The compositional tunability of non-isovalent multicomponent chalcogenide thin films and the extent of atomic ordering of their crystal structure is key to the performance of many modern technologies. In contrast, the effects of ordering are rarely studied for quantum-confined materials, such as colloidal nanocrystals. In this paper, the possibilities around composition tunability and atomic ordering are explored in ultrasmall ternary and quaternary quantum dots, taking I-III-VI-group Cu-Zn-In-Se semiconductor as a case study. A quantitative synthesis for 3.3 nm quaternary chalcogenide nanocrystals is developed and shown that cation and cationic vacancy ordering can be achieved in these systems consisting of only 100s of atoms. Combining experiment and theoretical calculations, the relationship between structural ordering and optical properties of the materials are demonstrated. It is found that the arrangement and ordering of cationic sublattice plays an important role in the luminescent efficiency. Specifically, the concentration of Cu-vacancy couples in the nanocrystal correlates with luminescence quantum yield, while structure ordering increases the occurrence of such optically active Cu-vacancy units. On the flip side, the detrimental impact of cationic site disorder in I-III-VI nanocrystals can be mitigated by introducing a cation of intermediate valence, such as Zn (II).

In this study, we developed a new fluorescence \"on-off-on\" sensor utilizing water-soluble cobalt/zinc-nitrogen co-doped graphene quantum dots (Co/Zn-N-GQDs) to recognize quinalphos pesticide in vegetable and fruit samples. Primarily, the synthesis method employed a one-pot hydrothermal approach, using betel leaves as a natural precursor and cobalt (\"Co\"), zinc (\"Zn\"), and urea (\"N\") as dopant sources. The Co/Zn-N-GQDs probes underwent comprehensive analytical characterization. The Co/Zn-N-GQDs were synthesized with a remarkable luminescence yield of 31.49%, exhibiting excitation at 320 nm and emission peak at 393 nm. Interestingly, the luminescence of Co/Zn-N-GQDs was selectively \"Turned Off\" by Cu2+ via a static quenching setup. Remarkably, quenched fluorescence was surprisingly reactivated upon adding quinalphos to the quench setup, indicating a direct correlation between luminescence reactivation and quinalphos concentration. Briefly, this phenomenon is ascribed to the functional groups in quinalphos, such as quinoxalinyl and phosphorothioate, which chelate with Cu2+ ions, disrupting the nonfluorescent Cu2+-Co/Zn-N-GQDs complex. The design sensor demonstrated a limit of detection (LOD) of 0.11 μM and a broad linear span of 0.5 to 200 μM. In conclusion, Cu2+-Co/Zn-N-GQDs sensor showed immediate applicability, stability, and reproducibility, making it highly effective for quinalphos sensing in various samples.

The poor fluorescence properties of magneto-fluorescent paramagnetic-ion (Gd, Mn, or Co) doped I-III-VI quantum dots (QDs) at higher paramagnetic-ion doping concentrations have limited their use in magnetic-driven water-based applications. This work presents, for the first time, the use of stable magneto-fluorescent Gd-doped AgInS2 QDs at high Gd mole ratios of 16, 20, and 30 for the fluorescence detection and adsorption of Ag+ ions in water environments. The effect of pH, initial concentration, contact time, and adsorbent dosage were systematically evaluated. The AgInS2 QDs with the least Gd mole ratio (16) exhibited the best fluorescence characteristics (LOD = 0.88, R2 = 0.9549) while all materials showed good adsorption properties under optimized conditions (pH of 2, initial concentration of 30 ppm, contact time of 10 min and adsorbent dosage of 0.02 g) and a pseudo 2nd order reaction was followed. The adsorption mechanism was proposed to be a combination of ion-exchange, electrostatic interaction, complexation, and diffusion processes. Application in environmental wastewater samples revealed complete removal of Ag + ions alongside Ti2+ Pb2+, Ni2+, Cr3+, and Zn2+ ions.

