Hydrogen-bonded OH Research Articles

Temperature-dependent vibrational energy relaxation of hydrogen-bonded and free OD groups at the air-water interface.

Water interfaces play a crucial role in regulating interactions and energy flow. Vibrational sum-frequency generation (vSFG) spectroscopy provides structural and dynamic information on water molecules at interfaces. It has revealed, for instance, the presence of the hydrogen-bonded and free OH groups at the air-water interface. Here, using temperature-dependent, time-resolved vSFG, we focus on the vibrational energy relaxation dynamics of interfacial heavy water (D2O). We reveal that while the relaxation timescale for hydrogen-bonded OD stretch modes is temperature-independent, the lifetime of the free OD stretch mode decreases with increasing temperature. Our data, supported by simulations, suggest that both intramolecular energy transfer and rotational reorientation mechanisms jointly contribute to the energy relaxation process of the free OD, with temperature influencing these mechanisms differently.

One-Step Organic Synthesis of 18β-Glycyrrhetinic Acid-Anthraquinone Ester Products: Exploration of Antibacterial Activity and Structure-Activity Relationship, Toxicity Evaluation in Zebrafish.

To combine the activity characteristics of 18β-glycyrrhetinic acid (18β-GA) and anthraquinone compounds (rhein and emodin), reduce toxicity, and explore the structure-activity relationship (SAR) of anthraquinones, 18β-GA-anthraquinone ester compounds were synthesized by one-step organic synthesis. The products were separated and purified by HPLC and characterized by NMR and EI-MS. It was finally determined as di-18β-GA-3-rhein ester (1, New), GA dimer (2, known), 18β-GA-3-emodin ester (3, known), and di-18β-GA-1-emodin ester (4, new). The MIC of three reactants and four products against Escherichia coli and Staphylococcus aureus were detected invitro. Its developmental toxicity and cardiotoxicity were assessed using zebrafish embryos. The experimental results showed that rhein had the best antibacterial activity against Staphylococcus aureus with MIC50 of 2.4 mM, and it was speculated that -COOH, -OH, and intramolecular hydrogen bonds in anthraquinone compounds would enhance the antibacterial effect, while the presence of-CH3 might weaken the antibacterial activity. Product 1 increased the hatching rate and survival rate of zebrafish embryos and reduced the malformation rate and cardiomyocyte apoptosis. This experiment lays the foundation for further studying the SAR of anthraquinones and providing new drug candidates.

Ultra-fast fabrication of MXene/PVA composite films through glutaraldehyde induced microgel framework

In this study, Ti3C2Tx/PVA microgels were assembled through the introduction of glutaraldehyde and PVA into Ti3C2Tx colloids. Subsequently, the microgels underwent vacuum-assisted filtration (VAF) and drying processes to fabricate Ti3C2Tx/PVA self-assembled films (MPGF). This research effectively reduced VAF time by introducing a small amount of glutaraldehyde. The findings demonstrate that glutaraldehyde's chemical crosslinking prompts the formation of temporary microgel frameworks between Ti3C2Tx and PVA, enhancing water molecule transfer during VAF and improving film formation efficiency. Further analysis links VAF time is related to the particle size distribution of the microgels. Adjusting crosslinking and PVA quantity alters microgel crystalline structure and –OH hydrogen bonds, affecting particle size and VAF time. Additionally, films produced via rapid VAF exhibit promising mechanical properties for practical applications.

Dispersion Control over Molecule Cohesion: Exploiting and Dissecting the Tipping Power of Aromatic Rings.

