Yan Lei, de Jesus Armando Jerome, Tamura Ryo, Li Victoria, Cheng Kui, Yin Hang
Center of Basic Molecular Science, Department of Chemistry, Tsinghua University, Beijing, China, 100082.
Department of Chemistry and Biochemistry, the BioFrontiers Institute, University of Colorado Boulder, Boulder, Colorado 80309-0596, USA.
J Pept Sci. 2015 Jul;21(7):577-585. doi: 10.1002/psc.2772. Epub 2015 Apr 8.
Membrane curvature and lipid composition plays a critical role in interchanging of matter and energy in cells. Peptide curvature sensors are known to activate signaling pathways and promote molecular transport across cell membranes. Recently, the 25-mer MARCKS-ED peptide, which is derived from the effector domain of the myristoylated alanine-rich C kinase substrate protein, has been reported to selectively recognize highly curved membrane surfaces. Our previous studies indicated that the naturally occurring L-MARCKS-ED peptide could simultaneously detect both phosphatidylserine and curvature. Here, we demonstrate that D-MARCKS-ED, composed by unnatural D-amino acids, has the same activities as its enantiomer, L-MARCKS-ED, as a curvature and lipid sensor. An atomistic molecular dynamics simulation suggests that D-MARCKS-ED may change from linear to a boat conformation upon binding to the membrane. Comparable enhancement of fluorescence intensity was observed between D- and L-MARCKS-ED peptides, indicating similar binding affinities. Meanwhile, circular dichroism spectra of D- and L-MARCKS-ED are almost symmetrical both in the presence and absence of liposomes. These results suggest similar behavior of artificial D- and natural L-MARCKS-ED peptides when binding to curved membranes. Our studies may contribute to further understanding of how MARCKS-ED senses membrane curvature as well as provide a new direction to develop novel membrane curvature probes.
膜曲率和脂质组成在细胞内物质和能量的交换中起着关键作用。已知肽曲率传感器可激活信号通路并促进分子跨细胞膜运输。最近,据报道,源自肉豆蔻酰化富含丙氨酸的C激酶底物蛋白效应域的25聚体MARCKS-ED肽能选择性识别高度弯曲的膜表面。我们之前的研究表明,天然存在的L-MARCKS-ED肽能同时检测磷脂酰丝氨酸和曲率。在此,我们证明由非天然D-氨基酸组成的D-MARCKS-ED作为曲率和脂质传感器,具有与其对映体L-MARCKS-ED相同的活性。原子分子动力学模拟表明,D-MARCKS-ED与膜结合后可能从线性构象转变为船型构象。在D-MARCKS-ED和L-MARCKS-ED肽之间观察到了相当的荧光强度增强,表明它们具有相似的结合亲和力。同时,无论有无脂质体,D-MARCKS-ED和L-MARCKS-ED的圆二色光谱几乎都是对称的。这些结果表明,人工合成的D-MARCKS-ED肽和天然的L-MARCKS-ED肽在与弯曲膜结合时表现出相似的行为。我们的研究可能有助于进一步理解MARCKS-ED如何感知膜曲率,并为开发新型膜曲率探针提供新的方向。