Article
Chemistry, Multidisciplinary
Aiting Kai, Benjamin D. Egleston, Andrew Tarzia, Rob Clowes, Michael E. Briggs, Kim E. Jelfs, Andrew I. Cooper, Rebecca L. Greenaway
Summary: The study presented the first examples of Type III porous liquids based on porous organic cages, showing that dispersion of porous microparticles in size-excluded liquids forms stable POC-based Type III porous liquids with diverse physicochemical properties. These liquids can be tailored for different applications and operating conditions, with potential for producing porous liquids with low viscosity or high thermal stability. One specific liquid comprising racemic POC microparticles and an ionic liquid showed significantly higher CO2 working capacity than the neat ionic liquid, with the added advantage of being recyclable without significant loss.
ADVANCED FUNCTIONAL MATERIALS
(2021)
Article
Engineering, Environmental
Abdul Ghaffar, Muhammad Hassan, Oleksiy V. Penkov, Cafer T. Yavuz, Kemal Celebi
Summary: A hierarchically networked porous organic cage membrane with dynamic control over pores has been developed, showing great potential in solvent separations. The membrane can reversibly modulate its geometry and pore size from water to methanol and DMF, resulting in stable solvent permeance and tunable dye rejection at different molecular weights.
ENVIRONMENTAL SCIENCE & TECHNOLOGY
(2023)
Review
Chemistry, Multidisciplinary
Lei Jia, Xianhui Tang, Yong Cui, Yan Liu
Summary: As a new class of porous solid materials, metal-organic cages (MOCs) have shown great potential as filler components for separation membranes due to their structural variability, notable porosity, and good dispersibility. This review summarizes current membranes based on MOCs, including mixed matrix membranes, cross-linked membranes, composite membranes, bilayer lipid membranes, and liquid membranes, and provides an overview of their applications. The challenges and opportunities in future developments are also discussed.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Physical
Michael C. Brand, Francesca Greenwell, Rob Clowes, Benjamin D. Egleston, Aiting Kai, Andrew Cooper, Thomas D. Bennett, Rebecca L. Greenaway
Summary: The study explores the melting and glass-forming behaviors of various organic cages, including shape-persistent POCs formed by imine condensation and more flexible, less shape-persistent amine POCs. Melting of organic cages leads to the formation of molecular glasses upon quenching of the resultant liquids. One molecular glass showed enhanced gas uptake for CO2 and CH4 compared to the starting amorphous cage. Additionally, foaming of the liquid resulted in a more stable, less soluble glass, demonstrating potential for an alternative approach to forming materials such as membranes without solution processing.
JOURNAL OF MATERIALS CHEMISTRY A
(2021)
Article
Chemistry, Multidisciplinary
Michael Wilms, Lesly V. Melendez, Rohan J. Hudson, Christopher R. Hall, Samantha Prabath Ratnayake, Trevor Smith, Enrico Della Gaspera, Gary Bryant, Timothy U. Connell, Daniel E. Gomez
Summary: We introduce a novel composite material composed of silver nanoparticles and three-dimensional molecular organic cages based on light-absorbing porphyrins. The porphyrin cages not only stabilize the particles but also enable diffusion and trapping of small molecules near the metallic surface. The combination of these two photoactive components leads to a Fano-resonant interaction, resulting in increased energy transfer and enhanced photocurrent for water-splitting applications. This composite structure demonstrates the potential of advanced photosensitizer systems with intrinsic porosity for photocatalytic and sensing applications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jessica Rimsza, Tina M. Nenoff
Summary: The cost of direct air capture of carbon can be reduced by developing new materials that have high CO2 selectivity and can be integrated into existing industrial processes. Porous liquids (PLs) are a promising class of materials for this purpose. This study used density functional theory simulations to investigate the interactions between nine solvents and a CC13 porous organic cage (POC). The findings suggest that the stability of solvent molecules is highest when placed inside the CC13 POC or in the pore window. The results also provide guidelines for designing PLs with flexible cage structures and solvent-POC combinations that can enhance solubility.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Physical
Yu Liang, Yu Fang, Yong Cui, Hongcai Zhou
Summary: A molecular capsule was reported to encapsulate and deliver drugs into the cell nucleus, displaying superior toxicity and inhibiting liver cancer growth. Modifying the properties of such capsules may lead to the design of therapeutic strategies targeting specific cell organelles.
Article
Nanoscience & Nanotechnology
Wan Wei, Mao Wang, Jianwen Jiang
Summary: This study utilized molecular simulation to examine the swelling behavior of three different porous organic cages (POCs) and a polymer composite membrane in various solvents, as well as explore their potential applications in water desalination and solvent recovery processes. The research revealed that the POCs play a crucial role in enhancing the permeability of water and methanol through the composite membrane, with the membranes exhibiting the highest swelling in methanol. The findings provide insights into the mechanisms of solvent permeation through POC/PIM membranes and showcase the potential for using POCs to enhance the performance of molecularly mixed composite membranes in industrial applications.
