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Doping quantum dots (QDs) with extra element presents a promising future for their applications in the fields of environmental monitoring, commercial products and biomedical sciences. However, it remains unknown for the influence of doping on the molecular biocompatibility of QDs and the underlying mechanisms of the interaction between doped-QDs and protein molecules. Using the "one-pot" method, we synthesized N-acetyl-l-cysteine capped CdTe: Zn 2+ QDs with higher fluorescence quantum yield, improved stability and better molecular biocompatibility compared with undoped CdTe QDs. Using digestive enzyme trypsin (TRY) as the protein model, the interactions of undoped QDs and Zn-doped QDs with TRY as well as the underlying mechanisms were investigated using multi-spectroscopy, isothermal titration calorimetry and dialysis techniques. Van der Waals forces and hydrogen bonds are the major driving forces in the interaction of both QDs with TRY, which leading to the loosening of protein skeleton and tertiary structural changes. Compared with undoped QDs, Zn-doped QDs bind less amount of TRY with a higher affinity and then release higher amount of Cd. Zn-doped QDs have a less stimulating impact on TRY activity by decreasing TRY binding and reducing Cd binding to TRY. Taken all together, Zn-doped QDs offer a safer alternative for the applications of QDs by reducing unwanted interactions with proteins and improving biocompatibility at the molecular level., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The bioaccumulation potential and toxic effects of engineered nanomaterials (ENMs) to earthworms are poorly understood. Two studies were conducted following OECD TG 222 on Eisenia fetida to assess the effects of CdTe QDs with different coatings and soil ageing respectively. Earthworms were exposed to carboxylate (COOH), ammonium (NH 4 + ), or polyethylene glycol (PEG) coated CdTe QDs, or a micron scale (bulk) CdTe material, at nominal concentrations of 50, 500 and 2000 mg CdTe QD kg -1 dry weight (dw) for 28 days in Lufa 2.2 soil. In the fresh soil study, earthworms accumulated similar amounts of Cd and Te in the CdTe-bulk exposures, while the accumulation of Cd was higher than Te during the exposures to CdTe QDs. However, neither the total Cd, nor Te concentrations in the earthworms, were easily explained by the extractable metal fractions in the soil or particle dissolution. There were no effects on survival, but some retardation of growth was observed at the higher doses. Inhibition of Na + / K + -ATPase activity with disturbances to tissue electrolytes, as well as tissue Cu and Mn were observed, but without depletion of total glutathione in the fresh soil experiment. Additionally, juvenile production was the most sensitive endpoint, with estimated nominal EC 50 of values >2000, 108, 65, 96 mg CdTe kg -1 for bulk, PEG-, COOH- and NH 4 + -coated CdTe QDs, respectively. In the aged soil study, the accumulation of Cd and Te was higher than in the fresh soil study in all CdTe QD exposures. Survival of the adult worms was reduced in the top CdTe-COOH and -NH 4 + QD exposures by 55 ± 5 and 60 ± 25%, respectively; and with decreases in growth. The nominal EC 50 values for juvenile production in the aged soil were 165, 88, 78 and 63 mg CdTe kg -1 for bulk, PEG-, COOH- and NH 4 + -coated CdTe QDs, respectively. In conclusion, exposure to nanoscale CdTe QDs, regardless of coating, caused more severe toxic effects that the CdTe bulk material and the toxicity increased after soil ageing. There were some coating-mediated effects, likely due to differences in the metal content and behaviour of the materials., Competing Interests: Declaration of competing interest The authors alone are responsible for the content and writing of the paper. The authors report no conflicts of interest., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