ConspectusWe have learned over the past years how London dispersion forces can be effectively used to influence or even qualitatively tip the structure of aggregates and the conformation of single molecules. This happens despite the fact that single dispersion contacts are much weaker than competing polar forces. It is a classical case of strength by numbers, with the importance of London dispersion forces scaling with the system size. Knowledge about the tipping points, however difficult to attain, is necessary for a rational design of intermolecular forces. One requires a careful assessment of the competing interactions, either by sensitive spectroscopic techniques for the study of the isolated molecules and aggregates or by theoretical approaches. Of particular interest are the systems close to the tipping point, when dispersion interactions barely outweigh or approach the strength of the other interactions. Such subtle cases are important milestones for a scale-up to realistic multi-interaction situations encountered in the fields of life and materials science. In searching for examples that provide ideal competing interactions in complexes and small clusters, aromatic systems can offer a diverse set of molecules with a variation of dispersion and electrostatic forces that control the dominant and peripheral interactions. Our combined spectroscopic and theoretical investigations provide valuable insights into the balance of intermolecular forces because they typically allow us to switch the aromatic substituent on and off. High-resolution rotational spectroscopy serves as a benchmark for molecular structures, as correct calculations should be based on correct geometries. When discussing the competition with other noncovalent interactions, obvious competitors are directional hydrogen bonds. As a second counterweight to aryl interactions, we will discuss aurophilic/metallophilic interactions, which also have a strong stabilization with a small number of atoms involved. Vibrational spectroscopy is most sensitive to interactions of light atoms, and the competition of OH hydrogen bonds with dispersion forces in a molecular aggregate can be judged well by the OH stretching frequency. Experiments in the gas phase are ideal for gauging the accuracy of quantum chemical predictions free of solvent forces. A tight collaboration utilizing these three methods allows experiment vs experiment vs theory benchmarking of the overall influence of dispersion in molecular structures and energetics.

Unified picture of vibrational relaxation of OH stretch at the air/water interface

The elucidation of the energy dissipation process is crucial for understanding various phenomena occurring in nature. Yet, the vibrational relaxation and its timescale at the water interface, where the hydrogen-bonding network is truncated, are not well understood and are still under debate. In the present study, we focus on the OH stretch of interfacial water at the air/water interface and investigate its vibrational relaxation by femtosecond time-resolved, heterodyne-detected vibrational sum-frequency generation (TR-HD-VSFG) spectroscopy. The temporal change of the vibrationally excited hydrogen-bonded (HB) OH stretch band (ν=1→2 transition) is measured, enabling us to determine reliable vibrational relaxation (T1) time. The T1 times obtained with direct excitations of HB OH stretch are 0.2-0.4 ps, which are similar to the T1 time in bulk water and do not noticeably change with the excitation frequency. It suggests that vibrational relaxation of the interfacial HB OH proceeds predominantly with the intramolecular relaxation mechanism as in the case of bulk water. The delayed rise and following decay of the excited-state HB OH band are observed with excitation of free OH stretch, indicating conversion from excited free OH to excited HB OH (~0.9 ps) followed by relaxation to low-frequency vibrations (~0.3 ps). This study provides a complete set of the T1 time of the interfacial OH stretch and presents a unified picture of its vibrational relaxation at the air/water interface.

Tuning electronic levels in photoactive hydroxylated titania nanosystems: combining the ligand dipole effect and quantum confinement.

Reducing the size of titania (TiO2) to the nanoscale promotes the photoactive anatase phase for use in a range of applications from industrial catalysis to environment remediation. The nanoscale dimensions of these systems affect the magnitude of the electronic energy gap by quantum confinement. Upon interaction with aqueous environments or water vapour, the surfaces of these systems will also be hydroxylated to some degree. In turn, this affects the electronic energy levels due to the cumulative electrostatic effect of the dipolar hydroxyl (-OH) ligands (i.e. the ligand dipole effect). Using accurate density functional calculations, we investigate the combined effects of quantum confinement and the hydration-induced ligand dipole effect on a set of realistic titania nanosystems over a wide range of hydroxylation. Our detailed investigation reveals that, contrary to previous models, the ligand dipole effect does not-linearly depend on the ligand coverage due to the formation of inter-ligand OH⋯OH hydrogen bonds. To account for the resulting effects, we propose a refined model, which describes the ligand dipole effect more accurately in our systems. We show that both hydroxylation (by the ligand dipole effect) and size (by quantum confinement) have significant but distinct impacts on the electronic energy levels in nanotitania. As an example, we discuss how variations in these effects can be used to tune the highest unoccupied energy level in nanotitania for enhancing the efficiency of the hydrogen evolution reaction. Overall, we show that any specific energy shift can be achieved by a range of different combinations of nanosystem size and degree of hydroxylation, thus providing options for energy-level tuning while also allowing consideration of practical constraints (e.g. synthetic limitations, operating conditions) for photochemical applications.

