Raman study of low-frequency modes in three glycine polymorphs

Surovtsev, N. V.; Malinovsky, V. K.; Boldyreva, Elena V.

doi:10.1063/1.3524342

Cited by 31 publications

(17 citation statements)

References 15 publications

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“…Raman spectroscopy failed to find a manifestation of any difference between solutions. [316] At the same time, the thermal effects of the eutectic melting in the H 2 O-glycine system were shown to depend on the glycine polymorph. [317] It is likely that the differences are so subtle that their detection by physical methods requires highly sensitive tools.…”

Section: Glycine As An Active Pharmaceutical Ingredientmentioning

confidence: 95%

Glycine: The Gift that Keeps on Giving

Boldyreva

2021

Israel Journal of Chemistry

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Glycine is a small molecule. It cannot change its conformation and is achiral. Despite the apparent simplicity, glycine shows endless diversity in its behavior over many phenomena. It was the first amino acid for which polymorphism was reported, first on crystallization and then on hydrostatic compression. The polymorphs differ in their physical properties and their biological activity. Glycine clusters persist in solution, leading to "solution memory". Phenomena at interfaces are critically important for crystal growth, dissolution, and for physical properties, which can be at times unexpected, like polarity in centrosymmetric αpolymorph. It is a great pleasure to remind of these remarkable phenomena in a special issue honoring professors Meir Lahav and Leslie Leiserowitz, who pioneered the study of the behavior of this unique molecule in many respects, and showed how complex and non-trivial phenomena can be at interfaces: between phases and between research fields.

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Section: Glycine As An Active Pharmaceutical Ingredientmentioning

confidence: 95%

Glycine: The Gift that Keeps on Giving

Boldyreva

2021

Israel Journal of Chemistry

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“…(1) 1(1) 0(1) 23 (1) For the small glycine molecule embedded in a network of intermolecular hydrogen bonds and other intermolecular contacts, only the four lowest frequency normal mode frequencies are significantly excited and can be reasonably determined in the limited temperature range of our experiment. The four lattice frequencies from KEK data (64.7, 75.2, 80.3, 121 cm -1 ; ADP Set 1 in Table 2) are in the range of those from Raman spectroscopy [40][41][42][43][44] ( Table 3). A frequency-to-frequency comparison has to be taken with a grain of salt because the meaning of the frequencies from ADP analysis and spectroscopy is different.…”

Section: Crystal Dynamicsmentioning

confidence: 99%

“…4a shows reasonable agreement between C p from ADP analysis and calorimetry. 1 The small C p difference of −0.6 cal mol -1 K -1 at 60 K is probably due to the fact that the lattice frequencies from ADP analysis are a bit lower than those from Raman spectroscopy [40][41][42][43][44] (Table 3). Note that the difference would be even larger if the frequencies derived from the ID11 data had been used.…”

Section: Crystal Dynamicsmentioning

confidence: 99%

Dynamics and Thermodynamics of Crystalline Polymorphs. 3. γ-Glycine, Analysis of Variable-Temperature Atomic Displacement Parameters, and Comparison of Polymorph Stabilities

et al. 2014

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In a series of systematic studies, we have investigated the molecular motion in crystals of the glycine polymorphs and determined their thermodynamic functions from an analysis of multitemperature atomic displacement parameters (ADPs) combined with ONIOM calculation on 15-molecule clusters. The studies are aimed at providing insight into the factors governing the relative stabilities of the -, -, and -polymorphs. This Article, the last in the series, focuses on the most stable polymorph, -glycine. Multitemperature diffraction data of the -glycine polymorph have been collected to 0.5 Å resolution between 10 and 300 K at two synchrotron beamlines, KEK Photon Factory and ID11 of the ESRF. The ADPs of -glycine from these sources differ significantly, as previously observed also for the other two polymorphs. A simple model of rigid body motion explains the ADPs from KEK and their temperature dependence. It provides lattice vibration frequencies that are in line with those from Raman spectroscopy. Together with the internal vibration frequencies from an ONIOM calculation, the thermodynamic functions are estimated using the Einstein, Debye, and Nernst-Lindemann models of heat capacity. The relative stabilities of the three polymorphs of glycine are discussed on the basis of the contributions to their free energies as obtained in this work and from various experimental and theoretical studies. The comparison shows that the free-energy differences are determined primarily by differences in lattice and zero-point vibrational energies.

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“…The study of dynamical response of biomolecules in a wide temperature range (from cryogenic to room temperatures) allows one to determine the intra-and intermolecular force constants and potentials by solving the inverse spectral problem and, finally, to predict conformations of biological associates and polymers and their changes with variation of ambient conditions [1][2][3][4][5][6][7][8]. This is especially important for hormones, because it allows their interaction with receptors to be predicted, which is the key problem of biochemistry and biomedicine.…”

Section: Introductionmentioning

confidence: 99%

Temperature effects in low-frequency Raman spectra of corticosteroid hormones

et al. 2015

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Experimental Raman spectra of the corticosteroid hormones corticosterone and desoxycorticosterone are recorded at different temperatures (in the range of 30−310 K) in the region of low-frequency (15−120 cm −1 ) vibrations using a solid-state laser at 532.1 nm. The intramolecular vibrations of both hormones are interpreted on the basis of Raman spectra calculated by the B3LYP/6-31G(d) density functional theory method. The intermolecular bonds in tetramers of hormones are studied with the help of the topological theory of Bader using data of X-ray structural analysis for crystalline samples of hormones. The total energy of intermolecular interactions in the tetramer of desoxycorticosterone (−49.1 kJ/mol) is higher than in the tetramer of corticosterone (−36.9 kJ/mol). A strong intramolecular hydrogen bond О 21 -Н···О=С 20 with an energy of −42.4 kJ/mol was revealed in the corticosterone molecule, which is absent in the desoxycorticosterone molecule. This fact makes the Raman spectra of both hormones somewhat different. It is shown that the low-frequency lines in the Raman spectra are associated with skeletal vibrations of molecules and bending vibrations of the substituent at the C 17 atom. The calculated Raman spectrum of the desoxycorticosterone dimer allows one to explain the splitting and shift of some lines and to interpret new strong lines observed in the spectra at low temperatures, which are caused by the intermolecular interaction and mixing of normal vibrations in a crystal cell. On the whole the calculated frequencies are in a good agreement with the experimental results.

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Raman study of low-frequency modes in three glycine polymorphs

Cited by 31 publications

References 15 publications

Glycine: The Gift that Keeps on Giving

Glycine: The Gift that Keeps on Giving

Dynamics and Thermodynamics of Crystalline Polymorphs. 3. γ-Glycine, Analysis of Variable-Temperature Atomic Displacement Parameters, and Comparison of Polymorph Stabilities

Temperature effects in low-frequency Raman spectra of corticosteroid hormones

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