Introduction

1,4-dihydroxyanthraquinone (1,4-DAQ;Figure 1) is an orange or red-brown crystalline powder, which is often used either as an intermediate for the synthesis of indanthrene and alizarin-derived dyesor as a spectroscopic analytical tool for the determination of metals. It is also used as a prominent family of pharmaceutically active and biologically relevant chromophores. [1] The 1,4-dihydroxyanthraquinone (1,4-DAQ), is critical structure in anthraquinone-based anticancer drug including AQ4N, doxorubicin. It is well known that 1,4-DAQ,commonly known as quinone Sin, whose space structure is very symmetrical and its color is solvent-sensible (when dissolved indifferent solvents, show different colors, along with a strong fluorescence change). Based on its characteristics, in recent years, 1,4-dihydroxyanthraquinone can be used to synthesize various dyes and are common structural subunits of many biologically active quinonoids-namely,anthracyclines, dynemicins, mitoxantrones, anthraquinonesteroid hybrids, and naphthacenedione organic dyes. It also can be modified into synthetic dyes intermediate, 1,4-diamino anthraquinone. In addition, under certain condition, 1,4-dihydroxyanthraquinone can be induced to self-assembly to form metallo-supramolecular coordination polymers; which demonstrate good selectivity and binding for planar aromatic guests, small organic molecules and transitional metal ions, such as methylene dichloride and iridium. Nematollahi et al. (2012) studied electrochemicaloxidation of 1,4-dihydroxyanthraquinone in the presence of arylsulfinic acids in synthesis of new sulfone derivatives of 1,4-DAQ. Recently, The interaction between 1,4-dihydroxyanthraquinone and metal ions were studied by UV–visible and fluorescence spectroscopy in solution using combined spectral experiment and theoretical calculations. Jin-qing andYujun (1995) reported spectrophotometeric determination of 1,4-dihydroxyanthraquinone [2].

The Fluorescence Sensing Capability of 1,4-dihydroxyanthraquinone

Fluorescence and colorimetric sensors have gained significant traction in diverse scientific domains, including environmental, agricultural, and pharmaceutical chemistry. This article comprehensively surveys recent advancements in developing sensors employing 1,4-dihydroxyanthraquinone. The study delves into the unique properties of 1,4-dihydroxyanthraquinone as a sensor, focusing on its capacity to detect Cu²⁺ ions and elucidating its fluorescence quenching mechanisms. Furthermore, the interaction of dihydroxyanthraquinone with Ga(III), Al(III), and In(III) ions is explored under both aqueous and non-aqueous conditions, leading to the formation of distinctive fluorescent species. The investigation extends to factors influencing ligand behavior, including time dependency, temperature, solvent type, counterions, and pH levels. These key parameters are systematically analyzed to understand sensor performance better. In conclusion, the article investigates the utility of the 1,4-dihydroxyanthraquinone-Zn²⁺ probe as a versatile sensing platform for phosphate anions, particularly in live cell imaging. The findings contribute to the evolving landscape of sensor technologies, offering insights into the diverse applications and potential advancements in this burgeoning field.[3]

The interaction of 1,4-dihydroxyanthraquinone for metal ions in solution

It is well known that 1,4-dihydroxyanthraquinone (1,4-DHA), commonly known as quinone Sin, its space structure is very symmetry, and its color is obvious (when dissolved in different solvents, it then show different colors, along with a strong fluorescence change). Based on its characteristics, in recent years, 1,4-dihydroxyanthraquinone can be used to synthesize various dyes and are common structural subunits of many biologically active quinonoids namely, anthracyclines, dynemicins, mitoxantrones, anthraquinonesteroid hybrids,and naphthacenedione organic dyes. It also can be modified into synthetic dyes intermediates, 1,4-diamino anthraquinone. In addition, under certain condition, 1,4-dihydroxyanthraquinonecan be induced to self-assembly to form a metallo-supramolecular coordination polymers which demonstrate good selectivity and binding for planar aromatic guests, small organic molecules and transitional metal ions, such as methylene dichloride and iridium. 1,4-dihydroxyanthraquinone with multi coordinating groups, can coordinate to many different metal ion (such as alkalimetal, alkaline earth metal, the third main group metals and transition metal).The interaction between 1,4-dihydroxyanthraquinone and metal ions was studied by UV-Visible and fluorescence spectroscopies in solution. Time-dependent density functional theory calculations confirmed complex structures. The investigation results showed 1,4-dihydroxyanthraquinone can selectively respond some metal ions and can be monitored by UV-Vis, fluorescence spectra and naked-eye. So 1,4-dihydroxyanthraquinone has a potential application in the design of metal ions probe. More, as typical metal ions, Hg²⁺ and Er³⁺, their reaction abilities for 1,4-dihydroxyanthraquinone were studied in detailed. Experimental results showed they have better response for 1,4-dihydroxyanthraquinone. And theoretical calculation concluded that Er3+ easily reacts with 1,4-dihydroxyanthraquinone over Hg²⁺ attributed to the low reaction energy of Er³⁺-1,4-DHA than Hg²⁺-1,4-DHA.[4]

References

1.Xuan X, Wang X, Wang N. Theoretical study of molecular structure and vibrational spectra of 1,4-dihydroxyanthraquinone. Spectrochim Acta A Mol Biomol Spectrosc. 2011;79(5):1091-1098. doi:10.1016/j.saa.2011.04.024

2.Nezhadali A, Senobari S, Mojarrab M. 1,4-dihydroxyanthraquinone electrochemical sensor based on molecularly imprinted polymer using multi-walled carbon nanotubes and multivariate optimization method. Talanta. 2016;146:525-532. doi:10.1016/j.talanta.2015.09.016

3.Shahzadi K, Mansha A, Asim S. The Fluorescence Sensing Capability of 1,4-dihydroxyanthraquinone Towards Metal Ions and Imaging Cells. J Fluoresc. 2025;35(4):1861-1874. doi:10.1007/s10895-024-03625-9

4.Yin C, Zhang J, Huo F. Combined spectral experiment and theoretical calculation to study the interaction of 1,4-dihydroxyanthraquinone for metal ions in solution. Spectrochim Acta A Mol Biomol Spectrosc. 2013;115:772-777. doi:10.1016/j.saa.2013.06.095