Reorganized, weak C–H⋯O interactions directly modify the mechanical properties and compaction performance of a series of nitrobenzoic acids

Singaraju, Aditya B.; Nguyen, Kyle; Swenson, Dale C.; Iyer, Mamta; Haware, Rahul V.; Stevens, Lewis L.

doi:10.1039/c7ce00238f

Cited by 12 publications

(9 citation statements)

References 44 publications

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“…using p-BLS. This connection was previously demonstrated by Singaraju et al using a series of nitrobenzoic acid derivatives 127. The p-BLS spectra acquired at two different mirror spacings are shown inFigure 7.18 for THY and the cocrystals.…”

supporting

confidence: 68%

“…The spectra are very material specific and very sensitive to the intermolecular interactions governing their packing. 127 For the cocrystal CAF: F-NBA we see high intensity shear mode distribution near the Raleigh line indicating weak intermolecular interactions in a specific direction. Similar features for observed for paraben esters in another study.…”

Section: Mechanical Properties Of Caf: F-nba and Caf: Cl-nbamentioning

confidence: 83%

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Crystallographic and spectroscopic assessment of pharmaceutical material mechanics

Singaraju¹

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AbbVie for the opportunity to intern in the Manufacturing Science & Technology group and giving me the chance to gain insights into drug product design. I would also like to acknowledge Dr. Yihong Qiu at AbbVie for his continued mentorship and help during my search for employment. I am extremely grateful to all the faculty and staff members of the Division of Pharmaceutics and Translational Therapeutics, College of Pharmacy, for their valuable support during the graduate study. I thank Dr. Keith Guillory, Drs. Guillory-Wurster-Flanagan-Matheson for offering financial support during my graduate work. I would also like to thank The University of Iowa Pharmaceuticals for providing funding in the form of a research assistantship.

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supporting

confidence: 68%

Section: Mechanical Properties Of Caf: F-nba and Caf: Cl-nbamentioning

confidence: 83%

Crystallographic and spectroscopic assessment of pharmaceutical material mechanics

Singaraju¹

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“…Although columns of the hydrogen-bonded coformer pairs running along the b-crystallographic axis exist, the orientation of adjacent coformer pairs differ by 180°. Such arrangement does not foster π-stacking interactions, unlike molecular columns in theophylline and 4-nitrobenzoic acid. , Therefore, they do not form rigid molecular columns that is a prerequisite for facile slipping. Although no active slip planes could be identified by visualization, the higher plasticity of Form 1 could be explained with the aid of energy framework calculations and topological analysis, as discussed later.…”

Section: Resultsmentioning

confidence: 99%

“…Following the model developed by Singaraju et al and refined by Bahl et al, the application of BLS to powders permits the calculation of engineering moduli that can be used to interpret the compaction performance of materials. Our expectation is that the acoustic frequency distributions from powder BLS (p-BLS) are reflective of the underlying interaction topology, and earlier studies with p-BLS demonstrate sensitivity of these spectra to the interaction topology and its adjustment through point substitution or cocrystallization. ,,, Furthermore, p-BLS was used to explain the compaction behavior of structurally similar materials ( p -aminobenzoates and paraben esters). The order of the mechanical properties follows the same order as their compressibility, yield pressures, and attachment energies .…”

Section: Introductionmentioning

confidence: 99%

Molecular Interpretation of the Compaction Performance and Mechanical Properties of Caffeine Cocrystals: A Polymorphic Study

et al. 2019

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The 1:1 caffeine (CAF) and 3-nitrobenzoic acid (NBA) cocrystal (CAF:NBA) displays polymorphism. Each polymorph shares the same docking synthon that connects individual CAF and NBA molecules within the asymmetric unit; however, the extended intermolecular interactions are significantly different between the two polymorphic modifications. These alternative interaction topologies translate to distinct structural motifs, mechanical properties, and compaction performance. To assist our molecular interpretation of the structure−mechanics−performance relationships for these cocrystal polymorphs, we combine powder Brillouin light scattering (p-BLS) to determine the mechanical properties with energy frameworks calculations to identify potentially available slip systems that may facilitate plastic deformation. The previously reported Form 1 for CAF:NBA adopts a 2D-layered crystal structure with a conventional 3.4 Å layer-to-layer separation distance. For Form 2, a columnar structure of 1D-tapes is displayed with CAF:NBA dimers running parallel to the (110) crystallographic direction. Consistent with the layered crystal structure, the shear modulus for Form 1 is significantly reduced relative to Form 2, and moreover, our p-BLS spectra for Form 1 clearly display the presence of low-velocity shear modes, which support the expectation of a low-energy slip system available for facile plastic deformation. Our energy frameworks calculations confirm that Form 1 displays a favorable slip system for plastic deformation. Combining our experimental and computational data indicates that the structural organization in Form 1 of CAF:NBA improves the compressibility and plasticity of the material, and from our tabletability studies, each of these contributions confers superior tableting performance to that of Form 1. Overall, mechanical and energy framework data permit a clear interpretation of the functional performance of polymorphic solids. This could serve as a robust screening approach for early pharmaceutical solid form selection and development.

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“…The study of intermolecular interactions together with their control is the key subject in the design and synthesis of solid‐state materials possessing desired properties. One of the most challenging task is understanding the fundamental concepts governing the crystal growth and learning of the relationship between crystal structures and the properties of the molecules building crystal three dimensional nets ,. The gained knowledge may find a use in designing of materials having layered and corrugated arrangement of molecules.…”

Section: Introductionmentioning

confidence: 99%

Quantitative Analysis of Intermolecular Interactions in 3‐Cyano‐2‐Pyridones: Evaluation through Single Crystal X‐ray Diffraction and Density Functional Theory

et al. 2018

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A series of 2-pyridones and their methyl derivatives has been studied in term of noncovalent interactions and molecular packing properties. These structural characteristics were then correlated with the quantitative analysis of the intermolecular interactions governing those compounds in three dimensional net. The electronic effect over the 2-pyridone ring on the packing property was analysed by locking the tautomers. The SC-XRD revealed that 4,6-dimethyl-3-cyano-2-pyridone and its O-methyl derivative owned the layered arrangement, while Nmethyl derivative possessed the corrugated arrangement with persistent of stacking between two pyridone rings. However, 4phenyl-6-methyl-3-cyano-2-pyridone and its N-methyl derivative showed the reverse face-to-face stacking due to modest torsion of bi-aryl rings. Similarly, 6-phenyl-4-methyl-3-cyano-2pyridone has also shown reverse face-to-face stacking while its N-methyl derivative stacking between pyridone ring and nitrile group was observed. Further, quantitative analysis of intermolecular interactions was done through Hirshfeld surface analysis and density functional theory.[a] Dr.

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Reorganized, weak C–H⋯O interactions directly modify the mechanical properties and compaction performance of a series of nitrobenzoic acids

Cited by 12 publications

References 44 publications

Crystallographic and spectroscopic assessment of pharmaceutical material mechanics

Crystallographic and spectroscopic assessment of pharmaceutical material mechanics

Molecular Interpretation of the Compaction Performance and Mechanical Properties of Caffeine Cocrystals: A Polymorphic Study

Quantitative Analysis of Intermolecular Interactions in 3‐Cyano‐2‐Pyridones: Evaluation through Single Crystal X‐ray Diffraction and Density Functional Theory

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