Special-point approach for optical absorption coefficient calculations on two-dimensional self-assemblies of type-II perovskite quantum dots.

All-inorganic perovskite quantum dots with the usual cubic shape have emerged as a successful and low-cost alternative to electronically functional nanomaterials motivating various fields of applications, including high-efficiency photovoltaics. Here, we present an efficient and almost analytic approach for optical absorption coefficient calculation on self-assembled perovskite quantum dot films with type-II band alignment. The approach takes advantage of the special point technique for integration over the two-dimensional Brillouin zone, which minimizes the computational cost. The set of special wave-vector points is generated using the Monkhorst and Pack method. The optical absorption spectrum for phenyl-C60-butyric acid methyl ester (PCBM)/CsPbI3quantum dot films is computed, in good agreement with the experiment assuming a homogeneous linewidth of 50 meV and considering a ten special-point set. We show that light absorption in these systems is a cooperative optoelectronic property resulting from the quantum-mechanical coupling between perovskite nanocubes, leading to extended system states. The generality of this approach makes it suitable for calculating the optical absorption coefficient in a broad class of perovskite quantum dot systems.

Caloric Effect Due to the Aharonov-Bohm Flux in an Antidot.

In this work, we report the caloric effect for an electronic system of the antidot type, modeled by combining a repulsive and attractive potential (parabolic confinement). In this system, we consider the action of a perpendicular external magnetic field and the possibility of having an Aharonov-Bohm flux (AB-flux) generated by a current passing through a solenoid placed inside the forbidden zone for the electron. The energy levels are obtained analytically, and the model is known as the Bogachek and Landman model. We propose to control the caloric response of the system by varying only the AB-flux, finding that, in the absence of an external magnetic field, the maximization of the effect always occurs at the same AB-flux intensity, independently of the temperature, while fixing the external magnetic field at a non-zero value breaks this symmetry and changes the point where the caloric phenomenon is maximized and is different depending on the temperature to which the process is carried. Our calculations indicate that using an effective electron mass of GaAs heterostructures and a trap intensity of the order of 2.896 meV, the modification of the AB-flux achieves a variation in temperature of the order of 1 K. Our analysis suggests that increasing the parabolic confinement twofold increases the effect threefold, while increasing the antidot size generates the reverse effect, i.e., a strong decrease in the caloric phenomenon under study. Due to the great diversity in technological applications that have antidots in electronics, the possibility of controlling their thermal response simply by varying the intensity of the internal current inside the solenoid (i.e., the intensity of AB-flux) can be a platform of interest for experimental studies.

Optical Properties in a ZnS/CdS/ZnS Core/Shell/Shell Spherical Quantum Dot: Electric and Magnetic Field and Donor Impurity Effects.

A theoretical analysis of optical properties in a ZnS/CdS/ZnS core/shell/shell spherical quantum dot was carried out within the effective mass approximation. The corresponding Schrödinger equation was solved using the finite element method via the 2D axis-symmetric module of COMSOL-Multiphysics software. Calculations included variations of internal dot radius, the application of electric and magnetic fields (both oriented along z-direction), as well as the presence of on-center donor impurity. Reported optical properties are the absorption and relative refractive index change coefficients. These quantities are related to transitions between the ground and first excited states, with linearly polarized incident radiation along the z-axis. It is found that transition energy decreases with the growth of internal radius, thus causing the red-shift of resonant peaks. The same happens when the external magnetic field increases. When the strength of applied electric field is increased, the opposite effect is observed, since there is a blue-shift of resonances. However, dipole matrix moments decrease drastically with the increase of the electric field, leading to a reduction in amplitude of optical responses. At the moment impurity effects are activated, a decrease in the value of the energies is noted, significantly affecting the ground state, which is more evident for small internal radius. This is reflected in an increase in transition energies.

Quantum-Dot-Based Iron Oxide Nanoparticles Activate the NLRP3 Inflammasome in Murine Bone Marrow-Derived Dendritic Cells.

Inflammasomes are cytosolic complexes composed of a Nod-like receptor, NLR, the adaptor protein, ASC, and a proteolytic enzyme, caspase-1. Inflammasome activation leads to caspase-1 activation and promotes functional maturation of IL-1ß and IL-18, two prototypical inflammatory cytokines. Besides, inflammasome activation leads to pyroptosis, an inflammatory type of cell death. Inflammasomes are vital for the host to cope with foreign pathogens or tissue damage. Herein, we show that quantum-dot-based iron oxide nanoparticles, MNP@QD, trigger NLRP3 inflammasome activation and subsequent release of proinflammatory interleukin IL-1ß by murine bone marrow-derived dendritic cells (BMDCs). This activation is more pronounced if these cells endocytose the nanoparticles before receiving inflammatory stimulation. MNP@QD was characterized by using imaging techniques like transmission electron microscopy, fluorescence microscopy, and atomic force microscopy, as well as physical and spectroscopical techniques such as fluorescence spectroscopy and powder diffraction. These findings may open the possibility of using the composite MNP@QD as both an imaging and a therapeutic tool.

Mathematical Modeling for an MTT Assay in Fluorine-Containing Graphene Quantum Dots.

