White‐Light‐Emitting Edge‐Functionalized Graphene Quantum Dots

Graphene quantum dots (GQDs) have received considerable attention for their potential applications in the development of novel optoelectronic materials. In the generation of optoelectronic devices, the development of GQDs that are regulated in terms of their size and dimensions and are unoxidized at the sp² surfaces is desired. GQDs functionalized with bulky Fréchet’s dendritic wedges at the GQD periphery were synthesized. The single‐layered, size‐regulated structures of the dendronized GQDs were revealed by atomic force microscopy. The edge‐functionalization of the GQDs led to white‐light emission, which is an uncommon feature.     

Anodic‐Stripping Voltammetric Immunoassay for Ultrasensitive Detection of Low‐Abundance Proteins Using Quantum Dot Aggregated Hollow Microspheres

A new anodic‐stripping voltammetric immunoassay protocol for detection of IgG1, as a model protein, was designed by using CdS quantum dot (QD) layer‐by‐layer assembled hollow microspheres (QDHMS) as molecular tags. Initially, monoclonal anti‐human IgG1 specific antibodies were anchored on amorphous magnetic beads preferably selective to capture F_ab of IgG1 analyte from the sample. For detection, monoclonal anti‐human IgG1 (F_c‐specific) antibodies were covalently coupled to the synthesized QDHMS. In a sandwich‐type immunoassay format, subsequent anodic‐stripping voltammetric detection of cadmium released under acidic conditions from the coupled QDs was conducted at an in situ prepared mercury film electrode. The immunoassay combines highly efficient magnetic separation with signal amplification by the multilayered QD labels. The dynamic concentration range spanned from 1.0 fg mL^?1 to 1.0 μg mL^?1 of IgG1 with a detection limit of 0.1 fg mL^?1. The electrochemical immunoassay showed good reproducibility, selectivity, and stability. The analysis of clinical serum specimens revealed good accordance with the results obtained by an enzyme‐linked immunosorbent assay method. The new immunoassay is promising for enzyme‐free, and cost‐effective analysis of low‐abundance biomarkers.     

DNA‐Templated Assembly of a Heterobivalent Quantum Dot Nanoprobe For Extra‐ and Intracellular Dual‐Targeting and Imaging of Live Cancer Cells

Quantum dots (QDs) hold great promise for the molecular imaging of cancer because of their superior optical properties. Although cell‐surface biomarkers can be readily imaged with QDs, non‐invasive live‐cell imaging of critical intracellular cancer markers with QDs is a great challenge because of the difficulties in the automatic delivery of QD probes to the cytosol and the ambiguity of intracellular targeting signals. Herein, we report a new type of DNA‐templated heterobivalent QD nanoprobes with the ability to target and image two spatially isolated cancer markers (nucleolin and mRNA) present on the cell surface and in the cell cytosol. Bypassing endolysosomal sequestration, this type of QD nanoprobes undergo macropinocytosis following the nucleolin targeting and then translocate to the cytosol for mRNA targeting. Fluorescence resonance energy transfer (FRET) based confocal microscopy enables unambiguous signal deconvolution of mRNA‐targeted QD nanoprobes inside cancer cells.     

Utilization of Red‐Light‐Emitting CdTe Nanoparticles for the Trace‐Level Detection of Harmful Herbicides in Adulterated Food and Agricultural Crops

Red‐light‐emitting water‐soluble semiconducting quantum dots (QDs) were synthesized by using a wide variety of commercially available thiol‐type capping agents. QDs with a negatively charged nanosurface showed excellent selectivity for paraquat (PQ) at pH 7.4 over other commonly encountered pesticides/herbicides, including diquat (DQ). The presence of a 4,4′‐bis‐pyridinium unit in PQ enabled it to initiate long‐range aggregation, thereby leading to the formation of nanostructures with excellent emission‐quenching behavior. Precoated quartz plates were developed as a low‐cost, portable sensor for the on‐site detection of PQ in both natural water and human urine. Estimation of the PQ concentration was performed in different commercial formulations and the detection of PQ contamination in adulterated dairy product was also achieved with excellent sensitivity. Finally, we screened more than 50 different food items, including vegetables, fruits, cereals, and fodders, to construct a generalized marker for any residual PQ in such specimens.     

