Review
Medicine, Research & Experimental
Andrea Pugliese, Michael Tobyn, Lucy E. Hawarden, Anuji Abraham, Frederic Blanc
Summary: Pharmaceutical amorphous solid dispersions are widely used to increase the bioavailability of active pharmaceutical ingredients. Solid-state nuclear magnetic resonance is a powerful technique for studying the interactions between the active pharmaceutical ingredients and polymers. This review specifically highlights recent experimental strategies using high magnetic field and ultrafast magic angle spinning to identify the interactions and design new dispersions.
MOLECULAR PHARMACEUTICS
(2022)
Article
Medicine, Research & Experimental
Zhenxuan Chen, Haichen Nie, Chris J. Benmore, Pamela A. Smith, Yong Du, Stephen Byrn, Allen C. Templeton, Yongchao Su
Summary: The structural investigation of amorphous pharmaceuticals is crucial for understanding their stability, but has been underexplored due to limited analytical tools. In this study, X-ray pair distribution functions and solid-state nuclear magnetic resonance techniques were used to probe the molecular packing of amorphous posaconazole. The findings provide insights into the intermolecular interactions and highlight the efficacy of combining X-ray PDF and ssNMR techniques for high-resolution exploration of amorphous structures.
MOLECULAR PHARMACEUTICS
(2023)
Article
Pharmacology & Pharmacy
Rahamatullah Shaikh, Saeed Shirazian, Sarah Guerin, Eoin Sheehan, Damien Thompson, Gavin M. Walker, Denise M. Croker
Summary: Research on novel cocrystal systems and their physicochemical properties improvement is prevalent, yet the focus on final product formulation is lacking. This study measured the impact of tablet excipients on pharmaceutical cocrystal formulations, supported by Density Functional Theory calculations of intermolecular binding energies. The presence of certain excipients, such as PEG, HPMC, or lactose, was found to yield purer cocrystals during co-milling.
INTERNATIONAL JOURNAL OF PHARMACEUTICS
(2021)
Article
Chemistry, Multidisciplinary
Marcellus Gedes Fernandes de Moraes, Amaro Gomes Barreto Jr, Argimiro Resende Secchi, Mauricio B. de Souza Jr, Paulo Laranjeira da Cunha Lage, Allan S. Myerson
Summary: This study systematically investigated the polymorphism of Praziquantel (PZQ) through cooling crystallization experiments. A novel dimethylacetamide (DMA) solvate and a new form were discovered. The results reveal that solvent selection and variation in supersaturation generation can lead to forms that are not obtained by more complicated techniques and potentially find new forms.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Analytical
Yong Du, Jochem Struppe, Barbara Perrone, Alia Hassan, Anna Codina, Yongchao Su
Summary: This study demonstrates the application of CPMAS CryoProbe technology to improve the sensitivity of C-13 and N-15 detection in solid-state analysis of pharmaceutical drug posaconazole. The enhanced sensitivity enables resonance assignment and structural elucidation through 2D C-13-C-13 and H-1-N-15 correlation experiments. The results reveal drug-drug and drug-polymer interactions in amorphous POSA and its solid dispersion formulation.
Article
Pharmacology & Pharmacy
Md Sadeque Hossain Mithu, Steven A. Ross, Andrew P. Hurt, Dennis Douroumis
Summary: Neat grinding and liquid-assisted grinding were used to prepare cocrystals and co-amorphous formulations of ketoconazole, with the latter resulting in high quality cocrystals and enhanced dissolution rates.
JOURNAL OF DRUG DELIVERY SCIENCE AND TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Karlis Berzins, Peter J. G. Remoto, Sara J. Fraser-Miller, Keith C. Gordon
Summary: Spatially offset low-frequency Raman spectroscopy (SOLFRS) was used to investigate the surface-driven isothermal dehydration of model tablets containing citric acid monohydrate. Multivariate curve resolution and complementary Raman microscopy analysis were employed to interpret the SOLFRS data and obtain detailed information on the spatial dehydration characteristics within the tablets.
CRYSTAL GROWTH & DESIGN
(2022)
Review
Pharmacology & Pharmacy
Yuan Chen, Tarun Tejasvi Mutukuri, Nathan E. Wilson, Qi Tony Zhou
Summary: This review explores the challenges in formulation development of biologics in solid form, as well as traditional and emerging drying techniques. Stresses during the drying process can impact the stability of protein solids, but the lack of reliable characterization techniques for biological solids makes it challenging to understand their effects on protein product quality. Advanced characterization tools offer potential for mechanistic investigations into local structural changes and interactions at higher resolutions.
