High-resolution 1H and 13C NMR of solid 2-Aminobenzoic acid

Three crystalline modifications of 2-aminobenzoic acid (anthranilic acid) have been studied by ¹³C CP/MAS and ¹H CRAMPS NMR. The peaks are assigned and discussed in relation to (a) the neutral or zwitterionic nature of the molecules, (b) the crystal structures, known for two of the polymorphs, (c) residual (N,C) dipolar splittings, (d) hydrogen bonding and (e) dynamic exchange. The value of applying both types of spectroscopy to such studies is stressed.     

In situ solid-state 1H NMR studies of hydration of the solid acid catalyst ZSM-5 in its ammonium form

Hydration of the ammonium form of the solid acid catalyst ZSM-5 is investigated by applying a technique that has been developed recently for carrying out in situ solid-state NMR studies of adsorption processes. From ¹H MAS NMR spectra recorded as a function of time and temperature during the hydration process, insights are established on the nature of the interaction between the adsorbed water molecules and the ammonium cations in the ZSM-5 material. The change in isotropic chemical shift for the ammonium cations is consistent with the formation of N–H?O hydrogen bonding with the water molecules. Studies of the adsorption of deuterated water, and dehydration of the hydrated material, are also reported.     

Some CNDO Calculations and Structural Spectroscopic Studies of Paracetamol Complexes

Through complete neglect of differential overlap (CNDO) calculations of the electronic energy among different possible structures of paracetamol (PA) molecule, it has been concluded that its structure has C_s point group symmetry of the cis‐form in which the methyl group has a restricted free rotation around its bond with the carbon atom of the amide group. The electronic spectra of PA compound were studied in different polar and nonpolar solvents. The temperature effect on the electronic spectra confirms the presence of one conformer only. The hydrogen bonding and the orientation energies of the polar solvents were determined from the studies of mixed solvents. Complexes of PA with metal ions M(II) (Cu⁺⁺, Zn⁺⁺, or Fe⁺⁺) of ratio 2:1, respectively, were prepared, and their structure has been confirmed by elemental analysis, atomic absorption spectra, IR spectra, and ¹H‐NMR spectra. It has been concluded that the structure of the complexes has C_2h point group symmetry in which two PA molecules are chelated to any one of the metal ions Cu⁺⁺, Zn⁺⁺, and Fe⁺⁺.     

Particular features of the ν(OH) absorption band of strongly hydrogen-bonded complexes in the gas phase,low-temperature matrices,and crystalline films at 12–600 K

The particular features of the ν(OH) absorption band of dimers with a strong hydrogen bond (ΔH = 24–50 kcal/mol = 8000–17000 cm^?1/molecule) formed by molecules of phosphinic acids R₂POOH N₂ are studied in the gas phase, low-temperature argon and nitrogen matrices, and crystalline films. It is found that, irrespective of the type of the acid, the ν(OH) IR absorption bands of dimers are broad (Δν_1/2 ～ 1000 cm^?1) and similar in shape, exhibiting a characteristic ABC structure. The formation of these anomalously broad absorption bands is shown to be primarily associated with vibrations of the ?POOH fragments, participating in the hydrogen bonding. A change in the temperature in the range 12–600 K and the passage from cyclic dimers in the gas phase to helical chains with hydrogen bonds in the crystalline state cause no significant changes in the shape, width, or structure of the dimer band. The contribution to the formation of the broad absorption band of the (R₂POOH)₂ dimers made by anharmonic interactions between the high-frequency ν(OH) vibration and the low-frequency intermolecular vibrations is estimated. The absorption spectra of weak complexes R₂POOH...N₂ in matrices at 12 K are discussed.     

A theoretical and experimental 1H NMR spectroscopy study of the stereoelectronic interactions that rule the conformational energies of alanine and valine methyl ester

Amino acids exhibit a bipolar zwitterionic structure (⁺H₃N‐CHR‐COO^?) in solution; hence, conformational studies of these compounds have been limited to the gas phase. The conformational preferences of amino acids have been widely attributed to intramolecular hydrogen bonding, despite steric and hyperconjugative effects. In this work, we propose the conformational study of alanine and valine methyl esters, which do not show zwitterionic structures in solution, by¹H NMR and theoretical calculations. The ³J_HH spin–spin coupling constants and theoretical calculations were found to be in agreement, showing that the interplay between steric hindrance and hyperconjugation is the forces that are responsible for determining the conformational preferences of alanine and valine methyl esters. Copyright © 2013 John Wiley & Sons, Ltd.     