A paper-based visual fluorescence immunoassay is presented for the detection of matrix metalloproteinase-7 (MMP7) that is related to renal cancer. The method is based on the distance-dependent fluorescence quenching of CdTe quantum dots (QDs) on a nitrocellulose membrane by Ag + following a sandwich-type immunoreaction on microtiter wells using silver nanoparticle (AgNP)-labeled secondary antibody- and primary antibody-coated microtiter wells. The silver nanoparticles captured in the well are dissolved with HNO 3 , while the quenching effect of QDs is based on silver ion-exchange reaction under 365-nm excitation light irradiation. Increasing concentration of released Ag + , thus higher concentration of the protein, leads to an increased distance of quenching on the nitrocellulose membrane. The paper-based immunoassay by combination of AgNP-assisted ion-exchange reaction with QD gives good distance-dependent responses and allows the detection of MMP7 at a concentration as low as 7.3 pg mL -1 . The coefficients of variation are less than 6.9% and 12.4% for intra-assay and inter-assay, respectively. High specificity and long-term stability are achieved during the assay. Importantly, the testing of human serum samples using our strategy shows well-matched results with commercial human MMP7 ELISA kits. Graphical abstract A distance-dependent visual immunoassay is developed for the determination of serum matrix metalloproteinase-7 on CdTe quantum dot-impregnated paper with silver ion-exchange reaction.

Introduction and Objective: Nuclear factor kappa B (NF-κB) signalling pathway plays a central role in the regulation of cellular response to stress. The aim of the study was to investigate the ability of silver nanoparticles (AgNPs), gold nanoparticles (AuNPs), CdTe quantum dots (CdTeQDs) or their binary mixtures to stimulate NF-κB binding in HepG2 cells. A dual luciferase reporter system was used to investigate NF-κB binding., Material and Methods: Cells were transiently transfected with a firefly luciferase reporter system and Renilla luciferase expression plasmid as a transfection efficiency control. Twenty- four hours after transfection, the cells were treated with nanoparticles (10 μg/cm 3 AgNPs, 10 μg/cm 3 AuNPs, 3 μg/cm 3 CdTeQDs) or with 10 ng/cm 3 TNFα as a positive control. Six hours later, the cells were lysed and the activities of the luminescence of firefly and Renilla luciferases were measured using the Dual-Luciferase Reporter Assay System., Results: AuNPs and CdTeQDs alone significantly inhibited NF-κB binding activity. Co-treatment with AgNPs and CdTeQDs resulted in an additive effect, whereas the presence of AgNPs diminished the inhibitory effect of AuNPs. Interestingly, significant antagonism was observed between AuNPs and CdTeQDs, suggesting a similar mode of action., Conclusions: Comparison of the NF-κB binding activity induced by the mixtures of NPs suggests that in some cases NF-κB binding activity might differ from that observed for the NPs alone.

Quantum dots have generated great interest because of their optical properties, both to life sciences and electronics applications. However, possible risks to the environment associated with these nanoparticles are still under investigation. The present study aimed to evaluate the toxicity of suspensions of cadmium telluride (CdTe) quantum dots to Biomphalaria glabrata mollusks, a very sensitive aquatic environmental bioindicator for physical and chemical agents. Toxicity was examined by using embryos and adult mollusks as well as hemocytes. The distribution of cadmium in the organs of adults was also assessed. Effects of the stabilizing agent of the quantum dots were also evaluated. Animals were exposed to suspensions of quantum dots for 24 h, at concentrations varying from 1.2 to 20 nM for embryos and from 50 to 400 nM for adult mollusks. Results showed that suspensions of quantum dots induced malformations and mortality in embryos and mortality in adults, depending on the concentration applied. In the cytotoxicity study, hemocyte apoptosis was observed in adults exposed to the highest concentration of quantum dots applied as well as to the stabilizing agent. Cell binucleation and micronucleus frequencies were not significative. Bioaccumulation evaluation revealed that quantum dots targeted the digestive gland (hepatopancreas). Taken together, outcomes suggested that specific nano-effects related directly not only to composition but also to the aggregation of quantum dots may be mediating the observed toxicity. Thus B. glabrata was determined to be a very sensitive species for interpreting possible nano-effects in aquatic environments. Environ Toxicol Chem 2019;38:2128-2136. © 2019 SETAC., (© 2019 SETAC.)