Concentration-dependence of specific rotation of optically active glycerol analogues and structurally related compounds: The significance of intermolecular hydrogen bonding

Specific rotation of optically active glycerol analogues, (S)-3-(benzyloxy)propane-1,2-diol [(S)-1], (S)-3-methoxypropane-1,2-diol [(S)-6] and (S)-3-phenoxypropane-1,2-diol [(S)-13], changed its sign from (+) to (–) with increasing concentration in CHCl3, whereas no significant concentration-dependent change was observed in MeOH. The 1H NMR spectrum of (S)-1 showed concentration-dependent changes of the chemical shift in CDCl3. Intermolecular interaction by OH⋯OH hydrogen bonds was suggested by single crystal X-ray crystallography of (S)-13. The concentration-dependent changes of specific rotation of (S)-1, (S)-6, and (S)-13 in CHCl3 can therefore be presumed to be due to self-assembly of these compounds via intermolecular hydrogen bonding at high concentration. The remarkable concentration-dependent changes in specific rotation were also observed to occur in the compounds with related chemical structures, such as (S)-3-hydroxy-4-methoxy-4-oxobutanoic acid [(S)-10], (S)-1-[(2-methylpropan-2-yl)oxycarbonyl]pyrrolidine-2-carboxylic acid [Boc-L-Pro-OH, (S)-14], (R)-3-hydroxy-4,4-dimethylhydrofran-2(3H)-one [(R)-15], (R)-tetrahydrofuran-2-carboxylic acid [(R)-16], (S)-3-methyl-2-[(2-methylpropan-2-yl)oxycarbonylamino]butanoic acid [Boc-L-Val-OH, (S)-17], (R)-oxiran-2-ylmethanol [(R)-18], and (4S)-4-isopropyloxazolidin-2-one [(S)-19]. The existence of intermolecular interaction by C=O⋯HO hydrogen bonds was suggested by single crystal X-ray crystallography of (S)-10, (S)-13, and (S)-14. Thus, this series of chiral compounds have multiple functional groups in appropriate positions that serve as hydrogen-bond donors and/or acceptors, resulting in significant concentration-dependent changes of specific rotation.

Lateral diffusion of ions near membrane surface.

Biological membranes isolate living cells from their environment, while allowing selective molecular transport between the inner and outer realms. For example, Na+ and K+ permeability through ionic channels contributes to neural conduction. Whether the ionic currents arise directly from cations in the bulk, or from the interface, is currently unclear. There are only scant results concerning lateral diffusion of ions on aquated membrane surfaces (and strong belief that this occurs through binding to a diffusing lipid). We performed classical molecular dynamics (MD) simulations of monovalent ions, Na+, K+, and Cl-, near the surface of the zwitterionic palmitoyl-oleoyl-phosphatidylcholine (POPC) membrane. Realistic force-fields for lipids (Amber's Lipid17 and Lipid21) and water (TIP4P-Ew) are tested for the mass and charge densities and the electrostatic potential across the membrane. These calculations reveal that the chloride can bind to the choline moiety through an intervening water molecule by forming a CH⋯OH hydrogen bond, while cations bind to both the phosphatic and carbonyl oxygens of phosphatidylcholine moieties. Upon transitioning from the bulk to the interface, a cation sheds some of its hydration water, which are replaced by headgroup atoms. Notably, an interfacial cation can bind 1-4 headgroup atoms, which is a key to understanding its surface hopping mechanism. We find that cation binding to three headgroup atoms immobilizes it, while binding to four energizes it. Consequently, the lateral cation diffusion rate is only 15-25 times slower than in the bulk, and 4-5 times faster than lipid self-diffusion. K+ diffusion is notably more anomalous than Na+, switching from sub- to super-diffusion after about 2 ns.

