Dimensional Assembly Engineering of Ce-MOF Interfaces for Selective Recognition of Phytic Acid

en This link goes to a English section zh This link goes to a Chinese section Selective molecular recognition is central to chemical sensing yet discriminating structurally similar molecules at complex interfaces remains challenging. Traditional strategies based on tuning size, charge, or binding-site chemistry often suffer from limited flexibility. Here, we employ dimensionality engineering of cerium-based metal-organic frameworks (Ce-MOFs), comparing 2D and 3D Ce-MOFs to modulate molecular interactions via spatial conformation matching. Phytic acid (PA), with its distinct 3D inositol hexaphosphate structure, exhibits dimension-dependent interfacial assembly behavior. In 2D Ce-MOF, PA acts as a “molecular bridge” inducing interlayer stacking (∼fivefold thickness increase) and leading to strong noncompetitive inhibition (IC 50 = 0.053 mM) of its hydrolase (phosphatase)-mimetic activity. Conversely, confinement within the large pores (14.42 Å) of 3D Ce-MOF allows partial pore penetration (PA cross section: 10.46 Å) resulting in weak competitive inhibition (IC 50 = 1.7 mM). Spectroscopy ( 31 P NMR, FTIR) and zeta potential testing confirmed analogous PA-Ce coordination modes in Ce-MOFs ruling out chemical disparity as the cause. Density functional theory (DFT) calculations further verified the interlayer bridging in 2D MOF and intrapore confinement in 3D MOF as distinct adsorption modes. This fundamental difference—interlayer stacking versus confined penetration driven by dimensionality engineering creates a unique “dimensional fingerprint” for PA. Leveraging this orthogonal response (noncompetitive vs. competitive inhibition), we demonstrate a sensing strategy for selective PA identification. This work establishes dimensionality engineering as a powerful paradigm for rational interface design and selective recognition based on analyte spatial architecture. 摘要 en This link goes to a English section zh This link goes to a Chinese section 选择性分子识别是化学传感的核心,但在复杂界面上实现对结构相似分子的精准区分仍具有挑战性。传统通过调整尺寸、电荷或结合位点化学性质的策略往往灵活性不足。本研究提出一种基于铈基金属有机框架(Ce-MOFs)的维度设计方法,通过构建二维与三维Ce-MOFs,并利用空间构型匹配调控其与植酸(PA)的相互作用。PA具有独特的三维肌醇六磷酸酯结构,因而呈现出显著的维度依赖界面组装行为: 在二维Ce-MOF中,PA作为“分子桥”诱导层间堆叠(厚度增加约5倍),从而对其水解酶活性产生强烈的非竞争性抑制; 而在具有大孔道(14.42 Å)的三维Ce-MOF中,PA(横截面约10.46 Å)可部分进入孔道,仅引起较弱的竞争性抑制。 31 P 核磁共振(NMR)、傅里叶变换红外光谱(FTIR)以及Zeta电位结果表明,两种Ce-MOFs中的PA-Ce配位方式相近,排除了配位化学差异导致响应分化的可能。密度泛函理论(DFT)计算进一步验证了两种截然不同的吸附模式: 二维MOF中的层间桥连与三维MOF中的孔内限域。这种由维度设计驱动的根本差异——层间堆叠与限域渗透,赋予PA独特的“维度指纹”。基于这种正交抑制响应(非竞争性 versus 竞争性),我们构建了用于PA选择性识别的传感策略。该研究确立了维度设计作为一种通用范式,可用于基于分析物空间结构的理性界面设计和选择性识别。