Water soluble host–guest chemistry involving aromatic N-oxides and sulfonateresorcinarene

Kwaku Twum; Nicholas Schileru; Bianca Elias; Jordan Feder; Leena Yaqoo; Rakesh Puttreddy; Małgorzata M. Szczesniak; Ngong Kodiah Beyeh

doi:10.3390/sym12111751

Water soluble host–guest chemistry involving aromatic N-oxides and sulfonateresorcinarene

Kwaku Twum
, Nicholas Schileru
, Bianca Elias
, Jordan Feder
, Leena Yaqoo
, Rakesh Puttreddy
, Małgorzata M. Szczesniak
, Ngong Kodiah Beyeh^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

5 Citations (Scopus)

24 Downloads (Pure)

Abstract

Resorcinarenes decorated with sulfonate groups are anionic in nature and water soluble with a hydrophobic electron-rich interior cavity. These receptors are shown to bind zwitterionic aromatic mono-N-oxides and cationic di-N-oxide salts with varying spacer lengths. Titration data fit a 1:1 binding isotherm for the mono-N-oxides and 2:1 binding isotherm for the di-N-oxides. The first binding constants for the di-N-oxides (K₁: 10⁴ M⁻¹) are higher compared to the neutral mono-N-oxide (K: 10³ M⁻¹) due to enhanced electrostatic attraction from a receptor with an electron-rich internal cavity and cationic and electron deficient N-oxides. The interaction parameter α reveals positive cooperativity for the di-N-oxide with a four-carbon spacer and negative cooperativity for the di-N-oxides that have spacers with more four carbons. This is attributed to shape complementarity between the host and the guest.

Original language	English
Article number	1751
Number of pages	8
Journal	Symmetry
Volume	12
Issue number	11
DOIs	https://doi.org/10.3390/sym12111751
Publication status	Published - Nov 2020
Publication type	A1 Journal article-refereed

