Article
Chemistry, Multidisciplinary
N. V. Cornelissen, R. Mineikaite, M. Erguven, N. Muthmann, A. Peters, A. Bartels, A. Rentmeister
Summary: mRNAs have potential as modalities for vaccination and protein replacement therapy. By modifying the 5' cap, we demonstrated the potential of an enzymatic cascade for post-synthetic modification of mRNA, which can increase protein production without eliciting an immune response.
Review
Chemistry, Inorganic & Nuclear
Ting Chen, Dan Zhao
Summary: Metal-organic frameworks (MOFs) are porous crystalline materials constructed by metal clusters and organic linkers. Recent research has focused on the development of engineered forms of MOFs, particularly MOF-based membranes for molecular separations. This review highlights the advances in post-synthetic modification of MOFs and their membranes for enhanced separation performance. Post-synthetic modification methods are categorized and examples of modified MOF membranes are discussed. The contributions of post-synthetic modification to improved molecular separation performance are emphasized, along with the challenges and opportunities for practical applications of MOF membranes.
COORDINATION CHEMISTRY REVIEWS
(2023)
Review
Chemistry, Physical
Leidy Figueroa-Quintero, David Villalgordo-Hernandez, Jose J. Delgado-Marin, Javier Narciso, Vijay Kumar Velisoju, Pedro Castano, Jorge Gascon, Enrique V. Ramos-Fernandez
Summary: Metal-organic frameworks (MOFs) are porous hybrid materials with potential applications in catalysis, adsorption, drug delivery, mixed matrix membranes, and stabilization of porous liquids. While there has been considerable focus on functionalizing the inner surface of MOF crystals, methods to selectively functionalize the outer crystal surface are less developed. This article provides an overview of different types of post-synthetic modifications and their applications in various fields.
Article
Chemistry, Multidisciplinary
Michael R. Dworzak, Christine M. Montone, Nicole I. Halaszynski, Glenn P. A. Yap, Christopher J. Kloxin, Eric D. Bloch
Summary: Novel cobalt calixarene-capped and zirconium-based porous coordination cages were prepared for post-synthetic modification using click chemistry. The calixarene-capped cages showed impressive stability under copper-catalyzed alkyne-azide cycloaddition conditions, while milder reaction conditions were needed for zirconium-based cages. Reaction kinetics were monitored using IR spectroscopy, showing rapid reaction times (<3 hours).
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Seyedeh Molood Masoom Nataj, Serge Kaliaguine, Frederic-Georges Fontaine
Summary: A post-synthetic modification of Zr-MOF using ionic nitrogen-based functional groups allows for the catalytic cycloaddition reaction of CO2 with epoxides. The functionalized MOFs show high catalytic performance under mild conditions, and the aperture size of the MOF plays an important role in the diffusion of substrates in CO2 fixation reactions.
Article
Chemistry, Physical
Zilong Zhang, Yanchun Chen, Yiheng Sun, Zilu Chen, Zhan-Yun Zhang, Fupei Liang, Dongcheng Liu, Huan-Cheng Hu
Summary: Post-synthetic modification is an effective strategy for preparing new materials with superior performance. In this study, we quantitatively transformed aldehyde groups in ZIF-90 into mono- and bis-Schiff bases, resulting in new compounds that showed higher iodine uptake capacities compared to ZIF-90. Furthermore, we investigated the activation energies for iodine adsorption in Metal-Organic Frameworks (MOFs) for the first time and studied the adsorption kinetics and iodine species during the adsorption process in detail.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Applied
Soraia P. S. Fernandes, Laura Frey, Krystal M. Cid-Seara, Orlando Oliveira, Noelia Guldris, Enrique Carbo-Argibay, Carlos Rodriguez-Abreu, Yury Kolen'ko, Artur M. S. Silva, Dana D. Medina, Laura M. Salonen
Summary: A post-synthetic modification strategy was proposed to extend the pi-system of covalent organic framework (COF) backbone, resulting in boronic ester based pyrene-fused azaacene COFs. Optimized catalyst-free reaction conditions led to COFs with up to 33% conversion and intriguing optical properties. This chemistry is expected to be useful for tailoring the optical properties of COFs.
MICROPOROUS AND MESOPOROUS MATERIALS
(2022)
Article
Engineering, Environmental
Deyi Yan, Naiyun Gao, Xinni Wu, Haixuan Zhang, Huase Ou
Summary: In this study, a novel MIL-101(Fe)-TfmPU with superhydrophobicity was successfully synthesized using a postsynthetic modification method, leading to a significant improvement in water stability for its photocatalysis applications in aqueous mediums.
