Studies of molecular structure, hydrogen bonding and chemical activity of a nitrofurantoin-<scp>l</scp>-proline cocrystal: a combined spectroscopic and quantum chemical approach

Pandey, Jaya; Prajapati, Preeti; Shimpi, Manishkumar R.; Tandon, Poonam; Velaga, Sitaram P.; Srivastava, Anubha; Sinha, K.

doi:10.1039/c6ra13035f

Cited by 43 publications

(20 citation statements)

References 39 publications

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“…Therefore global reactivity descriptors, including energy band gap (∆E), absolute electron negativity (χ), chemical potential (µ), absolute hardness (η), global softness (S) and electrophilicity index (ω) can be determined using equations 1−6: 34,35 …”

Section: Methodsmentioning

confidence: 99%

“…While both samples showed this transition, the crystalline CIP required a much higher heating rate for the transition to be noticed. Computational analysis was therefore performed to investigate the 34 Electron density on the HOMO/LUMO frontier orbitals of CIP_UI in the basic state is distributed through various parts of the molecule. The HOMO resides on the piperazine residue and in part on the quinoline ring, while the LUMO sits mainly on the quinoline system, stretching as far as the carboxylic acid group ( Figure 9).…”

Section: Investigation Of Proton Transfer In Cipmentioning

confidence: 99%

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Two Faces of Ciprofloxacin: Investigation of Proton Transfer in Solid State Transformations

Mesallati

Mugheirbi

Tajber

2016

Crystal Growth & Design

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Ciprofloxacin (CIP) can exist in two different forms: the zwitterion and the unionized form. While the crystal structure of each has been described independently, the ability of CIP to transform from one to the other in the solid state has not been described. The crystal structures of unionized and zwitterionic CIP were therefore compared using computational methods, including their packing arrangement, hydrogen bonding, packing energy, intermolecular potentials and HOMO/LUMO energy gap. The pure amorphous form of CIP has also never been prepared or studied. Ball milling, cryomilling and spray drying were used in this study to prepare partially and fully amorphous CIP for the first time. The physical characteristics were examined by PXRD, FTIR and DSC. CIP proved to be very difficult to amorphize, and only spray drying in pure water resulted in a fully amorphous product. It was discovered that while most processing methods resulted in the more stable zwitterionic form of the drug, spray drying in an ethanol/water mixture produced the unionized form. The zwitterion was found to convert to the unionized form upon heating to its melting point, whereas the reverse transformation occurred when unionized CIP was exposed to high humidity. This study thus provides insight into the proton transfer which can occur in a zwitterionic drug in the solid state, and the resultant changes to its crystal structure. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 3 Abstract Ciprofloxacin (CIP) can exist in two different forms: the zwitterion and the unionized form.While the crystal structure of each has been described independently, the ability of CIP to transform from one to the other in the solid state has not been described. The crystal structures of unionized and zwitterionic CIP were therefore compared using computational methods, including their packing arrangement, hydrogen bonding, packing energy, intermolecular potentials and HOMO/LUMO energy gap. The pure amorphous form of this drug has also never been prepared or studied. Ball milling, cryomilling and spray drying were used in this study to prepare partially and fully amorphous CIP for the first time. The physical characteristics, and in particular ionization state, of these samples were examined by PXRD, FTIR and DSC. Analysis of the crystal packing of unionized and zwitterionic CIP revealed that the presence of ionic interactions between the charged groups of the latter results in a denser and more stable crystal lattice. A greater HOMO/LUMO energy gap was also calculated for this sample, confirming its lower reactivity. CIP proved to be very difficult to amo...

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Section: Methodsmentioning

confidence: 99%

Section: Investigation Of Proton Transfer In Cipmentioning

confidence: 99%

Two Faces of Ciprofloxacin: Investigation of Proton Transfer in Solid State Transformations

Mesallati

Mugheirbi

Tajber

2016

Crystal Growth & Design

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“…Peaks at 788–810 cm −1 corresponded to the absorption of benzene of ODA and PMDA groups. On the other hand, 3330 and 3225 cm −1 bands (N–H stretching) are totally absent, indicating that there are free –NH 2 without reaction with –COOH in this case [ 38 ].…”

Section: Resultsmentioning

confidence: 99%

“…Peaks at 1575 cm −1 (G band) and another at ~2880 cm −1 (2D band), historically designated as the G’ peak. The G band originates from the in-plane vibrations of aromatic carbon and is attributed to the doubly degenerate (E 2g ) phonon mode symmetry [ 36 , 37 , 38 , 39 , 40 , 41 , 42 ]. G’ peak is due to second-order zone boundary phonons, originating from a two-phonon double resonance process related to the band structure of the graphene layers.…”

Section: Resultsmentioning

confidence: 99%

Effects of Electrospun Carbon Nanofibers’ Interlayers on High-Performance Lithium–Sulfur Batteries

