Yuhui Jin

Ratiometric Temperature Sensing with Semiconducting Polymer Dots

This communication describes ultrabright single-nanoparticle ratiometric temperature sensors based on semiconducting polymer dots (Pdots). We attached the temperature sensitive dye-Rhodamine B (RhB), whose emission intensity decreases with increasing temperature-within the matrix of Pdots. The as-prepared Pdot-RhB nanoparticle showed excellent temperature sensitivity and high brightness because it took advantage of the light harvesting and amplified energy transfer capability of Pdots. More importantly, the Pdot-RhB nanoparticle showed ratiometric temperature sensing under a single wavelength excitation and has a linear temperature sensing range that matches well with the physiologically relevant temperatures. We employed Pdot-RhB for measuring intracellular temperatures in a live-cell imaging mode. The exceptional brightness of Pdot-RhB allows this nanoscale temperature sensor to be used also as a fluorescent probe for cellular imaging.

Design of Highly Emissive Polymer Dot Bioconjugates for In Vivo Tumor Targeting

Nanoparticle-based diagnostic and therapeutic agents have attracted considerable interest because of their potential for clinical oncology and other biomedical research.[1] Versatile nanostructures have been demonstrated for in vivo applications, such as lipid and polymeric nanocapsules for drug delivery,[2] iron oxide nanoparticles for magnetic resonance imaging,[3] gold nanoparticles for X-ray computed tomography,[4] and quantum dots (Qdots) for fluorescence imaging.[5] Qdots represent one of the exciting nanotechnologies translated to biology in the past decade. The size-tunable luminescence makes them appealing as multicolor fluorophores for biological labelling, imaging, and sensing.[6,7] For in vivo applications, however, the intrinsic toxicity of Qdots is of critical concern,[8] which may impede their final clinical translation. Therefore, the design of bright probes with biologically benign materials is highly desirable for many in vivo clinical applications.

Near-Infrared Fluorescent Dye-Doped Semiconducting Polymer Dots

Near-infrared (NIR) fluorescence sensing is desirable for in vivo biological measurements, but the method is currently limited by the availability of NIR fluorescent markers as well as by their poor performance, such as self-aggregation and dim fluorescence, in a physiological environment. To address this issue, this paper describes a NIR fluorescent polymer dot (Pdot) that emits at 777 nm. This Pdot was comparable in size to a water-soluble NIR quantum dot that emits at 800 nm (ITK Qdot800) but was about four times brighter and with a narrower emission peak. We formed the NIR Pdot by doping the NIR dye, silicon 2,3-naphthalocyanine bis(trihexylsilyloxide) (NIR775), into the matrix of poly (9,9-dioctylfluorene-co-benzothiadiazole) (PFBT) as the Pdot formed using a nanoscale precipitation technique. Free molecules of NIR775 aggregate in aqueous solution, but encapsulating them into the hydrophobic Pdot matrix effectively introduced them into aqueous solution for use in biological studies. Most importantly, the brightness of NIR775 was dramatically enhanced because of the excellent light-harvesting ability of PFBT and the very efficient energy transfer from PFBT to NIR775. We anticipate this bright NIR Pdot will be useful in biological measurements and cellular imaging where strong NIR emission is beneficial.

Copper(II) and iron(II) ion sensing with semiconducting polymer dots

This communication describes a simple platform that employs carboxyl functionalized semiconducting polymer dots as a fluorescent probe for sensitive ratiometric Cu(2+) and Fe(2+) detection, in which the sensing mechanism is based on aggregation-induced fluorescence quenching.

Hybrid Semiconducting Polymer Dot–Quantum Dot with Narrow-Band Emission, Near-Infrared Fluorescence, and High Brightness

This communication describes a new class of semiconducting polymer nanoparticle-quantum dot hybrid with high brightness, narrow emission, near-IR fluorescence, and excellent cellular targeting capability. Using this approach, we circumvented the current difficulty with obtaining narrow-band-emitting and near-IR-fluorescing semiconducting polymer nanoparticles while combining the advantages of both semiconducting polymer nanoparticles and quantum dots. We further demonstrated the use of this new class of hybrid nanomaterial for effective and specific cellular and subcellular labeling without any noticeable nonspecific binding. This hybrid nanomaterial is anticipated to find use in a variety of in vitro and in vivo biological applications.

A Compact and Highly Fluorescent Orange-Emitting Polymer Dot for Specific Subcellular Imaging

We demonstrate a new compact CN-PPV dot, which emits in the orange wavelength range with high brightness. The small particle size, high brightness, and the ability to highly specifically target subcellular structures make the CN-PPV dots promising probes for biological imaging and bioanalytical applications.

Importance of having low-density functional groups for generating high-performance semiconducting polymer dots.

Semiconducting polymers with low-density side-chain carboxylic acid groups were synthesized to form stable, functionalized, and highly fluorescent polymer dots (Pdots). The influence of the molar fraction of hydrophilic side-chains on Pdot properties and performance was systematically investigated. Our results show that the density of side-chain carboxylic acid groups significantly affects Pdot stability, internal structure, fluorescence brightness, and nonspecific binding in cellular labeling. Fluorescence spectroscopy, single-particle imaging, and a dye-doping method were employed to investigate the fluorescence brightness and the internal structure of the Pdots. The results of these experiments indicate that semiconducting polymers with low density of side-chain functional groups can form stable, compact, and highly bright Pdots as compared to those with high density of hydrophilic side-chains. The functionalized polymer dots were conjugated to streptavidin (SA) by carbodiimide-catalyzed coupling and the Pdot-SA probes effectively and specifically labeled the cancer cell-surface marker Her2 in human breast cancer cells. The carboxylate-functionalized polymer could also be covalently modified with small functional molecules to generate Pdot probes for click chemistry-based bio-orthogonal labeling. This study presents a promising approach for further developing functional Pdot probes for biological applications.

Generation of functionalized and robust semiconducting polymer dots with polyelectrolytes

We describe a facile method to functionalize semiconducting polymer dots (Pdots) with polyelectrolytes. The polyelectrolyte coating dramatically improves the colloidal stability of the Pdots in solutions which are either of high ionic strength or contain bivalent metal ions: this feature allows Pdots to be used under physiologically relevant environments without losing their functionality. We conjugated the polyelectrolyte-coated Pdots with streptavidin to demonstrate their application in specific cell labeling.

A versatile method for generating semiconducting polymer dot nanocomposites

This paper describes a method, based on co-precipitation, for generating small semiconducting polymer dot (Pdot) nanocomposites, which contain either gold or iron oxide nanoparticles within the Pdot matrix. We demonstrate the utility of Pdot-Au nanoparticles (Au-NP-Pdots) in dual-modality imaging in which co-localization of fluorescence from Pdot and scattering from Au was used to identify Au-NP-Pdot probes for downstream single-particle tracking and cellular imaging. We also demonstrate the potential of employing Pdot-FeO(x) nanoparticles (FeO(x)-NP-Pdots) for both sample preparation, where cells tagged with FeO(x)-NP-Pdots were isolated using an external magnet, and cellular imaging and detection, owing to the intense fluorescence from Pdots. The method we present here should be generalizable to the formation of other Pdot nanocomposites for creating the next generation of multi-functional Pdot probes.