JOURNAL OF WATER PROCESS ENGINEERING
(2021)
Article
Chemistry, Inorganic & Nuclear
Liancheng He, Rui-dong Wang, Shuyu Wang, Rong-Rong Zhu, Zhihao Li, Yuan-yuan Wu, Jie Ma, Lin Du, Qi-Hua Zhao
Summary: In this study, a luminescent complex with aggregation-induced emission (AIE) properties and time-dependent luminescence conversion phenomenon was achieved through covalent post-synthetic modification (PSM) using a Schiff base reaction. The new material inherited the luminescence properties of the original complex and demonstrated significant AIE properties in response to environmental conditions such as viscosity and temperature.
DALTON TRANSACTIONS
(2021)
Article
Engineering, Chemical
Mohammad Rad, Meghdad Karimi, Morteza Moradi, Vahid Safarifard
Summary: This study investigates the catalytic properties of alcohol oxidation through post-synthesis modification using iodide and bromide as active sites for the first time. The findings show that MIP-202-I is the best catalyst for improving alcohol oxidation, while MIP-202-Br and MIP-202-Cl also exhibit high catalytic efficiency.
JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS
(2022)
Article
Chemistry, Multidisciplinary
Bo Gui, Xuefen Liu, Yuanpeng Cheng, Ya Zhang, Pohua Chen, Minghui He, Junliang Sun, Cheng Wang
Summary: Three-dimensional covalent organic frameworks (3D COFs) have attracted increasing attention for their unique features, but face challenges in development due to synthetic difficulty and complex structure determination. This study presents a new strategy of post-synthetic modification to incorporate functional moieties into predetermined frameworks, offering a promising way to construct functional 3D COFs for various applications in the future.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Mengchu Li, Liying Zhang, Xuanhe Wang, Xuemin Zhang, Tieqiang Wang, Fuqiang Fan, Yu Fu
Summary: In this study, a functional nanocomposite membrane was prepared through post-synthetic modification. The results showed that the membrane exhibited a dye removal rate of over 93.0%.
INORGANIC CHEMISTRY COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Hailong Wang, Yinghua Jin, Nana Sun, Wei Zhang, Jianzhuang Jiang
Summary: Porous organic cages (POCs) are a class of organic materials with intrinsic porosity. Post-synthetic modification (PSM) has emerged as a highly viable strategy for broadening the functions and applications of POCs, leading to improved stability, tunable porosity, and selective guest binding. This approach allows for the realization of intricate structures and unique gas adsorption selectivity that cannot be achieved through traditional predesign methods.
CHEMICAL SOCIETY REVIEWS
(2021)
Review
Biotechnology & Applied Microbiology
Fady Abd El-malek, Alexander Steinbuchel
Summary: Biodegradable polymers, such as polyhydroxyalkanoates (PHA), have various industrial and biological uses. However, their processability and mechanical properties are not ideal, limiting their application range. Enzymes and chemicals can be used to modify and improve polymer performance, enhancing stability and production.
FRONTIERS IN BIOENGINEERING AND BIOTECHNOLOGY
(2022)
Article
Chemistry, Applied
Qi Cao, Yu Peng, Qingya Yu, Zhan Shi, Qiong Jia
Summary: In this research, a fluorescence sensor UiO-CPBA was designed by post synthetic modification of UiO-66NH2 with 4-carboxyphenylboronic acid (4-CPBA). This sensor utilized the interaction between the boronic acid group and sialic acid (SA) to achieve fluorescence detection of SA, providing a new approach for constructing SA sensing platforms for complex real samples.
Article
Chemistry, Multidisciplinary
Stephanie Yerdelen, Yihui Yang, Justin L. Quon, Charles D. Papageorgiou, Chris Mitchell, Ian Houson, Jan Sefcik, Joop H. ter Horst, Alastair J. Florence, Cameron J. Brown
Summary: This study performed a series of isothermal induction time studies and used machine learning techniques to analyze the correlations between vessel hydrodynamic features and nucleation kinetic parameters. The best performing models for nucleation rate were found to be a nonlinear random Forest model and a nonlinear gradient boosting model, while a nonlinear gradient boosting model outperformed other models for growth time. The ensemble of these models predicted the probability of nucleation solely from hydrodynamic features with an overall root mean square error of 0.16. This work demonstrates how machine learning approaches can provide insights into the scale-up of an unseeded crystallization process by analyzing limited datasets of induction times.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Robert E. Ducker, Oscar Siles Bruegge, Anthony J. H. M. Meijer, Graham J. Leggett
Summary: We demonstrate the mechanochemical regulation of a photochemical reaction using an atomic force microscope (AFM) probe to remove photocleavable nitrophenyl protecting groups from alkylsilane films. This process enables nanoscale differentiation of chemical reactivity with high spatial resolution. The study also shows that functionalization of nanolines with nitrilo triacetic acid allows for site-specific immobilization of histidine-tagged green fluorescent protein.
