Article
Chemistry, Multidisciplinary
Alessio Cataldo, Karolis Norvaisa, Lau Halgreen, Samantha E. Bodman, Kristin Bartik, Stephen J. Butler, Hennie Valkenier
Summary: A neutral receptor capable of transporting phosphate ions across lipid membranes has been discovered, opening possibilities for the development of transporters for various biological phosphates.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Areum Lee, Ju Ho Yang, Ju Hyun Oh, Benjamin P. Hay, Kyounghoon Lee, Vincent M. Lynch, Jonathan L. Sessler, Sung Kuk Kim
Summary: A cyclo[2]carbazole[2]pyrrole (2), composed of two carbazoles and two pyrroles, was synthesized by directly linking the carbazole 1- and 8-carbon atoms to the pyrrole alpha-carbon atoms. The resulting macrocycle 2 has an extensively conjugated 16-membered macrocyclic ring and a preorganized anion binding site consisting of two pyrrole subunits. H-1 NMR spectroscopic analysis revealed that only the diagonally opposed pyrrole NH protons are involved in anion binding, and cyclo[2]carbazole[2]pyrrole 2 binds anions with higher affinity than calix[4]pyrrole (1). Computational studies suggest that the higher anion affinity of receptor 2 is due to its larger binding energy and lower host strain energy associated with anion complexation. In the presence of excess fluoride or bicarbonate anions, compound 2 loses two pyrrolic NH protons and forms a stable dianionic macrocycle [2-2H](2-) with quenched fluorescence.
Article
Chemistry, Multidisciplinary
David Villaron, Guido E. A. Brugman, Maxime A. Siegler, Sander J. Wezenberg
Summary: Dithienylethene-strapped calix[4]pyrrole undergoes isomerization between ring-open and -closed isomers upon 300/630 nm light irradiation, which affects the size of the anion binding site. While the affinity for chloride shows only a minor change, that for larger bromide and iodide ions is significantly altered, resulting in modified selectivity.
CHEMICAL COMMUNICATIONS
(2023)
Review
Chemistry, Organic
Ishfaq Ahmad Rather, Rashid Ali, Ayaaz Ali
Summary: In recent years, the non-aromatic macrocyclic skeleton calix[4]pyrrole (C4P) has made significant advancements in the fields of molecular recognition and self-assembly in supramolecular chemistry. It has been widely used in a variety of applications, such as ion/ion-pair or neutral molecule binding/sensing, polymers, catalysis, drug delivery, etc. This article aims to compile the recent developments in C4P-based supramolecular systems, providing a valuable guide for researchers in this field.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Organic
Ishfaq Ahmad Rather, Rashid Ali, Ayaaz Ali
Summary: The design and development of diverse functional systems in recent years have achieved significant milestones in the molecular recognition and self-assembly aspects of supramolecular chemistry. The non-aromatic macrocyclic skeleton calix[4]pyrrole (C4P) has been widely utilized in various applications, such as ion/ion-pair or neutral molecule binding/sensing, polymers, catalysis, drug delivery, pharmacology, ion transport, molecular machines/switches, and adsorption. This article aims to compile recent advancements in C4P-based supramolecular systems, providing a valuable guide for researchers in this field.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
David Villaron, Maxime A. Siegler, Sander J. Wezenberg
Summary: This study presents a Calix[4]pyrrole receptor that can be reversibly switched by light between a strong chloride-binding Z-isomer and a weakly binding E-isomer. The significant difference in binding affinity between the Z- and E-isomer is quantified using H-1 NMR and ITC titrations in MeCN. Structural insights into the photogenerated E-isomer and the chloride-bound receptors are provided through DFT calculations and X-ray crystallographic analysis, offering new prospects for on-demand binding and release in extractions and membrane transport processes.