Mesomorphic and optical properties of undoped and doped azomethines

Three calamitic azomethines were prepared by the condensation of the benzene-1,4-dicarboxaldehyde with the three aliphatic amines (LCOA1–LCOA3). The structures of the azomethines were characterized by means of FTIR, ¹H, ¹³C NMR spectroscopies and elemental analysis; the results showed an agreement with the proposed structure. The azomethines emitted blue or green light. An influence of n-decyl sulfonic acid (DSA) on mesomorphic behaviors, absorption and emission wavelengths was investigated. The liquid crystalline properties of the azomethines were studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and wide and small angle X-ray diffraction (WAXS and SAXS). The mesomorphic properties of the compounds depend on both the length of the outer flexible spacers and the kind of connection between the alkyl groups and the imine group, i.e. directly via aliphatic chain or by phenyl ring. LCOA1–LCOA2 exhibited smectic and nematic phases, whereas the LCOA3 did not exhibit thermotropic liquid crystal properties. Basing on the comparison of thermal behaviors and optoelectronic properties of undoped (LCOAX) and doped (LCOAX/DSA) azomethines it was shown that ionic self-organized processes are powerful and are able to tune: i) the processability, ii) the LC behavior, and iii) the maximum of emission band of the synthesized azomethines.     

Numerical simulation of water vapor nucleation on electrically neutral nanoparticles

Atomic-level Monte Carlo simulations are performed to calculate the free energy, entropy, and work of nucleation for clusters of more than 6 × 10³ water molecules growing on silver iodide crystalline particles of size up to 4 nm at a temperature of 260 K. The Hamiltonian of the system includes explicit expressions for hydrogen bonding energy and Coulomb, dispersion, exchange, and polarization interactions. The work of nucleation exhibits complex behavior depending on the nucleation-site size. With increasing nanoparticle size, clusters become less stable and the probability of crystallization increases. Mutual polarization enhances the bonding between a cluster and a crystalline particle. Cluster growth on relatively large nanoparticles involves two stages characterized by two critical sizes: monolayer growth on the surface and growth normal to the surface. Spontaneous microdroplet polarization involving domain formation is found to occur at the crystal surface. The dependence of the ice-forming activity of an aerosol on particulate size observed in experiments is explained by combined effects of several competing factors, the dominant ones being the stabilizing and destabilizing effects of the nanoparticle electric field.     

原子氢、氘钝化以及质子注入掺杂硅的红外吸收

用FTIR研究了原子氢、原子氘钝化掺硼硅以及质子注入掺杂单晶硅,当原子氘钝化条件不同时分别产生了1360cm^-1和1263cm^-1的[BD]对局域振动模红外吸收带,这表明氘在单晶硅的硼受主邻近有两种可能的状态。质子注入掺杂硅的红外吸收光谱与不掺杂硅的明显不同,氢原子优先结合于硼的附近,注入氢仅约1%生成光效的缺陷,而绝大部份生成无光效的中心,它们可能是氢分子。 关键词：     

Spatial Structure of the Decapeptide Val-Ile-Lys-Lys-Ser-Thr-Ala-Leu-Leu-Gly in Water and in a Complex with Sodium Dodecyl Sulfate Micelles

We have studied the spatial structure of the decapeptide Val-Ile-Lys-Lys-Ser-Thr-Ala-Leu-Leu-Gly in aqueous solution and in a complex with sodium dodecyl sulfate (SDS) micelles by ¹H nuclear magnetic resonance (NMR) spectroscopy and two-dimensional (2-D) NMR spectroscopy (total correlation spectroscopy and nuclear Overhauser effect spectroscopy (NOESY)). The approach used to determine the decapeptide spatial structure was based on analysis of the ¹H?C¹³C residual dipolar couplings in the molecules partially aligned in lyotropic liquid crystalline media. Analysis of the interproton distances obtained from the 2-D NOESY NMR spectrum was used to reveal the spatial structure of the decapeptide in a complex with SDS micelles. Complex formation was confirmed by analysis of ¹H chemical shifts in the NMR spectrum of the decapeptide and analysis of the signs and values of NOEs in a solution with SDS micelles.     

