Owing to the importance of zinc and phosphate in biology and human health, [1] sensing such species is always important and continues to intrigue chemists to emerge with better receptor designs.[2] Our recent report on sensing of Zn 2 + in blood serum milieu by a calixarene derivative [2h] prompted us to employ biologically benign receptor systems and to investigate if these receptors can also extend their sensitivity towards anions (especially phosphates). In this regard, water-soluble and biologically benign [3] carbohydrate-based fluorescent sensors [4] would be of great relevance to explore their in vitro and in vivo applications. Among the derivatives of phosphate, adenosine-mono/di/triphosphate (AMP, ADP, ATP), DNA, and their hydrolytic species are important.[5] Therefore, it is essential to monitor the presence of phosphate related species in solution.[6] If a receptor can sense both the zinc and the phosphate group, it would be doubly advantageous.[5e] Therefore, herein we investigate the primary detection of Zn 2 + by switch-on fluorescence using 1-(d-glucopyranosyl-2'-deoxy-2'-iminomethyl)-2-hydroxynaphthalene conjugate L and the successive detection of phosphates by the corresponding zinc complex through fluorescence quenching (switch-off). To demonstrate the bio-suitability of L, titrations were carried out using nucleotides and DNA. To our knowledge, this is the first carbohydrate-based receptor system shown to be sensitive towards a cation followed by an anion, including biomolecular systems.Conjugate L has been synthesized by a one-pot condensation of the neutralized C2-deoxy-C2-amino-glucose with 2-hydroxy-1-naphthaldehyde and his structure has been characterized (see SI 01 in the Supporting Information).[7] Conjugate L has been crystallized in a non-centrosymmetric triclinic system by layering methanol on to a concentrated solution in DMSO and the structure was determined by single crystal XRD (for crystal and metric data see SI 02 in the Supporting Information). Conjugate L exhibits a preformed ONO core that is suitable for metal ion binding (Scheme 1). An intramolecular hydrogen bond present between the phenolic O4 À H···N1-imino orients the naphthyl moiety almost perpendicular to the mean plane of the carbohydrate moiety (see SI 02b in the Supporting Information). In the lattice, molecules form columns by interacting through two strong hydrogen bonds per each L and also by exhibiting hydrophobic p-p interactions with a centroid to centroid distance of 4.878 . The columnar structure formed in the lattice clearly exhibits hydrophobic (6 ) and hydrophilic (7 ) regions alternatively (see SI 02c in the Supporting Information).The selectivity of L has been demonstrated by titration against seven biologically and ecologically relevant metal ions, such as, Na + , K + , Ca 2 + , Mg 2 + , Zn 2 + , Cd 2 + , and Hg 2 + in methanol using fluorescence spectroscopy. In dry methanol, L exhibits approximately a 140-fold enhancement in the emission intensity against Zn 2 + , while none of the alkali and al...
A new anthracenyl-imino-glucosyl conjugate (L) selectively senses Hg(2+) by turn-on fluorescence with a 13 ± 1 fold enhancement by forming a 2 : 1 complex in pH 5 to 10 even in the presence of several biologically and ecologically relevant metal ions, with a 25 ± 2% fluorescence enhancement at the EPA limit of 2 ppb. L is equally sensitive towards Hg(2+) in the presence of albumin proteins and in blood serum and milk.
In the present work, six retrochalcones, namely echinatin, licochalcone A, B, C, D and E, have been studied using density functional theory at the B3LYP/6‐311++G** level. A comparative analysis of the non‐linear optical properties has been performed with two prototype standard molecules, urea and para‐nitroaniline. The computed first pKa values of all the deprotonation sites lie in the range of 8.9‐10.0, which suggests the predominance of the neutral form of the considered retrochalcones at the physiological pH. Further, the second pKa values of the hydroxyl groups of the mono‐anionic forms lie in the range of 10.0‐11.6 and the third pKa values for deprotonation from the dianionic forms of licochalcone B and D are ~17. Moreover, the electronic spectra, frontier molecular orbitals analysis and molecular electrostatic potential maps have been analyzed for a better understanding of the electro‐optical properties of the compounds under study.
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