Sensing Chiral Drugs by Using CdSe/ZnS Nanoparticles Capped with N‐Acetyl‐L‐Cysteine Methyl Ester

Chiral quantum dots (QDs), differing in their core or shell size and, consequently, in their optical properties, were synthesized by the treatment of commercially available amine‐capped quantum dots with methyl ester N‐acetyl‐L ‐cysteine (CysP). Interestingly, their colloidal methanol solutions remain stable for several months. Their NMR and IR spectra were in accordance with CysP binding to the QD surface through two anchoring groups; its thiolate (strongly bound) and the carbonyl group of its ester (weaker bound) group, whereas their circular dichroism (CD) spectra showed a new broad redshifted band, suggesting that the attachment to the QD surface modified the conformational equilibrium towards conformer(s) with optical activity in this region. These QDs were sufficiently fluorescent to perform studies of the chiral recognition of drugs, in particular the aryl propionic acids (APAs) ketoprofen (KP), naproxen (NP), flurbiprofen (FP), and ibuprofen (IP). We used different drug concentration ranges, depending on the QD solubility. All the assayed drugs quenched the QD emission in a concentration‐dependent mode. Quenching fluorescence assays with the chiral QDs (CS@CysP) showed their extraordinary capacity for the chiral recognition of KP, NP, and FP, and particularly in the case of KP and FP, a remarkable positive allosteric effect was detected for the R enantiomer. By using a drug/CS@CysP molar ratio of 5000:1 and 2500:1, the changes of intensity and the sign of the CD spectrum of the drug evidenced the dissociation of the drug carboxylic group in the presence of the QD.     

Detection of Hg2+ and F− Ions by Using Fluorescence Switching of Quantum Dots in an Au‐Cluster–CdTe QD Nanocomposite

A single probe of an Au nanocluster–CdTe quantum dots nanocomposite has been developed by using tripeptide‐capped CdTe quantum dots (QD) and bovine serum albumin (BSA) protein‐conjugated Au₂₅ nanocluster (NC) for detection of both Hg²⁺ ion and F^? ion. The formation of Au‐NC–CdTe QD nanocomposite has been confirmed by TEM, steady state and time resolved spectroscopy, CD and FTIR studies. A significant signal off (74 % PL quenching at 553 nm) phenomenon of this nanocomposite is observed in presence of 6.56×10^?7 M Hg²⁺ ion, due to salt‐induced aggregation. However, a dramatic PL enhancement (128 %) of the Au‐NC–CdTe QD nanocomposite is observed in presence of 8.47×10^?7 M F^? anion. The calculated limit of detections (LOD) of Hg²⁺ ion concentration and F^? ion concentration are found to be 9 and 117 nM , respectively, which are within the safety range set by the United States Environment Protection Agency. Thus, the simple Au‐NC–CdTe QD optical‐based sensor is very useful to detect both toxic cations and anions.     

One‐Pot Green Synthesis of Nitrogen‐Doped Carbon Quantum Dots for Cell Nucleus Labeling and Copper(II) Detection

The doping of nitrogen into carbon quantum dots is vitally important for improved fluorescence performance. However, the synthesis of nitrogen‐doped carbon quantum dots (N‐CQDs) is usually conducted under strong acid and high temperature, which results in environmental pollution and energy consumption. Herein, the N‐CQDs were prepared by a mild one‐pot hydrothermal process. The hydrothermal reaction temperature was adjusted to control the particle size, nitrogen/carbon atomic ratio, and quantum yield. The products were water soluble with a narrow particle size distribution and good dispersion stability over a wide pH range. The N‐CQDs could penetrate into the HeLa cell nucleus without any further functionalization. Moreover, the fluorescence of N‐CQDs could be selectively quenched by Cu²⁺, which suggested applications for the detection of Cu²⁺ in human plasma.     

Ribose‐Protonated DNA Base Excision Repair: A Combined Theoretical and Experimental Study

Living organisms protect the genome against external influences by recognizing and repairing damaged DNA. A common source of gene mutation is the oxidized guanine, which undergoes base excision repair through cleavage of the glycosidic bond between the ribose and the nucleobase of the lesion. We unravel the repair mechanism utilized by bacterial glycosylase, MutM, using quantum‐chemical calculations involving more than 1000 atoms of the catalytic site. In contrast to the base‐protonated pathway currently favored in the literature, we show that the initial protonation of the lesion’s ribose paves the way for an almost barrier‐free glycosidic cleavage. The combination of theoretical and experimental data provides further insight into the selectivity and discrimination of MutM’s binding site toward various substrates.     

