Polaron engineering promotes NIR-II absorption of carbon quantum dots for bioimaging and cancer therapy.

Recent years have witnessed a surge of interest in tuning the optical properties of organic semiconductors for diverse applications. However, achieving control over the optical bandgap in the second near-infrared (NIR-II) window has remained a major challenge. To address this, here we report a polaron engineering strategy that introduces diverse defects into carbon quantum dots (CQDs). These defects induce lattice distortions resulting in the formation of polarons, which can absorb the near-field scattered light. Furthermore, the formed polarons in N-related vacancies can generate thermal energy through the coupling of lattice vibrations, while the portion associated with O-related defects can return to the ground state in the form of NIR-II fluorescence. On the basis of this optical absorption model, these CQDs have been successfully applied to NIR-II fluorescence imaging and photothermal therapy. This discovery could open a promising route for the polarons of organic semiconductor materials as NIR-II absorbers in nanomedical applications.

Polylysine-modified near-infrared-emitting carbon dots assemblies: Amplification of tumor accumulation for enhanced tumor photothermal therapy.

A key challenge to enhance the therapeutic outcome of photothermal therapy (PTT) is to improve the efficiency of passive targeted accumulation of photothermal agents at tumor sites. Carbon dots (CDs) are an ideal choice for application as photothermal agents because of their advantages such as adjustable fluorescence, high photothermal conversion efficiency, and excellent biocompatibility. Here, we synthesized polylysine-modified near-infrared (NIR)-emitting CDs assemblies (plys-CDs) through post-solvothermal reaction of NIR-emitting CDs with polylysine. The encapsulated structure of plys-CDs was confirmed by determining morphological, chemical, and luminescent properties. The particle size of CDs increased to approximately 40 ± 8 nm after polylysine modification and was within the size range appropriate for achieving superior enhanced permeability and retention effect. Plys-CDs maintained a high photothermal conversion efficiency of 54.9 %, coupled with increased tumor site accumulation, leading to a high efficacy in tumor PTT. Thus, plys-CDs have a great potential for application in photothermal ablation therapy of tumors.

Constructing Oxygen-Related Defects in Carbon Nanodots with Janus Optical Properties: Noninvasive NIR Fluorescent Imaging and Effective Photocatalytic Therapy.

Noninvasive fluorescence (FL) imaging and high-performance photocatalytic therapy (PCT) are opposing optical properties that are difficult to combine in a single material system. Herein, a facile approach to introducing oxygen-related defects in carbon dots (CDs) via post-oxidation with 2-iodoxybenzoic acid is reported, in which some nitrogen atoms are substituted by oxygen atoms. Unpaired electrons in these oxygen-related defects rearrange the electronic structure of the oxidized CDs (ox-CDs), resulting in an emerging near-infrared (NIR) absorption band. These defects not only contribute to enhanced NIR bandgap emission but also act as trappers for photoexcited electrons to promote efficient charge separation on the surface, leading to abundant photo-generated holes on the ox-CDs surface under visible-light irradiation. Under white LED torch irradiation, the photo-generated holes oxidize hydroxide to hydroxyl radicals in the acidification of the aqueous solution. In contrast, no hydroxyl radicals are detected in the ox-CDs aqueous solution under 730 nm laser irradiation, indicating noninvasive NIR FL imaging potential. Utilizing the Janus optical properties of the ox-CDs, the in vivo NIR FL imaging of sentinel lymph nodes around tumors and efficient photothermal enhanced tumor PCT are demonstrated.

Visible-light-induced strong oxidation capacity of metal-free carbon nanodots through photo-induced surface reduction for photocatalytic antibacterial and tumor therapy.

Biocompatible metal-free carbon dots (CDs) with good photo-induced strong oxidation capacity in aqueous solutions are scarce for high-performance photocatalytic antibacterial and tumor therapy. In this work, we achieved effective visible light-induced cell death and antibacterial performance based on biocompatible metal-free CDs. The visible-light-induced reducing ability of the surface electron-withdrawing structure of the CDs allowed for the remaining photo-induced holes with high oxidation capacity to oxidize water molecules and generate hydroxyl radicals. Antibiotic-resistant bacteria were effectively inhibited by the CDs under xenon lamp irradiation with 450 nm long pass filter. Moreover, CD-based tumor photocatalytic therapy in mice was achieved using a xenon lamp with 450 nm long pass filter (0.3 W cm-2).

Photocatalytic Pt(IV)-Coordinated Carbon Dots for Precision Tumor Therapy.

Rapid, efficient, and precise cancer therapy is highly desired. Here, this work reports solvothermally synthesized photoactivatable Pt(IV)-coordinated carbon dots (Pt-CDs) and their bovine serum albumin (BSA) complex (Pt-CDs@BSA) as a novel orange light-triggered anti-tumor therapeutic agent. The homogeneously distributed Pt(IV) in the Pt-CDs (Pt: 17.2 wt%) and their carbon cores with significant visible absorption exhibit excellent photocatalytic properties, which not only efficiently releases cytotoxic Pt(II) species but also promotes hydroxy radical generation from water under orange light. When triggered with a 589 nm laser, Pt-CDs@BSA possesses the ultrastrong cancer cell killing capacities of intracellular Pt(II) species release, hydroxyl radical generation, and acidification, which induce powerful immunogenic cell death. Activation of Pt-CDs@BSA by a single treatment with a 589 nm laser effectively eliminated the primary tumor and inhibited distant tumor growth and lung metastasis. This study thus presents a new concept for building photoactivatable Pt(IV)-enriched nanodrug-based CDs for precision cancer therapy.

One step synthesis of efficient red emissive carbon dots and their bovine serum albumin composites with enhanced multi-photon fluorescence for in vivo bioimaging.