ACS APPLIED NANO MATERIALS
(2021)
Article
Chemistry, Physical
Ai He, Zhiwei Jiang, Yue Wu, Hadeel Hussain, Jonathan Rawle, Michael E. Briggs, Marc A. Little, Andrew G. Livingston, Andrew Cooper
Summary: In this study, the graded separation of three dyes is achieved by altering the pore size of a porous organic cage composite, demonstrating the potential of single membranes with both high permeance and high rejection.
Article
Chemistry, Multidisciplinary
Valentinos Mouarrawis, Eduard O. Bobylev, Bas de Bruin, Joost N. H. Reek
Summary: Confinement of a catalyst within a cage can enhance catalytic activity by increasing the local concentration of substrates, leading to higher catalytic efficiency.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Nanoscience & Nanotechnology
Wenjing Wang, Kongzhao Su, El-Sayed M. El-Sayed, Miao Yang, Daqiang Yuan
Summary: Porous organic cage materials show eight distinct solid-state solvatomorphs, affecting gas sorption capacities and separation abilities. A particular solvatomorph exhibits a significantly higher surface area and superior adsorption and separation abilities for acetylene and carbon dioxide compared to other solvatomorphs, indicating the potential for adjusting gas sorption and separation properties by controlling solvatomorphs.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Arkaprabha Giri, Niraj Nitish Patil, Abhijit Patra
Summary: The cage-to-network design strategy was successfully utilized to create a highly microporous organic polymer (NPOP) for catalyzing the conversion of CO2 to cyclic carbonates and for reducing nitroarenes with remarkable catalytic activity and excellent recyclability. The advantages of this design strategy were further demonstrated by the encapsulation of silver nanoparticles in NPOP, which exhibited enhanced catalytic performance.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Kai Qu, Jipeng Xu, Liheng Dai, Yixing Wang, Hongyan Cao, Dezhu Zhang, Yulin Wu, Weiyi Xu, Kang Huang, Cheng Lian, Xuhong Guo, Wanqin Jin, Zhi Xu
Summary: In this study, a crystal-rearrangement strategy induced by electrostatic attraction was used to design a POC membrane with heterostructure. The rearranged crystal layer, which was uniform and defect-free, displayed excellent CO2 separation performance and stability.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Engineering, Chemical
Tingting Xu, Bin Wu, Yifan Li, Yanran Zhu, Fangmeng Sheng, Liang Ge, Xingya Li, Tongwen Xu
Summary: This study investigates the ion transport properties of different porous organic cage membranes. The window-to-window alignment of CC3 membranes leads to continuous channels, resulting in high ion permeability and selectivity. Compared to CC19, the hydrophobic channels of CC3 membranes facilitate fast ion transport by suppressing the hydrogen-bonding interaction. Tuning the surface charge of CC3 membranes increases the selectivity towards mono-/divalent cations. This work provides guidelines for the construction of efficient ion separation membranes.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Aurelia Li, Rocio Bueno-Perez, David Fairen-Jimenez
Summary: A new methodology was developed to extract a large dataset of metal-organic cages and organic cages from the Cambridge Structural Database, which was then used for high-throughput screening for applications such as xenon/krypton separation.
Article
Chemistry, Physical
Ai He, Zhiwei Jiang, Yue Wu, Hadeel Hussain, Jonathan Rawle, Michael E. Briggs, Marc A. Little, Andrew G. Livingston, Andrew Cooper
Summary: In this study, the graded separation of three dyes is achieved by altering the pore size of a porous organic cage composite, demonstrating the potential of single membranes with both high permeance and high rejection.
Article
Chemistry, Organic
Aaron Gabriel Nunez Avila, Benoit Deschenes-Simard, E. Joseph Arnold, Mathieu Morency, Daniel Chartrand, Thierry Maris, Gilles Berger, Graeme M. Day, Stephen Hanessian, James D. Wuest
Summary: The nitrogen-rich compound 6-azidotetrazolo[5,1-a]phthalazine (ATPH) exhibits high polymorphism and diverse molecular organization due to its ability to form various N-H···N and C-H···N interactions. Crystal structures of ATPH reveal a polymorphic landscape with stacked sheets and herringbone packing. Exploring this landscape provides insights into fields such as energetic materials and molecular crystallization.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Qiang Zhu, Jay Johal, Daniel E. Widdowson, Zhongfu Pang, Boyu Li, Christopher M. Kane, Vitaliy Kurlin, Graeme M. Day, Marc A. Little, Andrew I. Cooper
Summary: This study used a combined approach to discover a rare low-density mesoporous hydrogen-bonded framework. The results show that this method can overcome the difficulties in comparing predicted molecular crystals with varying lattice parameters, providing a systematic approach for energy-structure comparison of chemically dissimilar molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Martins Balodis, Manuel Cordova, Albert Hofstetter, Graeme M. Day, Lyndon Emsley
Summary: The determination of the three-dimensional atomic-level structure of powdered solids is an important goal in current chemistry. This study successfully determined the crystal structures of ampicillin, piroxicam, cocaine, and two polymorphs of the drug molecule AZD8329 using machine-learned isotropic chemical shifts generated on-the-fly to guide a Monte Carlo-based structure determination process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Shiyue Yang, Graeme M. Day
Summary: Current crystal structure prediction methods lack the ability to provide information on the depth and energy barriers between polymorph structures. This study applies a Monte Carlo threshold algorithm to estimate the energy barriers and characterize the energy landscapes of polymorphic molecular crystal structures.