This study describes synthesis of N‑acetyl‑l‑cysteine-capped CdTe quantum dots (QDs) and investigates their interaction with plasma protein fibrinogen (FIB) and the structural changes of FIB. It is shown that the interaction of QDs with FIB is a spontaneous process and the major driving forces are van der Waals forces and hydrogen bonds. Multi-spectroscopic measurements show that the intrinsic fluorescence of FIB was quenched and secondary and tertiary structures were altered due to the interaction with QDs. In addition, the aggregation state of FIB was altered in the presence of QDs. Furthermore, the formed complexes of FIB with QDs reduced the cytotoxicity of QDs. The coating of FIB on QDs could lower intracellular QDs uptake and therefore result in less released cadmium ions and ROS productions. This study, therefore, might be helpful to the comprehensive understanding of QDs toxicity and provide evidence for assessing the safe application of nanoparticles., (Copyright © 2019. Published by Elsevier B.V.)

Quantum dots (QDs) are engineered nanoparticles (NPs) of semiconductor structure that possess unique optical and electronic properties and are widely used in biomedical applications; however, their risks are not entirely understood. This study investigated the tissue distribution and toxic effects of cadmium telluride quantum dots (CdTe-QDs) in male BALB/c mice for up to 1 week after single-dose intravenous injections. CdTe-QDs were detected in the blood, lung, heart, liver, spleen, kidney, testis and brain. Most CdTe-QDs accumulated in the liver, followed by the spleen and kidney. At high doses, exposure to CdTe-QDs resulted in mild dehydration, lethargy, ruffled fur, hunched posture, and body weight loss. Histological analysis of the tissues, upon highest dose exposures, revealed hepatic hemorrhage and necrotic areas in the spleen. The sera of mice treated with high doses of CdTe-QDs showed significant increases in alanine aminotransferase (ALT), aspartate aminotransferase (AST), and total bilirubin levels, as well as a reduction in albumin. CdTe-QD exposure also led to a reduced number of platelets and elevated total white blood cell counts, including monocytes and neutrophils, serum amyloid A, and several pro-inflammatory cytokines. These results demonstrated that the liver is the main target of CdTe-QDs and that exposure to CdTe-QDs leads to hepatic and splenic injury, as well as systemic effects, in mice. By contrast, cadmium chloride (CdCl 2 ), at an equivalent concentration of cadmium, appeared to have a different pharmacokinetic pattern from that of CdTe-QDs, having minimal effects on the aforementioned parameters, suggesting that cadmium alone cannot fully explain the toxicity of CdTe-QDs.

Microglial cells are resident immune cells in the central nervous system. Activation of microglia as induced by CdTe quantum dots (QDs) can trigger damage to neurons. To quantify the intracellular QDs, we monitored the intracellular Cd concentration in the QD-exposed mouse microglial cells (BV-2 cell line). The extent of cell injury at different times correlated with the Cd concentration in cells at that time. In addition to Cd ion detection, we also monitored the intracellular fluorescence of the QDs. More QDs accumulated in the nucleus than in the cytoplasm. Comet assays confirmed that QDs induce DNA damage. However, DNA cannot interact with QDs, so the DNA damage was not caused by CdTe QDs adducts to DNA but by the increase of the Cd ion concentration and the secondary oxidative damage. In addition to DNA damage, biofilm injury and endogenous reduced glutathione depletion were also apparent in QD-exposed BV-2 cells. These changes can be prevented or even reversed by exogenous reduced glutathione administration., (© 2018 John Wiley & Sons, Ltd.)

