Rational Design for Complementary Donor–Acceptor Recognition Pairs Using Self‐Complementary Hydrogen Bonds

Sikder, Amrita; Ghosh, Barindra Kumar; Chakraborty, Saptarshi; Paul, Ankan; Ghosh, Suhrit

doi:10.1002/chem.201504092

Cited by 20 publications

(14 citation statements)

References 46 publications

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“…This can be assigned to the π‐π stacking distance between PYCD and NDIAD. Wide angle XRD of PY‐NDI system previously reported was very similar to Figure S15 …”

Section: Resultssupporting

confidence: 80%

Hierarchical Self‐Assembly of Pyrene‐Linked Cyclodextrin and Adamantane‐Linked Naphthalene Diimide System: A Case of Inclusion‐Binding‐Assisted Charge‐Transfer Interaction

Jeevan

Gopidas

2019

ChemistrySelect

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Mixed stack charge transfer complexation between pyrene donor linked to β‐cyclodextrin and naphthalene diimide acceptor linked to adamantane, where the charge transfer interaction is augmented by inclusion binding of the adamantane moiety in β‐cyclodextrin, is studied. The association constant for the charge transfer complexation was 3.64 × 107 M−1, which is the highest value reported so far for any charge transfer complex. Complex formation was probed using 1H NMR, isothermal titration calorimetry, and circular dichroism studies. The results suggested that within the charge transfer complex the donor and acceptor exist as alternating units at an inter‐planar distance of 3.7 Å with a dihedral angle > 50° between them with each donor‐acceptor pair rotated slightly with respect to the preceding and succeeding pairs. The charge transfer complex undergo hierarchical self‐assembly to give twisted nanofibers as confirmed by Atomic force microscopic and Transmission electron microscopic studies. The excited state relaxation process in the charge transfer complex was investigated by femtosecond time‐resolved pump‐probe spectroscopy.

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“…This can be assigned to the π‐π stacking distance between PYCD and NDIAD. Wide angle XRD of PY‐NDI system previously reported was very similar to Figure S15 …”

Section: Resultssupporting

confidence: 80%

Hierarchical Self‐Assembly of Pyrene‐Linked Cyclodextrin and Adamantane‐Linked Naphthalene Diimide System: A Case of Inclusion‐Binding‐Assisted Charge‐Transfer Interaction

Jeevan

Gopidas

2019

ChemistrySelect

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“…H-bond reinforced alternate stacking of amide functionalized donor (py-1)–acceptor (NDI-24) chromophores as reported in ref . Red and black broken lines represent H-bonding and CT-interaction, respectively.…”

Section: Co-assembly Of Donor and Acceptor Containing Amphiphilesmentioning

confidence: 53%

“…With this objective, coassembly of NDI-25 was studied with anionic Py-2 or cationic Py-3 (Figure a) in water. Spacer length between the chromophore and the amide was the same in these pairs (Figure ) to ensure a synchronized H-bonding and CT interaction as optimized before …”

Section: Co-assembly Of Donor and Acceptor Containing Amphiphilesmentioning

confidence: 99%

Molecular Recognition Driven Bioinspired Directional Supramolecular Assembly of Amphiphilic (Macro)molecules and Proteins

et al. 2021

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Metrics & MoreArticle Recommendations CONSPECTUS: Bioinspired self-assembly has been explored with diverse synthetic scaffolds, among which amphiphiles are perhaps the most extensively studied systems. Classical surfactants or amphiphilic block copolymers, depending on the hydrophobic− hydrophilic balance, produce distinct nanostructures, which hold promise for applications ranging from biology to materials sciences. Nevertheless, their immiscibility-driven aggregation does not provide the opportunity to precisely regulate the internal order, morphology, or functional group display, which is highly desirable, especially in the context of biological applications.A new class of amphiphiles have emerged in the recent past in which the hydrophilic segment(s) is appended with a hydrophobic supramolecular-structure-directing-unit (SSDU), consisting of a π-conjugated chromophore and a H-bonding group. Selfrecognition of the SSDU by attractive directional interactions governs the supramolecular assembly, which is fundamentally different than the repulsive solvent-immiscibility driven aggregation of traditional amphiphiles. Such SSDU-appended hydrophilic polymers exhibit entropy-driven highly stable self-assembly producing distinct nanostructures depending on the H-bonding functional group. For example, polymers with the hydrazide-functionalized SSDU attached form a polymersome, while in a sharp contrast, the same polymers when connected to an amide containing SSDU produce a cylindrical micelle via a spherical-micelle intermediate. This relationship holds true for a series of SSDU-attached hydrophilic polymers irrespective of the hydrophobic/hydrophilic balance or chemical structure, indicating that the supramolecular-assembly is primarily controlled by the specific molecular-recognition motif of the SSDU, instead of the packing parameter-based norms. Beyond synthetic polymers, SSDU-attached proteins also exhibit similar molecular-recognition driven self-assembly as well as coassembly with SSDU-attached polymers or hydrophilic wedges, producing multi-stimuli-responsive nanostructures in which the protein gains remarkable protection from thermal denaturation or enzymatic hydrolysis and exhibits redox-responsive enzymatic activity. Furthermore, SSDU-derived bola-shape π-amphiphiles have been recognized as a useful scaffold for the synthesis of unsymmetric polymersomes, rarely reported in the literature. The building block consists of a hydrophobic naphthalene-diimide (NDI) π-system attached to a hydrophilic functional group (ionic or nonionic) and a nonionic wedge on its two opposite arms. Extended H-bonding among the hydrazide groups, placed only on one side of the central chromophore by design, ensures stacking of the NDIs with parallel orientation and induces a preferred direction of curvature so that the H-bonded chain and consequently the functional groups attached to the same side remain at the inner-wall of the supramolecular polymersome. Automatically, the functional groups, located on the other side, are displayed ...

