Characterization of cyclotriveratrylene inclusion compounds by means of solid state13C NMR

Solid inclusion compounds of cyclotriveratrylene (CTV) with benzene, toluene, acetone, tetrahydrofuran, acetic acid and chloroform, as well as two hydrated forms, were prepared and characterized by solid state¹³C NMR. The inclusion process for CTV appears to be quite selective, and in some instance depends critically on the presence or absence of water. A number of different structural types are indicated by the solid state¹³C NMR splitting paterns. For the guests listed above,¹H NMR in solution indicated a guest to host ratio close to 0.5, except for chloroform, for which the ratio is closer to 2.     

NMR studies on solid cyclohexaamylose inclusion compounds

Orthorhombic inclusion compounds of cyclohexaamylose with methanol,n-propanol, acetic acid and water as guest molecules were studied using¹³C and²H NMR techniques.¹³C chemical shifts were correlated with structural data, whereas²H NMR lineshapes were used to derive information on guest molecule motions.Issued as NRCC No. 25568. Presented in part at the 2nd International Symposium on Clathrate Compounds and Molecular Inclusion Phenomena, Parma, Italy, 30 Aug.–3 Sept. 1982     

Colorimetric sensing of polyhydroxy compounds by an inclusion complex of boronic acid-modified amylose

A novel sensing method for polyhydroxy compounds has been established based on the stimuli-responsive inclusion complex of boronic acid-modified amylose with iodine. An aqueous solution containing the boronic acid-modified amylose and iodine was coloured bluish purple due to encapsulation of iodine within the helical cavity of amylose. When polyhydroxy compounds were added, the solution gradually lost its colour with increasing concentration of polyhydroxy compounds. This colour change was attributed to the dissociation of iodine from the amylose cavity in response to the polyhydroxy compounds. According to detailed examinations, it was concluded that the origin of the responsiveness is derived from an electrostatic repulsion between anionic boronate groups and iodine.     

Characterization of dextrin hydrogels by FTIR spectroscopy and solid state NMR spectroscopy

Fourier transform infrared (FTIR) and ¹³C solid state nuclear magnetic resonance (NMR) spectroscopy were used to study dextrin structural changes occurring upon hydrogel formation by vinyl acrylate (VA) grafting and subsequent free radical polymerization. The degrees of VA substitution (DS) and polymerization (DP) were quantified up to 40%VA by FTIR intensity measurements and partial least squares (PLS)/FTIR, the latter being a faster and less error-prone method. Above 40%VA, both parameters are underestimated by FTIR. A spin counting NMR experiment showed high carbon observabilities for hydrogels and improved PLS/NMR models were achieved for DS and DP determination. Alternative NMR integration methods are hindered by the broad VA peaks and need for area correction, due to their CP dynamics. NMR changes in C1 profile showed that a single helical conformation predominates at lower %VA, being replaced by disordered conformations as %VA increases. Furthermore, a correlation FTIR/NMR study indicated that ring conformations are significantly affected in hydrogels, compared to unpolymerized dextrin.     

Broadband rotational resonance in solid state NMR spectroscopy

A new technique for restoring nuclear magnetic dipole-dipole couplings under magic-angle spinning (MAS) in solid state nuclear magnetic resonance (NMR) spectroscopy is described and demonstrated. In this technique, called broadband rotational resonance (BroBaRR), the coupling between a pair of nuclear spins with NMR frequency difference close (but not necessarily equal) to the MAS frequency is restored by the application of a train of weak radio-frequency pulses at a carrier frequency close to the average of the two NMR frequencies. Phase or amplitude modulation of the pulse train at half the MAS frequency splits the carrier into sidebands close to the two NMR frequencies. The pulse train then removes offsets from the exact rotational resonance condition, leading to dipolar recoupling over a bandwidth controlled by the amplitude of the pulse train. (13)C NMR experiments on uniformly (15)N,(13)C-labeled L-valineHClH(2)O powder validate the theoretical analysis. BroBaRR will be useful in studies of molecular structures by solid state NMR, for example in the detection of long-range couplings between carbons in uniformly labeled organic and biological materials.     