Background: Pig skin is a widely acknowledged surrogate for human skin for in vitro/ex vivo skin penetration studies with application for small molecules and nanosystems. We have investigated the influence of biological factors such as age and anatomical site on the penetration and distribution of nanoparticles (2.1 nm hydrophilic CdTe/CdS quantum dots: QDs) in adult pig skin (APS), weanling pig skin (WPS) and newborn pig skin (NBPS) at two different anatomical sites (ear and abdomen)., Methods: QDs in saline were applied to 1 × 1 cm2 skin (62.5 pmol/cm2) with 2-min finger rubbing using a standardized protocol. After 6- or 24-h incubation on Franz diffusion cells, tape stripping (×10) followed by manual follicular casting was conducted. Cadmium in QDs was quantified using inductively coupled plasma mass spectrometry for all samples. The presence of QDs in similarly treated skin samples was also captured using multiphoton tomography., Results: QDs were mainly localized in hair follicles after 6 and 24 h of exposure with no cadmium detected in the Franz cell receptor compartment regardless of pig age or anatomical site. The amount of QDs deposited in the follicles was similar at 6 h but higher on APS and WPS ears compared to NBPS ears at 24 h. This is associated with the high follicle density and small follicle diameter of the NBPS compared to the smaller density of much larger follicles on the APS. NBPS showed consistent QD distribution for ear and abdomen up to 24 h., Conclusions: There is minimal penetration of QDs through pig skin. Density and diameter of follicles in association with age of pigs and application site influenced the amount of QDs deposited in follicles. The structure of the stratum corneum, follicle density and diameter of NBPS are similar to human skin suggesting that NBPS is an appropriate model for human skin in the evaluation of topical applications of a range of chemicals including nanosystems., (© 2019 S. Karger AG, Basel.)

The purpose of this study was to determine the toxicity of two different sources of cadmium, i.e. CdCl 2 and Cd-based Quantum Dots (QDs), for freshwater model plant Lemna minor L. Cadmium telluride QDs were capped with two coating ligands: glutathione (GSH) or 3-mercaptopropionic acid (MPA). Growth rate inhibition and final biomass inhibition of L. minor after 168-h exposure were monitored as toxicity endpoints. Dose-response curves for Cd toxicity and EC50 168h values were statistically evaluated for all sources of Cd to uncover possible differences among the toxicities of tested compounds. Total Cd content and its bioaccumulation factors (BAFs) in L. minor after the exposure period were also determined to distinguish Cd bioaccumulation patterns with respect to different test compounds. Laser-Induced Breakdown Spectroscopy (LIBS) with lateral resolution of 200µm was employed in order to obtain two-dimensional maps of Cd spatial distribution in L. minor fronds. Our results show that GSH- and MPA-capped Cd-based QDs have similar toxicity for L. minor, but are significantly less toxic than CdCl 2 . However, both sources of Cd lead to similar patterns of Cd bioaccumulation and distribution in L. minor fronds. Our results are in line with previous reports that the main mediators of Cd toxicity and bioaccumulation in aquatic plants are Cd 2+ ions dissolved from Cd-based QDs., (Copyright © 2017 Elsevier Inc. All rights reserved.)

A novel sensitive method for detection of DNA methylation was developed with thioglycollic acid (TGA)-capped CdTe quantum dots (QDs) as fluorescence probes. Recognition of methylated DNA sites would be useful strategy due to the important roles of methylation in disease occurrence and developmental processes. DNA methylation occurs most often at cytosine-guanine sites (CpG dinucleotides) of gene promoters. The QDs significantly interacted with hybridized unmethylated and methylated DNA. The interaction of CpG rich methylated and unmethylated DNA hybrid with quantum dots as an optical probe has been investigated by fluorescence spectroscopy and electrophoresis assay. The fluorescence intensity of QDs was highly dependent to unmethylated and methylated DNA. Specific site of CpG islands of Adenomatous polyposis coli (APC), a well-studied tumor suppressor gene, was used as the detection target. Under optimum conditions, upon the addition of unmethylated dsDNA, the fluorescence intensity increased in linear range from 1.0 × 10 - 10 to 1.0 × 10 - 6 M with detection limit of 6.2 × 10 - 11 M and on the other hand, the intensity of QDs showed no changes with addition of methylated dsDNA. We also demonstrated that the unmethylated and methylated DNA and QDs complexes showed different mobility in electrophoresis assay. This easy and reliable method could distinguish between methylated and unmethylated DNA sequences.