Article
Chemistry, Multidisciplinary
Ashoke Kumar Patra, Soumya Srimayee, Dibakar Halder, Anik Roy, Souvik Mukherjee, Somenath Kundu, Maidul Hossain, Rajat Saha, Chang-Hee Lee, Debasis Manna, Indrajit Saha
Summary: Meso-3,5-bis(trifluoromethyl)phenyl picket calix[4]pyrrole 1 exhibited excellent fluoride anion transport activity across artificial lipid bilayers, with an EC50 value of 2.15 μM (at 450 s in EYPC vesicles), and high selectivity for fluoride over chloride ions. The high fluoride selectivity of compound 1 was attributed to the formation of a sandwich-like p-anion-p interaction complex.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Nam Jung Heo, Vincent M. Lynch, Dustin E. Gross, Jonathan L. Sessler, Sung Kuk Kim
Summary: The anion binding features of diphenylpyrrole-strapped calix[4]pyrrole 1 have been investigated, and it was found that the receptor can bind F-, Cl-, and Br- ions with high affinity and can extract fluoride and chloride ions from water.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Jinya Tian, Jie Ji, Yaling Zhu, Yanlei He, Hongbing Li, Yi Li, Dan Luo, Jiapeng Xing, Long Qie, Jonathan L. Sessler, Xiaodong Chi
Summary: A flexible solid supramolecular electrolyte that blends a new anion capture agent with a PEO matrix has been developed. This electrolyte showcases high ionic conductivity and a high Li+ transference number, as well as excellent cycling and rate performance.
ADVANCED MATERIALS
(2023)
Article
Polymer Science
Fatma Yelda Unlu, Abdullah Aydogan
Summary: This study reports the construction of a novel supramolecular hyperbranched polymer based on the anion recognition ability of calix[4]pyrrole. The polymer exhibits thermo-, pH-, and chemical responsiveness, as well as concentration dependent morphology tune. This research enriches the field of supramolecular polymers and provides a simple approach for the fabrication of smart polymer materials with multi-responsiveness and -morphologies.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Materials Science, Multidisciplinary
Fatma Yelda Unlu, Abdullah Aydogan
Summary: In this study, a cross-linked supramolecular polymer in chloroform was synthesized using azide-alkyne click chemistry. It was found that suberate anion acted as a suitable cross-linker. The performance of the monomers and the cross-linked supramolecular polymer was monitored using various techniques.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Chemistry, Physical
Ishfaq Ahmad Rather, Ufana Riaz, Rashid Ali
Summary: UV-vis spectroscopy and TD-DFT calculations were used to investigate the anion binding of meso-substituted one-walled phthalimide-based calix[4]pyrrole (m-PC4P, 6) in acetonitrile. The results showed that m-PC4P (6) exhibited higher anion binding affinities compared to the parent C4P system, possibly due to additional weak CH-anion interactions besides four NH-hydrogen bonds of the C4P framework. The binding affinity decreased with the increase in halide size from fluoride to iodide, and m-PC4P (6) showed better binding with nitrate anion compared to simple C4P (1).
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Physical
Xiangquan Liu, Jiaqi Tang, Jinglun Yang, Helan Zhang, Yu Fang
Summary: The study presents a new type of calix[4]pyrrole (C[4]P)-based nanofilms with excellent molecular sieving performance in nanofiltration, capable of rejecting water-soluble low molecular weight organic compounds. The nanofilms, prepared via confined dynamic condensation, exhibit high permeance and low molecular weight cutoff value, showing promising potential in high-performance nanofiltration.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Di Chen, Dan Luo, Yanlei He, Jinya Tian, Yao Yu, Hongyu Wang, Jonathan L. Sessler, Xiaodong Chi
Summary: Here, we report an easy-to-prepare calix[4]pyrrole-based azobridged porous organic polymer (C4P-POP) that efficiently captures bromine. C4P-POP has high uptake capacities for bromine in both vapor and cyclohexane solution. The experiments show that C4P-POP selectively captures bromine from a mixture of bromine and iodine in cyclohexane.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Inhong Hwang, Sheng-Yin Huang, Scott Smith, Vincent Lynch, Radu Custelcean, Bruce A. Moyer, Nitesh Kumar, Vyacheslav S. Bryantsev, Jonathan L. Sessler
Summary: This work introduces calix[4]pyrrole-based ion-pair receptors, cis/trans-1 and cis/trans-2, designed for extracting sodium hydroxide. The structure of the cis-1·NaOH isomer was analyzed using X-ray diffraction and revealed a unique dimeric supramolecular structure. The extraction efficiency of NaOH using purified receptors cis- and trans-2 was found to be 50-60%, but precipitation was observed in all cases. Precipitation was avoided by immobilizing the receptors onto a poly(styrene) resin, allowing for lower pH and salinity in the extraction process.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Engineering, Chemical
Zhixing Zhao, Bailing Tang, Xiaosheng Yan, Xin Wu, Zhao Li, Philip A. Gale, Yun-Bao Jiang
Summary: Synthetic crown ether-thiourea conjugates can act as a cation/anion symporter with high activity in transporting Na+ and Cl-, but the activity decreases in the presence of high concentrations of K+ ions.
