Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Sci Adv. 2019 Apr 19;5(4):eaav3179. doi: 10.1126/sciadv.aav3179. eCollection 2019 Apr.
Biological receptors distinguish and bind steroid sex hormones, e.g., androgen-, progestogen-, and estrogen-type hormones, with high selectivity. To date, artificial molecular receptors have been unable to discriminate between these classes of biosubstrates. Here, we report that an artificial polyaromatic receptor preferentially binds a single molecule of androgenic hormones, known as "male" hormones (indicated with ), over progestogens and estrogens, known as "female" hormones (indicated with ), in water. Competitive experiments established the binding selectivity of the synthetic receptor for various sex hormones to be testosterone () > androsterone () >> progesterone () > β-estradiol () > pregnenolone () > estriol (). These bindings are driven by the hydrophobic effect, and the observed selectivity arises from multiple CH-π contacts and hydrogen-bonding interactions in the semirigid polyaromatic cavity. Furthermore, micromolar fluorescence detection of androgen was demonstrated using the receptor containing a fluorescent dye in water.
生物受体能够高度选择性地识别和结合甾体性激素，如雄激素、孕激素和雌激素型激素。迄今为止，人工分子受体还无法区分这些类别的生物底物。在这里，我们报告了一种人工多环芳烃受体在水中优先结合雄激素激素（用“雄性”激素表示）中的单个分子，而不是孕激素和雌激素（用“雌性”激素表示）。竞争实验确定了合成受体对各种性激素的结合选择性为睾酮（）＞雄酮（）＞孕酮（）＞β-雌二醇（）＞孕烯醇酮（）＞雌三醇（）。这些结合是由疏水性效应驱动的，观察到的选择性源于半刚性多环芳烃腔中的多个 CH-π 接触和氢键相互作用。此外，使用含有荧光染料的受体在水中对雄激素进行了微摩尔级别的荧光检测。
