The synthesis, characterization and application of the binol-cages of R-/S-enantiomers

Abstract

In the past few years, significant efforts have been made to create and self-assemble covalent organic cages with increased complexity and functionality. However, although supramolecule cages have been widely recognized as probes to identify metal ions, the detection of mercury ions has not been fully developed. Here, we have designed and synthesized a pair of chiral cages with custom cavities based on the unique rigid structure of 1, 10-binaphthol (binol). Meanwhile, the supramolecular cage has excellent performance in high sensitivity and selectivity for detecting mercury ions. The UV titration results indicate that the binding ratio of the host to guest is 1:5. The titration curve conforms to the nonlinear fitting of the Hill function, which can obtain the binding constant K = 2.57 × 10⁵ M^-1. Furthermore, the detection limit of 1.9 × 10^-7 M can be obtained because the absorbance of cages exhibits a strong linear relationship with Hg²⁺ concentrations. This work provides a new method for selective recognition of ions by supramolecular cages.

Keywords

Covalent organic cage / mercury ion / detection / chemiluminescence / self-assembly

References

[1] Schwarzenbach RP,Fenner K.The challenge of micropollutants in aquatic systems.Science2006;313:1072-7

[2] Mohandoss S,Palanisamy S.Nitrogen, sulfur, and phosphorus Co-doped carbon dots-based ratiometric chemosensor for highly selective sequential detection of Al³⁺ and Fe³⁺ ions in logic gate, cell imaging, and real sample analysis.Chemosphere2023;313:137444

[3] Mohandoss S,You S,Lee YR.Rapid detection of silver ions based on luminescent carbon nanodots for multicolor patterning, smartphone sensors, and bioimaging applications.Anal Methods2021;13:5719-26

[4] Sonaimuthu M,Anand S.Multiple heteroatom dopant carbon dots as a novel photoluminescent probe for the sensitive detection of Cu²⁺ and Fe³⁺ ions in living cells and environmental sample analysis.Environ Res2023;219:115106.

[5] Li X,Meng X.Design and synthesis of an efficient nanoporous adsorbent for Hg²⁺ and Pb²⁺ ions in water.J Mater Chem A2016;4:5999-6005.

[6] Mao X,Wang C.Glutathione-functionalized melamine sponge, a mimic of a natural antidote, as a quick responsive adsorbent for efficient removal of Hg(II) from aqueous solutions.Environ Chem Lett2018;16:1429-34.

[7] Tajeu GS,Colantonio LD.Incident cardiovascular disease among adults with blood pressure <140/90 mm Hg.Circulation2017;136:798-812. PMCID:PMC5580500

[8] Wu P,Xu Y.Impact of engineering renovation on dynamic health risk assessment of mercury in a thermometer enterprise.Front Public Health2022;10:1037915 PMCID:PMC9704025

[9] Recknagel S,Kohlmeyer R.Survey of mercury, cadmium and lead content of household batteries.Waste Manag2014;34:156-61

[10] Mielke HW.Mercury (Hg) and lead (Pb) in interior and exterior New Orleans house paint films.Chemosphere2008;72:882-5

[11] Ariya PA,Dastoor A.Mercury physicochemical and biogeochemical transformation in the atmosphere and at atmospheric interfaces: a review and future directions.Chem Rev2015;115:3760-802

[12] Awual MR,Eldesoky GE,Rahman MM.Facile mercury detection and removal from aqueous media involving ligand impregnated conjugate nanomaterials.Chem Eng J2016;290:243-51.

[13] Chen GH,Yen YC,Chang HT.Detection of mercury(II) ions using colorimetric gold nanoparticles on paper-based analytical devices.Anal Chem2014;86:6843-9

[14] Chen G,Zeng G.Fluorescent and colorimetric sensors for environmental mercury detection.Analyst2015;140:5400-43

[15] Ding Q,Wang H,Kuang H.Electrochemical detection of heavy metal ions in water.Chem Commun2021;57:7215-31

[16] Guo Y,Shao H.Hydrothermal synthesis of highly fluorescent carbon nanoparticles from sodium citrate and their use for the detection of mercury ions.Carbon2013;52:583-9

[17] Gupta VK,Sharma R,Bharti A.Mercury selective potentiometric sensor based on low rim functionalized thiacalix [4]-arene as a cationic receptor.J Mol Liq2013;177:114-8.

