Functional metal-organic quadrangular macrocycle as luminescent sensor for ATP in aqueous media

Accepted Manuscript Functional metal-organic quadrangular luminescent sensor for ATP in aqueous media

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Xiao Wu, Dan Zhang, Shuping Deng, Jianjiang Wang, Chengbo Yang, De-Hui Wang, Yanfeng Bi PII: DOI: Reference:

S1387-7003(17)30431-8 doi: 10.1016/j.inoche.2017.08.025 INOCHE 6748

To appear in:

Inorganic Chemistry Communications

Received date: Revised date: Accepted date:

19 May 2017 19 August 2017 24 August 2017

Please cite this article as: Xiao Wu, Dan Zhang, Shuping Deng, Jianjiang Wang, Chengbo Yang, De-Hui Wang, Yanfeng Bi , Functional metal-organic quadrangular macrocycle as luminescent sensor for ATP in aqueous media, Inorganic Chemistry Communications (2017), doi: 10.1016/j.inoche.2017.08.025

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ACCEPTED MANUSCRIPT Functional metal-organic quadrangular macrocycle as luminescent sensor for ATP in aqueous media Xiao Wu,a Dan Zhang,a Shuping Deng,a Jianjiang Wang,a Chengbo Yang,a De-Hui Wang*b and Yanfeng Bi*b a. Department of Chemistry and materials Engineering, Yingkou Institute of Technology, Yingkou 115014, PR China b. College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University,

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Fushun 113001, PR China

ABSTRACT A new metal-organic quadrangular macrocycle Co(III) complex was achieved via self-assembly by comprising anthracene moieties as fluorophores, while the tridentate N2O units containing amide groups as guest binding sites and communicators, for specific responses to Adenosine-5’-triphosphate disodium over the other disodium 5’- ribonucleotides and inorganic phosphate anions. The M4L4 structure of macrocycle Co(III) complex

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was further confirmed by the crystal analysis of comparison.

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Keywords: Quadrangular macrocycle; Luminescent sensor; ATP; Co(III) complex

The self-assembly of metal-organic macrocycle (MOM) complexes has attracted immense attention over the past decades owing to not only their fascinating topological structures but also the

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potential applications as a simple model system to understand the self-assembly phenomenon in complicated metal-organic systems (MOSs), such as metal-organic frameworks (MOFs) and

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metal-organic polyhedral (MOP).1-7 MOMs are coordination compounds with ditopic organic ligands coordinating three or more metal centres, they have initiated revolution from classical

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coordination chemistry to extensive supramolecular concepts.8-13 Compared with traditional organic macrocycle, e.g. crown ether, calixarene, and cucurbituril, MOM had great advantages in terms of

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solubility, thermal stability, and flexibility. However, the host-guest chemistry of this architecture hasn’t been investigated very much, especially in sensing of special small biomolecules within the topological structures of the supramolecular architectures, despite the sensing of biomolecules being very important.14-18

On the other hand, Adenosine-5’-triphosphate disodium (ATP) injection is a coenzyme, used in the treatment of progressive muscular atrophy, cerebral hemorrhage sequela, cardiac dysfunction, myocardial disease etc. Also, ATP as a multifunctional nucleotide containing three negatively charged phosphate groups, plays an important role in understanding and evaluating several key biological processes.19-21 However, the structures of various types of nucleotides are similar, rich in a number of hydrogen bonds, such a recognition in the aqueous medium would be * Corresponding author. E-mail address: [email protected] (D. H. Wang) 1

ACCEPTED MANUSCRIPT limited due to the interference from hydroxyl groups of the sugar moiety and competitive hydrogen bonding of the solvent, the development of new approaches that could improve the simplicity and selectivity of ATP detection remain a challenge.22-27 Considerable efforts have been devoted to developing fluorescent chemosensors for ATP in the past decades. It is still not easy to find an example in which all of the twelve ribonucleoside polyphosphates were examined to evaluate the selectivity. Metal-organic macromolecular complexes are important models to realize the process of