Insight into the Binding of Argon to Cyclic Water Clusters from Symmetry-Adapted Perturbation Theory.

This work systematically examines the interactions between a single argon atom and the edges and faces of cyclic H2O clusters containing three-five water molecules (Ar(H2O)n=3-5). Full geometry optimizations and subsequent harmonic vibrational frequency computations were performed using MP2 with a triple-ζ correlation consistent basis set augmented with diffuse functions on the heavy atoms (cc-pVTZ for H and aug-cc-pVTZ for O and Ar; denoted as haTZ). Optimized structures and harmonic vibrational frequencies were also obtained with the two-body-many-body (2b:Mb) and three-body-many-body (3b:Mb) techniques; here, high-level CCSD(T) computations capture up through the two-body or three-body contributions from the many-body expansion, respectively, while less demanding MP2 computations recover all higher-order contributions. Five unique stationary points have been identified in which Ar binds to the cyclic water trimer, along with four for (H2O)4 and three for (H2O)5. To the best of our knowledge, eleven of these twelve structures have been characterized here for the first time. Ar consistently binds more strongly to the faces than the edges of the cyclic (H2O)n clusters, by as much as a factor of two. The 3b:Mb electronic energies computed with the haTZ basis set indicate that Ar binds to the faces of the water clusters by at least 3 kJ mol-1 and by nearly 6 kJ mol-1 for one Ar(H2O)5 complex. An analysis of the interaction energies for the different binding motifs based on symmetry-adapted perturbation theory (SAPT) indicates that dispersion interactions are primarily responsible for the observed trends. The binding of a single Ar atom to a face of these cyclic water clusters can induce perturbations to the harmonic vibrational frequencies on the order of 5 cm-1 for some hydrogen-bonded OH stretching frequencies.

Theoretical Study of the Two-Dimensional Vibrational Sum Frequency Generation Spectroscopy of the Air-Water Interface at Varying Temperature and Its Connections to the Interfacial Structure and Dynamics.

We performed a theoretical study of the temperature variation of two-dimensional vibrational sum frequency generation (2D-VSFG) spectra of the OH stretch modes at air-water interfaces in the mid-IR region. The calculations are performed at four different temperatures from 250 to 325 K by using a combination of techniques involving response function formalism of nonlinear spectroscopy, electronic structure calculations, and molecular dynamics simulations. Also, the calculations are performed for isotopically dilute solutions so that the intra- and intermolecular coupling between the vibrational modes of interest can be ignored. We have established the connections of temperature variation of various frequency- and time-dependent features of the calculated spectra to the changes in the underlying structure and dynamics of the interfaces. The results reveal that interfacial water is dynamically more heterogeneous than bulk water, with three dominant dynamical processes exhibiting their corresponding time-dependent features in the 2D-VSFG spectrum. These are the spectral diffusion of hydrogen-bonded OH groups at the interface, conversion of an initially hydrogen-bonded OH group to a dangling OH which is a stable state for surface water, unlike the bulk water, and the third one, which involves the conversion of an initially free or dangling OH group to its hydrogen-bonded state at the interface. The temporal appearance of the cross peaks corresponding to interconversion of the hydrogen-bonded state to the dangling state or vice versa of an interfacial OH group is found to take place at a slower rate than the dynamics of spectral diffusion of hydrogen-bonded molecules at the interface, which, in turn, is slower than the corresponding spectral diffusion of bulk water molecules. The temperature variation of these dynamic processes can be linked to the decay of appropriate hydrogen-bond and non-hydrogen-bond time correlation functions of interfacial water molecules for the different air-water systems studied in this work.