Article
Multidisciplinary Sciences
Weiwei Tang, Taimin Yang, Cristian A. Morales-Rivera, Xi Geng, Vijay K. Srirambhatla, Xiang Kang, Vraj P. Chauhan, Sungil Hong, Qing Tu, Alastair J. Florence, Huaping Mo, Hector A. Calderon, Christian Kisielowski, Francisco C. Robles Hernandez, Xiaodong Zou, Giannis Mpourmpakis, Jeffrey D. Rimer
Summary: Modifiers play a crucial role in crystallization, and tautomers as a new class of modifiers have been found to inhibit crystal growth by occluding within crystals. This study focuses on the crystallization of ammonium urate and demonstrates the potential of tautomers in controlling the mechanical or physicochemical properties of materials.
NATURE COMMUNICATIONS
(2023)
Article
Energy & Fuels
Mohammad Umair Jamal, Ashleigh J. Fletcher
Summary: Native Scottish wood samples were evaluated as potential feedstock for biochar production. Softwood was found to be the preferable material. The study investigated the influence of operational parameters on biochar characteristics and identified optimal conditions for maximum responses. The results highlighted the significance of the selected feedstock and the interplay of operational variables in biochar development.
BIOENERGY RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
Beatriz Donagueda Suso, Alexandre Legrand, Catherine Weetman, Alan R. Kennedy, Ashleigh J. Fletcher, Shuhei Furukawa, Gavin A. Craig
Summary: Three new ligands with a bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxydiimide unit were used to assemble lantern-type metal-organic cages with the formula [Cu4L4]. The functionalization of the ligands' backbone resulted in distinct crystal packing motifs for the three cages, as observed by single-crystal X-ray diffraction. The gas sorption behavior of the three cages varied, with the material's capacity for CO2 dependent on the activation conditions, and one of the cages exhibiting the highest BET surface area among lantern-type cages.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Polymer Science
Anam Safri, Ashleigh Jane Fletcher
Summary: A suite of composite materials consisting of carbon xerogel and TiO2 was synthesized using a modified sol-gel method. The properties of the composites were extensively characterized and correlated with their adsorption and photodegradation performances. The homogeneity and porous structure of the composites were found to depend on the amount of TiO2 deposited in the carbon xerogel.
Article
Energy & Fuels
Ashleigh Fletcher, Tosin Somorin, Oluwagbemi Aladeokin
Summary: The potential of peanut shell as a precursor for producing activated carbon was investigated in this study. The researchers optimized the activation variables and found that impregnation ratio and temperature had the most significant impact on the final characteristics of the activated carbon. Under the optimized conditions, a high surface area carbon material with a relatively high density and low ash content was produced. The material showed great potential as an adsorbent, removing up to 99.8% of a target dye. This study demonstrates the possibility of tailoring activated carbon materials from waste biomass.
BIOENERGY RESEARCH
(2023)
Article
Engineering, Chemical
Stephanie J. Urwin, Magdalene W. S. Chong, Wei Li, John McGinty, Bhavik Mehta, Sara Ottoboni, Momina Pathan, Elke Prasad, Murray Robertson, Mark McGowan, Mais al-Attili, Ekaterina Gramadnikova, Mariam Siddique, Ian Houson, Helen Feilden, Brahim Benyahia, Cameron J. Brown, Gavin W. Halbert, Blair Johnston, Alison Nordon, Chris J. Price, Chris D. Reilly, Jan Sefcik, Alastair J. Florence
Summary: A digital-first approach is proposed for the production of high-quality particles of an active pharmaceutical ingredient, reducing material requirements and experimental burden. Predictive modelling is used to produce two particle sizes via crystallisation, with solubility prediction aiding solvent selection. The study demonstrates the challenges associated with a digital-first approach and discusses the limitations in current first-principles models.