ADVANCED DRUG DELIVERY REVIEWS
(2021)
Article
Chemistry, Multidisciplinary
Yong Teoh, Ghada Ayoub, Igor Huskic, Hatem M. Titi, Christopher W. Nickels, Brad Herrmann, Tomislav Friscic
Summary: This study presents a rapid blending technology called SpeedMixing for fast mechanosynthesis and discovery of model pharmaceutical cocrystals. The method utilizes rapid spinning in the absence of bulk solvents and milling/grinding media. Syntheses of pharmaceutical cocrystals based on different active pharmaceutical ingredients demonstrate that SpeedMixing is a rapid, scalable, controllable, and selective method for the synthesis of cocrystals, cocrystal polymorphs, and stoichiomorphs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Analytical
Mingyue Li, Wei Xu, Yongchao Su
Summary: Solid-state NMR spectroscopy provides unique and comprehensive perspectives for analyzing pharmaceutical materials, offering insights into physiochemical stability and structural attributes of drug substances and products.
TRAC-TRENDS IN ANALYTICAL CHEMISTRY
(2021)
Article
Pharmacology & Pharmacy
Kenneth C. Waterman, Alisa K. Waterman, Teslin M. Botoy, Jane Li, Fenghe Qiu, Michael Hawley
Summary: An efficient protocol is proposed for assessing the chemical and physical stability of cocrystalline forms of APIs. The protocol involves preparing standard formulations using cocrystalline material, conducting stress testing to determine shelf-life, and carrying out a physical assessment of the cocrystal stability. This process was exemplified using model cocrystals of APIs.
PHARMACEUTICAL DEVELOPMENT AND TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Jennifer T. J. Freitas, Luan F. Diniz, Daniele S. Gomes, Pedro M. A. F. de Paula, Sergio H. A. de Castro, Larissa S. Martins, Daniely F. Silva, Ana L. M. Horta, Felipe A. S. Guimaraes, Victoria F. M. Calisto, Renata Diniz
Summary: This study proposes a new physicochemical approach to predict the solubility of drugs. By calculating the intermolecular interaction energy of crystalline solids, it can be correlated with their aqueous solubility. The results show that the greater the solubility, the lower the interaction energy, validating the feasibility of this approach.
Article
Chemistry, Multidisciplinary
Shan Huang, Dean S. Venables, Simon E. Lawrence
Summary: In this study, six novel pharmaceutical salts of PRM and MEL were prepared and characterized. The results showed that these salts exhibited significantly improved solubility and dissolution rate, and some of them had enhanced fluorescence.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Physical
Minghao Sun, Tiefeng Liu, Yifei Yuan, Min Ling, Nan Xu, Yanyan Liu, Lijing Yan, Hui Li, Chengyong Liu, Yingying Lu, Yao Shi, Yi He, Yongsheng Guo, Xinyong Tao, Chengdu Liang, Jun Lu
Summary: The study provides important insights into the growth mechanisms of lithium dendrites within a working lithium battery through in situ microscopic observation of lithium deposition inside the solid-state electrolyte (SSE). It revealed the direct nucleation and propagation of Li within the SSE, leading to structural cracking, possibly caused by crystalline defects present in the SSE.
ACS ENERGY LETTERS
(2021)
Review
Chemistry, Multidisciplinary
Ashlea R. Hughes, Frederic Blanc
Summary: Solid state nuclear magnetic resonance (NMR) spectroscopy plays a significant role in the field of supramolecular chemistry, offering unique insights into the atomic level structure and dynamics of guest molecules adsorbed in solid materials.
