Advances in Functional Cocrystals

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Crystal Engineering".

Deadline for manuscript submissions: closed (20 February 2023) | Viewed by 6966

Special Issue Editors


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Guest Editor
Centre for Pharmaceutical Engineering Science, University of Bradford, Bradford BD7 1DP, UK
Interests: crystal engineering; supramolecular chemistry; crystallisation; X-ray diffraction; pharmaceutical technology; cocrystals; polymorphs; hydrates; salts; amorphous materials; pre-formulation; physicochemical stability; drug formulation

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Guest Editor
Crystallization and Particle Sciences, Institute of Chemical and Engineering Sciences, A*STAR (Agency for Science, Technology and Research Singapore), Singapore, Singapore
Interests: pharmaceuticals; encapsulation; structure-property relationships; crystal engineering; polymorphism; drug formulations
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Special Issue Information

Dear Colleagues,

The field of cocrystals is rapidly growing in solid-state science, comprising crystal engineers, pharmaceutical researchers, chemists, chemical engineers, computational researchers from academia and industry. Cocrystals, being the multicomponent solids incorporating two or more solids in a crystal lattice, show great promise in modulating physicochemical properties of the constituents. Last few decades have witnessed an enormous advancement in the design and synthesis of cocrystals which paved the way for novel drug products and improved functional materials.

The current special issue makes an attempt to showcase recent developments in the functional cocrystals and current research interests within the broad theme of cocrystals. The focus of the issue covers, but not limited to, control of physicochemical attributes henceforth bioavailability, stability and manufacturability of active pharmaceutical ingredient into solid dosage form via pharmaceutical cocrystals, polymorphism in cocrystals, behaviour of cocrystals in solution media, cocrystal formulations and scale up of cocrystals from laboratory to large-scale production. Recent studies show that, beside pharmaceuticals, cocrystallization can also be used to modify the properties of nutraceuticals, agrochemicals and specialty chemicals, explosives, and optical properties of materials such as thermochromism, modulated fluorescence and photolithography. Tailored modulation of magnetic and electronic properties of materials by cocrystallization is an emerging area of research in the recent times. In addition to experimental approaches with cocrystals, there has been considerable success with rational design and computational prediction of cocrystals supported by over million crystal structures and statistical information that can be retrieved from Cambridge Structural Database.

The current Special Issue on “Advances in Functional Cocrystals” serves as an excellent international platform to report results that highlight design and synthesis of cocrystals and their potential applications in wide-range of research fields. We invite contributions from scientists working in all disciplines related to the development of cocrystals. We hope that readers will find this issue both interesting and stimulating.

Dr. Venu Vangala
Dr. Srinivasulu Aitipamula
Guest Editors

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Keywords

  • crystal engineering and supramolecular chemistry
  • cocrystals, pharmaceutical cocrystals, functional cocrystals
  • supramolecular synthesis, homo and heterosynthons
  • salts, polymorphs, hydrates, solvates, eutectics, coamorphous compounds
  • pharmaceuticals/ drug development/ solid dosage form
  • nutraceuticals/agrochemicals/optical/ magnetic/explosive materials
  • x-ray diffraction (single crystal x-ray diffraction, powder x-ray diffraction)
  • thermal, spectroscopy and advanced analytical characterizations
  • structure-property relationships
  • physicochemical properties, micromeritics, biopharmaceutical properties
  • solubility, dissolution rate
  • permeability, pharmacokinetic and pharmacodynamic properties
  • physical stability, hygroscopicity, chemical stability and photostability
  • mechanical properties, tabletability, compressibility
  • mechanical grinding, neat and liquid assisted grinding
  • solution and solvent-free crystallizations
  • cambridge structural database
  • crystal structure prediction

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Published Papers (3 papers)