Aptamer‐Based Turn‐On Detection of Thrombin in Biological Fluids Based on Efficient Phosphorescence Energy Transfer from Mn‐Doped ZnS Quantum Dots to Carbon Nanodots

This paper presents the first example of a sensitive, selective, and stable phosphorescent sensor based on phosphorescence energy transfer (PET) for thrombin that functions through thrombin–aptamer recognition events. In this work, an efficient PET donor–acceptor pair using Mn‐doped ZnS quantum dots labeled with thrombin‐binding aptamers (TBA QDs) as donors, and carbon nanodots (CNDs) as acceptors has been constructed. Due to the π–π stacking interaction between aptamer and CNDs, the energy donor and acceptor are taken into close proximity, leading to the phosphorescence quenching of donors, TBA QDs. A maximum phosphorescence quenching efficiency as high as 95.9 % is acquired. With the introduction of thrombin to the “off state” of the TBA‐QDs‐CNDs system, the phosphorescence is “turned on” due to the formation of quadruplex‐thrombin complexes, which releases the energy acceptor CNDs from the energy donors. Based on the restored phosphorescence, an aptamer‐based turn‐on thrombin biosensor has been demonstrated by using the phosphorescence as a signal transduction method. The sensor displays a linear range of 0–40 nM for thrombin, with a detection limit as low as 0.013 nM in pure buffers. The proposed aptasensor has also been used to monitor thrombin in complex biological fluids, including serum and plasma, with satisfactory recovery ranging from 96.8 to 104.3 %. This is the first time that Mn‐doped ZnS quantum dots and CNDs have been employed as a donor–acceptor pair to construct PET‐based biosensors, which combines both the photophysical merits of phosphorescence QDs and the superquenching ability of CNDs and thus affords excellent analytical performance. We believe this proposed method could pave the way to a new design of biosensors using PET systems.     

A General Route to Prepare Low‐Ruthenium‐Content Bimetallic Electrocatalysts for pH‐Universal Hydrogen Evolution Reaction by Using Carbon Quantum Dots

A challenging but pressing task to design and synthesize novel, efficient, and robust pH‐universal hydrogen evolution reaction (HER) electrocatalysts for scalable and sustainable hydrogen production through electrochemical water splitting. Herein, we report a facile method to prepare an efficient and robust Ru‐M (M=Ni, Mn, Cu) bimetal nanoparticle and carbon quantum dot hybrid (RuM/CQDs) for pH‐universal HER. The RuNi/CQDs catalysts exhibit outstanding HER performance at all pH levels. The unexpected low overpotentials of 13, 58, and 18 mV shown by RuNi/CQDs allow a current density of 10 mA cm^?2 in 1 m KOH, 0.5 m H₂SO₄, and 1 m PBS, respectively, for Ru loading at 5.93 μgRu cm^?2. This performance is among the best catalytic activities reported for any platinum‐free electrocatalyst. Theoretical studies reveal that Ni doping results in a moderate weakening of the hydrogen bonding energy of nearby surface Ru atoms, which plays a critical role in improving the HER activity.     

Förster Resonance Energy Transfer Investigations Using Quantum‐Dot Fluorophores

F?rster resonance energy transfer (FRET), which involves the nonradiative transfer of excitation energy from an excited donor fluorophore to a proximal ground-state acceptor fluorophore, is a well-characterized photophysical tool. It is very sensitive to nanometer-scale changes in donor-acceptor separation distance and their relative dipole orientations. It has found a wide range of applications in analytical chemistry, protein conformation studies, and biological assays. Luminescent semiconductor nanocrystals (quantum dots, QDs) are inorganic fluorophores with unique optical and spectroscopic properties that could enhance FRET as an analytical tool, due to broad excitation spectra and tunable narrow and symmetric photoemission. Recently, there have been several FRET investigations using luminescent QDs that focused on addressing basic fundamental questions, as well as developing targeted applications with potential use in biology, including sensor design and protein conformation studies. Herein, we provide a critical review of those developments. We discuss some of the basic aspects of FRET applied to QDs as both donors and acceptors, and highlight some of the advantages offered (and limitations encountered) by QDs as energy donors and acceptors compared to conventional dyes. We also review the recent developments made in using QD bioreceptor conjugates to design FRET-based assays.     

Near‐Infrared Active Lead Chalcogenide Quantum Dots: Preparation,Post‐Synthesis Ligand Exchange,and Applications in Solar Cells

Quantum dots (QDs) of lead chalcogenides (e.g. PbS, PbSe, and PbTe) are attractive near‐infrared (NIR) active materials that show great potential in a wide range of applications, such as, photovoltaics (PV), optoelectronics, sensors, and bio‐electronics. The surface ligand plays an essential role in the production of QDs, post‐synthesis modification, and their integration to practical applications. Therefore, it is critically important that the influence of surface ligands on the synthesis and properties of QDs is well understood for their applications in various devices. In this Review we elaborate the application of colloidal synthesis techniques for the preparation of lead chalcogenide based QDs. We specifically focus on the influence of surface ligands on the synthesis of QDs and their solution‐phase ligand exchange. Given the importance of lead chalcogenide QDs as potential light harvesters, we also pay particular attention to the current progress of these QDs in photovoltaic applications.