[18] Lin ZH,Zhou YS.A self-powered triboelectric nanosensor for mercury ion detection.Angew Chem Int Ed Engl2013;52:5065-9.

[19] Shi Y,Feng X.Sensing of mercury ions in porphyra by Copper @ gold nanoclusters based ratiometric fluorescent aptasensor.Food Chem2021;344:128694.

[20] Wang L,Fu H,Li Y.Recent advances in the development of electrochemical aptasensors for detection of heavy metals in food.Biosens Bioelectron2020;147:111777

[21] Wang Y,Han X,Wang X.Fluorescent probe for mercury ion imaging analysis: strategies and applications.Chem Eng J2021;406:127166.

[22] Du J,Shao Q.Colorimetric detection of mercury ions based on plasmonic nanoparticles.Small2013;9:1467-81

[23] Ali S,Ahmad S.Morphology-controllable bimetallic gold nanostructures for mercury detection: recent developments, challenges and prospects.Arab J Chem2023;16:104997

[24] Bansod B,Thakur R,Singh I.A review on various electrochemical techniques for heavy metal ions detection with different sensing platforms.Biosens Bioelectron2017;94:443-55

[25] Hasan A,Salihi A.Nanozyme-based sensing platforms for detection of toxic mercury ions: an alternative approach to conventional methods.Talanta2020;215:120939

[26] Pierce CE,Nicholas SL.Role of ester sulfate and organic disulfide in mercury methylation in peatland soils.Environ Sci Technol2022;56:1433-44.

[27] Miao J,Dou S.Association between mercury exposure and lung function in young adults: A prospective cohort study in Shandong, China.Sci Total Environ2023;878:162759

[28] Yang Y,Lin Y.Point discharge optical emission spectrometer as a gas chromatography (GC) detector for speciation analysis of mercury in human hair.Anal Chem2018;90:11996-2003

[29] Kosta L,Dermelj M.Trace elements in some human milk samples by radiochemical neutron activation analysis.Sci Total Environ1983;29:261-8.

[30] Song Y,Zeng P,Wang Y.Simultaneous measurements of Cr, Cd, Hg and Pb species in ng L^-1 levels by interfacing high performance liquid chromatography and inductively coupled plasma mass spectrometry.Anal Chim Acta2022;1212:339935

[31] Li W,Liu C.Supramolecular Fe^II4L₄ cage for fast ammonia sensing.J Mater Chem C2022;10:9216-21

[32] Zhang Z,Wu L.Emissive platinum(II) cages with reverse fluorescence resonance energy transfer for multiple sensing.J Am Chem Soc2020;142:2592-600.

[33] Bhandari P.Covalent organic cages in catalysis.ACS Catal2023;13:6126-43

[34] Ham R,Pullen S.Supramolecular coordination cages for artificial photosynthesis and synthetic photocatalysis.Chem Rev2023;123:5225-61. PMCID:PMC10176487

[35] Bell DJ,Riddell IA.Design of lanthanide based metal-organic polyhedral cages for application in catalysis, sensing, separation and magnetism.Coordin Chem Rev2022;472:214786

[36] Hou YJ,Wei ZW.Design and enantioresolution of homochiral Fe(II)-Pd(II) coordination cages from stereolabile metalloligands: stereochemical stability and enantioselective separation.J Am Chem Soc2018;140:18183-91.

[37] Giri N,Melaugh G.Liquids with permanent porosity.Nature2015;527:216-20

[38] Rimsza JM.Porous liquids: computational design for targeted gas adsorption.ACS Appl Mater Interfaces2022;14:18005-15

[39] Kim T,Hwang J,Kim Y.Supramolecular two-dimensional systems and their biological applications.Adv Mater2020;32:e2002405.

[40] Shi L.Precise carbon dots synthesis: building bridges between organic chemistry and inorganic chemistry.Sci Bull2022;67:2369-71

[41] Shi L,Lu S.Efficient bottom-up synthesis of graphene quantum dots at an atomically precise level.Matter2023;6:728-60

[42] Han X,Xu C.Water-soluble metallo-supramolecular nanoreactors for mediating visible-light-promoted cross-dehydrogenative coupling reactions.ACS Nano2023;17:3723-36

[43] Zheng S,Su P.Anion-induced differential assembly and structural transformation of supramolecular coordination cages.Chinese Chem Lett2023;108477.