Article
Chemistry, Multidisciplinary
Ewa Patyk-Kazmierczak, Michal Kazmierczak, Shi-Qiang Wang, Michael J. Zaworotko
Summary: This study investigates the structural changes of a square lattice coordination network under high pressure. The results show that the interlayer separation of the network does not increase under high pressure, but the crystals are compressed and the adsorbed molecules are released. The changes induced by pressure are discussed in terms of structural voids, framework conformation, and molecular packing. Additionally, analysis of the electron count in the pores confirms the multistep evacuation of the adsorbed molecules and suggests the existence of intermediate phases.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Xia Li, Debobroto Sensharma, Varvara I. Nikolayenko, Shaza Darwish, Andrey A. Bezrukov, Naveen Kumar, Wansheng Liu, Xiang-Jing Kong, Zhenjie Zhang, Michael J. Zaworotko
Summary: In this study, a new two-dimensional square lattice coordination network, sql-(azpy)(pdia)-Ni, was reported to exhibit guest-induced switching between closed and open phases. The structural transformations were enabled by the presence of a pendant phenyldiazenyl moiety on the pdia2- ligand. Various guests were accommodated through parallel slippage of layers and interlayer expansion. The network also exhibited elastic-like properties induced by adaptive guest binding.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Mei-Yan Gao, Debobroto Sensharma, Andrey A. A. Bezrukov, Yassin H. H. Andaloussi, Shaza Darwish, Chenghua Deng, Matthias Vandichel, Jian Zhang, Michael J. J. Zaworotko
Summary: A molecular porous material, MPM-2, comprised of cationic [Ni-2(AlF6)(pzH)(8)(H2O)(2)] and anionic [Ni2Al2F11(pzH)(8)(H2O)(2)] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. MPM-2 exhibits excellent stability in both water and organic solvents. It shows high selectivity for C2H2 over CO2 and can effectively separate C2H2 from a mixture.
Article
Chemistry, Multidisciplinary
Andrey A. Bezrukov, Daniel J. O'Hearn, Victoria Gascon-Perez, Shaza Darwish, Amrit Kumar, Suresh Sanda, Naveen Kumar, Kurt Francis, Michael J. Zaworotko
Summary: As the freshwater crisis looms, metal-organic frameworks (MOFs) with stepped isotherms are at the forefront of desiccant development for atmospheric water harvesting (AWH). Diffusion to the sorbent bed surface limits the AWH kinetics of seven known MOFs and the industry-standard desiccant Syloid. A quantitative model exploiting isotherm shape reveals that steady-state oscillation optimizes productivity and dense ultramicroporous MOFs with a step at low relative humidity offer superior volumetric performance.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Medicine, Research & Experimental
Bhushan Munjal, Kevin DeBoyace, Fengjuan Cao, Joseph F. Krzyzaniak, Kapildev K. Arora, Raj Suryanarayanan
Summary: Continuous tablet manufacturing technology has been used to obtain regulatory approval for new drug products. The impact of processing conditions and formulation composition on the dehydration behavior of hydrates during continuous manufacturing has not been studied. Dehydration kinetics of carbamazepine dihydrate were monitored in different formulations using powder X-ray diffractometry. The dehydration was most significant in the presence of DCPA. The unintended formation of an amorphous dehydrated phase warrants further investigation.
MOLECULAR PHARMACEUTICS
(2023)
Article
Chemistry, Multidisciplinary
Bai-Qiao Song, Mohana Shivanna, Mei-Yan Gao, Shi-Qiang Wang, Cheng-Hua Deng, Qing-Yuan Yang, Sousa Javan Nikkhah, Matthias Vandichel, Susumu Kitagawa, Michael J. Zaworotko
Summary: This study reports that linker ligand substitution involving just one atom induces a shape-memory effect in a flexible coordination network. The material shows excellent performance in CO2/N-2 separation and exhibits a shape-memory phase induced by CO2.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Molly M. Haskins, Oisiin N. Kavanagh, Rana Sanii, Sanaz Khorasani, Jia-Mei Chen, Zhi-Yuan Zhang, Xia-Lin Dai, Bo-Ying Ren, Tong-Bu Lu, Michael J. Zaworotko
Summary: Quercetin is a widely studied nutraceutical with potential therapeutic properties. However, its poor solubility and oral bioavailability hinder its clinical development. In this study, cocrystallization was used to improve the physicochemical properties of quercetin, resulting in enhanced dissolution rate and oral bioavailability.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Li Zhao, Pengxiao Liu, Chenghua Deng, Ting Wang, Sha Wang, Yong-Jun Tian, Jin-Sheng Zou, Xue-Cui Wu, Ying Zhang, Yun-Lei Peng, Zhenjie Zhang, Michael J. Zaworotko
Summary: This study reports three isomorphic ultra-microporous metal-organic frameworks with high density of open metal sites and suitable pore structure, which can efficiently separate ethane and propane with excellent selectivity and reusability.
