Article
Biochemistry & Molecular Biology
Andrew J. Peloquin, Srikar Alapati, Colin D. McMillen, Timothy W. Hanks, William T. Pennington
Summary: By varying reaction solvent and stoichiometry, a series of S-diiodine adducts were successfully isolated and characterized, revealing significant halogen and chalcogen bonding interactions in the structures.
Article
Chemistry, Multidisciplinary
Andrew J. Peloquin, Colin D. McMillen, Scott T. Iacono, William T. Pennington
Summary: In this study, the solid-state structure of the 10H-phenothiazinium radical cation was obtained using molecular diiodine for one-electron oxidation, with various cation:iodide ratios and solvates. Additionally, the radical coupling product 10-(3-phenothiazinyldene)phenothiazinium was characterized for the first time through oxidation of 10H-phenothiazine with molecular diiodine, revealing interactions involving chalcogen, halogen, and hydrogen bonding.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Andrew J. Peloquin, Khadijatul Kobra, Yuxuan Li, Colin D. McMillen, William T. Pennington
Summary: The study examined the role of the triiodide (I-3)(-) anion in establishing various halogen bonding patterns through synthesis of cocrystals and the use of single-crystal X-ray crystallography. It was found that organoiodine molecules formed different dimensional packing arrangements with the triiodide anion, acting as a halogen bond acceptor. Significant asymmetry was observed within the triiodide anion, and the melting points of the cocrystalline materials varied with the identity of the organoiodine incorporated into the crystal lattice.
Article
Chemistry, Applied
Dhananjoy Pal, Tim Steinke, Lukas Vogel, Elric Engelage, Sascha Heinrich, Dana Kutzinski, Stefan M. Huber
Summary: This article describes the synthesis of a mixed chalcogen- and halogen-bond donor and provides a first indication of its catalytic activity in a benchmark reaction.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Engineering, Chemical
Ueslei G. Favero, Nicolas Schaeffer, Helena Passos, Kaique A. M. L. Cruz, Duarte Ananias, Sandrine Dourdain, Maria C. Hespanhol
Summary: This study investigates the effects of hydrophobic eutectic solvents (HES) on the extraction of lanthanides from nitrate media. It is found that the structured nature of HES and solvent-solute interactions significantly influence the extraction and metal selectivity.
SEPARATION AND PURIFICATION TECHNOLOGY
(2023)
Article
Chemistry, Physical
Simone Di Muzio, Annalisa Paolone, Olga Russina, Fabio Ramondo
Summary: Non-ionic deep eutectic solvents are innovative and alternative solvents that deviate from thermodynamic ideality due to the strength of hydrogen bonds between different components. In this study, we investigated the phase diagram and structural properties of cyclohexanol and phenol mixtures to understand the role of hydrogen bonding in the non-ideality of phenolic and alcoholic compounds. The results showed that the deviations from ideal mixing were smaller compared to a thymol-menthol mixture, and the intermolecular interactions were influenced by both hydrogen bonding and van der Waals contributions.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Multidisciplinary
Andrew J. Peloquin, Colin D. McMillen, Scott T. Iacono, William T. Pennington
Summary: This study investigates the roles of chalcogen and halogen bonding in the formation of cocrystals of Ph3P=E (E=O, S, Se) with organoiodines. Different structures and interactions were observed among the chalcogenides and organoiodines, with some selenium...organoiodine ChB formations being rare examples. The strength of the interactions was analyzed using natural bond orbital (NBO) theory, with calculated energies falling between 3.14 kcal/mol and 12.81 kcal/mol.
Article
Biochemistry & Molecular Biology
Massimiliano Aschi, Giorgia Toto Brocchi, Gustavo Portalone
Summary: This study analyzed the structural aspects of bromo derivatives of cytosine through experimental and theoretical approaches, uncovering a unique formation mechanism of halogen bonds (XBs) and evaluating the nature and strength of the interactions. The results showed that the supramolecular architectures of the compounds involve extensive classical intermolecular hydrogen bonds, with weak to moderate XBs appearing in most cases, providing insights into the crystal packing arrangement.
Article
Physics, Applied
Yuta Araki, Yuma Hamada, Norika Imamura, Koki Yamasaka, Mina Sakuragi
Summary: We investigated the use of carboxylic acid-terpene-based deep eutectic solvents (DESs) as skin permeation enhancers. Through transdermal experiments, we found that DESs with longer hydrocarbon chains can enhance the skin permeability of both hydrophilic and hydrophobic drugs. We also evaluated the structural changes in the stratum corneum and observed that DESs disrupt lipid layers and enhance permeation. Overall, DESs with longer hydrocarbon chains can be used to improve drug permeation while reducing skin irritation.