Funding

tetra1sodiumsulfonatomethyleneresorcinarene is presented. 1H-NMR reve1 als the significant shielding 4. ConshTicheluseld iinobgnins odfinagro moaft ic aprroomtoantsic, whmicohnois-Ng-roexaitdeer foarnddi -Nd-oi-xNid-oexsidcoems painre dwtoattehre irbmy onao -NC-o1-xide of aromatic protons, which is greater for di-N-oxides compared1 to their mono-N-oxide counterparts tetracsooudnituemrpsaurltfsownahteonmleotchaytelednienrseisdoerctihneareelencetrios np-rreiscehnctaevdi.t yH. T-NhMe bRin rdevinegalps rtohcee ssisgensiqfiucaannttisfhieideldthinrogugh when located inside the electron-rich cavity. The binding processes quantified through ITC of aIrToCmaextipceprrimoteonntss, dwehmicohnsistr gatreeaatemr ufochr dhiig-Nhe-orxbiidnedsi ncogmafpf1ianrietyd ftoor tthheeird mi-Non-oox-iNd-eosxtihdaen cmouonntoe-rNpa-ortxsi des. experiments demonstrate a much higher binding affinity for the di-N-oxides than mono-N-oxides. wheTnh eloficrasttebdi nidnisnigdee vtehnet iesloencteroonrd-reicrho fcmavaigtny.i tuTdhee stbrionndgienrgt hparnoctheessseesc oqnudanfotirfideid-N t-horxoiduegsh. PIoTsCit ive The first binding event is one order of magnitude stronger than the second for di-N-oxides. Positive expecoriompeenratsti vdietymwonasstorabtseerav emdufcohr thhieghdei-rN b-ionxdidinegwaiftfhinaitfyoufor-rc athrbeodni-sNp-aocxeird, wesh tihleanne mgaotnivoe-Nco-oopxiedraesti.v ity cooperativity was observed for the di-N-oxide with a four-carbon spacer, while negative Thew fiarsst obbinsedrivnegd evfoerntd iis- Non-oex oidrdeesr wofitmh amgnoirteudtheasntrofonugre-rc athrbanon thsepsaecceor.ndCfoorm dpiu-Nta-toixoindesst.uPdoiessitiovfe the cooperativity was observed for di-N-oxides with more than four-carbon spacer. Computation studies coopsterruacttivuirteys owfaths eodbis-Ner-voexdid efosrs htohwe tdhia-tNt-hoexifdoeur-wcaitrhbona sfpoaucre-dcaorbnoenb eslopnagcesrt, owahsiylem mneegtraytigvreoup of the structures of the di-N-oxides show that the four-carbon spaced one belongs to a symmetry cooptheartatmivaintydwataess othbesezrevreoddfioprodlei-mNo-omxiednets, wwhitihchm, ionretuthrna,nr efoduurc-ecsartbhoenth srpeaec-ebro.dCyormeppuultsaitvioenp sotluardiizeastion group that mandates the zero dipole moment, which, in turn, reduces the three-body repulsive of thefef escttr.uTchtuisrews oorfktshheowdis-Nth-aotxrideseosr csihnoawrenthesatp tohsese fsosuar-scuairtbabolne bspinadceindgopnoec kbeetlofonrgasr otomaa tsicymNm-oxetidrye s in polarization effect. This work shows that resorcinarenes possess a suitable binding pocket for grouaqputehoautsmmaenddiaa,tewshtihche szheoroulddihpeollpeamccoemleerantte, dwiahgicnho,s tiinc atuprpnli, craetidouncseos ftbhieo lothgriecea-lbaordomy arteipc-uNls-iovxeides. aromatic N-oxides in aqueous media, which should help accelerate diagnostic applications of polarization effect. This work shows that resorcinarenes possess a suitable binding pocket for biological aromatic-N-oxides. Supplementary Materials: The following are available online at http://www.mdpi.com/2073-8994/12/11/1751/s1, polarization effec1t. This work show2 s that resorcinarenes possess a suitable binding pocket for arSoumcpoapmtliecpm leNexn-etosa,xrTiyda MbelseatSien1ri:aaTlsqh:ue Trehmoeou fdosyllnmowaemidniicga ba, rinew dahivniacgihlpa baslrhea omonueltidenres haoetf wlpfow rawmc.ecmdedlceporima.ctpoemledx/xieaxsgxb/neso1tw,s Fteiiecgn uarthepsep Srl1iec–caSetp7i:to o1nHrssN aonMfdRt he spectra (D2O, 2298 K) of host–guest complexes, Figures S7 and S8: ITC traces of host–guest complexes, Table S1: Supipnlebminednitnagryc oMnasttearnitaslsf:o Trhteh eformlloowdiynnga amreic asvianildabeiloe noinzleindeH at2 Ow,wTwab.mledSp3i:.cEoqmu/ixlxibxr/isu1m, Fisgtururecstu Sr1e–sSa7n: 1dHpNroMpRer ties spectra (D2O, 298 K) of host–guest complexes, Figures S7 and S8: ITC traces of host–guest complexes, Table S1: Supplementary Materials: The following are available online at www.mdpi.com/xxx/s1, Figures S1–S7: H NMR Thermodynamic binding parameters of formed complexes between the receptors and the guests in H2O by ITC., spectra (D2O, 298 K) of host–guest complexes, Figures S7 and S8: ITC traces of host–guest complexes, Table S1: TablAe uSt2h: oCroCmopnlterxiabtuiotino ndse:rivCeodn cinetpetruaacltiizoant ipoanr,aNm.eKte.Br .(αan) dthaRt. Pd.e;smcreibtheos dcooloopgeyr,aKtiv.Tit.,y Nin.Sb.,inBd.iEn.g, Jc.Fo.n,sLta.Yn.t,sM fo.rM .S.; B3LYP-D3 calculations with a 6-31G** basis set within the implicit PCM water solvent; the electrostatic potential software, M.M.S.; validation, K.T., N.S., B.E., J.F., L.Y. and M.M.S.; writing—original draft preparation, K.T., Table S2: Complexation derived interaction parameter (scalewriting—rshown is in eviewkJ/mole.and editing, K.T., R.P., M.M.S., N.K.B.;α) that describsupervision,es cooperativity inN.K.B.; projectbinding constadministration,ants for N.K.B.; B3LYP-D3 calculations with a 6-31G** basis set within the implicit PCM water solvent; the electrostatic potential thermfuonddyinngamaciqcsuiisnitidoeni,oNni.zKe.dB .,HK2O.T.,,TRa.Pb.lAe lSl3a:u Ethqourislihbarivuemresatdruacntduraegsreaenddtoprthoepeprutibelsishofedguveersst iomnoolefctuhleems farnoumscript. scale shown is in kJ/mole. B3LYP-D3 calculations with a 6-31G** basis set within the implicit PCM water solvent; the electrostatic potential Funding: This research was funded by the Academy of Finland, grant number 298817. scale shown is in kJ/mole. Acknowledgments: The authors gratefully acknowledge the financial support from the Provost Graduate Student Research grant and Oakland University.

