Xylylene Clips for the Topology-Guided Control of the Inclusion and Self-Assembling Properties of Cyclodextrins

Neva, Tania; Carmona, Thais; Benito, Juan M.; Przybylski, Cédric; Mellet, Carmen Ortiz; Mendicuti, Francisco; Fernández, José Manuel Garcı́a

doi:10.1021/acs.joc.8b00602

Cited by 8 publications

(13 citation statements)

References 82 publications

(99 reference statements)

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“…Such a one‐ring conformational flip forces a drastic alteration of the overall CD shape, from conical to ellipsoidal torus, as compared with a noninverted structure. The aromatic segment is then projected wide apart from the CD vertical axis, an orientation that was previously found to strongly disfavor the formation of self‐assembled supramolecular dimers [20a,b] …”

Section: Resultsmentioning

confidence: 98%

Tuning the Topological Landscape of DNA–Cyclodextrin Nanocomplexes by Molecular Design

Neva

Carbajo-Gordillo

Benito

et al. 2020

Chemistry A European J

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Original molecular vectors that ensure broad flexibility to tune the shape and surface properties of plasmid DNA (pDNA) condensates are reported herein.T he prototypic design involves ac yclodextrin (CD) platform bearing a polycationic cluster at the primary face and ad oubly linked aromatic module bridging two consecutive monosaccharide units at the secondary face that behaves as at opology-encoding element.S ubtle differences at the molecularl evel then translate into disparatem orphologies at the nanoscale, including rods, worms, toroids, globules, ellipsoids, and spheroids. In vitro evaluation of the transfection capabilities revealedm arked selectivity differences as af unction of nanocomplexm orphology. Remarkably high transfection ef-ficiencies were associatedw ith ellipsoidal or spherical shapesw ith al amellar internal arrangemento fp DNA chains and CD bilayers. Computational studies support that the stability of such supramolecular edifices is directly related to the tendency of the molecular vectort of orm noncovalent dimers upon DNA templating.B ecause the stabilityo ft he dimers depends on the protonation state of the polycationic clusters,t he coaggregates display pH responsiveness, which facilitates endosomal escapea nd timely DNA release, ak ey step in successful transfection. The results provide av ersatile strategy for the construction of fully synthetic and perfectly monodispersen onviral gene delivery systems uniquely suitedf or optimizations chemes.

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Section: Resultsmentioning

confidence: 98%

Tuning the Topological Landscape of DNA–Cyclodextrin Nanocomplexes by Molecular Design

Neva

Carbajo-Gordillo

Benito

et al. 2020

Chemistry A European J

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“…The methods used for the conformational study of the monomeric 4 and 5 and for their dimer formation were similar to those described previously for 1 (González-Álvarez et al, 2008) and 2 or 3 (Neva et al, 2018). 2-ns MD simulations in the vacuum were performed at several temperatures ranging from 250 to 600 K on initial 4 and 5 conformations.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…Every structure was optimized (1.5 kcal · mol −1 Å −1 ) and saved for further analysis. Minima binding energy (MBE) structures for dimers were optimized once again (gradient 0.5 kcal · mol −1 Å −1 ) and used as the starting conformations for the 1.0 ns MD simulations following the same strategy described earlier (González-Álvarez et al, 2008; Gonzalez-Álvarez et al, 2009b; González-Álvarez et al, 2011; Neva et al, 2018).…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

“…Differently, “clip-type” positional isomers in which the o -xylylene group intertwines the O -2 I and O -3 II positions in consecutive monosaccharide units (e.g., 2 ) preferentially take semi-open arrangements due to the reduced flexibility at the cyclic benzylic area. As a result, dimeric species with higher interfacial distances that readily dissociate in the presence of a suitable CD cavity-fitting guest are formed, which can be exploited for the spatiotemporal control of the recognition properties (Neva et al, 2018). Interestingly, the supramolecular abilities were drastically influenced by the type of joint between the aromatic and the cyclooligosaccaride parts: replacing the o -xylylene into a m -xylylene moiety in the clip-type geometry (e.g., 3 ) led to a fully open topology that abolished self-recognition and favored instead non-inclusion complexation of planar guests (Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…Structures of the doubly-linked isomeric βCD-xylylene conjugates 1 – 3 (Left) and 3D molecular models of the corresponding minima binding energy dimer (for 1 and 2 ) or monomer species (for 3 ) present in water solution (Right) . Note that the aromatic ring (in green) orientation, relative to the CD cavity, shifts from cap-like to semi-open to fully open on moving from 1 to 3 (González-Álvarez et al, 2013; Neva et al, 2018). …”

Section: Introductionmentioning

confidence: 99%

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Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions

et al. 2019

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The presence of a doubly-linked naphthylene clip at the O -2 I and O -3 II positions in the secondary ring of β-cyclodextrin (βCD) derivatives promoted their self-assembly into head-to-head supramolecular dimers in which the aromatic modules act either as cavity extension walls (if the naphthalene moiety is 1,8-disubstituted) or as folding screens that separate the individual βCD units (if 2,3-disubstituted). Dimer architecture is governed by the conformational properties of the monomer constituents, as determined by NMR, fluorescence, circular dichroism, and computational techniques. In a second supramolecular organization level, the topology of the assembly directs host-guest interactions and, reciprocally, guest inclusion impacts the stability of the supramolecular edifice. Thus, inclusion of adamantane carboxylate, a well-known βCD cavity-fitting guest, was found to either preserve the dimeric arrangement, leading to multicomponent species, or elicit dimer disruption. The ensemble of results highlights the potential of the approach to program self-organization and external stimuli responsiveness of CD devices in a controlled manner while keeping full diastereomeric purity.

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Encapsulation of doxorubicin in carboxymethyl-β-cyclodextrin in aqueous medium mediated by pH-modulated electrostatics interactions

Carmona

Fernández-Clavero

Marcelo

et al. 2023

Journal of Molecular Liquids

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Xylylene Clips for the Topology-Guided Control of the Inclusion and Self-Assembling Properties of Cyclodextrins

Cited by 8 publications

References 82 publications

Tuning the Topological Landscape of DNA–Cyclodextrin Nanocomplexes by Molecular Design

Tuning the Topological Landscape of DNA–Cyclodextrin Nanocomplexes by Molecular Design

Dynamic Control of the Self-Assembling Properties of Cyclodextrins by the Interplay of Aromatic and Host-Guest Interactions

Encapsulation of doxorubicin in carboxymethyl-β-cyclodextrin in aqueous medium mediated by pH-modulated electrostatics interactions

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