In this paper, a systematic investigation of the interaction of bovine serum albumin (BSA) with water-soluble CdTe quantum dots (QDs) of two different sizes capped with carboxylic thiols is presented based on steady-state and time-resolved fluorescence measurements. Efficient Förster resonance energy transfer (FRET) was observed to occur from BSA donor to CdTe acceptor as noted from reduction in the fluorescence of BSA and enhanced fluorescence from CdTe QDs. FRET parameters such as Förster distance, spectral overlap integral, FRET rate constant and efficiency were determined. The quenching of BSA fluorescence in aqueous solution observed in the presence of CdTe QDs infers that fluorescence resonance energy transfer is primarily responsible for the quenching phenomenon. Bimolecular quenching constant (k q ) determined at different temperatures and the time-resolved fluorescence data provide additional evidence for this. The binding stoichiometry and various thermodynamic parameters are evaluated by using the van 't Hoff equation. The analysis of the results suggests that the interaction between BSA and CdTe QDs is entropy driven and hydrophobic forces play a key role in the interaction. Binding of QDs significantly shortened the fluorescence lifetime of BSA which is one of the hallmarks of FRET. The effect of size of the QDs on the FRET parameters are discussed in the light of FRET parameters obtained., (Copyright © 2016 John Wiley & Sons, Ltd.)

The present study reports the localization and interaction of thioglycolic acid (TGA) capped CdTe quantum dots (TGA@CdTe QDs) within the extracellular matrix (ECM) of Haematococcus pluvialis (Chlorophyceae) microalgae (HPM) after an incubation period of 5 min. Changes in the Raman spectrum of HPM induced by the adsorption of the TGA@CdTe QDs are successfully found by using naked gold anisotropic structures as nano-sensors for surface-enhanced Raman scattering (SERS effect). Raman spectroscopy results show that TGA@CdTe QDs interact with the biomolecules present in the ECM. Sample preparation and characterization by complementary techniques such as confocal and electron microscopy are also used to confirm the presence and localization of the nanoparticles in the algae. This research shows new evidence on early accumulation of QDs in plant cells and would further improve our understanding about their environmental impact., (© The Author(s) 2016.)

Background: Fluorescent nanoparticles or quantum dots (QDs) have been intensely studied for basic and applied research due to their unique size-dependent properties. There is an increasing interest in developing ecofriendly methods to synthesize these nanoparticles since they improve biocompatibility and avoid the generation of toxic byproducts. The use of biological systems, particularly prokaryotes, has emerged as a promising alternative. Recent studies indicate that QDs biosynthesis is related to factors such as cellular redox status and antioxidant defenses. Based on this, the mixture of extreme conditions of Antarctica would allow the development of natural QDs producing bacteria., Results: In this study we isolated and characterized cadmium and tellurite resistant Antarctic bacteria capable of synthesizing CdS and CdTe QDs when exposed to these oxidizing heavy metals. A time dependent change in fluorescence emission color, moving from green to red, was determined on bacterial cells exposed to metals. Biosynthesis was observed in cells grown at different temperatures and high metal concentrations. Electron microscopy analysis of treated cells revealed nanometric electron-dense elements and structures resembling membrane vesicles mostly associated to periplasmic space. Purified biosynthesized QDs displayed broad absorption and emission spectra characteristic of biogenic Cd nanoparticles., Conclusions: Our work presents a novel and simple biological approach to produce QDs at room temperature by using heavy metal resistant Antarctic bacteria, highlighting the unique properties of these microorganisms as potent natural producers of nano-scale materials and promising candidates for bioremediation purposes.

