the ionic liquids (ILs) modification strategy was proposed to improve the stability and catalytic performance of immobilized laccase. The laccase-ILs-MGO exhibited remarkable enzymatic properties, with significant enhancements in organic solvent tolerance, thermal and operational stability. The laccase-ILs-MGO system exhibited a remarkable removal efficiency of 95.5% towards 2,4-dichlorophenol (2,4-DCP) within 12 h and maintained over 70.0% removal efficiency after seven reaction cycles. In addition, the efficient elimination of other phenolic compounds and recalcitrant polycyclic aromatic hydrocarbons could also be accomplished. Molecular dynamics simulation and molecular docking studies demonstrated that immobilized laccase exhibited superior structural rigidity and stronger hydrogen bond interactions with substrates compared to free laccase, which was beneficial for the stability of both the laccase and substrate degradation efficiency. Therefore, this study proposed a simple and practical strategy for modifying GO with ILs, providing novel insights into developing efficient enzyme immobilization techniques.

Green preparation of β-chitins from squid pens by using alkaline deep eutectic solvents

Based on the assumption that protein could be removed by the combined mechanism of alkaline induced degradation and strong hydrogen bond interactions of deep eutectic solvents (DESs), β-chitins were successfully prepared from squid pens by using alkaline DESs formed by potassium carbonate and glycerol. The chemical structures of the DESs were investigated by 1H nuclear magnetic resonance (1H NMR), attenuated total reflection Fourier transform infrared (ATR-FTIR) and molecular modeling, and the physicochemical property of the prepared β-chitins were characterized. The preparation yields was about 32 %, and DESs with K2CO3/glycerol of 1/10 could be reused for three times while maintaining high preparation yields (31 %–32 %) and degree of deacetylation of 66.9 %–76.9 %. The mechanisms of deproteinization and demineralization by the alkaline DESs were proposed to follow the degradation and dissolution steps, and proteins and minerals were removed from squid pens through the synergistic actions of alkaline degradation and hydrogen bonding interactions. This alkaline DESs are promising to be used as a green and efficient approach for commercial production of β-chitin.

Structural Studies of Monounsaturated and ω-3 Polyunsaturated Free Fatty Acids in Solution with the Combined Use οf NMR and DFT Calculations-Comparison with the Liquid State.

Molecular structures, in chloroform and DMSO solution, of the free fatty acids (FFAs) caproleic acid, oleic acid, α-linolenic acid, eicosapentanoic acid (EPA) and docosahexaenoic acid (DHA) are reported with the combined use of NMR and DFT calculations. Variable temperature and concentration chemical shifts of the COOH protons, transient 1D NOE experiments and DFT calculations demonstrate the major contribution of low molecular weight aggregates of dimerized fatty acids through intermolecular hydrogen bond interactions of the carboxylic groups, with parallel and antiparallel interdigitated structures even at the low concentration of 20 mM in CDCl3. For the dimeric DHA, a structural model of an intermolecular hydrogen bond through carboxylic groups and an intermolecular hydrogen bond between the carboxylic group of one molecule and the ω-3 double bond of a second molecule is shown to play a role. In DMSO-d6 solution, NMR and DFT studies show that the carboxylic groups form strong intermolecular hydrogen bond interactions with a single discrete solvation molecule of DMSO. These solvation species form parallel and antiparallel interdigitated structures of low molecular weight, as in chloroform solution. This structural motif, therefore, is an intrinsic property of the FFAs, which is not strongly affected by the length and degree of unsaturation of the chain and the hydrogen bond ability of the solvent.

Roles of specific hydrogen-bonding interactions in the crystallization kinetics of polymers

Polyamides hold specific hydrogen-bonding interactions as the hierarchical thermodynamic driving forces for crystallization. Their roles in crystallization kinetics are worthy of further investigation. We performed dynamic Monte Carlo simulations to compare crystallization kinetics among 16-mer melts holding hydrogen-bonding interactions with variable strengths specifically assigned to 2, 4 and 8 monomers on the chain, respectively. The results demonstrate higher densities and strengths of hydrogen-bonding interactions generally accelerating the cooling and isothermal crystallization as well as the lateral growth of lamellar crystals, consistent with the experimental observations of polyamide crystallization. Too strong hydrogen-bonding interactions will slow down polymer diffusion and thus bring retardation to crystallization kinetics. Furthermore, hydrogen-bonding interactions at the central 8–9 monomers make higher crystal growth rates than those at the evenly distributed 5–12 monomers, demonstrating the dominant roles of specific interactions in the hierarchical parallel packing of polymer chains at the lateral growth front of lamellar crystals.

Effects of non-specific and specific solvation on structure of tripropylammonium-based protic ionic liquids: Insight from computational modeling

To explore the structure of three protic ionic liquids based on tripropylammonium cation and anions of strong acids – methanesulfonic, sulfuric, and triflic acids – we employed different computational methods, including quantum chemical calculations and molecular dynamics simulations. Solvation effects (non-specific and specific) were considered in order to evaluate the applicability of the methods used for the description of the ionic liquid’s structure. In each of the ionic liquids, we identified the cation–anion pair where a strong hydrogen bond and coulombic interactions kept the ions together. The results of both gas phase and implicit solvation calculations show an increase in the strength of the hydrogen bond and the magnitude of the ion-ion interaction energy in the ion pairs with tripropylammonium cation in the order of anions: triflate < hydrogen sulfate < mesylate, but the absolute values become smaller when going from the gas phase to the continuum medium. The molecular dynamics simulations reveal that the cation–anion pairs are preserved in the bulk phase of these liquids, but besides this, the formation of hydrogen bonds between anions in the tripropylammonium hydrogen sulfate is also possible.