Article
Chemistry, Multidisciplinary
Essi Taipale, Marcel Siepmann, Khai-Nghi Truong, Kari Rissanen
Summary: The synthesis and characterization of iodine(I) complexes with benzoimidazole or carbazole-derived sp(2) N-containing Lewis bases, as well as their corresponding silver(I) complexes, were investigated. The results showed the presence of a three-center four-electron (3c-4e) [N-I-N](+) bond in the iodine(I) complexes, with some Ag+ complexes exhibiting deviations from linearity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Karolis Norvaisa, Sophie Maguire, Claire Donohoe, John E. O'Brien, Brendan Twamley, Ligia C. Gomes-da-Silva, Mathias O. Senge
Summary: Inspired by 'picket-fence' systems, this study utilized strain to introduce intramolecular tension, leading to selective compound atropisomer conversion and the formation of distinctive supramolecular nanostructures.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Karolis Norvaisa, John E. O'Brien, Daire J. Gibbons, Mathias O. Senge
Summary: This study sheds light on the fundamental issue of atropisomerism in porphyrins, using benzenesulfonic acid for host-guest interactions and NMR spectroscopy to characterize all four rotamers. The research suggests that charge-assisted complexation is key to unraveling the atropisomeric enigma in porphyrinoids. Additionally, X-ray structural analysis was used to investigate weak host-guest interactions in nonplanar porphyrins.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Kaisa Helttunen
Summary: A calix[4]pyrrole receptor with two proximally meso-meso linking isophthaloyl straps displays open and closed states depending on the calix[4]pyrrole conformation. Anion binding triggers a closed state of the receptor providing two types of interactions with an aromatic benzoate guest. NMR experiments show slow exchange dynamics of benzoate, acetate, and chloride anions in the receptor.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Daniel A. Decato, Asia Marie S. Riel, James H. May, Vyacheslav S. Bryantsev, Orion B. Berryman
Summary: This paper experimentally quantifies a Hydrogen Bond-Enhanced Halogen Bond (HBeXB) for the first time, showing that electron-rich halogen bond donors are strengthened most by an adjacent hydrogen bond, and stronger hydrogen bond donors enhance the halogen bond the most. X-ray crystal structures and F-19 NMR titrations support the findings, laying the foundation for future studies on hydrogen bonds and halogen bonds in close proximity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jie Shen, Ruijuan Ye, Zhiwei Liu, Huaqiang Zeng
Summary: This study introduces a novel biomimetic channel system that can replicate the high selectivity and permeation rate of natural protein channels. These artificial channels demonstrate high selectivity and fast proton transport rate, and utilize a unique proton transport mechanism to facilitate transmembrane flux.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Filip Perlitius, Anna Walczak, Miroslava Conkova, Grzegorz Markiewicz, Jack Harrowfield, Artur R. Stefankiewicz
Summary: This study investigates the non-covalent aggregation of four benzene-1,3,5-tricarboxamide (BTA) derivatives formed from glycine or L-valine esters in both solid-state and chloroform solution. The study reveals the significant role of the steric bulk of the C-terminus protecting group in supramolecular aggregation in the solid-state and highlights the essential influence of substituent steric bulk on the nature and stability of BTA aggregates in distinct phases.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Multidisciplinary
Shilin Yu, Jas S. Ward, Khai-Nghi Truong, Kari Rissanen
Summary: Neutral halogen-bonded O-I-N complexes were prepared using carbonyl hypoiodites and aromatic organic bases. Modulating the Lewis basicity led to halogen-bonded complexes where the O-I...N bond transforms more into an asymmetric ion pair. X-ray analyses and NMR studies confirmed the geometries of the complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Materials Science, Multidisciplinary
Elisa Calabrese, Liberata Guadagno, Marialuigia Raimondo, Andrea Sorrentino, Simona Russo, Pasquale Longo, Annaluisa Mariconda
Summary: This study reports the synthesis and characterization of PEGMA-based copolymers incorporating different percentages of HEMA-UPy and evaluates their thermal properties and healing efficiency. The results show that increasing the amount of HEMA-UPy moiety leads to slight changes in glass transition temperature and significant changes in crystallization and melting temperatures. Dynamic mechanical analysis demonstrates the ability of the copolymer to recover its original storage modulus values.