CdTe quantum dots (QDs) were synthesized in aqueous solution using thioglycolic acid (TGA) as stabilizing agents. The interaction between TGA-CdTe QDs and fat mass and obesity-associated (FTO) protein was investigated by fluorescence, UV-visible absorption, synchronous fluorescence and three-dimensional fluorescence spectroscopy. Results revealed that TGA-CdTe QDs could strongly quench the intrinsic fluorescence of FTO protein with a static quenching procedure. Both the van der Waals and hydrogen bonding played a major role in stabilizing the complex. The binding constant and thermodynamic parameters at different temperatures were obtained. In addition, we found that the fluorescence intensity of QDs was significantly enhanced by the addition of FTO protein. Based on this, a sensitive method for detecting FTO protein was obtained in the linear range of 5.52×10(-9)-6.62×10(-7) mol L(-1) with the detection limit of 1.14×10(-9) mol L(-1). The influences of factors on the interaction between FTO protein and TGA-CdTe QDs were studied., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Quantum dots (QDs) are one of the most promising nanomaterials, due to their size-dependent characteristics as well as easily controllable size during the synthesis process. They are promising label material and their interaction with biomolecules is of great interest for science. In this study, CdTe QDs were synthesized under optimal conditions for 2 nm size. Characterization and verification of QDs synthesis procedure were done by fluorimetric method and with CE. Afterwards, QDs interaction with chicken genomic DNA and 500 bpDNA fragment was observed employing CE-LIF and gel electrophoresis. Performed interaction relies on possible matching between size of QDs and major groove of the DNA, which is approximately 2.1 nm., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Fluorescent quantum dots (QDs) have been widely applied in biological and biomedical areas, but relatively little is known about the interaction of QDs with some natural enzymes. Herein, the interactions between 3-mercaptopropionic acid-capped CdTe QDs (MPA-QDs) and papain were systematically investigated by UV-Vis absorption spectra, fluorescence spectra and circular dichroism (CD) spectra under the physiological conditions. The fluorescence spectra results indicated that MPA-QDs quenched the fluorescence intensity of papain. The modified Stern-Volmer quenching constant K a at different temperatures and the corresponding thermodynamic parameters ΔH, ΔG and ΔS were also calculated. The binding of MPA-QDs and papain is a result of the formation of QDs-papain complex and the electrostatic interactions play a major role in stabilizing the complex. The CD technique was further used to analyze the conformational changes of papain induced by MPA-QDs and the results indicated that the biological activity of papain was affected by MPA-QDs dramatically.

The bioaccumulation kinetics of thioglycolic acid stabilized CdTe quantum dots (TGA-CdTe-QDs) in a freshwater alga Ochromonas danica was comprehensively investigated. Their photoluminescence (PL) was determined by flow cytometry. Its cellular intensity increased hyperbolically with exposure time suggesting real internalization of TGA-CdTe-QDs. This hypothesis was evidenced by the nanoparticle uptake experiment with heat-killed or cold-treated cells and by their localization in the vacuoles. TGA-CdTe-QD accumulation could further be well simulated by a biokinetic model used previously for conventional pollutants. Moreover, macropinocytosis was the main route for their internalization. As limited by their diffusion from the bulk medium to the cell surface, TGA-CdTe-QD uptake rate increased proportionally with their ambient concentration. Quick elimination in the PL of cellular TGA-CdTe-QDs was also observed. Such diminishment resulted mainly from their surface modification by vacuolar biomolecules, considering that these nanoparticles remained mostly undissolved and their expulsion out of the cells was slow. Despite the significant uptake of TGA-CdTe-QDs, they had no direct acute effects on O. danica. Overall, the above research shed new light on nanoparticle bioaccumulation study and would further improve our understanding about their environmental behavior, effects and fate.