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recognition and mimicking enzyme catalysis.28-33 1H NMR and X-ray crystallography remained the most utilised techniques in the history of host-guest complexation chemistry until more sensitive optical techniques such as steady-state and time-resolved fluorescence became popular. Compared to 1H NMR or X-ray crystallography, fluorescence optical technique can conveniently and easily monitor target molecule in the visible range with fast response, convenient procedures, and high sensitivity.34-35 However, only a handful of “artificial systems” achieved the detection and imaging

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techniques in biological systems. The major challenge at stake here goes beyond the introducing of an optical measurable output, the active sites and specific weak effect response sites. By combining

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these functional groups into MOMs with considerable stabilities, Duan and co-workers have first constructed relatively enclosing and open MOMs for biological molecules recognition and simulating enzyme catalysis researches.36-40 Through modulation of the tridentate N2O units

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containing amide groups within a central benzene ring at the meta sites, Duan and co-workers developed a new strategy for preparing helical triangles,38 which the UV-Vis responses for 5’-ATP

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in DMF : H2O (v : v= 2 : 1) aqueous solutions exhibited high selectivity through hydrogen-bonding patterns between the amide group and the nucleoside. By introducing the dansyl sulphonamide as

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fluorophore into the helical triangles, the fluorescence response is size-selective for nucleotides, the luminescence enhancements were quite similar for all four ribonucleoside triphosphates. As well-known, the anthracene group is an excellent fluorescent chromophore and would

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facilitate π-stacking interactions. Ramaiah and co-workers have designed a series of cyclophane derivatives based on the anthracene chromophore to investigate various nucleosides and nucleotides.41-43 They have also reported a MOM based on Cu(II) ions and anthracene groups, which showed uniquely selective complexation with 5’-GMP as compared to other nucleotides and nucleosides.44 The successful applications of the fluorescent anthracene groups inspired us to further extend the research in the field of design novel fluorescent receptor for other nucleotides and nucleosides. As a continuation of our research work on the MOMs for fluorescence recognition nucleotides,38-39 we herein report on the synthesis of new MOM quadrangular macrocycle for discriminating of ATP over other tested nucleotides. The anthracene group from ligand was chosen as fluorophore, while the tridentate N2O units containing amide groups were used as guest binding 2

ACCEPTED MANUSCRIPT sites and communicators. Co-An1 was synthesized with cobalt ions and ligand H2An1 via self-assembly, which has both of optical responding anthracene groups and guest binding amide groups (Scheme 1). Comparing with helical triangles previously reported,38 we reasoned that the fluorescence responses of the Co-An1 for ATP will exhibit unique selectivity.

Scheme 1

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Ligand H2An1 was synthesized according to the synthetic route outlined in Scheme S1. Adding NaClO4 into the methanol solution of ligand H2An1 and Co(NO3)2•6H2O led to the formation of the compound Co-An1. The Electrospray ionization mass spectrometry (ESI-TOF) spectrum of Co-An1 in high performance liquid chromatography (HPLC) pure acetonitrile and water exhibited an intense peak at m/z = 557.3654 with the isotopic distribution patterns separated by 0.25 Dalton, a relatively weak peak at m/z = 776.1354 with the isotopic distribution patterns separated by (0.33 ±

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0.01) Dalton (Fig.1). The peaks were assignable to [Co4(An1)4]4+ and [Co4(An1)4(ClO4)]3+, respectively, through the exact comparison of the experimental peaks with the simulation results

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obtained on the basis of natural isotopic abundances, which were clearly demonstrates the formation of M4L4 species in the solution. The valence state of cobalt was +3 compared with other Co(II) complexes reported,37,

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the change in the oxidation state of colbat may be due to i)

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self-assembly behavior,45, 46 ii) the ligand H2An1 containing an anthracene ring. In addition, the valence state of Co(III) was further confirmed by X-ray Photoelectron Spectroscopy (XPS) (Fig.

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S8).