Keywords

Cooperative binding
Host–guest complex
N-oxides
Resorcinarenes

Publication forum classification

Publication forum level 1

ASJC Scopus subject areas

Computer Science (miscellaneous)
Chemistry (miscellaneous)
General Mathematics
Physics and Astronomy (miscellaneous)

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Water soluble host–guest chemistry 2020
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http://urn.fi/URN:NBN:fi:tuni-202011178024Licence: CC BY

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@article{13ce80bf18914341b623ba1d586741e4,

title = "Water soluble host–guest chemistry involving aromatic N-oxides and sulfonateresorcinarene",

abstract = "Resorcinarenes decorated with sulfonate groups are anionic in nature and water soluble with a hydrophobic electron-rich interior cavity. These receptors are shown to bind zwitterionic aromatic mono-N-oxides and cationic di-N-oxide salts with varying spacer lengths. Titration data fit a 1:1 binding isotherm for the mono-N-oxides and 2:1 binding isotherm for the di-N-oxides. The first binding constants for the di-N-oxides (K1: 104 M−1) are higher compared to the neutral mono-N-oxide (K: 103 M−1) due to enhanced electrostatic attraction from a receptor with an electron-rich internal cavity and cationic and electron deficient N-oxides. The interaction parameter α reveals positive cooperativity for the di-N-oxide with a four-carbon spacer and negative cooperativity for the di-N-oxides that have spacers with more four carbons. This is attributed to shape complementarity between the host and the guest.",

keywords = "Cooperative binding, Host–guest complex, N-oxides, Resorcinarenes",

author = "Kwaku Twum and Nicholas Schileru and Bianca Elias and Jordan Feder and Leena Yaqoo and Rakesh Puttreddy and Szczesniak, \{Ma{\l}gorzata M.\} and Beyeh, \{Ngong Kodiah\}",

note = "Funding Information: This research was funded by the Academy of Finland, grant number 298817. Acknowledgments: The authors gratefully acknowledge the financial support from the Provost Graduate Student Research grant and Oakland University. Publisher Copyright: {\textcopyright} 2020 by the authors. Licensee MDPI, Basel, Switzerland. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",

year = "2020",

month = nov,

doi = "10.3390/sym12111751",

language = "English",

volume = "12",

number = "11",

}

TY - JOUR

T1 - Water soluble host–guest chemistry involving aromatic N-oxides and sulfonateresorcinarene

AU - Twum, Kwaku

AU - Schileru, Nicholas

AU - Elias, Bianca

AU - Feder, Jordan

AU - Yaqoo, Leena

AU - Puttreddy, Rakesh

AU - Szczesniak, Małgorzata M.

AU - Beyeh, Ngong Kodiah

N1 - Funding Information: This research was funded by the Academy of Finland, grant number 298817. Acknowledgments: The authors gratefully acknowledge the financial support from the Provost Graduate Student Research grant and Oakland University. Publisher Copyright: © 2020 by the authors. Licensee MDPI, Basel, Switzerland. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/11

Y1 - 2020/11

N2 - Resorcinarenes decorated with sulfonate groups are anionic in nature and water soluble with a hydrophobic electron-rich interior cavity. These receptors are shown to bind zwitterionic aromatic mono-N-oxides and cationic di-N-oxide salts with varying spacer lengths. Titration data fit a 1:1 binding isotherm for the mono-N-oxides and 2:1 binding isotherm for the di-N-oxides. The first binding constants for the di-N-oxides (K1: 104 M−1) are higher compared to the neutral mono-N-oxide (K: 103 M−1) due to enhanced electrostatic attraction from a receptor with an electron-rich internal cavity and cationic and electron deficient N-oxides. The interaction parameter α reveals positive cooperativity for the di-N-oxide with a four-carbon spacer and negative cooperativity for the di-N-oxides that have spacers with more four carbons. This is attributed to shape complementarity between the host and the guest.

AB - Resorcinarenes decorated with sulfonate groups are anionic in nature and water soluble with a hydrophobic electron-rich interior cavity. These receptors are shown to bind zwitterionic aromatic mono-N-oxides and cationic di-N-oxide salts with varying spacer lengths. Titration data fit a 1:1 binding isotherm for the mono-N-oxides and 2:1 binding isotherm for the di-N-oxides. The first binding constants for the di-N-oxides (K1: 104 M−1) are higher compared to the neutral mono-N-oxide (K: 103 M−1) due to enhanced electrostatic attraction from a receptor with an electron-rich internal cavity and cationic and electron deficient N-oxides. The interaction parameter α reveals positive cooperativity for the di-N-oxide with a four-carbon spacer and negative cooperativity for the di-N-oxides that have spacers with more four carbons. This is attributed to shape complementarity between the host and the guest.

KW - Cooperative binding

KW - Host–guest complex

KW - N-oxides

KW - Resorcinarenes

U2 - 10.3390/sym12111751

DO - 10.3390/sym12111751

M3 - Article

AN - SCOPUS:85093958279

SN - 2073-8994

VL - 12

JO - Symmetry

JF - Symmetry

IS - 11

M1 - 1751

ER -

Water soluble host–guest chemistry involving aromatic N-oxides and sulfonateresorcinarene

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