Analytical barriers impose work at nanoparticles (NPs) concentrations orders of magnitude higher than the expected NPs concentrations in the environment. To overcome these limitations, the use of nontraditional stable isotope tracers incorporated in NPs (spiked-NPs) coupled with HR-ICP-MS has been proposed. The performance and efficiency of this analytical method was assessed in the case of quantum dots (QDs). Multi-isotopically labeled 111Cd77Se/68ZnS QDs were synthesized and their dissemination in natural aquatic matrices (river, estuarine and sea waters) was modeled at very low concentrations (from 0.1 to 5000 ppt). The QD limits of quantification (QD-LOQ) in each matrix were calculated according to the isotopic tracer. In ultrapure and simple medium (HNO3 2%), Zn, Cd, and Se originated from the QDs were quantifiable at concentrations of 10, 0.3, and 6 ppt, respectively, which are lower than the conventional HR-ICP-MS LOQs. In aquatic matrices, the QD-LOQs increase 10-, 130-, and 250-fold for Zn, Cd, and Se, respectively, but remain relevant of environmental concentrations (3.4 ppt ≤ QD-LOQs ≤ 2.5 ppb). These results validate the use of isotopically labeled ENPs at relevant concentrations in experimental studies related to either their fate, behavior, or toxicity in most aquatic matrices.

The determination of multiple biomarkers from cancer cells features a considerable step toward early diagnosis of cancers. However, realizing different biomarkers detection with single electrochemiluminescence (ECL) luminophore and regenerating the sensing platform remain a compelling goal. Herein, dual miRNAs-fueled DNA nanogears were designed for an enzyme-free ECL biosensor construction to perform the multiple sensitive detection of the microRNA (miRNA) biomarkers with single luminophore. The nanogears were assembled on CdS quantum dots (QDs) modified sensing surface. Using miRNA-21 as motive power, Au nanoparticles (AuNPs)-labeled nanogears B could be activated to roll against nanogear A, increasing the distance between AuNPs and CdS QDs. Thus, the significant ECL enhancement of CdS QDs was obtained owing to the ECL energy transfer between AuNPs and CdS QDs, simultaneously realizing the detection of miRNA-21. After the incubation of miRNA-155, nanogear B revolved against nanogear A continuously and realized the close-range of AuNPs and CdS QDs, resulting in the quenching of ECL intensity due to the Förster energy transfer and realizing the analysis of miRNA-155. The successive locomotion of the nanogears led to a significant ECL increasing for analysis of miRNA-21 down to 0.16 fM and a remarkable ECL suppression for determination of miRNA-155 down to 0.33 fM. Impressively, the proposed biosensor was able to be regenerated along with the gears roll against each other. In general, this enzyme-free strategy initiates a new thought to realize the multiple ECL detection with single luminophore, paving the way for applications of nanomachines in biosensing and clinical diagnosis.

Bacteriophytochromes are promising tools for tissue microscopy and imaging due to their fluorescence in the near-infrared region. These applications require optimization of the originally low fluorescence quantum yields via genetic engineering. Factors that favour fluorescence over other non-radiative excited state decay channels are yet poorly understood. In this work we employed resonance Raman and fluorescence spectroscopy to analyse the consequences of multiple amino acid substitutions on fluorescence of the iRFP713 benchmark protein. Two groups of mutations distinguishing iRFP from its precursor, the PAS-GAF domain of the bacteriophytochrome P2 from Rhodopseudomonas palustris, have qualitatively different effects on the biliverdin cofactor, which exists in a fluorescent (state II) and a non-fluorescent conformer (state I). Substitution of three critical amino acids in the chromophore binding pocket increases the intrinsic fluorescence quantum yield of state II from 1.7 to 5.0% due to slight structural changes of the tetrapyrrole chromophore. Whereas these changes are accompanied by an enrichment of state II from ~40 to ~50%, a major shift to ~88% is achieved by remote amino acid substitutions. Additionally, an increase of the intrinsic fluorescence quantum yield of this conformer by ~34% is achieved. The present results have important implications for future design strategies of biofluorophores.