JAPANESE JOURNAL OF APPLIED PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Lauri Happonen, Milla Mattila, Ivan Peshev, Arttu Lehikoinen, Arto Valkonen
Summary: A series of thiourea-based tritopic receptor molecules were synthesized to be used as building blocks for halogen-bonded assemblies. The alkyl substituents in the benzene ring proved to be important for isothiocyanate group formation instead of competing thiocyanate group. The synthesized receptor molecules were used to study their halogen-bond acceptor properties with diiodotetrafluorobenzene donors by single-crystal X-ray diffraction method.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Laura E. Bickerton, Andrew Docker, Alistair J. Sterling, Heike Kuhn, Fernanda Duarte, Paul D. Beer, Matthew J. Langton
Summary: Synthetic anion transporters have shown great potential as potential anticancer agents and therapeutics for diseases associated with mis-regulation of protein anion channels. Highly active bidentate halogen bonding and chalcogen bonding anion carriers have been reported, demonstrating record nanomolar chloride transport activity and remarkably high chloride over proton/hydroxide selectivity. Computational studies suggest sigma-hole mediated anion recognition and desolvation as crucial for achieving high transport activity and selectivity in synthetic anionophores.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Biochemistry & Molecular Biology
Rosa M. Gomila, Antonio Frontera
Summary: This manuscript compares matere bonds with well-known sigma-hole interactions (halogen and chalcogen bonds) using both experimental and computational methods. The study also describes sigma-hole interactions in Se(VI) for the first time. The novelty of this work lies in the utilization of a neutral Re(VII) system as the matere bond donor and multivalent chalcogen and halogen donors.
Article
Nanoscience & Nanotechnology
Rajib Ghosh, Tamal Kanti Ghosh, Sourav Pramanik, Abu Saleh Musha Islam, Pradyut Ghosh
Summary: A water-soluble tetrapodal iodoimidazolium receptor based on halogen bonding has been found to efficiently extract ReO4- from aqueous solutions with a high degree of efficiency and excellent reusability. The receptor demonstrates the ability to retain its extraction efficiency in the presence of competing anions. It also outperforms its hydrogen-bond donor analogue in terms of ReO4- extraction.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Biochemistry & Molecular Biology
Nikita A. Korobeynikov, Andrey N. Usoltsev, Alexander S. Novikov, Pavel A. Abramov, Maxim N. Sokolov, Sergey A. Adonin
Summary: In this study, structurally diverse, bromine-rich polybromine-bromoselenates(IV) compounds were synthesized by reactions between bromoselenate(IV)-containing solutions, dibromine, and salts of pyridinium-family organic cations. These compounds exhibit halogen and chalcogen bonding in the solid state, leading to the formation of supramolecular architectures of different dimensionality. The energies of non-covalent interactions in the compounds were estimated by DFT calculations and characterized by Raman spectroscopy.
Article
Chemistry, Multidisciplinary
Hongming Chen, Miao Lin, Yanan Zhu, Dongwei Zhang, Jingru Chen, Qingsong Wei, Siqi Yuan, Yibin Liao, Fuhai Chen, Yong Chen, Meijin Lin, Xin Fang
Summary: The incorporation of supramolecular halogen bonding improves the radioluminescence properties of organic scintillators by enhancing their X-ray absorption coefficient and radioluminescence intensity. This method successfully increases the radioluminescence intensity of 9,10-bis(4-pyridyl)anthracene (BPA) and bromophenyl-methyl-pyridinium (PY), providing new opportunities for the development of organic scintillator materials.
Article
Materials Science, Multidisciplinary
Ashton W. Craig, Matthew C. Knott, Rahul Shankar, Sarah E. Morgan, Andrew J. Peloquin, Jena M. McCollum
Summary: Energetic filaments composed of aluminum and poly(vinylidene fluoride) with varying hexafluoropropylene content were tested for processability and combustion characteristics. Results showed that hexafluoropropylene disrupted the aluminum-binder interfacial interactions and fuel consumption scaled with aluminum particle size. Additionally, smaller particle diameters resulted in higher char yield, reflecting the diffusive nature of reactions.
ADVANCED ENGINEERING MATERIALS
(2022)
Article
Crystallography
Andrew J. Peloquin, Sarah C. Hill, Hadi D. Arman, Colin D. McMillen, Daniel Rabinovich, William T. Pennington
Summary: A new polymorph of N-tert-butyl-2-thioimidazole, along with its cocrystals with various compounds, has been synthesized. Different intermolecular interactions lead to the formation of various structural units and crystal forms.
