Search results for "Cooperativity"
showing 10 items of 78 documents
Achieving Strong Positive Cooperativity through Activating Weak Non-Covalent Interactions
2018
Positive cooperativity achieved through activating weak non-covalent interactions is common in biological assemblies but is rarely observed in synthetic complexes. Two new molecular tubes have been synthesized and the syn isomer binds DABCO-based organic cations with high orientational selectivity. Surprisingly, the ternary complex with two hosts and one guest shows a high cooperativity factor (α=580), which is the highest reported for synthetic systems without involving ion-pairing interactions. The X-ray single-crystal structure revealed that the strong positive cooperativity likely originates from eight C-H⋅⋅⋅O hydrogen bonds between the two head-to-head-arranged syn tube molecules. Thes…
Spin Transition of 1D, 2D and 3D Iron(II) Complex Polymers The Tug-of-War between Elastic Interaction and a Shock-Absorber Effect
2003
The structures of linear chain Fe(II) spin-crossover compounds of α,β- and α,ω-bis (tetrazol-1-yl)alkane type ligands are described in relation to their magnetic properties. The first threefold interlocked 3-D catenane Fe(II) spin-transition system, [μ-tris(1,4-bis(tetrazol-1-yl)butane-N1,N1′) iron(II)] bis(perchlorate), will be discussed. An analysis is made among the structures and the cooperativity of the spin-crossover behaviour of polynuclear Fe(II) spin-transition materials.
Synergy of Axial and Point Chirality to Construct Helical N -Heterotriangulene-Based Supramolecular Polymers
2018
Small-Angle Scattering Techniques for Analyzing Conformational Transitions in Hemocyanins
2004
Publisher Summary The precise delivery of oxygen from respiratory surfaces to the tissues is mediated by cooperative and allosterically regulated carrier proteins, such as hemoglobin or hemocyanin. To establish cooperativity, these proteins must be able to adopt different conformations. These conformations are characterized by different ligand affinities, which have their basis in different structures as is the case for the deoxy and oxy states of human hemoglobin. To understand the cooperative interaction of these molecules at the molecular level, the structures of these conformations must be resolved and the transitions between them must be monitored. Because of the nature of sample prepa…
Hofmann-Like Frameworks Fe(2-methylpyrazine)n[M(CN)2]2 (M = Au, Ag) : Spin-Crossover Defined by the Precious Metal
2020
Hofmann-like cyanometalates constitute a large class of spin-crossover iron(II) complexes with variable switching properties. However, it is not yet clearly understood how the temperature and cooperativity of a spin transition are influenced by their structure. In this paper, we report the synthesis and crystal structures of the metal–organic coordination polymers {FeII(Mepz)[AuI(CN)2]2} ([Au]) and {FeII(Mepz)2[AgI(CN)2]2} ([Ag]), where Mepz = 2-methylpyrazine, along with characterization of their spin-state behavior by variable-temperature SQUID magnetometry and Mössbauer spectroscopy. The compounds are built of cyanoheterometallic layers, which are pillared by the bridging Mepz…
Unravelling the chemical design of spin-crossover nanoparticles based on iron(ii)–triazole coordination polymers: towards a control of the spin trans…
2015
A systematic study of the key synthetic parameters that control the growth of spin-crossover (SCO) nanoparticles (NPs) using the reverse micelle technique has been undertaken in the system [Fe(Htrz)2(trz)](BF4)·H2O, (Htrz = 1,2,4-triazole). This has permitted us to modulate the physical properties of the NPs in a controlled and reproducible manner. In particular, a control over the size of the NPs (in the range 4 to 16 nm) has been achieved by varying the water to surfactant molar ratio. The consequences of this size variation on the cooperativity of the spin transition are discussed. Finally, this approach has been extended to the chemical alloy [Fe(Htrz)2.95(NH2trz)0.05](ClO4)2 in order t…
Molecular Mobility in Oriented and Unoriented Membranes Based on Poly[2-(Aziridin-1-yl)ethanol]
2021
Unoriented and oriented membranes based on dendronized polymers and copolymers obtained by chemical modification of poly[2-(aziridin-1-yl) ethanol] (PAZE) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate were considered. DSC, XRD, CP-MAS NMR and DETA, contribute to characterize the tendency to crystallize, the molecular mobility of the benzyloxy substituent, the dendritic liquid crystalline group and the clearing transition. The orientation of the mesogenic chain somewhat hindered this molecular motion, especially in the full substituted PAZE. The fragility, free volume and thermal expansion coefficients of these membranes near the glass transition are related to the orie…
Cooperative Binding of Divalent Diamides by N-Alkyl Ammonium Resorcinarene Chlorides
2015
N-Alkyl ammonium resorcinarene chlorides, stabilized by an intricate array of hydrogen bonds leading to a cavitand-like structure, bind amides. The molecular recognition occurs through intermolecular hydrogen bonds between the carbonyl oxygen and the amide hydrogen of the guests and the cation-anion circular hydrogen-bonded seam of the hosts, as well as through CH⋅⋅⋅π interactions. The N-alkyl ammonium resorcinarene chlorides cooperatively bind a series of di-acetamides of varying spacer lengths ranging from three to seven carbons. Titration data fit either a 1:1 or 2:1 binding isotherm depending on the spacer lengths. Considering all the guests possess similar binding motifs, the first bin…
Influence of negative allosteric cooperativity in cation transport.
1992
Abstract The bis-macrocyclic ether5 seems to have a negative allosteric cooperativity and is able to transport double the amount of Na+ and K+ cations as monocyclic systems. This compound could be used as a simple model of the plasma membrane Na+−K+ ATPase which actively pumps Na+ out and K+ into the cell, respectively.