Efficient red emissive carbon dots (CDs) in aqueous solutions are very scarce for high performance bioimaging applications. In this work, we report a one-step solvothermal treatment to synthesize pure red emissive CDs (FA-CDs) from citric acid and urea in formic acid without complicated purification procedures. Photoluminescence quantum yield (PLQY) of 43.4% was observed in their dimethyl sulfoxide solutions. High PLQY up to 21.9% in aqueous solutions was achieved in their bovine serum albumin (BSA) composites (FA-CDs@BSA) with significantly enhanced multi-photon fluorescence. The strong surface electron-withdrawing structure of FA-CDs caused by the high content of C = O groups contributes for their pure red emission. Owing to the significantly enhanced single and multi-photon red fluorescence and enlarged particle sizes after composing with BSA, in vivo tumor imaging and two-photon fluorescence imaging of blood vessels in mouse ear have been realized via intravenous injection of FA-CDs@BSA aqueous solutions.

Aluminum-Based Surface Polymerization on Carbon Dots with Aggregation-Enhanced Luminescence.

Aggregation-induced luminescence quenching of carbon nanodots (CDs) is the main obstacle for their applications in solid-state light emitting devices. Herein, we developed a one-step synthesis of solid-state emissive CDs with surface aluminum-based polymerization by adding AlCl3 in citric acid and urea via a microwave-heating dehydration process. Due to the strong coordination ability of Al ions with N and O atoms, considerable steric hindrance of Al-based cross-linked polymerization was introduced on the surface of the CDs, which not only avoided aggregation of the green emissive carbon cores but also facilitated efficient energy transfer from the blue emissive polymerized surface to the green emissive carbon cores in aggregates, leading to enhanced green emissions with a photoluminescence quantum yield (PLQY) of 72.7% in the solid state.

Chiral CdSe nanoplatelets as an ultrasensitive probe for lead ion sensing.

As opposed to traditional photoluminescence and ultra-violet based optical sensing, we present here a sensing system based on resolved optically active polarization with promising applications. It is based on the ultrathin CdSe nanoplatelets (NPLs) when modified with either l or d-cysteine molecules (l/d-cys) as bio-to-nano ligands. The chiral ligand transfers its chiroptical activity to the achiral nanoplatelets with an anisotropy factor of ∼10-4, which unlocks the chiral excitonic transitions and allows lead ion detection with a limit of detection (LOD) as low as 4.9 nM. Simulations and modelling based on time-dependent density functional theory (TD-DFT) reveal the chiral mechanism of l/d-cys capped CdSe NPLs. The presented CD-based sensing system illustrates an alternative possibility of using chiral CdSe NPLs as competitive chiral sensors for heavy metal ion detection.

Tunable Chiroptical Properties from the Plasmonic Band to Metal-Ligand Charge Transfer Band of Cysteine-Capped Molybdenum Oxide Nanoparticles.

Understanding the interactions between a semiconducting nanocrystal surface and chiral anchoring molecules could resolve the mechanism of chirality induction in nanoscale and facilitate the rational design of chiral semiconducting materials for chiroptics. Now, chiral molybdenum oxide nanoparticles are presented in which chirality is transferred via a bio-to-nano approach. With facile control of the amount of chiral cysteine molecules under redox treatment, circular dichroism (CD) signals are generated in the plasmon region and metal-ligand charge-transfer band. The obtained enhanced CD signals with tunable lineshapes illustrate the possibility of using chiral molybdenum oxide nanoparticles as potentials for chiral semiconductor nanosensors, optoelectronics, and photocatalysts.

Structural Engineering for High Sensitivity, Ultrathin Pressure Sensors Based on Wrinkled Graphene and Anodic Aluminum Oxide Membrane.

Nature-motivated pressure sensors have been greatly important components integrated into flexible electronics and applied in artificial intelligence. Here, we report a high sensitivity, ultrathin, and transparent pressure sensor based on wrinkled graphene prepared by a facile liquid-phase shrink method. Two pieces of wrinkled graphene are face to face assembled into a pressure sensor, in which a porous anodic aluminum oxide (AAO) membrane with the thickness of only 200 nm was used to insulate the two layers of graphene. The pressure sensor exhibits ultrahigh operating sensitivity (6.92 kPa-1), resulting from the insulation in its inactive state and conduction under compression. Formation of current pathways is attributed to the contact of graphene wrinkles through the pores of AAO membrane. In addition, the pressure sensor is also an on/off and energy saving device, due to the complete isolation between the two graphene layers when the sensor is not subjected to any pressure. We believe that our high-performance pressure sensor is an ideal candidate for integration in flexible electronics, but also paves the way for other 2D materials to be involved in the fabrication of pressure sensors.

Magnetic and highly recyclable macroporous carbon nanotubes for spilled oil sorption and separation.

Development of sorbent materials with high selectivity and sorption capacity, easy collection and recyclability is demanding for spilled oil recovery. Although many sorption materials have been proposed, a systematic study on how they can be reused and possible performance degradation during regeneration remains absent. Here we report magnetic carbon nanotube sponges (Me-CNT sponge), which are porous structures consisting of interconnected CNTs with rich Fe encapsulation. The Me-CNT sponges show high mass sorption capacity for diesel oil reached 56 g/g, corresponding to a volume sorption capacity of 99%. The sponges are mechanically strong and oil can be squeezed out by compression. They can be recycled using through reclamation by magnetic force and desorption by simple heat treatment. The Me-CNT sponges maintain original structure, high capacity, and selectivity after 1000 sorption and reclamation cycles. Our results suggest that practical application of CNT macrostructures in the field of spilled oil recovery is feasible.