Article
Materials Science, Multidisciplinary
Zhaoyi Liu, Zhifang Wang, Shi-Qiang Wang, Jiamin Li, Yao Chen, Peng Cheng, Michael J. Zaworotko, Zhenjie Zhang
Summary: Fabricating smart humidity-responsive actuators that can convert the potential of humidity into other forms of energy is crucial in the intelligence age and energy crisis. In this study, a flexible porous organic cage that can undergo reversible structural transformation upon humidity stimulation is successfully fabricated by using a polymer (PIM-1) as a matrix. The inherent porosity of PIM-1 significantly enhances the performance of the resulting actuator. These actuators can perform bionic motions and output stable voltage-level power when coupled with a piezoelectric film.
ACS MATERIALS LETTERS
(2023)
Article
Materials Science, Multidisciplinary
Xia Li, Debobroto Sensharma, Kyriaki Koupepidou, Xiang-Jing Kong, Michael J. J. Zaworotko
Summary: Gas or vapor-induced phase transformations in flexible coordination networks (CNs) have the potential to outperform their rigid counterparts for separation and storage applications. Ligand modification has been used to alter the properties of these materials, but they have received less attention compared to rigid CNs. In this study, a family of Zn2+ CNs with variable flexibility was investigated, and it was found that the substituent moieties attached to a linker influenced both the structure and gas sorption properties of the networks. Some networks exhibited reversible transformation from small pore to large pore phases. The insights from this study can be applied to other classes of CNs.
ACS MATERIALS LETTERS
(2023)
Article
Chemistry, Physical
Varvara I. I. Nikolayenko, Dominic C. C. Castell, Debobroto Sensharma, Mohana Shivanna, Leigh Loots, Ken-ichi Otake, Susumu Kitagawa, Leonard J. J. Barbour, Michael J. J. Zaworotko
Summary: Compared to rigid physisorbents, switching coordination networks offer promise for gas/vapour storage and separation due to their improved working capacity and thermal management properties. X-dmp-1-Co, a coordination network exhibiting switching enabled by transient porosity, is the parent member of a family of transiently porous coordination networks [X-dmp-1-M] (M = Co, Zn, and Cd). Each member exhibits different threshold pressures for CO2, H2O, and CH4, with tuning attributed to differences and changes in metal coordination spheres and ligand rotation.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Yassin H. Andaloussi, Andrey A. Bezrukov, Debobroto Sensharma, Michael J. Zaworotko
Summary: In this study, a new N-donor carboxylate linker, β-(3,4-pyridinedicarboximido)propionate (PyImPr), was used to synthesize Cd(PyImPr)(2)via two different methods, resulting in 2D or 3D supramolecular isomers. Crystal structure analysis revealed that both isomers consist of the same carboxylate bridged rod building block (RBB), and the ethylene moiety of PyImPr enabled structural flexibility. Furthermore, analysis of the Cambridge Structural Database (CSD) provided insights into the relative frequency of RBB topologies in related ML2 coordination networks.
Article
Chemistry, Inorganic & Nuclear
Shi-Qiang Wang, Shaza Darwish, Michael J. Zaworotko
Summary: In this study, the selection and optimization of synthesis routes for porous metal-organic materials were compared. Mechanochemistry, slurry, and solution methods were assessed for the synthesis of a 1D chain coordination polymer, and it was found that both water slurry and water-assisted mechanochemical syntheses were successful in yielding the desired intermediate. However, the resulting products exhibited different CO2 sorption profiles depending on the synthesis methods used.
INORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Mei-Yan Gao, Shi-Qiang Wang, Andrey A. Bezrukov, Shaza Darwish, Bai-Qiao Song, Chenghua Deng, Catiuprimecia R. M. O. Matos, Lunjie Liu, Boya Tang, Shan Dai, Sihai Yang, Michael J. Zaworotko
Summary: Separation of C-8 aromatic isomers is crucial to the petrochemical industry. This study introduces a new coordination network, sql-4,5-Zn, which exhibits high sorption capacity and selectivity for C-8 aromatics.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Kyriaki Koupepidou, Andrey A. Bezrukov, Dominic C. Castell, Debobroto Sensharma, Soumya Mukherjee, Michael J. Zaworotko
Summary: This paper introduces a new square lattice topology coordination network, sql-(1,3-bib)(ndc)-Ni, and details its gas and vapour induced phase transformations. The results show that the material has potential utility as a desiccant, as evidenced by the formation of an S-shaped isotherm profile when exposed to humidity.
CHEMICAL COMMUNICATIONS
(2023)