Metal coordination in polymer drives efficient phonon transfer through self-assembled microstructures

Molecular interactions such as hydrogen bond, van der Waals force, covalent bond in association with heat transfer in polymeric materials have been reported, while the relationship between metal-polymer coordination and thermal conduction has not been studied yet. In this work, the molecularly-assembled microstructure of the composites produced by metal coordination with polyvinyl alcohol (PVA) reveals a qualitative correlation between microstructure and thermal conductivity (TC). The ellipsoid-shaped domain and increased coil size create stable phonon transmission channels, which are beneficial for boosting TC by lengthening the mean free path of phonon propagation. Strong coordination between the metal ions and the hydroxyl groups in the polyvinyl alcohol chains results in competition between the inter- and intra-molecular OH–OH hydrogen bonds, which eventually takes precedence. Such coordination structure creates distinctive micro-crystal domains and is discovered to be essential for TC enhancement. Moreover, the power generation value of thermal conversion using PVA-H/2.0Fe(NO3)3 film is twice that of pure PVA-H film, which has higher and faster conversion efficiency. These materials have been demonstrated as excellent candidates for improving the conversion efficiency of thermoelectric devices. In summary, this work offers a new strategy for regulating TC through metal coordination and a fundamental comprehension of the link between metal coordination, microstructure, and TC in polymer composites.

Study of the Graphene Oxide Nanosheets Synthesized from Pencil Electrode Using Electrochemical Method and Solar Energy as a Source of Power

Graphene Oxide nanosheets were synthesized using electrochemical exfoliation of pencil electrodes in aqueous solution containing 2% of magnesium sulfate salt. A solar panel of 20V was used as a power supply to turn the synthesis into a green method. Several measurements were carried out to investigate the product, namely: Raman scattering, X-ray diffraction, photoluminescence, UV-VIS-NIR spectroscopy, and FTIR spectroscopy. Raman scattering showed the existence of both D-band and G-band, which are an indication of graphene oxide existence. The D-to-G band ratio was 1.5. The results of X-ray showed a diffraction peak at 2θ = 20.7° corresponding to the space distance between graphene oxide nanosheets and a diffraction peak at 2θ = 26.25° corresponding to the short range interplanar spacing. Photoluminescence showed two peaks of emission (at wavelengths 355nm & 701nm) regarding to the π-π* transition. UV-VIS-NIR spectroscopy exhibited a 4.2eV photon energy absorption peak corresponding to the aromatic C=C bonds and 5.4eV photon energy absorption peak corresponding to the carbonyl groups. FTIR showed peaks related to hydroxyl groups, hydrogen-bonded OH groups of COOH, and functional groups such as C-OH (1375 cm-1), and C-O (1039 cm-1). FTIR results approved that graphene oxide nanosheets are functionalized. TEM images show that the synthesized graphene oxide is single-, double-, and multi-layer stacks with an amount of impurities.

Understanding solvent effects on solvatomorphisms of donepezil-maleic acid

The aim of this work is to investigate the action of solvents in the preparation of donepezil-maleic acid. Five forms of donepezil-maleic acid, including: anhydrous donepezil-maleic acid (DM), donepezil-maleic acid-acetone (DM-A), donepezil-maleic acid-ethyl acetate (DM-EA), donepezil−maleic acid-ethanol (DM-E) and donepezil-maleic acid-water (DM-W), were prepared by mechanochemistry. The crystal structures of the four solvates were determined by single crystal X-ray diffraction, and structure analysis showed that solvents without OH hydrogen bond donors (acetone and ethyl acetate) were weakly connected with donepezil-maleic acid only by atypical hydrogen bonds in the lattice, while solvents containing hydrogen bond donors (ethanol and water) provided strong intermolecular interactions to maintain the spatial structure. Furthermore, the desolvation process and stability of five forms were investigated by various analytical techniques including powder X-ray diffraction, differential scanning calorimetry and thermogravimetric analysis. In addition, the crystal transformation relationship of the mentioned forms was explored. The result showed that DM-W was the most stable form among the five forms, which was attributed to the strong hydrogen bonding network.