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Research

17 pages, 5427 KiB  
Article
Control of 11-Aza:4-X-SalA Cocrystal Polymorphs Using Heteroseeds That Switch On/Off Halogen Bonding
by Keyao Li, Monalisa Roy, Madiha Nisar, Lawrence W-Y. Wong, Herman H-Y. Sung, Richard K. Haynes and Ian D. Williams
Crystals 2022, 12(10), 1368; https://doi.org/10.3390/cryst12101368 - 27 Sep 2022
Viewed by 1813
Abstract
A family of: 1:1 cocrystals 11-Aza:4-X-SalA have been prepared from the potent anti-malarial compound 11-azaartemisinin with 4-halosalicylic acids. When X = 4-Cl, 4-Br and 4-I, two conformational polymorphs can be isolated in each case. Monoclinic type-I was found previously for parent 11-Aza:SalA ( [...] Read more.
A family of: 1:1 cocrystals 11-Aza:4-X-SalA have been prepared from the potent anti-malarial compound 11-azaartemisinin with 4-halosalicylic acids. When X = 4-Cl, 4-Br and 4-I, two conformational polymorphs can be isolated in each case. Monoclinic type-I was found previously for parent 11-Aza:SalA (1) and 11-Aza:4-Br-SalA (3a) which have polar 21 stacks of molecular pairs with no short halogen bond contacts between stacks. Orthorhombic type-II is found for 4-Cl (3b) and 4-I (4b) from solution growth. This has a translational stack of molecular pairs involving a conformational change of the acid-lactam hetero-synthon and supramolecular association of stacks via halogen bonds. Notably, phase pure polymorph type-I can be formed for 4-Cl (3a) and 4-I (4a) by hetero-seeding with 11-Aza:SalA, whist conversely phase pure type-II for 4-Br (2b) can be formed using homo-seeding from liquid assisted grinding (LAG) product. This work demonstrates both the viability of engineering polymorphic cocrystal forms using hetero-seeds and the involvement of halogen bonds in helping to discriminate quite different polymorphic types. Full article
(This article belongs to the Special Issue Advances in Functional Cocrystals)
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8 pages, 4959 KiB  
Article
Thermal Properties and Ionic Conductivity of Tetra-n-Butylammonium Perchlorate
by Nikolai F. Uvarov, Nargiz B. Asanbaeva, Artem S. Ulihin, Yulia G. Mateyshina and Konstantin B. Gerasimov
Crystals 2022, 12(4), 515; https://doi.org/10.3390/cryst12040515 - 7 Apr 2022
Cited by 4 | Viewed by 2207
Abstract
The thermal parameters of the phase transitions and transport properties of tetra-n-butylammonium (TBA) perchlorate (n-C4H9)4NClO4 (TBAClO4) were investigated. TBAClO4 has a polymorphous transition at 330 K and melts at 487 K. The structure [...] Read more.
The thermal parameters of the phase transitions and transport properties of tetra-n-butylammonium (TBA) perchlorate (n-C4H9)4NClO4 (TBAClO4) were investigated. TBAClO4 has a polymorphous transition at 330 K and melts at 487 K. The structure of the high-temperature (HT) phase belongs to cubic symmetry and is similar to the HT phases of TBABF4 and TBAI salts. The conductivity parameters of the low-temperature and HT phases of TBAClO4 were determined from the Arrhenius plots. The thermodynamic parameters and transport properties of TBAClO4 were compared with those of other TBA salts having isostructural HT phases. The polymorphous phase transition entropy was found to correlate with the conductivity of HT phases of TBA salts; TBAClO4 has the lowest conductivity compared to TBABF4 and TBAI salts. Full article
(This article belongs to the Special Issue Advances in Functional Cocrystals)
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12 pages, 9070 KiB  
Communication
Intermolecular Interactions Drive the Unusual Co-Crystallization of Different Calix[4]arene Conformations
by Dominic Taylor, Irene Ling, Filipe Vilela and Scott J. Dalgarno
Crystals 2022, 12(2), 250; https://doi.org/10.3390/cryst12020250 - 12 Feb 2022
Cited by 2 | Viewed by 2297
Abstract
Crystallization of 5,17-dibromo-11,27,23,25-tetraone-26,28-dipropoxycalix[4]arene results in the rare observation of two different calix[4]arene conformations (partial cone and 1,3-alternate) co-crystallized within the same single crystal X-ray structure. Analysis using 1H and 13C NMR spectroscopy revealed that only a single conformation (the cone) was [...] Read more.
Crystallization of 5,17-dibromo-11,27,23,25-tetraone-26,28-dipropoxycalix[4]arene results in the rare observation of two different calix[4]arene conformations (partial cone and 1,3-alternate) co-crystallized within the same single crystal X-ray structure. Analysis using 1H and 13C NMR spectroscopy revealed that only a single conformation (the cone) was present in solution, and in contrast to the structures of other reported calix[4]arenes and calix[4]quinones, both conformations of the compound present in this crystal structure have a “pinched” shape, drastically reducing Br-Br separation and associated cavity sizes. Full article
(This article belongs to the Special Issue Advances in Functional Cocrystals)
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