MACROMOLECULAR MATERIALS AND ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Nikki A. Tzioumis, Duncan A. Cullen, Katrina A. Jolliffe, Nicholas G. White
Summary: A simple biphenyl bis-amidinium compound (1.Cl-2) can selectively precipitate sulfate from water even at low concentrations. It shows complete selectivity against monovalent anions and high selectivity even against CO32- and HPO42-. It is highly effective in removing sulfate (>90%) from both seawater and highly acidic conditions relevant to mining waste-streams. X-ray crystallography reveals the structure of 1.SO4 with tightly packed, anhydrous arrangement where each sulfate anion receives eight hydrogen bonds from amidinium N-H hydrogen bond donors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Erez Cohen, Liat Avram, Elena Poverenov
Summary: This study suggests using non-covalent supramolecular interactions to improve the mechanical and barrier properties of nature-sourced polymers. By controlling the modification of chitosan, biopolymers with tailored thermal, mechanical, and surface properties can be obtained. These findings have the potential to become a method for the formation of high-performance biodegradable alternatives to petroleum-based polymers, with applications in packaging, food, agriculture, and medicine.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Yanrong Jiang, Qinqin Yuan, Wenjin Cao, Zhubin Hu, Yan Yang, Cheng Zhong, Tao Yang, Haitao Sun, Xue-Bin Wang, Zhenrong Sun
Summary: This study reveals the important role of hydrogen bonds in water environments and demonstrates that B-H···O DHBs are stronger than conventional B-X···O HBs.
Article
Chemistry, Multidisciplinary
Selina Beatrice van Der Meer, Theresa Seiler, Christin Buchmann, Georgia Partalidou, Sophia Boden, Kateryna Loza, Marc Heggen, Jurgen Linders, Oleg Prymak, Cristiano L. P. Oliveira, Laura Hartmann, Matthias Epple
Summary: The study demonstrates that precision macromolecules carrying cysteine can effectively surface functionalize ultrasmall gold nanoparticles, with each nanoparticle carrying between 40 and 100 ligands and each ligand having a footprint of about 0.074 nm². Additionally, the presence of a PEG chain in the ligands significantly increases the hydrodynamic diameter of both dissolved macromolecules and macromolecule-conjugated gold nanoparticles.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Malgorzata Pamula, Evgeny Bulatov, Kaisa Helttunen
Summary: In this study, an aryl-extended calix[4]pyrrole with four meso-p-hydroxyphenyl substituents was used as a host molecule for chloride, acetate, and benzoate anions. Experimental results showed that chloride ions form hydrogen bonds with the upper rim hydroxyl groups, and the aromatic cations are bound to the shallow cavity of the host. Additionally, a dimeric capsule was formed by the inclusion of adiponitrile guest in the endo-cavity binding site. NMR titrations revealed that the host preferentially binds anionic guests in solution, with benzoate anion exhibiting the highest binding constant in acetonitrile. Density functional theory calculations indicated the preference of the exo-cavity complex with chloride anions over the endo-cavity complex, while the energies of the endo- and exo-cavity benzoate complexes were similar.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Multidisciplinary
Lorenz M. Urner, Ga Young Lee, Joseph W. Treacy, Aneta Turlik, Saeed Khan, K. N. Houk, Michael E. Jung
Summary: The 4-anilino-6,7-ethylenedioxy-5-fluoroquinazoline scaffold is proposed as a novel model system for studying weak NH...F hydrogen bonding interactions, with experimental and theoretical methods used to characterize this interaction. The results demonstrate that fluorine can act as a weak hydrogen bond acceptor, and the strength of the hydrogen bond can be modulated through changes in electron distribution and resonance.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Sander J. Wezenberg, Li-Jun Chen, Jasper E. Bos, Ben L. Feringa, Ethan N. W. Howe, Xin Wu, Maxime A. Siegler, Philip A. Gale
Summary: Membrane transport proteins have important regulatory functions in biology and can respond to environmental stimuli. Using bis(thio)ureas derived from stiff-stilbene, photocontrol of transmembrane transport and electric potential has been demonstrated through UV-vis and H-1 NMR spectroscopy. The (Z)-isomers show stronger binding properties and are more active in transmembrane transport compared to the (E)-isomers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Editorial Material