Construction of silsesquioxane and phosphinum‐based ionic porous hypercrosslinked polymers for efficient heterogeneous catalytic CO2 cycloaddition

AbstractIn this work, we reported a facile one‐pot route to construct polyhedral oligomeric silsesquioxane (POSS) and phosphonium‐based ionic porous hypercrosslinked polymers (denoted as P‐iPHCPs) with multiple catalytic active sites, which could be regarded as efficient heterogeneous catalysts for the conversion of carbon dioxide (CO2) to highly value‐added cyclic carbonates. The targeted polymers P‐iPHCPs were prepared from a rigid building block octavinylsilsesquioxane (VPOSS) and a low‐cost commercially available organic ionic salt methyltriphenylphosphonium bromide ([Ph3PMe]Br) by the AlCl3‐catalyzed Friedel‐Crafts reaction. The series of polymers P‐iPHCPs that synthesized by different molar ratios of VPOSS to [Ph3PMe]Br possess hierarchical micro/mesoporous structures with high surface areas ranging from 376 to 429 m2 g−1 and behave the flower‐like nano‐morphology. Especially, the desired multiple active sites involved the mixed anions including free Cl−, Br− anions and the in‐situ formed metal‐halogen complex anion [AlCl3Br]− within phosphonium segments, and the enriched POSS‐derived SiOH hydrogen bond donor (HBD) groups that derived from the breakage of POSS cages during the synthetic process. The typical polymer P‐iPHCP‐14 has the aforementioned nucleophilic‐electrophilic multiple catalytic active sites, which was regarded as an efficient recyclable heterogeneous catalyst for synergistic catalytic conversion of CO2 with various epoxides into cyclic carbonates under mild conditions.

Evolution of Solute-Water Interactions in the Benzaldehyde-(H2O)1-6 Clusters by Rotational Spectroscopy.

The investigation on the preferred arrangement and intermolecular interactions of gas phase solute-water clusters gives insights into the intermolecular potentials that govern the structure and dynamics of the aqueous solutions. Here, we report the investigation of hydrated coordination networks of benzaldehyde-(water)n (n = 1-6) clusters in a pulsed supersonic expansion using broadband rotational spectroscopy. Benzaldehyde (PhCHO) is the simplest aromatic aldehyde that involves both hydrophilic (CHO) and hydrophobic (phenyl ring) functional groups, which can mimic molecules of biological significance. For the n = 1-3 clusters, the water molecules are connected around the hydrophilic CHO moiety of benzaldehyde through a strong CO···HO hydrogen bond and weak CH···OH hydrogen bond(s). For the larger clusters, the spectra are consistent with the structures in which the water clusters are coordinated on the surface of PhCHO with both the hydrophilic CHO and hydrophobic phenyl ring groups being involved in the bonding interactions. The presence of benzaldehyde does not strongly interfere with the cyclic water tetramer and pentamer, which retain the same structure as in the pure water cluster. The book isomer instead of cage or prism isomers of the water hexamer is incorporated into the microsolvated cluster. The PhCHO molecule deviates from the planar structure upon sequential addition of water molecules. The PhCHO-(H2O)1-6 clusters may serve as a simple model system in understanding the solute-water interactions of biologically relevant molecules in an aqueous environment.