[44] Liu W,Zhu X.Tailored metal-organic tetrahedral nanocages with aggregation-induced emission for an anti-counterfeiting ink and stimulus-responsive luminescence.New J Chem2022;46:8062-8

[45] Miao L,Liu G.Tunable aggregation-induced fluorescent and pressure-responsive luminescence supramolecular cages achieved by subcomponent self-assembly.Chinese Chem Lett2023;34:107921

[46] Wang QQ,Bowman-James K.Chemistry and structure of a host-guest relationship: the power of NMR and X-ray diffraction in tandem.J Am Chem Soc2013;135:392-9

[47] Zhang D,Greenfield JL.Enantiopure [Cs⁺/Xe⊂Cryptophane]⊂Fe^II₄L₄ hierarchical superstructures.J Am Chem Soc2019;141:8339-45

[48] Liu X,Xie M.Single-handed double helix and spiral platelet formed by racemate of dissymmetric cages.Angew Chem Int Ed Engl2021;60:15080-6.

[49] Fantozzi N,Insuasty A.Selective detection of choline in pseudophysiological medium with a fluorescent cage receptor.Org Lett2023;25:2444-9.

[50] Chakraborty S.Terpyridine-based metallosupramolecular constructs: tailored monomers to precise 2D-motifs and 3D-metallocages.Chem Soc Rev2018;47:3991-4016

[51] Chen Y,Chen B.Self-assembly of a purely covalent cage with homochirality by imine formation in water.Angew Chem Int Ed Engl2021;60:18815-20.

[52] Harris K,Fujita M.Giant hollow M_nL_2n spherical complexes: structure, functionalisation and applications.Chem Commun2013;49:6703-12.

[53] Yan LL,Ng M.Stimuli-responsive and structure-adaptive three-dimensional gold(I) cluster cages constructed via "de-aurophilic" interaction strategy.J Am Chem Soc2021;143:19008-17

[54] Ono K.Dynamic behavior of covalent organic cages.Chemistry2018;24:17856-68

[55] Wilson A,Matile S.Functional systems with orthogonal dynamic covalent bonds.Chem Soc Rev2014;43:1948-62

[56] Frank M,Clever GH.Interpenetrated cage structures.Chemistry2016;22:14104-25

[57] Montà-González G,Martínez-Máñez R.Purely covalent molecular cages and containers for guest encapsulation.Chem Rev2022;122:13636-708 PMCID:PMC9413269

[58] Wang H,Sun N,Jiang J.Post-synthetic modification of porous organic cages.Chem Soc Rev2021;50:8874-86

[59] Quan MLC.Constrictive binding of large guests by a hemicarcerand containing four portals.J Am Chem Soc1991;113:2754-5

[60] Bravin C,Licini G.Tris(2-pyridylmethyl)amines as emerging scaffold in supramolecular chemistry.Coordin Chem Rev2021;427:213558.

[61] Fernández-Caro H,Martínez-Calvo M,Mascareñas JL.Supramolecular caging for cytosolic delivery of anionic probes.Chem Sci2019;10:8930-8 PMCID:PMC7017865

[62] Hashikawa Y.Probing the regioselectivity with encapsulated H₂: diels-alder reaction of an open-cage C₆₀ derivative with anthracene.Chemistry2019;25:2482-5.

[63] Plessius R,Ivanović-Burmazović I,Reek JNH.Reversible multi-electron storage in dual-site redox-active supramolecular cages.Chem Commun2019;55:12619-22

[64] Wu SY,Zhou LP.Fine-tuned visible and near-infrared luminescence on self-assembled lanthanide-organic tetrahedral cages with triazole-based chelates.Inorg Chem2019;58:7091-8

[65] Bhatta SR,Vijaykumar G.ICT-isomerization-induced turn-on fluorescence probe with a large emission shift for mercury ion: application in combinational molecular logic.Inorg Chem2017;56:11577-90

[66] Yan Z,Li N.Preparation of 4,4'-bis-(carboxyl phenylazo)-dibenzo-18-crown-6 dye and its application on ratiometric colorimetric recognition to Hg²⁺.Spectrochim Acta A Mol Biomol Spectrosc2011;79:661-5