With the rise of 2D materials, such as graphene and transition metal dichalcogenides, as viable materials for numerous experimental applications, it becomes more necessary to maintain fine control of their properties. One expedient and efficacious technique to regulate their properties is surface functionalization. In this study, DFT calculations are performed on triangular MoS2 quantum dots (QDs) either partially or completely doped with nanoparticles (NPs) of the noble metals Au, Ag, and Pt. The effects of these dopants on the geometry, electronic properties, magnetic properties, and chemical bonding of the QDs are investigated. The calculations show that the structural stability of the QDs is reduced by Au or Ag dopants, whereas Pt dopants have a contrasting effect. The NPs diminish the metallicity of the QD, the extent of which is contingent on the number of NPs adsorbed on the QD. However, these NPs exert distinctly disparate charge transfer effects-Ag NPs n-dope the QDs, whereas Au and Pt NPs either n- or p-dope. The molecular electrostatic potential maps of the occupied states show that metallic states are removed from the doping sites. Notwithstanding the decrease of magnetization in all three types of hybrid QD, the distribution of spin density in the Pt-doped QD is inherently different from that in the other QDs. Bond analyses using the quantum theory of atoms in molecules and the crystal orbital Hamilton population suggest that bonds between the Pt NPs and the QDs are the most covalent and the strongest, followed by the Au-QD bonds, and then Ag-QD bonds. The versatility of these hybrid QDs is further examined by applying an external electric field in the three orthogonal orientations, and comparing their properties with those in the absence of the electric field. There are two primary observations: 1) dopants at the tail, head and tail, and in the fully encased configuration are most effective in modifying the distribution of metallic states if the electric field is absent, and 2) the metallic states in these aforementioned QDs are generally insensitive to the electric field. Conversely, the asymmetric electric effects on the charge transfer in these QDs have to be carefully monitored to allow finer control of their structural stability. This study aptly demonstrates the value of noble metal dopants for manipulating the properties of MoS2 QDs, and shows the versatility of these hybrid QDs as tunable nanodevices. This notably extends the functionality of these nanostructures for applications such as catalysis and nanoelectronics.

We explored the impact of quantum dot (QD) coat characteristics on NP stability, uptake, and translocation in Arabidopsis thaliana, and subsequent transfer to primary consumers, Trichoplusia ni (T. ni). Arabidopsis was exposed to CdSe/CdZnS QDs with three different coatings: Poly(acrylic acid-ethylene glycol) (PAA-EG), polyethylenimine (PEI) and poly(maleic anhydride-alt-1-octadecene)-poly(ethylene glycol) (PMAO-PEG), which are anionic, cationic, and relatively neutral, respectively. PAA-EG-coated QDs were relatively stable and taken up from a hydroponic medium through both Arabidopsis leaf petioles and roots, without apparent aggregation, and showed generally uniform distribution in leaves. In contrast, PEI- and PMAO-PEG-coated QDs displayed destabilization in the hydroponic medium, and generated particulate fluorescence plant tissues, suggesting aggregation. PAA-EG QDs moved faster than PEI QDs through leaf petioles; however, 8-fold more cadmium accumulated in PEI QD-treated leaves than in those exposed to PAA-EG QDs, possibly due to PEI QD dissolution and direct metal uptake. T. ni caterpillars that fed on Arabidopsis exposed to QDs had reduced performance, and QD fluorescence was detected in both T. ni bodies and frass, demonstrating trophic transfer of intact QDs from plants to insects. Overall, this paper demonstrates that QD coat properties influence plant nanoparticle uptake and translocation and can impact transfer to herbivores.

We report the evolution and confinement of atomically precise and luminescent gold clusters in a small protein, lysozyme (Lyz) using detailed mass spectrometric (MS) and other spectroscopic investigations. A maximum of 12 Au(0) species could be bound to a single Lyz molecule irrespective of the molar ratio of Lyz : Au(3+) used for cluster growth. The cluster-encapsulated protein also forms aggregates similar to the parent protein. Time dependent studies reveal the emergence of free protein and the redistribution of detached Au atoms, at specific Lyz to Au(3+) molar ratios, as a function of incubation time, proposing inter-protein metal ion transfer. The results are in agreement with the studies of inter-protein metal transfer during cluster growth in similar systems. We believe that this study provides new insights into the growth of clusters in smaller proteins.

Most nanomaterials enter the natural environment as nanoenabled products, which are typically composites with primary nanoparticles bound on substrates or embedded in liquid or solid matrices. The environmental risks associated with these products are expected to differ from those associated with the as-produced particles. This article presents a case study on the end-of-life emission of a commercial prototype polymer/quantum-dot (QD) composite used in solid-state lighting for homes. We report the extent of cadmium release upon exposure to a series of environmental and biological simulant fluids, and track the loss of QD-characteristic fluorescence as a marker for chemical damage to the CdSe/ZnS nanoparticles. Measured cadmium releases after 30-day exposure range from 0.007 to 1.2 mg/g of polymer, and the higher values arise for low-pH simulants containing nitric or gastric acid. Centrifugal ultrafiltration and ICP was used to distinguish soluble cadmium from particulate forms. The leachate is found to contain soluble metals with no evidence of free QDs or QD-containing polymeric debris. The absence of free nanoparticles suggests that this product does not raise nanotechnology-specific environmental issues associated with degradation and leaching, but is more usefully regarded as a conventional chemical product that is a potential source of small amounts of soluble cadmium.