JOURNAL OF CHEMICAL CRYSTALLOGRAPHY
(2022)
Article
Chemistry, Multidisciplinary
Arianna C. Ragusa, Andrew J. Peloquin, Colin D. McMillen, William T. Pennington
Summary: In this study, the halogen bonding of iodine-substituted thiophene compounds was investigated through a series of co-crystallization experiments. It was found that different halogen bonding motifs are mainly determined by the halogen bond donor/acceptor stoichiometry. Discrete units through C-I center dot center dot center dot I halogen bonds are commonly observed in acceptor-rich stoichiometries, while donor-rich stoichiometries tend to form two-dimensional halogen bonding networks.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Chemistry, Multidisciplinary
Arianna C. Ragusa, Andrew J. Peloquin, Marjan M. Shahani, Keri N. Dowling, James A. Golen, Colin D. McMillen, Daniel Rabinovich, William T. Pennington
Summary: Utilizing N-heterocyclic chalcogenones as halogen-bond acceptors, a total of 24 new cocrystals were prepared. By reacting with molecular diiodine and undergoing oxidative addition of acetone, different types of halogen and covalent bonds were formed. Common halogen-bond donors also facilitated cocrystal formation. The cocrystals of SDiazMesS and SDiazMesSe showed similar crystal structures.
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE CRYSTAL ENGINEERING AND MATERIALS
(2022)
Article
Chemistry, Physical
Pau Saldana-Baque, Jared W. Strutton, Rahul Shankar, Sarah E. Morgan, Jena M. McCollum
Summary: This study investigates the effect of interlayer adhesion on the mechanical performance of fluorinated thermoplastics produced by fused deposition modeling (FDM). The research reveals that a higher concentration of poly (methyl methacrylate) (PMMA) improves tensile strength, reduces ductility, and decreases the crystallization of poly (vinylidene fluoride) (PVDF). Injection-molded samples exhibit better mechanical properties compared to 3D printed samples. Interestingly, 3D printed blends with lower PMMA content demonstrate better diffusion across interfaces.
Article
Chemistry, Multidisciplinary
Spencer Watts, Andrew J. Peloquin, Madhushi Bandara, Colin D. McMillen, William T. Pennington
Summary: By combining heterocyclic thiones with variation in the identity of the heterocyclic elements, a series of 18 new crystalline structures were characterized. N-H...S hydrogen bonding was observed in most cases, resulting in two-dimensional motifs or dimeric pairs. The packing was consolidated through C-I...S and C-I...I halogen bonding, as well as C=S...I chalcogen bonding, linking the hydrogen-bonding ribbons or dimeric pairs.
ACTA CRYSTALLOGRAPHICA SECTION C-STRUCTURAL CHEMISTRY
(2022)
Article
Polymer Science
Shruti Venkatram, Jena McCollum, Natalie Stingelin, Blair Brettmann
Summary: In the polymer field, it is crucial to differentiate between the degree of crystallinity and the crystalline quality. These structural features have a significant impact on the properties of plastic materials and determine various processes in semiconducting polymers. Therefore, it is important to establish clear correlations between structure, processing, and properties, attributing specific functions to the degree of crystallinity and/or crystalline quality. This article discusses the challenges of identifying and distinguishing these structural characteristics using commonly applied measuring techniques and theoretical approaches.
POLYMER INTERNATIONAL
(2023)
Article
Materials Science, Multidisciplinary
Jared W. Strutton, Levi M. J. Moore, Jacob C. Marcischak, Cassandra D. Alabada, Kamran B. Ghiassi, Jena M. McCollum
Summary: This study analyzed the curing process of HTPB polyurethane networks using spectroscopy, rheology, and molecular simulations, highlighting the importance of better understanding the location-specific reaction process for high-fidelity DIW implementation through coupled rheology and spectroscopy.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Materials Science, Multidisciplinary
Jared W. Strutton, Levi M. J. Moore, Jacob C. Marcischak, Cassandra D. Alabada, Kamran B. Ghiassi, Jena M. McCollum
Summary: This study analyzed the curing process of hydroxyl-terminated polybutadiene (HTPB) polyurethane networks in direct ink writing (DIW) using spectroscopy, rheology, and molecular simulations. The results showed the importance of understanding the location-specific reaction process for high-fidelity DIW implementation through coupled rheology and spectroscopy.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Nicolas Cena, Andrew J. Peloquin, Jerry A. Boatz, Sarah Costa, Steven R. Gralinski, Alan L. Balch, Kamran B. Ghiassi
Summary: This study investigates the structure and energetics of the reaction product formed by the reaction between RuCl2(PPh3)(3) and 1,2-diphenylhydrazine, using experimental and computational chemistry approaches.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Andrew J. Peloquin, Colin D. McMillen, William T. Pennington
Summary: Thioamides can be used as useful building blocks for synthesizing complex heterocyclic molecules. By reacting pyridine-4-thiocarboxamide and pyridine-3-thiocarboxamide with I-2, protonated forms of known products and new salts were obtained. The reaction of pyridine-2-thiocarboxamide resulted in the formation of a different compound. Similar reactions with other thiocarboxamides yielded different heterocyclic products formed through the condensation of thioamide equivalents. The inclusion of bismuth triiodide allowed for further study of these organic products.