CHEMICAL ENGINEERING RESEARCH & DESIGN
(2023)
Article
Pharmacology & Pharmacy
Thomas Hibbard, Hannah Mitchell, Yoonha Kim, Kenneth Shankland, Hisham Al-Obaidi
Summary: The aim of this study was to investigate inhaled formulations of progesterone through spray drying and analyze how spray drying affects the physicochemical properties of progesterone. X-ray diffraction, spectroscopy, and thermal analysis were used to characterize the formulations. The addition of HPMCAS was shown to increase the solubility of progesterone and temporarily enable a supersaturated state. Additionally, spray drying improved the inhalation performance of progesterone. Therefore, HPMCAS is suggested as a suitable excipient to improve the solubility and inhalation properties of spray-dried progesterone formulations.
EUROPEAN JOURNAL OF PHARMACEUTICS AND BIOPHARMACEUTICS
(2023)
Article
Chemistry, Physical
Magdalene W. S. Chong, Andrew J. Parrott, David J. Ashworth, Ashleigh J. Fletcher, Alison Nordon
Summary: The study demonstrates the application of Raman spectroscopy in discriminating the phases of metal-organic frameworks (MOFs) by analyzing F4_MIL-140A(Ce) and F4_UiO-66(Ce), which are analogues prepared from the same metal and ligand sources. Each analogue shows unique Raman peaks, especially in the low-frequency region, indicating their structural variations. Non-invasive Raman monitoring of F4_MIL-140A(Ce) synthesis reveals the evolution of a specific MOF Raman peak that correlates well with the extent of crystallization determined by synchrotron diffraction method. Raman spectroscopy is a promising technique for rapid screening of MOFs and studying their formation mechanism with kinetic insight into the reaction medium.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Laura Pereira Diaz, Cameron J. Brown, Ebenezer Ojo, Chantal Mustoe, Alastair J. Florence
Summary: Understanding powder flow in the pharmaceutical industry is important for developing robust production routes and effective manufacturing processes. This study explores the use of machine learning models to predict powder flow behavior in pharmaceutical materials. The models show promising results in predicting flow properties based on physical properties of the powders, and important variables such as particle size distribution and aspect ratio were identified.
Article
Chemistry, Multidisciplinary
Matthew R. Wilkinson, Laura Pereira Diaz, Antony D. Vassileiou, John A. Armstrong, Cameron J. Brown, Bernardo Castro-Dominguez, Alastair J. Florence
Summary: This study proposes the use of deep learning methods to predict powder flow from microscopy images in the pharmaceutical industry. By achieving high validation accuracy, this approach reduces the need for experimental flowability measurements and saves time and costs during early drug development when material is limited.
Article
Chemistry, Multidisciplinary
Alexander J. Auty, Paul A. Scattergood, Theo Keane, Tao Cheng, Guanzhi Wu, Heather Carson, James Shipp, Andrew Sadler, Thomas Roseveare, Igor V. Sazanovich, Anthony J. H. M. Meijer, Dimitri Chekulaev, Paul I. P. Elliot, Mike Towrie, Julia A. Weinstein
Summary: Through comparing the effects of different acceptors conjugated into the donor-bridge-acceptor (DBA) systems, the role of driving force and structural changes in directing the photoinduced pathways was revealed. Direct conjugation of a strong acceptor into the bridge can switch the lowest excited state and an increased acceptor strength leads to a decrease in the formation rate and an increase in the lifetime of the charge-separated state.
Article
Chemistry, Multidisciplinary
Antony D. Vassileiou, Murray N. Robertson, Bruce G. Wareham, Mithushan Soundaranathan, Sara Ottoboni, Alastair J. Florence, Thoralf Hartwig, Blair F. Johnston
Summary: A single machine learning-based model is proposed to predict the solubility of drug/drug-like compounds in organic solvents. This model leverages cross-solvent data structure to exploit the valuable relational information between systems. The study shows that even a single experimental measurement of a solute in a different solvent can greatly improve the predictions, and successive measurements further enhance the accuracy of the predictions.
Article
Chemistry, Multidisciplinary
Alexander J. Auty, Paul A. Scattergood, Theo Keane, Tao Cheng, Guanzhi Wu, Heather Carson, James Shipp, Andrew Sadler, Thomas Roseveare, Igor V. Sazanovich, Anthony J. H. M. Meijer, Dimitri Chekulaev, Paul I. P. Elliot, Mike Towrie, Julia A. Weinstein
Summary: This study investigates the role of driving force and structural changes in directing the photoinduced pathways in donor-bridge-acceptor (DBA) systems. The ultrafast dynamics in different DBA systems with the same donor and bridge, but different acceptors, were compared. It was found that the conjugation of a strong acceptor into the bridge has a significant impact on the lowest excited state and charge-separated state. The stronger acceptor leads to a slower formation rate and longer lifetime of the charge-separated state, as well as an increased rate of intersystem crossing.