The coordination of the ligand to the metal ions could be also identified by the relatively

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broadened and shifted resonance signals in 1H NMR spectra. 1H NMR spectra of Co-An1 in d6-DMSO indicated that acetylpyridine rings signals of H2An1 were significantly shifted downfield, -N=C(CH3)- signals were shifted downfield (δ = 0.87 ppm) especially, while anthracene unit signals of H2An1 were distinct shifted up-field (δ ≈ 0.2 ppm) (Figure S1). At the same time, only one set of signals were observed, indicating that all the ligands in each complex were in an identical environment. The UV-Vis measurement of compound Co-An1 (5 M) in acetonitrile (HPLC) and phosphate buffer (pH = 7.4) (v : v = 4: 1) exhibits distinct broad red band at about 400 ~ 525 nm compared with ligand H2An1 (20 M) (Figure S2), which can further affirm the coordination of the ligand to the metal ions. 3

ACCEPTED MANUSCRIPT The crystal of Co-An1 was polycrystal and easy to efflorescence, it was unsuitable for single crystal analysis. To better understand the structure of Co-An1, the ligand HAn2 was synthesized, which has single tridentate N2O units containing amide groups. Compound 3 was gained from the purification of compound 1 (Scheme S1). The synthesis method of HAn2 was exactly the same with H2An1 (Scheme S2). Fortunately, crystals of Co-An2 suitable for single crystal analysis were easily obtained by slowing volatilizing the solution at room temperature for about two days. From the crystal analysis of Co-An2, the rigidly separated N2O tridentate chelating units were vertical to the

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anthracene groups (Fig. 2). Jones and co-workers has reported that compound 1 (dimethyl-9, 10-anthracenedicarboxylate) was a centrosymmetric transoid molecule.47 Thus, we judged that the two rigidly separated N2O tridentate chelating units of Co-An1 were trans-form and perpendicular to anthracene group. The bond lengths and angles are in the normal ranges compared with other similar Co(III) complexes reported.37-38 Based on the results mentioned above, the M4L4 structure of

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Co-An1 was further confirmed.

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Fig. 2

The emission bands of compound Co-An1 (5M) in acetonitrile (HPLC) and phosphate buffer (pH = 7.4, v : v = 4: 1) (excitation at 364 nm) appears at about 400 nm, 425 nm, and 445 nm. The

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wavelengths of the emission band and luminescence intensity of Co-An1 did not change upon the addition of 20 equiv. of ATP. Adding 30 equiv. of ATP, less spectral changes were found under the

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same experimental conditions. While the addition of 40 equiv. of ATP led to a 74% luminescence quenching of the solution and the luminescence intensity at 400 nm showed an almost linear

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decrease upon adding ATP from 30 equiv. to 40 equiv. (Fig. 3). The result is attributed to ATP being gradually encapsulated inside the hydrophobic hollow of macrocycles instead of the solvents or

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anions, and interacting with the amide groups. The UV-Vis absorptions of Co-An1 (5M) were almost unaltered with the addition of 40 equiv. of ATP in acetonitrile (HPLC) and phosphate buffer (pH = 7.4, v : v = 4: 1), indicating that the Co-An1 is stable in the process of luminescence responses (Fig. S3). To confirm the stoichiometry of the host-guest behaviour, ESI-TOF investigation of Co-An1 upon the addition of ATP was displayed (Fig. S4). Upon the addition of five equiv. of ATP, the new peaks appeared at m/z = 911.7601, 919.0432 and 926.4145, which the simulation on the basis of natural isotopic abundances reveals that these +3 charged species were assignable to [Co4(An1)4⊃ATP+H]3+, [Co4(An1)4⊃ATP·Na]3+ and [Co4(An1)4⊃ATP·Na2-H]3+ (ATP = C10H14N5O13P32-) respectively, providing evidence for the 1 : 1 stoichiometric host-guest complexation. While 1H NMR spectra of the Co-An1 solution in the presence of ATP were failed due to the solubility of Co-An1 and ATP is not coordinated at intense concentrations. 4

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The luminescence intensity of Co-An1 in CH3CN (HPLC) : H2O (v : v = 4 : 1) solution was a slight change at pH of 6.0 to 8.0 (Figure S5), which shows that Co-An1 has little influence within this concentration range of acid/base. Adding the acid/base to adjust the solution pH value of 6.0 to 8.0 respectively, luminescence intensities of Co-An1 (5 M) and ATP (0.2 mM) in CH3CN (HPLC) :

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H2O (v : v = 4: 1) solution were almost unchanged (Fig. S5). The host-guest interactions of Co-An1 with ATP were less affected by acid or base in this rang of pH value.

