Qianling Cui

Phenyl-Modified Carbon Nitride Quantum Dots with Distinct Photoluminescence Behavior

A novel type of quantum dot (Ph-CN) is manufactured from graphitic carbon nitride by lining the carbon nitride structure with phenyl groups through supramolecular preorganization. This approach requires no chemical etching or hydrothermal treatments like other competing nanoparticle syntheses and is easy and safe to use. The Ph-CN nanoparticles exhibit bright, tunable fluorescence, with a high quantum yield of 48.4u2009% in aqueous colloidal suspensions. Interestingly, the observed Stokes shift of approximately 200u2005nm is higher than the maximum values reported for carbon nitride based fluorophores. The high quantum yield and the large Stokes shift are related to the structural surface organization of the phenyl groups, which affects the π-electron delocalization in the conjugated carbon nitride networks and induces colloidal stability. The remarkable performance of the Ph-CN nanoparticles in imaging is demonstrated by a simple incubation study with HeLa cells.

Controllable metal-enhanced fluorescence in organized films and colloidal system.

In recent years, considerable efforts have been devoted to better understand the unique emission properties of fluorophores enhanced by the localized surface plasmon resonance of metal nanoparticles (NPs), due to the widespread applications of fluorescence techniques. It is demonstrated by experiment and theoretical calculation that the enhancement efficiency strongly depends on the morphology of the metal NPs, the spectral overlap between metal and fluorophores, the separation distance between them, and other factors. Among these aspects to be considered are suitable spacer material and assembling methods to control the spatial arrangement of plasmonic NPs and fluorophore with proper optical properties and interactions. In this contribution, we provide a brief overview on recent progress of metal-enhanced fluorescence in organized films and colloidal systems.

Fabrication of Au@Pt Multibranched Nanoparticles and Their Application to In Situ SERS Monitoring

Here, we present an Au@Pt core-shell multibranched nanoparticle as a new substrate capable of in situ surface-enhanced Raman scattering (SERS), thereby enabling monitoring of the catalytic reaction on the active surface. By careful control of the amount of Pt deposited bimetallic Au@Pt, nanoparticles with moderate performance both for SERS and catalytic activity were obtained. The Pt-catalyzed reduction of 4-nitrothiophenol by borohydride was chosen as the model reaction. The intermediate during the reaction was captured and clearly identified via SERS spectroscopy. We established in situ SERS spectroscopy as a promising and powerful technique to investigate in situ reactions taking place in heterogeneous catalysis.

Fabrication of Bifunctional Gold/Gelatin Hybrid Nanocomposites and Their Application

Herein, a facile method is presented to integrate large gold nanoflowers (∼80 nm) and small gold nanoparticles (2-4 nm) into a single entity, exhibiting both surface-enhanced Raman scattering (SERS) and catalytic activity. The as-prepared gold nanoflowers were coated by a gelatin layer, in which the gold precursor was adsorbed and in situ reduced into small gold nanoparticles. The thickness of the gelatin shell is controlled to less than 10 nm, ensuring that the small gold nanoparticles are still in a SERS-active range of the inner Au core. Therefore, the reaction catalyzed by these nanocomposites can be monitored in situ using label-free SERS spectroscopy. In addition, these bifunctional nanocomposites are also attractive candidates for application in SERS monitoring of bioreactions because of their excellent biocompatibility.

Hybridizing Carbon Nitride Colloids with a Shell of Water-Soluble Conjugated Polymers for Tunable Full-Color Emission and Synergistic Cell Imaging

We present the preparation of a new multicolor emission system constructed from two complementary conjugated materials that are highly photoluminescent, that is, phenyl-modified carbon nitride (PhCN) colloids as the core and water-soluble conjugated polymers (WSCPs) adsorbed as the shell. The fluorescence bands of the PhCN and WSCPs effectively complement each other and the overall emission can be simply adjusted to fully cover the visible light spectrum with white light emission also accessible. Photophysical insights imply that the interactions between PhCN and WSCPs preserve the binary system from emission distortion and degradation, which is essential to delicately tune the overall fluorescence bands. Notably, the continuously tunable emission color is achieved under single-wavelength excitation (365 nm). This hybrid shows a synergistic permeation performance in cell imaging, that is, PhCN nanoparticles help the WSCP to enter the cells and therefore multicolor cellular imaging achieved.

