http://pubs.acs.org/doi/pdf/10.1021/cr400546e

Fluorescent Sensors for Measuring Metal Ions in Living Systems

CONTENTS 1. Introduction 1.1. Fundamental Theory of Surface-Enhanced Raman Scattering 1.2. Optical Properties of SERS Tags 2. Synthesis of SERS Tags 2.1. Noble Metal Nanosubstrates 2.1.1. Single Particle-Based SERS Substrates 2.1.2. Nanoparticle Cluster-Based Substrates 2.2. Raman Reporter Molecules 2.2.1. Selection Principles and Reporter Types 2.2.2. Self-Assembled Monolayer Coverage Strategy 2.3. Surface Coating for Protection 2.3.1. Biomolecule Coating 2.3.2. Polymer Coating 2.3.3. Liposome Coating 2.3.4. Silica Coating 2.4. Attachment of Targeting Molecules 3. Bioanalysis Applications 3.1. Ionic and Molecular Detection 3.2. Pathogen Detection 3.3. Live-Cell Imaging 3.3.1. Cancer Marker Detection 3.3.2. Intercellular Microenvironment Sensing 3.4. Tissue SERS Imaging 3.5. In Vivo SERS Imaging 4. Challenges and Perspectives 4.1. Reproducible Signal of SERS Tags 4.1.1. Precisely Controlled Hot Spots for Nanosubstrates 4.1.2. Calibration of SERS Intensities and Enhancements 4.2. Improving Multiplexing Capability 4.3. Reduced Size for Subcellular Imaging 4.4. Development of Multifunctional Nanoplatforms 4.4.1. Magnetic SERS Dots 4.4.2. Multimodal Imaging Dots 4.4.3. SERS Tag-Based Therapeutic Systems 4.5. Biocompatibility 5. Conclusions and Remarks

SERS Tags: Novel Optical Nanoprobes for Bioanalysis

Surface-enhanced Raman spectroscopy (SERS) inherits the rich chemical fingerprint information on Raman spectroscopy and gains sensitivity by plasmon-enhanced excitation and scattering. In particular, most Raman peaks have a narrow width suitable for multiplex analysis, and the measurements can be conveniently made under ambient and aqueous conditions. These merits make SERS a very promising technique for studying complex biological systems, and SERS has attracted increasing interest in biorelated analysis. However, there are still great challenges that need to be addressed until it can be widely accepted by the biorelated communities, answer interesting biological questions, and solve fatal clinical problems. SERS applications in bioanalysis involve the complex interactions of plasmonic nanomaterials with biological systems and their environments. The reliability becomes the key issue of bioanalytical SERS in order to extract meaningful information from SERS data. This review provides a comprehensive over...

Surface-Enhanced Raman Spectroscopy for Bioanalysis: Reliability and Challenges

This critical review will present the role of nanoparticles (NPs) in the directions that are vital to the new field of nanomedicine, including imaging and drug delivery. We reflect on the physical properties that make NPs advantageous for in vivo efficacy, and review recent advances in major NP based biomedical applications. Critical questions of transport, uptake, and clearance will be discussed and illustrated through the success and opportunities of NP imaging and therapy on a photodynamic therapy (PDT) based NP system that has been developed in our lab over the past decade (540 references).

The unique role of nanoparticles in nanomedicine: imaging, drug delivery and therapy

Metal halide perovskites represent a flourishing area of research, driven by both their potential application in photo-voltaics and optoelectronics, and for the fundamental science underpinning their unique optoelectronic properties. The advent of colloidal methods for the synthesis of halide perovskite nanocrystals has brought to the attention inter-esting aspects of this new type of materials, above all their defect-tolerance. This review aims to provide an updated survey of this fast-moving field, with a main focus on their colloidal synthesis. We examine the chemistry and the ca-pability of different colloidal synthetic routes to control the shape, size and optical properties of the resulting nano-crystals. We also provide an up to date overview of their post-synthesis transformations, and summarize the various so-lution processes aimed at fabricating halide perovskite-based nanocomposites. We then review the fundamental optical properties of halide perovskite nanocrystals, by focusing on their linear optical properties, on the effects of quantum confinement and, then, on the current knowledge of their exciton binding energies. We also discuss the emergence of non-linear phenomena such as multiphoton absorption, biexcitons and carrier multiplication. At last, we provide an outlook in the field, with the most cogent open questions and possible future directions.

Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications and Their Optical Properties

A new concept of optical encoding approach, surface enhanced Raman scattering (SERS)-fluorescence joint spectral encoding method (SFJSE), was demonstrated by using organic-metal-quantum dot (QD) hybrid nanoparticles (OMQ NPs) with a nanolayered structure. This method has two distinct characteristics, which make it more feasible to achieve enormous codes in practice, compared with a sole fluorescence- or SERS-based encoding protocol. One of the two characteristics is to use the joint SERS and fluorescence spectra as the encoding elements instead of an individual optical signal, resulting in a broadened optical spectrum range for efficient encoding. The other is to assemble SERS reporters and fluorescent agents onto different layers of OMQ NPs, leading to an easier fabrication protocol when a large number of agents need to be involved into encoding carriers. By conjugating different antibodies to OMQ NPs with varied codes, the potential application of such an encoding system in high-throughput detection has been investigated by multiplex sandwich immunoassays. The high specificity and sensitivity of the assays suggest that the SFJSE method could be developed as a powerful encoding tool for high-throughput bioanalysis with the use of OMQ NPs.

SERS-fluorescence joint spectral encoding using organic-metal-QD hybrid nanoparticles with a huge encoding capacity for high-throughput biodetection: putting theory into practice.

Unlike widely used postsynthetic halide exchange for CsPbX3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange-driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn-doped CsPb(Cl/Br)3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core–shell structured mid states with triple emission bands, and dopant molecules composition-dependent doping process. As-prepared dual-emitting Mn-doped CsPb(Cl/Br)3 NCs are available for ratiometric temperature sensing.

Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

A SERS and fluorescence dual mode cancer cell targeting probe based on silica coated Au@Ag core-shell nanorods.

A redox-responsive drug carrier based on nanoscale graphene oxide (NGO) loaded with Ag nanoparticles, whose intracellular release behavior can be investigated by SERS-fluorescence combined spectroscopy, is presented. In this demonstrated drug carrier, to make the carrier integrated with the redox responsive property, we utilized disulfide linkages to load drug molecules to the surfaces of NGO directly, which can be cleaved by glutathione (GSH). Covalent drug loading and GSH-responsive release strategy can reduce the influence of the surface diffusion barriers introduced by multifunctionalization. Interestingly, the intracellular real-time drug release dynamics can be monitored by the combined SERS-fluorescence signals of the drugs, while the distribution of the drug carrier can simultaneously be tracked by the intrinsic SERS signals of NGO in the whole process. Our results show that upon the internalization of doxorubicin (DOX)-loaded nanocarriers into living cells, DOX was efficiently released under a GS...

SERS-fluorescence monitored drug release of a redox-responsive nanocarrier based on graphene oxide in tumor cells.

The passivation of defects at perovskite grain boundaries (GB) is crucial in achieving highly efficient and stable perovskite solar cells. Unlike the widely used additive passivation method where a mixture of additives and perovskite precursor is used for preparing perovskite films, we herein developed a new defect post-healing method via dip-coating trioctylphosphine oxide (TOPO) ligands on pre-fabricated carbon-based mesoscopic perovskite solar cells (MPSCs). Since perovskites have formed before post-healing, TOPO ligands are selectively adsorbed onto the exposed perovskite surface and hence have little influence on charge extraction of interfaces. The defects are post-healed via O atoms in PO bonds coordinated to halide-deficient sites, leading to an enhancement of the power conversion efficiency (PCE) from 11.0% to 12.8%. Moreover, due to the three hydrophobic long chain alkyls in TOPO, the humidity stability of the device has also been improved simultaneously.

Shuhong Xu

Papers

SERS-fluorescence joint spectral encoding using organic-metal-QD hybrid nanoparticles with a huge encoding capacity for high-throughput biodetection: putting theory into practice.

Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

A SERS and fluorescence dual mode cancer cell targeting probe based on silica coated Au@Ag core-shell nanorods.

SERS-fluorescence monitored drug release of a redox-responsive nanocarrier based on graphene oxide in tumor cells.

Post-healing of defects: an alternative way for passivation of carbon-based mesoscopic perovskite solar cells via hydrophobic ligand coordination