Copper(II) and zinc(II) complexes bridged by benzenoid aromatic oxocarbon and dicarboxylate dianions

A novel series of Cu(II) and Zn(II) complexes were constructed through the bridging croconate (C5O5)2−, squarate (C4O4)2− and 2,5-pyridine-dicarboxylate (Py2,5-dc)2− dianions. These include pent- [Cu5(epdmpy)4(C5O5)2(H2O)6](ClO4)6‧12H2O (1) and tri-nuclear [Cu3(bepza)2(Py2,5-dc)2(ClO4)2(H2O)2]‧2H2O (4), dinuclear [Zn2(MeDPA)2(C4O4)(H2O)4](ClO4)2 (7), and 1-D- coordination polymers (CPs) catena-{[Cu2(bpzpy)2(C5O5)](ClO4)2‧MeOH} (2) and catena-{[Zn(4,4′-bipy)(H2O)4](C5O5)(H2O)} (6) as well as the mononuclear [Cu(HBph2,2′-dc)(pmdien)]ClO4 (5) have been synthesized and spectroscopically characterized as well as by single crystal X-ray crystallography. The reaction of aqueous solution Cu(ClO4)2, pymeea and C5O52− resulted in the unprecedently bis(oxalato) [Cu2(Pymeea)2(C2O4)(ClO4)2(H2O)2] (3). In these complexes, (C5O5)2−, squarate (C4O4)2− and (Py2,5-dc)2− ligands display a variety of coordination bonding modes. In complexes 1 and 2 the croconato is binding as 1,2-bidentate-3-monodentate but in addition 5-mono-dentate semi-coordinate bonding was detected for 2, whereas in 6 as counter dianion. The bonding mode in the squarato 7 was achieved through the trans μ1,3-mono-dentate. In the di-carboxylato compounds, only five-membered chelate ring was formed in 5via one of the carboxylate groups, whereas in 4 bridging was conducted through a mono-carboxylate and five-membered chelate ring including the second carboxylate and pyridyl nitrogen. In complexes 1–5 and 7, hydrogen bonds of type OH⋯O and/or NH⋯O are connecting the complex cations with the perchlorate anions/ligands to generate different dimensional supramolecular network structures, whereas in 6, the 3D network was formed through hydrogen bonding between the coordinated aqua and lattice water molecules. Non-covalent ring⋯ring interactions were also observed between pyridyl rings in complexes 1, 6 and 7, and between pyrazolyl rings as well as pyridyl ring in 2.

Steric hindrance affects interactions of poly(styrene–alt–DMHPMI) copolymer with strongly hydrogen-bond-accepting homopolymers

In this study, we synthesized the monomer N-(2,6-dimethylhydroxyphenyl)maleimide (DMHPMI) in three steps from 2,6-dimethylphenol and then reacted it with styrene through free radical copolymerization to prepare the alternating copolymer poly(styrene–alt–dimethylhydroxyphenylmaleimide) [poly(S–alt–DMHPMI)]. We used Fourier transform infrared (FTIR) spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and mass-analyzed laser desorption ionization/time-of-flight (MALDI-TOF) mass spectrometry to confirm its structure. Differential scanning calorimetry revealed that blends of the alternating copolymers poly(S–alt–DMHPMI) and poly(styrene–alt–(para–hydroxyphenylmaleimide)) [poly(S–alt–pHPMI)] with the Strongly Hydrogen-Bond-Accepting homopolymers poly(4-vinylpyridine) (P4VP) and polyvinylpyrrolidone (PVP) each exhibited single-value glass transition temperatures (Tg) over the entire compositional range, indicative of full miscibility. Nevertheless, a negative deviation from the linear rule occurred for the Tg behavior of the PS–alt–PHPMI/P4VP blends, due to the weak acidity of the HPMI units, while the intermolecular interactions of the PS–alt–PHPMI coplymers were also inhibited because of strong self-association of the PHPMI units. FTIR spectral analyses of the ratio of hydrogen-bonded OH and pyridyl groups confirmed this behavior. In contrast, slightly positive deviations from the linear rule occurred for the Tg behavior when blending poly(S–alt–DMHPMI) or poly(S–alt–pHPMI) with the PVP homopolymer; here, the intermolecular interactions of the poly(S–alt–DMHPMI)/PVP blends were weaker than those of the poly(S–alt–pHPMI)/PVP blends, due to the steric hindrance of the DMHPMI units being greater than that of the pHPMI units.

