A tight 1:1 complex between an allosteric receptor and an organic effector with hydrogen and coordination bonds

Sasaki, Yoshito; Suzuki, Shuichi; Okada, Keiji; Kozaki, Masatoshi

doi:10.1016/j.tetlet.2016.07.088

Cited by 4 publications

(13 citation statements)

References 31 publications

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“…The smaller values of K 1 ⋅ 2 ⋅PhPy / K 1 ⋅PhPy indicate stronger inhibition. The K 1 ⋅ 2 ⋅PhPy / K 1 ⋅PhPy was calculated as 0.089 that is significantly smaller than that of the previously reported receptor (0.24) . In spite of the conformal flexibility of the side chains, the sterically bulky shielding panels significantly enhanced the degree of allosteric inhibition.…”

Section: Resultsmentioning

confidence: 56%

“…The absorption bands observed at λ max =551, 594, and 655 nm before the addition decreased in intensity and new bands appeared at λ max =563, 605, and 679 nm. Isobestic points were observed at 558, 625, and 664 nm . These results indicate that PhPy coordinates with both P1 and P2 in 1 .…”

Section: Resultsmentioning

confidence: 66%

“…The observed absorption change indicates the axial coordination of PY on the zinc atom of P1. On the other hand, blue shift and a decrease in intensity were observed at λ max =655 nm which is assigned to P2, indicating the interaction between the shielding panel and P2 . The coordination between PY and P2 is insignificant under these conditions because of the negligible intensity of a characteristic band in the wavelength region longer than 655 nm by the axial coordination .…”

Section: Resultsmentioning

confidence: 93%

“…Recently, we reported stimulus‐responsive receptor that has a zinc 5,15‐diethynyl‐10,20‐diphenylporphyrin unit (P0) as ligand binding sites (Scheme S1) . Activity of this sites was suppressed by neutral organic molecule (effector).…”

Section: Introductionmentioning

confidence: 99%

“…Recently,w er eported stimulus-responsive receptor that has az inc 5,15-diethynyl-10,20-diphenylporphyrin unit (P0) as ligand binding sites (Scheme S1). [6] Activity of this sites was suppressed by neutralo rganic molecule (effector). Theb inding constant of 4-phenylpyridinew ith P0, however,r educed only by 0.24 times by the effector.Here, we designed closely related receptor 1 with ap air of sterically bulky shieldingpanelstoenhance the degree of the allosteric inhibition by organic effector 2 (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

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Inhibition of Ligand Binding Ability of Three Porphyrins by an Organic Effector

Nishimura

Sasaki

Tachi

et al. 2020

Chemistry An Asian Journal

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A stimulus‐responsive receptor 1 was designed and prepared to control the ligand‐binding ability of three active sites, two zinc tetraphenylporphyrin units (P1) and one zinc diethynyldiphenylporphyrin unit (P2), with one effector molecule 2. Bulky hexarylbenzene units were incorporated as shielding panels in the middle of the flexible side arms of 1. Spectroscopic titrations indicated that a stable supramolecular complex 1⋅2 (K1⋅2=6.7×106 m−1) was produced by the cooperative formation of multiple hydrogen and coordination bonds. As a result, the binding of a ligand to P1 was inhibited by 2 in a competitive manner. Additionally, the formation of 1⋅2 brought about conformational restriction of the side arms to cover both faces of P2 with the shielding panels. The binding constant of 4‐phenylpyridine with P2 in 1⋅2 decreased to 8.9 % of that in 1. Namely, the ligand‐binding ability of P2 was inhibited according to an allosteric mechanism.

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Section: Resultsmentioning

confidence: 56%

Section: Resultsmentioning

confidence: 66%

Section: Resultsmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Inhibition of Ligand Binding Ability of Three Porphyrins by an Organic Effector

Nishimura

Sasaki

Tachi

et al. 2020

Chemistry An Asian Journal

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Chemical Stimulus‐responsive Folding and Unfolding of a Dendrimeric Assembly