Proton and Carbon - 13 NMR Assignments for Fluorinated and Nonfluorinated Aromatic Ketimines

The ¹H and ¹³C NMR spectra of three aromatic ketimines with varying degrees of fluoro substitution have been extensively studied using one and two dimensional techniques. COSY experiments were conducted to identify the protons on each of the aromatic groups, HETCORR experiments were then utilized to identify the corresponding carbon atoms, and then the order of the carbon atoms was established by long-range HETCORR (HRTCORRLR) results. These studies have allowed rigorous assignments to be made for most of the carbon and hydrogen atoms present in these compounds. Fluorine splittings were very helpful in the analyses. In the course of this study, the NMR absorbances (¹H and ¹³C) of related aldimines have also been assigned. This constitutes the first report on the assignments of ¹H and ¹³C absorbances for ketimines. The observed spectral properties suggest that the structure of aromatic ketimines is one in which the aromatic rings are in three different planes. Two of the aromatic rings, the N-substituted ring and the C-substituted ring in the cis configuration, are twisted substantially out of the plane with respect to the -C=N- bond. The remaining C-substituted aromatic ring, trans to the N-substituted ring, lies in the deshielding zone of the imine bond.     

NMR and EPR Study of the Nitroxide Radical Tempo Interaction with Phenols

The 2,2,6,6-tetramethyl-I-piperidinyloxy free radical (TEMPO) was used as a probe to study the changes in hydrogen bonding between the phenolic OH group and the ON group of the radical by means of NMR and EPR. ¹³C NMR contact shifts induced by TEMPO were measured for five phenols. Formation of intermolecular hydrogen bond between a phenol and TEMPO molecule causes noticeable increase of ¹⁴N hyperfme coupling constant in the radical and appearance of negative spin density on carbon nuclei of C-OH fragment in the phenol.     

Radical-Recombination Luminescence of the Uranyl Nitrate Complex in the Adsorbed State

We have investigated the luminescence of uranyl nitrate molecules on the surface of powdery SiO₂ upon excitation by UV light (PhL) and hydrogen atoms (radical-recombination luminescence (RRL)). It has been found that the PhL and RRL spectra have a clearly defined vibrational structure. The luminescence peaks of the adsorbed UO₂ ^2– ion are characterized by a systematic longwave shift from the same peaks of crystalline uranyl nitrate (by 230–430 cm^–1 at 130 K). Moreover, in the adsorption centers the vibration frequencies of UO₂ ^2– are 20–80 cm smaller than in crystalline salt and the RRL bands are 150–350 cm^–1 (130 K) wider than the corresponding PhL bands.     

Investigation of cation–anion interaction in 1‐(2‐hydroxyethyl)‐3‐methylimidazolium‐based ion pairs by density functional theory calculations and experiments

Gas‐phase structure, hydrogen bonding, and cation–anion interactions of a series of 1‐(2‐hydroxyethyl)‐3‐methylimidazolium ([HOEMIm]⁺)‐based ionic liquids (hereafter called hydroxyl ILs) with different anions (X = [NTf₂]^–, [PF₆]^–, [ClO₄]^–, [BF₄]^–, [DCA]^–, [NO₃]^–, [AC]^– and [Cl]^–), as well as 1‐ethyl‐3‐methylimizolium ([EMIm]⁺)‐based ionic liquids (hereafter called nonhydroxyl ILs), were investigated by density functional theory calculations and experiments. Electrostatic potential surfaces and optimized structures of isolated ions, and ion pairs of all ILs have been obtained through calculations at the Becke, three‐parameter, Lee–Yang–Parr/6‐31 + G(d,p) level and their hydrogen bonding behavior was further studied by the polarity and Kamlet–Taft Parameters, and ¹H‐NMR analysis. In [EMIm]⁺‐based nonhydroxyl ILs, hydrogen bonding preferred to be formed between anions and C2–H on the imidazolium ring, while in [HOEMIm]⁺‐based hydroxyl ILs, it was replaced by a much stronger one that preferably formed between anions and OH. The O–H···X hydrogen bonding is much more anion‐dependent than the C2–H···X, and it is weakened when the anion is changed from [AC]^– to [NTf₂]^–. The different interaction between [HOEMIm]⁺ and variable anion involving O–H···X hydrogen bonding resulted in significant effect on their bulk phase properties such as ¹H‐NMR shift, polarity and hydrogen‐bond donor ability (acidity, α). Copyright © 2011 John Wiley & Sons, Ltd.     