FRONTIERS OF CHEMICAL SCIENCE AND ENGINEERING
(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)
Article
Chemistry, Multidisciplinary
Wei Zhou, Aimin Li, Philip A. Gale, Qing He
Summary: This paper details a highly selective anion recognition and extraction method that can effectively remove pollutants from the environment and recover valuable chemicals. The method allows for efficient separation of solid mixtures and aqueous media containing traces of ReO4- ions, as well as complex waste streams containing perrhenate.
CELL REPORTS PHYSICAL SCIENCE
(2022)
Article
Chemistry, Organic
Faiza Diaba, Gisela Trenchs
Summary: The first violet light-mediated synthesis of gamma- and delta-lactams from N-alkenyl trichloroacetamides is reported in this paper. The reactions are conducted in tetrahydrofuran or 2-methyltetrahydrofuran as the sole solvent without catalysts or additives, under non-anhydrous conditions in an air atmosphere where the solvent serves as the radical initiator.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Feroze Hussain, Sajjad Ahmed, Ashiq Hussain Padder, Qazi Naveed Ahmed
Summary: This study reports a novel and efficient one-pot synthesis method for mixed phosphorotrithioates, which does not require supplementary additives and shows broad applicability.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Hyunjin Oh, Ikyon Kim
Summary: A new 1,2,4-triazole-pyrrolo[1,2-a]pyrazine hybrid system, 6-acylpyrrolo[1,2-a][1,2,4]triazolo[5,1-c]pyrazine, was synthesized using a catalyst-free method. This method involved sequential exposure of pyrrole-2-carbonitrile-derived substrates to DMF-DMA and acyl hydrazide, resulting in the formation of acylated pyrazine and 1,2,4-triazole rings, enabling the installation of various substituents at specific positions on the core skeleton.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Ming Yan, Si-fan Wang, Yong-po Zhang, Jin-zhong Zhao, Zhuo Tang, Guang-xun Li
Summary: Here we developed an efficient photocatalytic approach for the convenient preparation of sulfinamides. The reaction allows for the gram-scale preparation of sulfinamides and the one-pot synthesis of various sulfonyl amides.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Farzaneh Bandehali-Naeini, Zahra Tanbakouchian, Noushin Farajinia-Lehi, Nicolas Mayer, Morteza Shiri, Martin Breugst
Summary: Two tandem catalytic systems were developed for the synthesis of novel 3,4-disubstituted maleimides using the same Ugi adducts. Different maleimide structures can be synthesized using either Pd or Cu catalysis.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Article
Chemistry, Organic
Tanya Raghava, Anjan Chattopadhyay, Subhadeep Banerjee, Nivedita Sarkar
Summary: Amine substitution of two ortho fluorine atoms of tetrafluoroterephthalonitrile through SNAr chemistry is easily achievable. But further fluorine substitution is only possible under forcing conditions, yielding valuable fluorophores for bioimaging.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
Review
Chemistry, Organic
Anju Chadha, Santosh Kumar Padhi, Selvaraj Stella, Sowmyalakshmi Venkataraman, Thangavelu Saravanan
Summary: Alcohol dehydrogenases are enzymes that use cofactors for oxidation or reduction reactions of alcohols or carbonyl compounds. They are utilized in green chemistry and have applications in the production of pharmaceuticals. Recombinant enzymes have solved the challenge of producing purified enzymes in large quantities. Engineered alcohol dehydrogenases have been used in asymmetric synthesis in industry. Various methods have been established for regenerating expensive cofactors to make the enzymatic process more efficient and economically viable.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2024)
