[论文解读] Sel-assembled Rhodium Nanoantennas for Single-Protein UV SERS
展示自组装铑纳米二聚天线,实现单蛋白质的紫外SERS,具有偏振可调响应,通过在热点处检测到一个丝锥亲和素分子来证明。
Surface-enhanced Raman scattering (SERS) provides critical insights into analyte structure, dynamic processes, and intermolecular interactions at the single-molecule level. By exploiting the hotspot formation in the vicinity of plasmonic structures, SERS constitutes an established tool for fundamental biological research, particularly for early-stage disease diagnostics. In this context, the DNA Origami technique, with its high addressability, enables both the assembly of plasmonic nanostructures with nanometric accuracy, and the deterministic placement of a single analyte molecule precisely at the generated hotspot within them. To date, most DNA Origami based nanoantennas rely on gold or silver nanoparticles (NPs), whose plasmonic resonances are confined to the visible spectrum, severely limiting their use in other spectral ranges. To extend the operating range, we have recently established a robust strategy for self-assembling programmable ultraviolet (UV)-plasmonic dimer antennas using rhodium nanocubes. Herein, we leverage this tailored architecture to systematically investigate its performance for single-molecule UV-SERS. We demonstrated how biofabricated Rh-dimers can be used to detect the characteristic SERS signal of a single streptavidin molecule linked at the dimer s gap. Our results are validated through polarization dependent measurements that yield the expected signal modulation depending on the the dimer orientation only for the DNA origami with a protein at the hotspot. This work establishes a highly sensitive and polarization-tunable UV-SERS platform, laying a solid foundation for label-free optical investigation and bio-spectroscopy of individual biomolecules in the UV spectral range.
研究动机与目标
- 通过使用铑立方体创建紫外等离子体双极天线,将紫外SERS能力扩展至金/银之外。
- 利用DNA origami在纳米天线间隙处确定性地定位单个蛋白质在SERS热点处。
- 证明单分子紫外SERS信号并研究偏振依赖性以确认热点定位和取向效应。
- 提供一个偏振可调、无标记的光学平台,用于在紫外范围内对单个生物分子进行生物光谱学研究。
提出的方法
- 利用铑纳米立方体自组装制备铑二聚天线,创建紫外等离子体热点。
- 通过DNA origami在二聚间隙处连接单个蛋白(streptavidin),以确保热点定位的确定性。
- 进行紫外SERS测量,在热点处检测单个蛋白的特征信号。
- 进行偏振相关测量,验证当热点处存在蛋白质时二聚取向对信号的调制。
实验结果
研究问题
- RQ1铑基紫外等离子体二聚是否能支持来自单个生物分子的可检测SERS信号?
- RQ2在纳米天线热点处确定性定位单个蛋白是否能实现清晰的紫外SERS读出?
- RQ3当蛋白位于热点时,铑二聚的偶极取向是否如偏振依赖性所预测地调制紫外SERS信号?
主要发现
- 生物制造的铑二聚体能够在二聚间隙处检测到单丝锥亲和素的SERS信号。
- 偏振相关测量表明仅当热点处存在蛋白时,信号调制才依赖于二聚取向。
- 该工作为在紫外范围内对个体生物分子进行无标记光学研究提供了一种敏感且可偏振调谐的紫外SERS平台。
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