Hydrogen bonding in homochiral dimers of hydroxyesters studied by Raman optical activity spectroscopy

Spectroscopic analysis of homochiral dimerization is important for the understanding of the homochirality of life and enantioselective catalysis. In this paper, (S)‐methyl lactate and related molecules were studied to provide detailed structural information on hydrogen bonding in homochiral dimers of chiral α‐hydroxyesters through the experimental and theoretical study of Raman optical activity. Different homochiral dimers can be distinguished by comparing their simulated Raman optical activity spectra with the experimental results. Hydrogen bonding motions are decoded with the aid of vibrational motion analysis, which are apparently involved in vibrational motions below 800 cm^–1. A common feature related to the chain‐bending mode also indicates the absolute configuration of methyl lactate and related molecules. The differing behavior of electric dipole–electric quadrupole invariants (β(A)²) compared with the electric dipole–magnetic dipole invariant (β(G′)²), suggests that the intermolecular hydrogen bonding motion behaves differently from the intramolecular one in the asymmetric molecular electric and magnetic fields. These results may help understand hydrogen‐bonded self‐recognition and other dynamical features in chiral recognition. Copyright © 2011 John Wiley & Sons, Ltd.     

Inter‐ and intramolecular hydrogen bonds in polyamines: variable‐concentration 1H‐NMR studies

Inter‐ and intramolecular hydrogen bonding play an important role in determining the arrangement, physical properties, and reactivity of a great diversity of structures in chemical and biological systems. Several aromatic nucleophilic substitutions (ANS) in nonpolar aprotic, (non‐HBD), solvents recently studied in our laboratory have demonstrated the importance of self‐association of amines by hydrogen‐bond interactions. In this paper, we describe ¹H‐NMR studies carried out at room temperature on bi‐ and polyfunctionalized amines, namely: N‐(3‐amino‐1‐propyl)morpholine (3‐APMo), histamine, 2‐guanidinobenzimidazole (2‐GB), 1,2‐diaminoethane (EDA), 3‐dimethylamino‐l‐propylamine (DMPA), and 1‐(2‐aminoethyl)piperidine (2‐AEPip). By ¹H‐NMR measurements of amine solutions at variable concentrations we have shown that 3‐APMo, histamine and 2‐GB are able to form a six‐membered ring by intramolecular hydrogen bonding, while EDA, DMPA, and 2‐AEPip form dimers by intermolecular hydrogen bonds. Likewise, variable concentration ¹H‐NMR studies allowed estimation of the corresponding equilibrium constants for the dimerization. These results are correlated with experimental kinetic results of ANS, confirming hereto the relevance of the “dimer mechanism” in reactions involving these amines. Copyright © 2011 John Wiley & Sons, Ltd.     

Melting of Naphthalene Confined in Mesoporous Silica MCM-41

The ²H nuclear magnetic resonance (NMR) solid-echo spectra of naphthalene molecules as guests in the mesopores of neat MCM-41 with a pore width of 3.3 nm were measured in the temperature regime from 180 to 250 K. A strong reduction of the melting point of the naphthalene molecules by 152 K is observed. The line shape changes in the melting region were simulated with two different models, namely, the model of a narrow distribution of activation energies, which is typical for a crystal-like phase, and a two-phase model. Both models indicate a relatively narrow distribution of melting points of the naphthalene molecules inside the pores, indicative of a rather well-defined structure of the naphthalene molecules inside the pores. This finding supports the proposal of a plastic crystalline phase previously proposed by other groups.     

H and C NMR studies of molecular orientation and dynamics in liquid crystal 6BA

The dynamics and orientation of dimers accompanying the formation and destruction of hydrogen bonds in the nematic phases of 4-n-hexylbenzoic acid (6BA) were studied by ¹³C and ²H NMR. The orientational order parameter S in the nematic phase was estimated from the quadrupole splitting of the ²H NMR spectrum. The intermolecular interaction energy for the molecular order in the nematic phase decreased with increasing temperature. The flexibility of dimers due to the destruction of the hydrogen bond is closely related to a decrease in the intermolecular interaction energy. The proportion of ²H NMR spin-lattice relaxation time (T₁) to S, which reveals the coupling of the orientational fluctuations with the hydrogen bonding processes, was observed.     