COMMUNICATIONS CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Norbert M. Villeneuve, Joshua Dickman, Thierry Maris, Graeme M. Day, James D. Wuest
Summary: Mixed crystals are formed when components of the structure are randomly replaced by analogues, and their properties can be adjusted by changing the ratio of components. However, there are no clear rules to predict when two compounds can form mixed crystals. Through various methods, it has been discovered that mixed crystals can have compositions and properties that vary continuously over wide ranges. The results of experiments and computational modeling show that predictions about mixed crystallization can be made reliably.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Caitlin E. Shields, Xue Wang, Thomas Fellowes, Rob Clowes, Linjiang Chen, Graeme M. Day, Anna G. Slater, John W. Ward, Marc A. Little, Andrew I. Cooper
Summary: Designing hydrogen-bonded organic frameworks (HOFs) with low densities and high porosities is challenging due to the preference for close packing in most molecules. Crystal structure prediction (CSP) can rank alternative crystal packings for organic molecules based on their lattice energies. By combining CSP with structure-property predictions, a previously unknown low-energy HOF (TH5-A) with remarkably low density and three-dimensional pores was discovered for triptycene trisquinoxalinedione (TH5). This TH5-A polymorph demonstrates high porosity with a surface area of 3,284 m(2) g(-1), making it one of the most porous HOFs reported.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Patrick W. V. Butler, Graeme M. Day
Summary: Crystal structure prediction is a valuable tool for assessing polymorphism of crystalline molecular compounds, but it tends to overpredict the number of polymorphs. One cause of this overprediction is the neglect of the coalescence of potential energy minima into a single basin at finite temperature. To address this issue, we propose a method based on the threshold algorithm to cluster potential energy minima into basins, thus identifying kinetically stable polymorphs and reducing overprediction.
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
(2023)
Article
Chemistry, Multidisciplinary
Joseph E. E. Arnold, Graeme M. M. Day
Summary: The synthesis and experimental testing of energetic materials can be hazardous, but their applications in various industries and military necessitate continuous research and development. This study evaluates computational methods for predicting crystal structures of energetic molecular organic crystals, which can guide experimental work. Crystal structure prediction is assessed on 10 energetic materials using a force field approach initially, followed by reoptimization using solid-state density functional theory. The results show that the force field method provides good predictions for some molecules, but they are more variable compared to other small organic molecules. Reoptimization using solid-state DFT leads to reliable predictions, demonstrating the usefulness of crystal structure prediction in the discovery and development of energetic materials.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Rachel J. Kearsey, Andrew Tarzia, Marc A. Little, Michael C. Brand, Rob Clowes, Kim E. Jelfs, Andrew I. Cooper, Rebecca L. Greenaway
Summary: The synthesis of a new porous organic cage (CC21) with isopropyl moieties was achieved from the reaction of triformylbenzene and an isopropyl functionalised diamine. The challenging synthesis was rationalised using control experiments and computational modelling, highlighting the competitive aminal formation. The addition of an extra amine increased the conversion to the desired cage.
CHEMICAL COMMUNICATIONS
(2023)
Article
Physics, Fluids & Plasmas
Miloslav Torda, John Y. Goulermas, Vitaliy Kurlin, Graeme M. Day
Summary: The study focuses on the dense packings of regular convex polygons and their applications in physical and biological systems, as well as discrete and computational geometry. By restricting the configuration space, the authors formulate the problem as a nonlinear constrained optimization problem and solve it using the Entropic Trust Region Packing Algorithm. The study examines the densest packings of various polygons in all 17 plane groups and proposes conjectures about the common symmetries of the densest plane group packings.
Article
Materials Science, Multidisciplinary
Rebecca J. Clements, Joshua Dickman, Jay Johal, Jennie Martin, Joseph Glover, Graeme M. Day
Summary: The field of crystal structure prediction has undergone significant changes, and machine learning methods are expected to have a great impact by improving energy evaluation, analyzing structure landscapes, and identifying promising molecules.
Article
Chemistry, Multidisciplinary
Megan O'Shaughnessy, Peter R. Spackman, Marc A. Little, Luca Catalano, Alex James, Graeme M. Day, Andrew Cooper
Summary: A porous molecular crystal, TSCl, was discovered during the synthesis of tetrakis(4-sulfophenylmethane). The crystal structure prediction (CSP) explains the driving force and intermolecular interactions behind the formation of this porous phase. Gas sorption analysis revealed its permanent porosity and selective adsorption of CO2 over other gases.
CHEMICAL COMMUNICATIONS
(2022)
