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Nature of intermolecular interaction in squaraine dimers.

ABSTRACT: Squaraine dyes are known for their particular optical properties. They exhibit intense photochemically stable fluorescence in usually (near) infra red region that can be quenched by intermolecular interactions. Moreover, even the centrosymmetric dyes feature non-zero second harmonic generation upon aggregation. Therefore, the detailed knowledge of the squaraine dye interaction nature both in homogenic aggregates and with other species present in the environment can be of importance for the design of new materials of desired properties. In the present study, interaction in squaraine dimers is investigated with quantum chemistry tools. Four structures: two stacked and two hydrogen-bonded are analyzed in terms of supermolecular approach and symmetry-adapted perturbation theory. MP2C/aug-cc-pVTZ supermolecular calculations confirm the particular stability of the stacked dimers and the favoured dispersion attraction for the long-displaced system.

SUBMITTER: Kaczmarek-Kedziera A

PROVIDER: S-EPMC7665223 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Nature of intermolecular interaction in squaraine dimers.

Kaczmarek-Kędziera Anna A Żuchowski Piotr S PS Kędziera Dariusz D

Scientific reports 20201112 1

Squaraine dyes are known for their particular optical properties. They exhibit intense photochemically stable fluorescence in usually (near) infra red region that can be quenched by intermolecular interactions. Moreover, even the centrosymmetric dyes feature non-zero second harmonic generation upon aggregation. Therefore, the detailed knowledge of the squaraine dye interaction nature both in homogenic aggregates and with other species present in the environment can be of importance for the desig ...[more]

PMID: 33184323

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Project description:UnlabelledBacteriophytochrome photoreceptors (BphPs) and their cognate response regulators make up two-component signal transduction systems which direct bacteria to mount phenotypic responses to changes in environmental light quality. Most of these systems utilize single-domain response regulators to transduce signals through unknown pathways and mechanisms. Here we describe the photocycle and autophosphorylation kinetics of RtBphP1, a red light-regulated histidine kinase from the desert bacterium Ramlibacter tataouinensis RtBphP1 undergoes red to far-red photoconversion with rapid thermal reversion to the dark state. RtBphP1 is autophosphorylated in the dark; this activity is inhibited under red light. The RtBphP1 cognate response regulator, the R. tataouinensis bacteriophytochrome response regulator (RtBRR), and a homolog, AtBRR from Agrobacterium tumefaciens, crystallize unexpectedly as arm-in-arm dimers, reliant on a conserved hydrophobic motif, hFWAhL (where h is a hydrophobic M, V, L, or I residue). RtBRR and AtBRR dimerize distinctly from four structurally characterized phytochrome response regulators found in photosynthetic organisms and from all other receiver domain homodimers in the Protein Data Bank. A unique cacodylate-zinc-histidine tag metal organic framework yielded single-wavelength anomalous diffraction phases and may be of general interest. Examination of the effect of the BRR stoichiometry on signal transduction showed that phosphorylated RtBRR is accumulated more efficiently than the engineered monomeric RtBRR (RtBRRmon) in phosphotransfer reactions. Thus, we conclude that arm-in-arm dimers are a relevant signaling intermediate in this class of two-component regulatory systems.ImportanceBphP histidine kinases and their cognate response regulators comprise widespread red light-sensing two-component systems. Much work on BphPs has focused on structural understanding of light sensing and on enhancing the natural infrared fluorescence of these proteins, rather than on signal transduction or the resultant phenotypes. To begin to address this knowledge gap, we solved the crystal structures of two single-domain response regulators encoded by a region immediately downstream of that encoding BphPs. We observed a previously unknown arm-in-arm dimer linkage. Monomerization via deletion of the C-terminal dimerization motif had an inhibitory effect on net response regulator phosphorylation, underlining the importance of these unusual dimers for signal transduction.

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Nature of intermolecular interaction in squaraine dimers.

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Nature of intermolecular interaction in squaraine dimers.

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