Aggregation-Induced Energy Transfer of Conjugated Polymer Materials for ATP Sensing

Water-soluble conjugated polymers are attractive fluorescent materials for applications in chemical and biological sensing. The molecular wire effect of such polymers amplifies changes in the fluorescence signal, which can be used for detecting various analytes with high sensitivity. In this work, we report an efficient ratiometric fluorescent probe based on a water-soluble conjugated polymer that showed high sensitivity and selectivity toward adenosine 5-triphosphate (ATP). The macromolecular probe consisted of a polyfluorene backbone doped with 5 mol % 1,4-dithienylbenzothiadiazole (DBT) modified by bis-imidazolium and oligo(ethylene glycol) moieties. Solutions of the polymer emitted purple fluorescence, which changed to red upon addition of ATP molecules. The addition of ATP caused the polymer to aggregate, which enhanced fluorescence resonance energy transfer efficiency from the fluorene segments to DBT units, leading to an increase in red emission. The ratio of the fluorescence at these different wavelengths (I655/I423) showed a strong dependence on the ATP concentration. PF-DBT-BIMEG also exhibited high selectivity for ATP sensing over other representative anions and discriminated it from adenosine 5-diphosphate (ADP) and adenosine 5-monophosphate (AMP). This can be explained by the much stronger electrostatic interactions between the polymer and ATP than the interactions between the polymer and ADP or AMP, as confirmed through molecular dynamics simulations.

Graphitic Carbon Nitride as a Distinct Solid Stabilizer for Emulsion Polymerization

g-C3 N4 has been found to be highly functional in many fields, such as photocatalysis, electrocatalysis, and chemical analysis. Pickering emulsion polymerization is a fascinating strategy to fabricate a range of nanomaterials, in which the emulsion is stabilized by solid particles, rather than molecular surfactants. Herein, we demonstrate that g-C3 N4 can act as a remarkable stabilizer for Pickering emulsion polymerization. Contrary to normal Pickering systems, monodisperse polystyrene microspheres with tunable size, surface charge, and morphology were achieved using this approach. Importantly, the g-C3 N4 hybridized latex is highly processable and has exhibited multiple functions: manufacture of photonic crystals via self-organization, stabilizing Pickering emulsion owing to proper wettability, and acting as bioimaging agents with enriched fluorescent colors. Considering the easy synthesis and low cost of g-C3 N4 , our approach has a high potential for scale-up synthesis and practical translation.

Direct Observation of Carbon Nitride-Stabilized Pickering Emulsions

Pickering emulsions are emulsions stabilized by solid particles located at surfaces/interfaces of liquid droplets that have promising applications for drug delivery and in nanomaterials synthesis. Direct observation of Pickering emulsions can be challenging. Normally, cryoelectron microscopy needs to be used to better understand these types of emulsion systems, but cryofreezing these emulsions may cause them to lose their original morphologies. In this work, we demonstrate that graphitic carbon nitride (g-C3N4) can stabilize oil-in-water (o/w) emulsions, with hexane illustrated as a typical oil phase. The g-C3N4-stabilized emulsions can act as an excellent platform for in situ study of emulsifying behavior from the mechanical point of view. Owing to its large lateral size and blue, stable fluorescence, the locations and motions of the g-C3N4 stabilizer can be finely in situ monitored by light microscopy, fluorescence microscopy, and confocal microscopy. Accordingly, we illustrate two stabilizing configurations of the g-C3N4 particles with respect to the emulsion droplets under static conditions. Further, we demonstrate the capability to manipulate emulsion droplets and investigate their response to external forces. We perform real-time observations of the g-C3N4 particles and the emulsion droplets that move in the continuous phase and study their adsorption kinetics toward each other. Finally, the π-π interaction between the stabilizer and aromatic liquid phase (e.g., toluene) is considered and studied as an influencing factor on emulsifying behavior.

A Diarylethene-Based Super Photoswitch and Its Photomodulation Performance on Fluorescence of Conjugated Polymer

Photochromic diarylethene derivatives, which can reversibly switch the fluorescence of adjacent fluorophores between the ON and OFF states under light irradiation, have been widely used to construct photoswitchable materials. Herein, eight dithienylethene (DTE) groups are integrated onto one polyhedral oligomeric silsesquioxane (POSS) core, obtaining a novel super molecular photoswitch. After being doped into conjugated polymer nanoparticles, the POSS-DTE8 molecules show a higher contrast on/off photoswitching performance and a quicker responsive speed than free DTE molecules at same molar concentration of photochromic units. This enhanced photoswitching efficiency is attributed to the increased molecular interaction of the ring-open form and lowered energy of the ring-closed form of the DTE units on the POSS core, which is beneficial for the ring-closing reaction and subsequent energy transfer between photoswitch and fluorophores. In addition, POSS-DTE8 also exhibits good photomodulation behavior in the conjugated polymer film, giving it potential applications in optical devices.