Gao

Yang

et al. 2017

Materials

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Two different interlayers were introduced in lithium–sulfur batteries to improve the cycling stability with sulfur loading as high as 80% of total mass of cathode. Melamine was recommended as a nitrogen-rich (N-rich) amine component to synthesize a modified polyacrylic acid (MPAA). The electrospun MPAA was carbonized into N-rich carbon nanofibers, which were used as cathode interlayers, while carbon nanofibers from PAA without melamine was used as an anode interlayer. At the rate of 0.1 C, the initial discharge capacity with two interlayers was 983 mAh g−1, and faded down to 651 mAh g−1 after 100 cycles with the coulombic efficiency of 95.4%. At the rate of 1 C, the discharge capacity was kept to 380 mAh g−1 after 600 cycles with a coulombic efficiency of 98.8%. It apparently demonstrated that the cathode interlayer is extremely effective at shutting down the migration of polysulfide ions. The anode interlayer induced the lithium ions to form uniform lithium metal deposits confined on the fiber surface and in the bulk to strengthen the cycling stability of the lithium metal anode.

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“…[17][18][19] Vibrational spectroscopic investigations combined with quantum chemical calculations have been utilized as one of the most effective tools for providing information about structure, composition, conformation and intra/intermolecular interactions and vibrational analysis of cocrystals. 20,21 Solid state NMR (SS-NMR) spectroscopy has proved to be a remarkable tool to explain the molecular structure and conformation at the molecular level. 22 The isotropic chemical shifts provide the useful information regarding the geometry and reactivity of the atoms within the molecule.…”

Section: Introductionmentioning

confidence: 99%

Study of molecular interactions and chemical reactivity of the nitrofurantoin–3-aminobenzoic acid cocrystal using quantum chemical and spectroscopic (IR, Raman, ¹³C SS-NMR) approaches

et al. 2017

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This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication.Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available.You can find more information about Accepted Manuscripts in the author guidelines. The investigations of structural reactivity, molecular interactions and vibrational characterization of pharmaceutical drug are helpful to understand their behaviour. The aim of this study is to determine the molecular, electronic and chemical properties of an antibiotic drug, nitrofurantoin (NF), after cocrystallisation with 3-aminorbenzoic acid (3ABA) and to understand as to how those changes lead to variation of properties in the cocrystal, NF-3ABA. NF-3ABA formation is explained by the stabilization via hydrogen-bond network between NF and 3ABA molecules. To validate the results obtained by QTAIM theory and to study the long-range forces, such as van der Waals interactions, steric effects in NF-3ABA, the reduced density gradient (RDG) and the isosurface have been plotted using Multiwfn software. QTAIM and isosurface analysis suggested that the hydrogen bonding interactions present in the NF-3ABA are moderate in nature. The calculated HOMO-LUMO energy gap shows that the NF-3ABA is more active than NF and 3ABA. Chemical reactivity descriptors are calculated to understand the various aspects of pharmacological sciences. Chemical reactivity parameters show that the NF-3ABA is more softer and chemically more reactive than NF. The results suggest that cocrystals can be a feasible alternative for positively changing the targetted physicochemical properties of an active pharmaceutical ingredient (API).

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Studies of molecular structure, hydrogen bonding and chemical activity of a nitrofurantoin-l-proline cocrystal: a combined spectroscopic and quantum chemical approach

Abstract: Nitrofurantoin (NTF) as an API and l-proline (LP) as a co-former being used as components to form a model of cocrystal NTF-LP to predict its crystal structure.

Cited by 43 publications

References 39 publications

Two Faces of Ciprofloxacin: Investigation of Proton Transfer in Solid State Transformations

Two Faces of Ciprofloxacin: Investigation of Proton Transfer in Solid State Transformations

Effects of Electrospun Carbon Nanofibers’ Interlayers on High-Performance Lithium–Sulfur Batteries

Study of molecular interactions and chemical reactivity of the nitrofurantoin–3-aminobenzoic acid cocrystal using quantum chemical and spectroscopic (IR, Raman, ¹³C SS-NMR) approaches

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Studies of molecular structure, hydrogen bonding and chemical activity of a nitrofurantoin-l-proline cocrystal: a combined spectroscopic and quantum chemical approach

Abstract: Nitrofurantoin (NTF) as an API and l-proline (LP) as a co-former being used as components to form a model of cocrystal NTF-LP to predict its crystal structure.

Cited by 43 publications

References 39 publications

Two Faces of Ciprofloxacin: Investigation of Proton Transfer in Solid State Transformations

Two Faces of Ciprofloxacin: Investigation of Proton Transfer in Solid State Transformations

Effects of Electrospun Carbon Nanofibers’ Interlayers on High-Performance Lithium–Sulfur Batteries

Study of molecular interactions and chemical reactivity of the nitrofurantoin–3-aminobenzoic acid cocrystal using quantum chemical and spectroscopic (IR, Raman, 13C SS-NMR) approaches

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Study of molecular interactions and chemical reactivity of the nitrofurantoin–3-aminobenzoic acid cocrystal using quantum chemical and spectroscopic (IR, Raman, ¹³C SS-NMR) approaches