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1. Anion–anion and anion–neutral triel bonds

   https://doi.org/10.1039/D0CP06547A  

   Wysokiński, Rafał ; Michalczyk, Mariusz ; Zierkiewicz, Wiktor ; Scheiner, Steve ( March 2021 , Physical Chemistry Chemical Physics)

   null (Ed.)

   The ability of a TrCl 4 − anion (Tr = Al, Ga, In, Tl) to engage in a triel bond with both a neutral NH 3 and CN − anion is assessed by ab initio quantum calculations in both the gas phase and in aqueous medium. Despite the absence of a positive σ or π-hole on the Lewis acid, strong triel bonds can be formed with either base. The complexation involves an internal restructuring of the tetrahedral TrCl 4 − monomer into a trigonal bipyramid shape, where the base can occupy either an axial or equatorial position. Although this rearrangement requires a substantial investment of energy, it aids the complexation by imparting a much more positive MEP to the site that is to be occupied by the base. Complexation with the neutral base is exothermic in the gas phase and even more so in water where interaction energies can exceed 30 kcal mol −1 . Despite the long-range coulombic repulsion between any pair of anions, CN − can also engage in a strong triel bond with TrCl 4 − . In the gas phase, complexation is endothermic, but dissociation of the metastable dimer is obstructed by an energy barrier. The situation is entirely different in solution, with large negative interaction energies of as much as −50 kcal mol −1 . The complexation remains an exothermic process even after the large monomer deformation energy is factored in. 

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2. Orthogonal, modular anion–cation and cation–anion self-assembly using pre-programmed anion binding sites

   https://doi.org/10.1039/D2SC05121D  

   Dhara, Ayan ; Fadler, Rachel E. ; Chen, Yusheng ; Köttner, Laura A. ; Van Craen, David ; Carta, Veronica ; Flood, Amar H. ( March 2023 , Chemical Science)

   Subcomponent self-assembly relies on cation coordination whereas the roles of anions often only emerge during the assembly process. When sites for anions are instead pre-programmed, they have the potential to be used as orthogonal elements to build up structure in a predictable and modular way. We explore this idea by combining cation (M + ) and anion (X − ) binding sites together and show the orthogonal and modular build up of structure in a multi-ion assembly. Cation binding is based on a ligand (L) made by subcomponent metal-imine chemistry (M + = Cu + , Au + ) while the site for anion binding (X − = BF 4 − , ClO 4 − ) derives from the inner cavity of cyanostar (CS) macrocycles. The two sites are connected by imine condensation between a pyridyl-aldehyde and an aniline-modified cyanostar. The target assembly [LM-CS-X-CS-ML], + generates two terminal metal complexation sites (LM and ML) with one central anion-bridging site (X) defined by cyanostar dimerization. We showcase modular assembly by isolating intermediates when the primary structure-directing ions are paired with weakly coordinating counter ions. Cation-directed (Cu + ) or anion-bridged (BF 4 − ) intermediates can be isolated along either cation–anion or anion–cation pathways. Different products can also be prepared in a modular way using Au + and ClO 4 − . This is also the first use of gold( i ) in subcomponent self-assembly. Pre-programmed cation and anion binding sites combine with judicious selection of spectator ions to provide modular noncovalent syntheses of multi-component architectures. 

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3. High-Fidelity Multistate Switching with Anion-Anion and Acid-Anion Dimers of Organophosphates in Cyanostar Complexes

   https://doi.org/10.1002/ange.201707869  

   Zhao, Wei ; Qiao, Bo ; Chen, Chun-Hsing ; Flood, Amar H. ( October 2017 , Angewandte Chemie)
4. High-Fidelity Multistate Switching with Anion-Anion and Acid-Anion Dimers of Organophosphates in Cyanostar Complexes

   https://doi.org/10.1002/anie.201707869  

   Zhao, Wei ; Qiao, Bo ; Chen, Chun-Hsing ; Flood, Amar H. ( October 2017 , Angewandte Chemie International Edition)
5. Molecular and electrophysiological characterization of anion transport in Arabidopsis thaliana pollen reveals regulatory roles for pH , Ca 2+ and GABA

   https://doi.org/10.1111/nph.15863  

   Domingos, Patrícia ; Dias, Pedro N. ; Tavares, Bárbara ; Portes, Maria Teresa ; Wudick, Michael M. ; Konrad, Kai R. ; Gilliham, Matthew ; Bicho, Ana ; Feijó, José A. ( May 2019 , New Phytologist)

   We investigated the molecular basis and physiological implications of anion transport during pollen tube (PT) growth inArabidopsis thaliana(Col‐0).

   Patch‐clamp whole‐cell configuration analysis of pollen grain protoplasts revealed three subpopulations of anionic currents differentially regulated by cytoplasmic calcium ([Ca²⁺]_cyt). We investigated the pollen‐expressed proteinsAtSLAH3,AtALMT12,AtTMEM16 andAtCCCas the putative anion transporters responsible for these currents.

   AtCCC‐GFPwas observed at the shank andAtSLAH3‐GFPat the tip and shank of thePTplasma membrane. Both are likely to carry the majority of anion current at negative potentials, as extracellular anionic fluxes measured at the tip ofPTs with an anion vibrating probe were significantly lower inslah3^−/−andccc^−/−mutants, but unaffected inalmt12^−/−andtmem16^−/−. We further characterised the effect ofpHandGABAby patch clamp. Strong regulation by extracellularpHwas observed in the wild‐type, but not intmem16^−/−. Our results are compatible withAtTMEM16 functioning as an anion/H⁺cotransporter and therefore, as a putativepHsensor.GABApresence: (1) inhibited the overall currents, an effect that is abrogated in thealmt12^−/−and (2) reduced the current inAtALMT12 transfectedCOS‐7 cells, strongly suggesting the direct interaction ofGABAwithAtALMT12.

   Our data show thatAtSLAH3 andAtCCCactivity is sufficient to explain the major component of extracellular anion fluxes, and unveils a possible regulatory system linkingPTgrowth modulation bypH,GABA, and [Ca²⁺]_cytthrough anionic transporters.

    

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