Halogenation is widespread in Nature, as witnessed by the several thousands of naturally occurring halogenated compounds. This review seeks to provide an overview on the pathways and multiple roles of halogenation in Nature, as a source of inspiration to chemists. Remarkably, several halogenation pathways were recently found in humans, sparking an increasing interest into halogens as biomolecular recognition sites. A description of the molecular mechanisms underlining the role of halogenation in the biomolecular context is provided, highlighting how the strategic use of halogen-driven interactions can be exploited to tune the properties of both small compounds and macromolecules. The complexity, versatility and bio-orthogonality of halogen-driven interactions are indeed key figures of merit in promoting novel opportunities for halogenation in a range of applications, spanning from drug design to self-assembly and biomolecular engineering. Specifically, the most relevant and impactful recent contributions in the field of peptide and protein science are presented and critically discussed, with a particular emphasis on the existing opportunities to control their conformational and self-assembly properties towards novel therapeutics and functional materials.

数千种天然存在的卤代化合物见证了卤化在大自然中的广泛分布。这篇综述旨在概述卤化在自然界中的途径和多种作用，以此为化学家提供灵感。值得注意的是，最近在人类中发现了几种卤化途径，激发了人们对卤素作为生物分子识别位点的兴趣。提供了分子机制的说明，该分子机制强调了卤化作用在生物分子环境中的作用，强调了如何利用卤素驱动的相互作用的战略用途来调节小化合物和大分子的性质。复杂性 卤素驱动的相互作用的多功能性和生物正交性确实是在从药物设计到自组装和生物分子工程的一系列应用中促进卤化的新机会的关键绩效指标。特别是，提出并严格讨论了肽和蛋白质科学领域中最相关和最有影响力的近期贡献，特别强调了控制其构象和自组装特性对新型疗法和功能材料的现有机会。