Chemistry, Organic
Katrina (Kate) A. Jolliffe, Philip A. Gale
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Emma Alcock, Pamela Mackey, Aneta Turlik, Khushi Bhatt, Mark E. Light, Kendall N. Houk, Gerard P. McGlacken
Summary: In this study, a highly diastereoselective method was developed to synthesize acyclic 3-amino-1,5-diol derivatives using a tandem double-aldol-Tishchenko reaction. The reaction achieved high diastereoselectivity (dr up to >99 : 1) using a butanone derived sulfinylimine. The reaction also showed regioselectivity and could be applied to challenging cyclobutanone and 3-pentanone derivatives, although with modest diastereomeric ratios.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Claudio Mendicute-Fierro, Paul D. Smith, Mark E. Light
Summary: In this study, a dicompartmental macrocyclic complex, [Ni2(L1)](DMF)2(BPh4)2, was prepared by reacting [Ni(tn)3]Cl2 with 2,6-diformyl-4-methylphenyl disulfide in methanol and in the presence of NaBPh4. The reaction involved a solvent assisted reduction of the disulfide bond and formation of two thiolate ligands. The crystal structure of the complex revealed a binuclear Ni2S2 core bridged by two thiolates within a macrocyclic framework.
Article
Multidisciplinary Sciences
Alexander M. Gilchrist, Xin Wu, Bryson A. Hawkins, David E. Hibbs, Philip A. Gale
Summary: Synthetic anion transporters have potential in treating life-threatening diseases and fluorination has been shown to tune their properties. In this study, a series of fluorinated tetrapodal anion transporters were designed and their effects on lipophilicity, solubility, deliverability, and anion transport selectivity were investigated. The most fluorinated tetrathiourea displayed the highest transport activity and an interesting inversion of Cl- vs NO3- transport selectivity was observed.
Article
Chemistry, Multidisciplinary
Lei Gan, Makenzie T. Nord, Jacob M. Lessard, Noah Q. Tufts, Arunraj Chidambaram, Mark E. Light, Hongliang Huang, Eduardo Solano, Julio Fraile, Fabian Suarez-Garcia, Clara Vinas, Francesc Teixidor, Kyriakos C. Stylianou, Jose G. Planas
Summary: The removal of organophosphorus (OP) herbicides from water has been studied using various methods such as adsorptive removal, chemical oxidation, electrooxidation, enzymatic degradation, and photodegradation. In this study, a Zr-based metal-organic framework (mCB-MOF-2) was used for the adsorption and photodegradation of the OP herbicide glyphosate (GP). The mCB-MOF-2 demonstrated a high adsorption capacity for GP and selectively converted it to non-toxic sarcosine and orthophosphate under UV-vis light irradiation. These findings suggest that mCB-MOF-2 is a promising material for removing OP herbicides from water.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Biochemistry & Molecular Biology
Esther Matamoros, Mark E. Light, Pedro Cintas, Juan C. Palacios
Summary: This paper investigates the formation of Schiff bases and 1,3-oxazolidines derived from salicylaldehydes and a conformationally restricted amino alcohol. The study provides experimental evidence, including crystallographic analyses and DFT-based calculations, on imine/enamine tautomerism. The mechanistic studies reveal the prevalence of imines under thermodynamic control and the formation of 2,4-trans-oxazolidines under acylating conditions.
Article
Nanoscience & Nanotechnology
Nikolaos Aspiotis, Katrina Morgan, Benjamin Maerz, Knut Mueller-Caspary, Martin Ebert, Ed Weatherby, Mark E. Light, Chung-Che Huang, Daniel W. Hewak, Sayani Majumdar, Ioannis Zeimpekis
Summary: This work demonstrates a scalable process for producing large area atomically thin 2D semiconductors with uniform performance. The new atomic layer deposition (ALD) and conversion technique allows for independent control of layer thickness, stoichiometry, and crystallinity. Field effect transistors (FETs) fabricated using this process exhibit high field effect mobility, low subthreshold slope, and high on/off ratios. Additionally, non-volatile memory transistors using ferroelectric FETs (FeFETs) with multiple state switching and a wide memory window are demonstrated, showing the applicability of the process to flexible neuromorphic applications.
