Nanoparticle Hybrid Materials Using Plasmonic-Enhanced Upconversion FRET for Multiplexed Sensing and Optical Barcoding

具有特定光物理特性的光致发光纳米材料的开发是材料科学的一个动态领域。通过调整光致发光（PL）的颜色、强度和寿命，在传感中的高阶多路复用以及用于安全应用和质量控制的光学条形码方面已经投入了大量的努力。nir激发上转换纳米粒子（UCNPs）是一种新兴的纳米粒子，具有在水和生物组织中较高的穿透深度、强抗stokes位移发射、高光稳定性和强减弱的自身荧光背景。尽管UCNPs被认为是上述应用的理想候选者，但它们面临着低PL量子产率（QY）、有限的颜色和寿命可调性以及水溶液稳定性低的挑战。来自3个欧洲国家的5个知名研究团队组成nanohype概念驱动项目联盟，将计算建模、合成和实验验证相结合，设计新型金属壳UCNPs，获得：- 50倍PL QY增强-可调谐PL寿命在100 ns - 600µs之间-可调谐PL颜色通过多路Förster共振能量转移（FRET）到量子点（QDs）或染料。新型PNMs将由硅嵌入的UCNPs和金属表面涂层组成，用于等离子体PL增强，寿命可调谐和不同的QD或染料FRET受体，用于PL颜色和寿命由UCNP调整到QD/染料距离安排。为此，将在预测建模和仿真的基础上进一步优化荧光纳米材料、金属纳米壳和UCNPs的合成技术。通过结合计算建模、材料工程和合成来精确调整距离和材料参数，将获得具有改进QY的最佳多路复用能力的目标PL特性。可变PNM结构的计算建模的预测能力将为具有目标PL性质的PNM合成提供一个配方。建模的结构属性将产生如下。将合成无缺陷的UCNPs并涂覆未掺杂的镧系元素和具有精确控制厚度的二氧化硅壳，这将使FRET受体在壳内或壳上精确定位。然后将这些pmms涂上完全或部分开放的金属壳，以利用等离子体相互作用增强激发和发射，并使分析物能够接触到FRET受体。所建议的建模/综合方法将导致为这种基于ucnp的项目管理系统制定设计标准。我们将提供用于传感和光学条形码的新型pmms的预测目标特性的实验验证，并展示其定制合成的优势。多学科联盟将大大有助于加强欧洲综合计算材料工程社区。

The development of photoluminescent nanomaterials (PNMs) with tailored photophysical properties is a dynamic area of materials science. Much effort has been devoted to high-order multiplexing in sensing as well as optical barcoding for security applications and quality control using PNMs by tuning of the photoluminescence (PL) color, intensity, and lifetime. NIR-excitable upconverting nanoparticles (UCNPs) are newly emerging PNMs, which provide higher penetration depths in water and biological tissues, strongly anti-Stokes shifted emission, high photostability and strongly reduced autofluorescence background. Although UCNPs are considered ideal candidates for the applications mentioned above, they face challenges regarding low PL quantum yields (QY), limited color and lifetime tunability, and low stability in aqueous solution.5 renowned research teams from 3 European countries form the nanohype concept-driven project consortium, which combines computational modeling, synthesis, and experimental validation to design novel metal-shelled UCNPs to obtain: - 50-fold PL QY enhancement- tunable PL lifetimes between 100 ns - 600 µs- tunable PL colors by multiplexed Förster Resonance Energy Transfer (FRET) to quantum dots (QDs) or dyesThe novel PNMs will consist of silica-embedded UCNPs with metal surface coatings for plasmonic PL enhancement, and lifetime tunability and different QD or dye FRET acceptors for PL color and lifetime tuning by UCNP to QD/dye distance arrangement. For this purpose, techniques of synthesizing fluorescent nanomaterials, metal nanoshells, and UCNPs will be further optimized based on predictive modeling and simulation. By precisely tuning the distance and material parameters by combined computational modeling, materials engineering and synthesis, targeted PL properties for optimal multiplexing capabilities with improved QY will be obtained.The predictive power of computational modeling of the variable PNM structures will provide a recipe for PNM synthesis with targeted PL properties. The modeled structural properties will be produced as follows. Defect-free UCNPs will be synthesized and coated with undoped lanthanides and silica shells with precisely controlled thickness, which will enable precise positioning of FRET acceptors in or on the shells. These PNMs will then be coated with complete or partly open metal shells to utilize plasmonic interactions for an enhancement in excitation and emission and to enable access of analytes to the FRET acceptors. The proposed modeling/synthesis approach will result in the development of design criteria for such UCNP-based PNMs. We will provide the experimental validation of the predicted target properties of the novel PNMs for sensing and optical barcoding and demonstrate their superiority resulting from tailored synthesis. The multidisciplinary consortium will significantly contribute to strengthen the European Integrated Computational Materials Engineering community.