Helix change of polypeptides in the solid state as studied by NMR spectroscopy

The conformational characterization of solid polypeptides has been carried out by means of high-resolution solid-state NMR. It has been demonstrated that high-resolution solid-state NMR spectroscopy is a very useful means for elucidating the structure of polypeptides and proteins in the solid state.     

Molecular dynamics and ordering of pyridine in its cyclophosphazene inclusion compound as evaluated by solid state 2H NMR spectroscopy

Variable temperature 2H NMR experiments (line shape analysis, relaxation studies) were carried out on the pyridine-d5-tris-(1,2-dioxyphenyl)-cyclotriphosphazene inclusion compound in the temperature range between 110-300 K. It is found that the pyridine guests are highly mobile throughout the whole temperature range covered here. The observation of three superimposed 2H NMR signals can be understood in terms of a particular (motionally averaged) orientation of the pyridine molecules, which is a consequence of the molecular symmetry of the pyridine guests and the imposed channel restrictions. The experimental data are consistent with a combined rotation on cone-small angle fluctuation model, which assumes a fast molecular reorientation between two superimposed cones with an opening angle for the inner cone between 59-73 degrees (angle of fluctuation between 1-3 degrees ). On the basis of this model assumption it is possible to reproduce both the experimental 2H NMR line shapes and the spin-lattice relaxation data in a quantitative way. The analysis of the partially relaxed spectra (inversion recovery experiments) yields the correlation times for this overall motional process. They follow an Arrhenius behavior from which an activation energy of 8.7 +/- 0.4 kJ mol(-1) is derived. The results are discussed in the framework of the published data for related systems.     

Fabrication of novel multilayered thin films based on inclusion complex formation between amylose derivatives and guest polymers

Novel types of layer-by-layer (LbL) assembly films were successfully fabricated onto a solid substrate through the inclusion complex formation between partially 2,3- O-methylated amyloses (MAs) and polytetrahydrofuran (PTHF). The formation of the LbL assembly films was confirmed by quartz crystal microbalance (QCM) analysis, atomic force microscopy (AFM) observation, and X-ray diffraction (XRD) measurement. The film formation was significantly affected by the methylation degree of amylose. When MAs with 8 and 20% methylation were used as hosts, the formation of LbL assembly films with PTHF was clearly observed. On the other hand, MAs with more than 33% methylation barely formed LbL assembly films with PTHF.     

Solid state analysis in mechanochemistry by high resolution 27Al solid state NMR spectroscopy

Modern solid state NMR techniques [one-dimensional magic angle spinning (MAS) and two-dimensional quadrupole nutation experiments with MAS] are applied for the characterization of mechanochemically activated inorganic powders such as hydrargillite [γ-Al(OH)₃] and pseudo-boehmite [synthetic γ-AlO(OH)]. The materials were activated in a vibration mill.     

Sensitive high resolution inverse detection NMR spectroscopy of proteins in the solid state

A new indirect detection scheme for obtaining (15)N/(1)H shift correlation spectra in crystalline proteins is described. Excellent water suppression is achieved without the need for pulsed field gradients, and using only a 2-step phase cycle. Careful attention to overall NMR instrument stability was found critical for obtaining the best resolution and sensitivity. Magnetic dilution by deuteration of the protein in combination with high-speed magic angle spinning produces (1)H resonances averaging only 0.22 ppm in width, and in some cases lines as narrow as 0.17 ppm are obtained. In application to two different polymorphs of ubiquitin, structure dependent differences in both (15)N and (1)H amide chemical shifts are observed. In one case, distinct shifts for different molecules in the asymmetric unit are seen, and all differ substantially from solution NMR shifts. A gain of 7 in sensitivity makes the method competitive with solution NMR as long as nanocrystalline samples are available.     

Solid state analysis in mechanochemistry by high resolution 27Al solid state NMR spectroscopy

Modern solid state NMR techniques [one-dimensional magic angle spinning (MAS) and two-dimensional quadrupole nutation experiments with MAS] are applied for the characterization of mechanochemically activated inorganic powders such as hydrargillite [-Al(OH)₃] and pseudo-boehmite [synthetic -AlO(OH)]. The materials were activated in a vibration mill.     

Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy

Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by¹³C and ¹⁵N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists.     

Preparation and physicochemical characterization of omeprazole:methyl-beta-cyclodextrin inclusion complex in solid state

In this work, we illustrate the usefulness of cyclodextrins, namely, methyl-β-cyclodextrin (MβCD), an amorphous, methylated derivative of the natural β-cyclodextrin (βCD), as a tool to form an inclusion complex with omeprazole (OME), a poorly water soluble drug. Solid binary systems between OME and MβCD were prepared experimentally in a stoichiometry 1:1 by different techniques (physical mixing, kneading, spray-drying and freeze-drying). Afterward these products were characterized by Fourier transformation-infrared spectroscopy (FTIR); X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The results obtained suggest that spray-drying and freeze-drying methods yield a higher degree of amorphous entities suggesting the formation of inclusion complexes between OME and MβCD.     

Structural studies of methyl brevifolincarboxylate in solid state by means of NMR spectroscopy and DFT calculations

Methyl brevifolincarboxylate isolated from the herb of Potentilla argentea L. (Rosaceae) is a representative of the naturally occurring polyphenols. The compound is of pharmaceutical interest mainly because of its antiviral and antioxidant properties. ¹³C NMR spectra were recorded for solution and solid phase. ¹³C CPMAS spectra were assigned by comparison with solution data, dipolar dephasing and short contact time experiments. The correctness of assignments was verified by GIAO DFT calculations of shielding constants. The differences between the solution and solid state chemical shift values were explained in terms of orientation of OH groups and intramolecular hydrogen bonds. The splitting of the C1O resonance shows that there exists a polymorphism in the solid phase, which might be due to the formation of intramolecular hydrogen bond involving carbonyl or methoxy oxygen (i.e. C10OH⋯OC or C10OH⋯OCH₃).     

Slow diffusion by singlet state NMR spectroscopy

Small diffusion coefficients can be measured by using populations of singlet states that have a relaxation time constant, T(s), which can be much longer than the longitudinal relaxation time, T1. Spatial information can be encoded with pulsed field gradients in the manner of stimulated echo sequences. Singlet states can be excited via double-quantum coherences to enhance the efficiency of phase encoding and decoding.     

Polymorphism of phenylpyruvic acid studied by IR, Raman and solid state C NMR spectroscopy

Polymorphs I and II of phenylpyruvic acid are obtained as mixtures of both crystal forms or relatively pure crystals, from different solvents. Polymorph I is more stable than polymorph II at room temperature. Spectral characteristics of these polymorphs are discussed on the basis of IR, Raman and solid state ¹³C NMR spectra. Also, the assignment of the IR features observed in the 1600–1700 cm⁻¹ region is re-investigated by referring to the spectra of heavy-atom substituted derivatives. It is suggested that the C=O stretching band is split by the crystal field for both polymorphs.     

Structural characterization of polypyrrole in the solid state by high resolution 15N NMR spectroscopy [II]

The solid-state ¹⁵N CP/MAS NMR spectra and ¹⁵N spin-lattice relaxation times (T₁) of doped and dedoped ¹⁵N-labeled polypyrroles prepared by electrochemical polymerization, have been measured by means of high-resolution solid-state ¹⁵N NMR. The ¹⁵N signal of polypyrrole consists of four peaks decomposed by line shape analysis. The four peaks obtained have been assigned to the various structures of polypyrrole. Further, the half-width of the ¹⁵N NMR spectra of polypyrroles is discussed as related to the electrical conductivity. © 1995 John Wiley & Sons, Inc.     

Conformations and 13C NMR chemical shifts of some polyamides in the solid state as studied by high-resolution 13C NMR spectroscopy

High-resolution ¹³Carbon nuclear magnetic resonance (NMR) spectra of Nylons 4, 6, and 66 in the solid state were measured over a wide range of temperature. From the results, it was found that resonance lines of crystalline and noncrystalline components were separable and their chemical shifts were determined. The ¹³C chemical shift behavior is closely related to their conformation. The origin of the conformational effects on the chemical shifts is discussed.