NPJ 2D MATERIALS AND APPLICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhen Li, Xiao-Bao Li, Mark E. Light, Anna E. Carrillo, Ana Arauzo, Manuel Valvidares, Claudio Roscini, Francesc Teixidor, Clara Vinas, Felipe Gandara, Elena Bartolome, Jose Giner Planas
Summary: This work demonstrates the successful synthesis of a multi-metallic MTV RE MOF incorporating two, four, six, or eight different RE ions without any compositional segregation. The incorporation of all RE cations is characterized via compositional and structural characterization. The more complex MTV MOF, including all eight RE ions, is characterized using optical, thermal, and magnetic techniques.
ADVANCED FUNCTIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Juan Garcia de la Concepcion, Mirian Flores-Jimenez, Louis A. Cuccia, Mark E. Light, Cristobal Viedma, Pedro Cintas
Summary: This paper documents and reinvestigates the solid-state and crystal structures of 4,4'-azobis-4-cyanopentanoic acid (ACPA), a water-soluble azobis-nitrile of immense utility as a radical initiator in living polymerizations and a labile mechanophore that can be embedded within long polymer chains to undergo selective scission under mechanical activation. The X-ray crystal structures of all stereoisomers of ACPA have been reported for the first time, along with further details on enantiodiscrimination and the aggregation behavior of ACPA enantiomers.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Organic
Mark Power, Katrina Mackey, Mark E. Light, David J. Jones, Gerard P. Mcglacken
Summary: Dibenzofuran and its derivatives are important medicinal and natural products, but their synthesis is challenging. This study reports a new C-H functionalization method that works with electron-rich arenes, using tetrabutylammonium acetate as the catalyst, achieving efficient synthesis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Edward York, Daniel A. Mcnaughton, Meryem-Nur Duman, Philip A. Gale, Tristan Rawling
Summary: It has been discovered that bisaryl urea compounds can mediate mitochondrial uncoupling, leading to inhibition of breast cancer cell growth. Furthermore, substituting the urea group in bisaryl ureas can alter the activity of the compounds, with different substituents yielding different effects.
Article
Chemistry, Organic
Mohamed Fares, Xin Wu, Daniel A. McNaughton, Alexander M. Gilchrist, William Lewis, Paul A. Keller, Alain Arias-Betancur, Pere Fontova, Ricardo Perez-Tomas, Philip A. Gale
Summary: A series of fluorescent coumarin bis-ureas 1-4 were synthesized and found to act as highly potent HCl co-transport agents in lipid bilayer membranes. Compound 4, the most lipophilic transporter, exhibited a cytotoxic effect against three cancer cell lines and was able to cross the plasma membrane and localize in the cytoplasm. Furthermore, compound 4 showed co-localization with LysoTracker Red in the lysosome, despite lacking lysosome targeting groups.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Roberta A. Kehoe, Mark E. Light, David J. Jones, Gerard P. McGlacken
Summary: One-pot processes offer an environmentally friendly and time-saving approach to building complex molecules. This study presents a phosphine-free, inorganic base free, multi-step, one-pot reaction sequence for the rapid synthesis of complex medicinally relevant heterocycles. The approach combines three distinct reactions using a single pre-catalyst and achieves excellent yields. The study also reports favorable mass productivity, environmental impact factor, solvent intensity, and process mass intensity values.
Article
Chemistry, Physical
Daniel J. M. Irving, Mark E. Light, Matilda P. Rhodes, Terence Threlfall, Thomas F. Headen
Summary: Through X-ray and neutron total scattering, as well as Empirical Potential Structure Refinement (EPSR), the prenucleation structures of saturated aqueous magnesium sulfate are explored. The provided atomistic model reveals isolated octahedral aquo magnesium species, magnesium sulfate pairs, and extended clusters built from corner-sharing MgO6 and SO4 polyhedra. The average first solvation shell of the sulfate anion exhibits a complex and flexible environment, with water molecules brought into proximity by a coordinated hydrated magnesium. Ions' tendency to aggregate into clusters allows for differences in structure between bulk water and pure water.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