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“…[5] We envisaged extending such supramolecular designs from single to two/multicomponent amphiphilic systems wouldf urthere nhance the complexity and functional value of these emergingn anostructures. In fact two component D-A systems have been extensively used as complementary supramolecular building blocks as they form ac harge-transfer (CT) complex [6] through alternating stacks.H owever,t he weak binding constant of the majority of the D-A complexes [7] has been the major limitation.T oc ircumventt his issue, we have designeda mide-group-appended Da nd Ac hromophores (Py-1 and NDI-1 in Scheme1)w ith pre-estimated matching spacer lengths [8] between the chromophoresa nd the amideg roup so that they could exhibit H-bonding-assisted alternating D-A supramolecular copolymerization in water with long-range order. NDI-1 containst he electron-deficient naphthalene diimide (NDI)c hromophore, to whichab enzamide group and a hydrophilic wedgea re attached on its two opposite arms.…”

Section: Introductionmentioning

confidence: 99%

“…However, the weak binding constant of the majority of the D–A complexes has been the major limitation. To circumvent this issue, we have designed amide‐group‐appended D and A chromophores ( Py‐1 and NDI‐1 in Scheme ) with pre‐estimated matching spacer lengths between the chromophores and the amide group so that they could exhibit H‐bonding‐assisted alternating D–A supramolecular copolymerization in water with long‐range order. NDI‐1 contains the electron‐deficient naphthalene diimide (NDI) chromophore, to which a benzamide group and a hydrophilic wedge are attached on its two opposite arms.…”

Section: Introductionmentioning

confidence: 99%

Multi‐Stimuli‐Responsive Directional Assembly of an Amphiphilic Donor–Acceptor Alternating Supramolecular Copolymer

Chakraborty

Ray

Aswal

et al. 2018

Chemistry A European J

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The stimuli-responsive supramolecular co-assembly of two π-amphiphiles, NDI-1 and Py-1, in which an acceptor (A) (naphthalene diimide) and a donor (D) (pyrene) chromophore, respectively, serve as the hydrophobic segment, is described. In addition, both contain an amide group in a designated location so that H-bonding and D-A charge-transfer (CT) interactions can operate simultaneously. H-bonding among the amide groups not only enhanced the CT interaction promoted by the alternating D-A stacking propensity, but also fixed the lateral orientation of the two chromophores and thus compelled the anionic and nonionic hydrophilic head groups, appended with the D and A amphiphiles, respectively, to remain segregated on two opposite sides of the amphiphilic alternating supramolecular copolymer. This copolymer showed spontaneous polymersome assembly with the D-appended anionic groups displayed at the outer surface, whereas the A-appended hydrophilic wedge converged at the inner lacuna. In contrast, spherical or cylindrical micellar structures were produced by Py-1 and NDI-1, respectively. Effective functional-group display in the D-A supramolecular polymersome enabled protein-surface recognition and inhibition of the enzymatic activity of Cht. Under a reducing environment, formation of NDI jeopardized the D-A interaction and thus the A chromophores were ejected out of the membrane of the polymersome causing its gradual contraction in size by >75 %. D-A supramolecular polymersomes also exhibited a lower critical solution temperature that could be tuned across a temperature window of 40 to 70 °C by varying the ratio of the A and D components in the alternating supramolecular copolymer.

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Rational Design for Complementary Donor–Acceptor Recognition Pairs Using Self‐Complementary Hydrogen Bonds

Cited by 20 publications

References 46 publications

Hierarchical Self‐Assembly of Pyrene‐Linked Cyclodextrin and Adamantane‐Linked Naphthalene Diimide System: A Case of Inclusion‐Binding‐Assisted Charge‐Transfer Interaction

Hierarchical Self‐Assembly of Pyrene‐Linked Cyclodextrin and Adamantane‐Linked Naphthalene Diimide System: A Case of Inclusion‐Binding‐Assisted Charge‐Transfer Interaction

Molecular Recognition Driven Bioinspired Directional Supramolecular Assembly of Amphiphilic (Macro)molecules and Proteins

Multi‐Stimuli‐Responsive Directional Assembly of an Amphiphilic Donor–Acceptor Alternating Supramolecular Copolymer

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