Kimura

Suzuki

Okada

et al. 2017

Chemistry An Asian Journal

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Ad endrimeric trimer undergoes folding and unfolding in response to ac hemical stimulus. The trimer of interest contains ac entral dendrimer with ab utadiynelinked zinc porphyrin dimer ((ZnP) 2 )c ore, in addition to two terminal dendrimers with zinc porphyrin (ZnP) cores. The obtaineda bsorption spectra indicate that the unfolded form is the exclusive conformer in chloroform, while the addition of 1,4-diazabicyclo[2.2.2]octane (DABCO) in chloroform leads to transformation from the unfolded to the folded structure containing two DABCO units per trimer;t he folded structure originates from the cross-linking of (ZnP) 2 and ZnP with DABCO. Moreover,t he addition of excess DABCO promotes the generation of the unfolded structure containing four DABCO units.The folding of proteinsi sk nown to create organized three-dimensional structurest hat are essential for imparting aw ide range of biological functions. This process can also be simulated by the cross-linkage of single-chain polymers to produce discrete nanoscale macromolecules, such as organic nanoparticles (ONPs).[1] However,t he application of such methods to the construction of organized arrays of functional units is challenging due to structural diversity at the molecular level. To date, dendrimers have attracted attention as building blocks for ONPs, as the well-defineds tructures of dendrimers allow the precise arrangemento ff unctional units.[2] Indeed,w ep reviously reported au nique method for the construction of ONPs using dendrimers with rigid backbones. [3] In this method, dendrimersw ere linearly connected using alkyl chains and the self-folding of the resulting assembly produced ONPs with rigid backbones. Although such rigid backbonesa ppear to be au seful framework for the precise arrangement of functional units in ONPs,t he random aggregation of these backbones limits their utility.In contrast, folding of the dendrimer assembly through the cross-linking of rigid backbones is am ore sophisticated approach to create ONPs since the rigid cross-linkers can produce an extended backbone with ap redictable structure (Figure 1a). Thus, we herein report the preparation of at rimer of dendrimers containing ab utadiyne-linked zinc porphyrin dimer( (ZnP) 2 ) as the core of the central dendrimer,i na ddition to two terminal dendrimers containing zinc porphyrin (ZnP) cores (Figure 1b). Such porphyrins are considered particularly valuable for the formation of noncovalentc ross-linkages.[4] We expect that upon the addition of suitable bidentate ligands as crosslinkers, the trimer will undergo folding and unfolding as shown in Figure 1a.I na ddition, ZnP and (ZnP) 2 can be independently monitored by spectroscopicm easurements, thereby allowing the folding and unfolding processes to be disclosed. [5] As such, we will employ spectroscopic techniques to examine trimerf olding and unfolding in response to ac hemical stimulus.Trimer 1 andd endrimers 2 and 3 were synthesized as outlined in Scheme1.F ollowing the initial reaction of two hydroxyl groups in 2a wi...

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Trimeric Assembly of Dendritic Light-Harvesting Antenna with Two Kinds of Porphyrin Cores

et al. 2017

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A trimeric assembly of light-harvesting antennas was prepared using a copper-catalyzed Hüisgen 1,3-dipolar cycloaddition reaction between a dendrimer having a zinc diethynyldiphenylporphyrin core (ZnDEDPP) with two azide terminals and two equivalents of dendrimers having a zinc tetraphenylporphyrin core (ZnTPP) with one ethynyl terminal. The absorptions of the trimer appear in a longer-wavelength region compared to monomeric references in toluene; however, there is almost no shift in wavelength in 1,1,2,2-tetrachloroethane (TCE). Fluorescence spectra of the trimer show that the singlet energy transfer from ZnTPP to ZnDEDPP takes place more effectively in toluene than in TCE. These absorption and fluorescence studies are compatible with solvent-dependent conformation; the extended forms of the trimers are favored by solvation in polar TCE, and the folded conformation is stabilized by the attractive van der Waals and dipole-dipole interactions between the dendritic chains in nonpolar toluene.

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A tight 1:1 complex between an allosteric receptor and an organic effector with hydrogen and coordination bonds

Cited by 4 publications

References 31 publications

Inhibition of Ligand Binding Ability of Three Porphyrins by an Organic Effector

Inhibition of Ligand Binding Ability of Three Porphyrins by an Organic Effector

Chemical Stimulus‐responsive Folding and Unfolding of a Dendrimeric Assembly

Trimeric Assembly of Dendritic Light-Harvesting Antenna with Two Kinds of Porphyrin Cores

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