Upon addition of the ATP, an acetonitrile (HPLC) and phosphate buffer (pH = 7.4, v : v = 4: 1) solution of Co-An2 remained negligible changes in the fluorescent spectra (excitation at 364 nm) (Fig. S6). From this vantage point, it should be noted that the macrocycles play an important role in

fluorescent quenching of the anthracene band.

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binding ATP by a possible multi-site coordination complexation mode, leading to the observed

In the meantime, the addition of 40 mole equivalent of other disodium 5’-ribonucleotides

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(XNP·Na2, where X = U (uridine), C (cytidine), and G (guanosine), N = mono-, di-, and tri-, and P = phosphate) and inorganic phosphate anions Pi or PPi could not cause any spectral changes of the fluorescence spectra under the same experimental conditions (Fig. 4 and S7). These results

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indicated that the affinity of Co-An1 for ATP was stronger than that for the other disodium 5’-ribonucleotides and inorganic phosphate anions. The specific selectivity of Co-An1 for ATP

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suggests that the amide groups in Co-An1 situate in the correct place and are able to conceivably interact with ATP. However, comparing with the previous reports, the advantages are not only that

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the Co-An1 has an exclusive fluorescence response to ATP but also the reactions occur in acetonitrile (HPLC) and phosphate buffer (pH = 7.4, v : v = 4: 1) thanks to Co-An1 having better

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solubility and larger cavities than helical triangles.

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In conclusion, a new anthracene-based metal-organic quadrangular macrocycle (Co-An1) has been synthesized and characterized. Co-An1 exhibits a selective “turn-down” fluorescent property for ATP over other disodium 5’-ribonucleotides and inorganic phosphate anions in acetonitrile (HPLC) and phosphate buffer (pH = 7.4, v : v = 4: 1). Preliminary data of comparison Co-An2, fluorescence, NMR, and ESI-MS spectra demonstrate the strong binding property may be an important factor influencing the fluorescence response to ATP. Further studies are underway in this area, which will be reported in due course. 5

ACCEPTED MANUSCRIPT Acknowledgment This work was supported by the Education Department of Liaoning Province (L2013537, L2016021), the China Offshore Oil Corporation (CNOOC) (HLOOFW(P)2014-0005).

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Scheme 1.Structures of H2An1, HAn2, Co-An1, and Co-An2.

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Fig. 1 ESI-TOF spectra of Co-An1 in CH 3CN (HPLC)/H 2O solution, the inset is the measured and the

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simulated isotopic patterns at 557.3654.

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Fig. 2 Single-crystal X-ray structure of complex Co-An2. All hydrogen atoms, solvent molecules and

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counter-ions are omitted for clarity. Color codes: cobalt (turquiose), oxygen (red), nitrogen (blue), bromine

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(oriange), and carbon (gray).

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Intensity

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Wavelength(nm) Fig. 3 Emission spectra of Co-An1 (5 uM) upon addition of different concentration of ATP in CH 3CN

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(HPLC) and phosphate buffer (pH = 7.4, v : v = 4: 1), up to 40 mole equivalent, excitation at 364 nm. The inset shows the change of fluorescence intensity of Co–An1 upon addition of ATP from 30 equiv. to

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40 equiv. at 400 nm.

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ATP ADP AMP CTP CDP CMP GTP GDP GMP UTP UDP UMP

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Fig.4 Fluorescence responses (400 nm) of Co-An1 (5uM) upon the addition of 40 equiv. of disodium

5’-ribonucleotides and inorganic phosphate anions in CH 3CN (HPLC) and phosphate buffer (pH = 7.4, v

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: v = 4: 1). Excitation at 364 nm.

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Graphical abstract

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A novel anthracene-based metal-organic quadrangular macrocycle as a selective “turn-down” fluorescent probe was designed and synthesized for selectively sensing ATP in aqueous media.

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ACCEPTED MANUSCRIPT Highlights

1. A novel metal-organic quadrangular macrocycle was designed and synthesized. 2. Co(III) complex showed high selectivity for ATP in aqueous media.

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3. The addition of ATP led to a 74% luminescence quenching of the intensity.

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