Solid state C NMR analysis of human gallstones from cancer and benign gall bladder diseases

Natural abundance ¹³C cross polarized (CP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) analysis of human gall bladder stones collected from patients suffering from malignant and benign gall bladder disease was carried out which revealed different polymorphs of cholesterol in these stones. All gall bladder stones in present study had cholesterol as their main constituent. ¹³C CP-MAS NMR analysis revealed three forms of cholesterol molecules in these stones, which are anhydrous form, monohydrate crystalline with amorphous form and monohydrate crystalline form. Our study revealed that stones collected from patients associated with chronic cholecystitis (CC) disease have mostly different polymorph of cholesterol than stones collected from patients associated with gall bladder cancer (GBC). Such study will be helpful in understanding the mechanism of formation of gallstones which are associated with different gall bladder diseases. This is the first study by solid state NMR revealing different crystal polymorphism of cholesterol in human gallstones, extending the applicability of ¹³C CP-MAS NMR technique for the routine study of gallstones.     

Hydrogen bonding in different pyrimidine–methanol clusters probed by polarized Raman spectroscopy and DFT calculations

We report on the hydrogen bonding between pyrimidine (Pd) and methanol (M) as H‐donor in this study. Hydrogen bonds between pyrimidine and methanol molecules as well as those between different methanol molecules significantly influence the spectral features at high dilution. The ring‐breathing mode ν₁ of the reference system Pd was chosen as a marker band to probe the degree of hydrogen bonding. Polarized Raman spectra in the region 970–1020 cm⁻¹ for binary mixtures of (pyrimidine + methanol) at 28 different mole fractions were recorded. A Raman line shape analysis of the isotropic Raman line profiles at all concentrations revealed three distinct spectral components at mole fractions of Pd below 0.75. The three components are attributed to three distinct groups of species: ‘free Pd’ (pd), ‘Pd with low methanol content’ (pd1) and ‘Pd with high‐methanol content’ (pd2). The two latter species differ considerably in the pattern and the strengths of the hydrogen bonds. The results of density functional theory calculations on structures and vibrational spectra of neat Pd and eight Pd/M complexes with varying methanol content support our interpretations of the experimental results. A nice spectra–structure correlation for the different cluster subgroups was obtained, similar to earlier results obtained for Pd and water. Apart from N···H and O···H hydrogen bonds between pyrimidine and methanol, O···H hydrogen bonds formed among the methanol molecules in the cluster at high methanol content also play a crucial role in the interpretation of the experimental results. Copyright © 2010 John Wiley & Sons, Ltd.     

On structural and spectroscopic differences between quinoline‐2‐carboxamides and their N‐oxides in the solution and solid state

Intramolecular hydrogen bonding in the primarily and secondarily substituted quinoline‐2‐carboxamides and their N‐oxides has been studied in the solution by multinuclear NMR spectroscopy. Hydrogen bonding patterns and supramolecular arrangement in the solid state have been determined by single crystal X‐ray analysis. In quinoline‐2‐carboxamides weak, nonlinear intramolecular N? H…N hydrogen bond is present, but in the solid state the intermolecular hydrogen bonds and packing forces are the factors that decide on the properties of 3D structures. In quinoline‐2‐carboxamide N‐oxides the most important structural features are the intramolecular hydrogen bonds. Details of different weak interactions and resulting 3D arrangement of molecules are discussed. In the solution, two separate ¹H signals are observed for the primary quinoline‐2‐carboxamides in the range from ca. 5.8 to 8.1 ppm. The chemical shifts of the NH group's proton for studied R′‐quinoline‐2‐R‐carboxamides are in the range from 8.1 to 8.4 ppm. For the N‐oxide of 4‐R′‐quinoline‐2‐carboxamides (R′ = H, Me, OPh, Cl and Br), the values of the proton chemical shifts of the NH group in the range from 10.78 to 11.38 ppm (for primary amides) indicating that this group forms hydrogen bonds with the oxygen of the N‐oxide group. This bond is stronger than the N? H…N bond in quinoline‐2‐carboxamides. For the secondary amide N‐oxides, the δ(NH) values are increasing from 11.25 to 11.77 ppm in the sequence of substituents 4‐Br < 4‐Cl < 4‐H < 4‐Me < 4‐OPh. For 4‐substituted compounds these values depend also on the substituent effect. Copyright © 2009 John Wiley & Sons, Ltd.