Computational study of electronic-vibrational spectrum of rotamers of 2-(2'-hydroxyphenyl)benzoxazole

UV-vis absorption spectrum of internally hydrogen-bonded enol structures of 2-(2'-hydroxyphenyl)benzoxazole is calculated for the transitions to the first excited state using the Franck-Condon approximation and harmonic model for vibrations. It is shown that the absorption spectrum of the structure with the hydrogen bond OH...O is shifted to larger energy by about 0.13 eV compared to the spectrum of the most stable structure with the hydrogen bond OH...N. The largest intensity of vibronic transitions to the first electronic state of the OH...O structure demonstrates high-frequency vibrations involving deformation mode of the oxazole ring, stretching of the both aromatic rings, and stretching of the bond linking the benzoxazole and phenyl moieties.

Ultra-high resolution near-infrared spectrum by wavelet packet transform revealing the hydrogen bond interactions

Resolution is always an obstacle to analyzing the fine structure of a spectrum. The problem is particularly serious in the analysis of the near-infrared (NIR) spectra of aqueous solutions, because the spectrum is generally composed of overlapping broad peaks making the understanding of the structures and the interactions notoriously difficult. In this work, wavelet packet transform (WPT) was adopted to enhance the resolution of the NIR spectra of aqueous mixtures. Due to the microscopic ability of WPT in both position and frequency, the fine details of a spectrum can be observed in the spectral components of different frequencies obtained by WPT decomposition. Ultra-high resolution spectrum can be obtained from the high-frequency component representing the spectral features. Spectral features of different hydrogen-bonded OH, as well as the OH in HOH and HOD, were identified from the high-resolution NIR spectra of water and heavy water mixtures and validated by the variation of the spectral intensity with the mole ratio of H2O and D2O. The high-resolution spectrum was further applied in analyzing the interaction of amine and water. The spectral features of the hydrogen bonding between CH/NH in tert-butylamine (TBA) and OH in water were observed. The structures of CH bonded to one water molecule, and the structures of NH connecting with one and two water molecules were identified.

FTIR-based study on the effect of deashing on the molecular structure of Hefeng sub-bituminous coal and its liquefaction residue

ABSTRACT Mineral presents an important effect on the structure and reactivity of coal, and deashing pretreatment is one of the most effective ways to remove mineral from coal. However, deashing pretreatment can change the molecular structure of coal, thus affecting its clean and efficient utilization. To understand the effect of deashing on the molecular structure of Hefeng coal (HF) and its liquefaction residue (LR), HF, LR, Hefeng deashed coal (HFAC), and its liquefaction residue (LRAC) were investigated by Fourier transform infrared spectroscopy (FTIR). Results showed that the deashing treatment could destroy the chemical structure of the coal, while the removal of mineral is not conducive to the liquefaction process of HF. After deashing treatment, the relative content of OH–π hydrogen bonds and self-associated –OH hydrogen bonds declined by 22.40% and 32.10%, respectively. For the aliphatic structure, the content of aliphatic –CH2 changed obviously, among which the asymmetric –CH2 reduced by 12.23%, while the symmetric –CH2 added by 15.27%. For the oxygen-containing functional groups, the carboxyl group increased by 118.95%, and the relative content of C–O group reduced by 49.35%. The 5-substitutions of benzene ring almost disappeared after the deashing process, and the 2-substitutions of benzene ring remarkably increased by 148%, which are predominant in the aromatic structure. After liquefaction, compared to HF, the characteristic peaks ascribed to hydroxyl structure, aliphatic structure, and C=O in LR almost vanished, while the intensity of these peaks in LRAC was stronger than that in LR. The relative content of 5- and 4-substitutions of benzene rings dropped by 33.9%, while the content of 2- and 3-substitutions of benzene rings were increased by 45.47% in LRAC. Structural parameters from functional groups indicated that the length of aliphatic chain was shortened in HFAC and LRAC, and the aromaticity and the condensation degree of aromatic ring were decreased.