Institute of Pharmacy, Faculty of Chemistry and Pharmacy, University of Regensburg , Universitätsstrasse 31, D-93053 Regensburg, Germany.
Department of Chemistry and Pharmacy, Emil Fischer Center, Friedrich Alexander University , Schuhstrasse 19, D-91052 Erlangen, Germany.
J Med Chem. 2016 Mar 10;59(5):1925-45. doi: 10.1021/acs.jmedchem.5b01495. Epub 2016 Feb 11.
Derivatization of biologically active peptides by conjugation with fluorophores or radionuclide-bearing moieties is an effective and commonly used approach to prepare molecular tools and diagnostic agents. Whereas lysine, cysteine, and N-terminal amino acids have been mostly used for peptide conjugation, we describe a new, widely applicable approach to peptide conjugation based on the nonclassical bioisosteric replacement of the guanidine group in arginine by a functionalized carbamoylguanidine moiety. Four arginine-containing peptide receptor ligands (angiotensin II, neurotensin(8-13), an analogue of the C-terminal pentapeptide of neuropeptide Y, and a neuropeptide FF analogue) were subject of this proof-of-concept study. The N(ω)-carbamoylated arginines, bearing spacers with a terminal amino group, were incorporated into the peptides by standard Fmoc solid phase peptide synthesis. The synthesized chemically stable peptide derivatives showed high receptor affinities with Ki values in the low nanomolar range, even when bulky fluorophores had been attached. Two new tritiated tracers for angiotensin and neurotensin receptors are described.
通过与荧光团或放射性核素标记部分缀合来衍生生物活性肽是制备分子工具和诊断剂的一种有效且常用的方法。虽然赖氨酸、半胱氨酸和 N 末端氨基酸已被广泛用于肽缀合,但我们描述了一种新的、广泛适用的肽缀合方法,该方法基于精氨酸中非经典的生物等排体取代胍基为功能化的碳酰胺胍部分。本概念验证研究以四个含有精氨酸的肽受体配体(血管紧张素 II、神经降压素(8-13)、神经肽 Y 末端五肽类似物和神经肽 FF 类似物)为研究对象。带有末端氨基的间隔基的 N(ω)-碳酰胺化精氨酸通过标准的 Fmoc 固相肽合成被掺入到肽中。合成的化学稳定的肽衍生物具有高受体亲和力,Ki 值在纳摩尔范围内,即使连接了大体积的荧光团也是如此。还描述了两种用于血管紧张素和神经降压素受体的新放射性标记示踪剂。