The paper reports on a new mathematical model, starting with the original Hill equation which is derived to describe cell viability (V) while testing nanomaterials (NMs). Key information on the sample's morphology, such as mean size (⟨s⟩) and size dispersity (σ) is included in the new model via the lognormal distribution function. The new Hill-inspired equation is successfully used to fit MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) data from assays performed with the HepG2 cell line challenged by fluorine-containing graphene quantum dots (F:GQDs) under light (400-700 nm wavelength) and dark conditions. The extracted "biological polydispersity" (light: ⟨sMTT⟩=1.77±0.02 nm and σMTT=0.21±0.02); dark: ⟨sMTT⟩=1.87±0.02 nm and σMTT=0.22±0.01) is compared with the "morphological polydispersity" (⟨sTEM⟩=1.98±0.06 nm and σTEM=0.19±0.03), the latter obtained from TEM (transmission electron microscopy). The fitted data are then used to simulate a series of V responses. Two aspects are emphasized in the simulations: (i) fixing σ, one simulates V versus ⟨s⟩ and (ii) fixing ⟨s⟩, one simulates V versus σ. Trends observed in the simulations are supported by a phenomenological model picture describing the monotonic reduction in V as ⟨s⟩ increases (V~pa/(s)p-a; p and a are fitting parameters) and accounting for two opposite trends of V versus σ: under light (V~σ) and under dark (V~1/σ).

Graphene quantum dots decorated with imatinib for leukemia treatment.

The use of graphene quantum dots as biomedical device and drug delivery system has been increasing. This nanoplatform of pure carbon has showed unique properties and showed to be safe for human use. The imatinib is a molecule designed to specifically inhibit the tyrosine kinase, used for leukemia treatment. In this study, we successfully decorated the graphene quantum dots (GQDs@imatinb) by a carbodiimide crosslinking reaction. The GQDs@imatinb were characterized by FTIR and AFM. The nanoparticles' in vitro behaviors were evaluated by cellular trafficking (internalization) assay and cell viability and apoptosis assays in various cancer cell lines, including suspension (leukemia) cells and adherent cancer cells. The results showed that the incorporation of the imatinib on the surface of the graphene quantum dots did not change the nanoparticles' morphology and properties. The GQDs@imatinb could be efficiently internalized and kill cancer cells via the induction of apoptosis. The data indicated that the prepared GQDs@imatinb might be a great drug nano-platform for cancer, particularly leukemia treatments.

Effect of Serum Albumin on Porphyrin-Quantum Dot Complex Formation, Characteristics and Spectroscopic Analysis.

The effect of bovine serum albumin (BSA) upon interaction between CdTe QD functionalized by 3-Mercaptopropionic Acid (CdTe-3-MPA QD) and two water soluble porphyrins: positively charged meso-tetra methyl pyridyl porphyrin (TMPyP) and negatively charged meso-tetrakis(p-sulfonato-phenyl) porphyrin (TPPS4), was studied in function of pH using the steady-state and time resolved optical absorption and fluorescence spectroscopies. It was shown that, depending on the charge state of the components, interaction with albumin could either prevent the formation of the QD…PPh complex, form a mixed QD…PPh…BSA complex or not affect PPh complexation with QD at all. The obtained results may be of interest for application in photomedicine.

Bond order effects on the optoelectronic properties of oxygen/sulfur functionalized adamantanes.

The objective of this work, is to study adamantanes and to tune their bandgap, since pure adamantane is considered as an insulator due to its high bandgap energy. For this, we doped adamantane with oxygen and sulfur atoms, thus obtaining 730 different structures with double bonds and 730 different structures with single bonds, for a total of 1460 structures, and compared their properties. Among all, 31 molecules were selected that best represented the reduced bandgap behavior. The calculations with greater precision in its results were made using the Local Density Approximation (LDA), in the Density-Functional Theory (DFT) formalism, with PWC functional and TNP basis set. The electronic and optical properties were analyzed, by calculating the energy gap and absorption spectrum. Importantly, we observed that molecules doped with sulfur atoms (double bonds) had their energy gap reduced significantly compared to molecules doped with sulfur and/or oxygen atom with single bonds and pristine adamantane. It was found that in the absorption spectrum, the sulfur-doped structures had their spectrum shifted to the visible region, a fact that becomes relevant for potential dyes and optoelectronic applications. From the seven selected functionalized adamantanes (ADD-04, ADD-05, ADD-07, ADD-19, ADD-20, ADD-41, and ADD-48), any of these could be used as a dye. However, the ADD-20 molecule in particular, which presented optical absorption near (RGB) primary colors, could indicate a potential quantum dot material for application in developing screens of various electronic devices.

Hydrothermal Synthesis of Aqueous-Soluble Copper Indium Sulfide Nanocrystals and Their Use in Quantum Dot Sensitized Solar Cells.

A facile hydrothermal method to synthesize water-soluble copper indium sulfide (CIS) nanocrystals (NCs) at 150 °C is presented. The obtained samples exhibited three distinct photoluminescence peaks in the red, green and blue spectral regions, corresponding to three size fractions, which could be separated by means of size-selective precipitation. While the red and green emitting fractions consist of 4.5 and 2.5 nm CIS NCs, the blue fraction was identified as in situ formed carbon nanodots showing excitation wavelength dependent emission. When used as light absorbers in quantum dot sensitized solar cells, the individual green and red fractions yielded power conversion efficiencies of 2.9% and 2.6%, respectively. With the unfractionated samples, the efficiency values approaching 5% were obtained. This improvement was mainly due to a significantly enhanced photocurrent arising from complementary panchromatic absorption.

Donor impurity energy and optical absorption in spherical sector quantum dots.

The properties of the conduction band energy states of an electron interacting with a donor impurity center in spherical sector-shaped GaAs-Al0.3Ga0.7As quantum dots are theoretically investigated. The study is performed within the framework of the effective mass approximation through the numerical solution of the 3D Schrödinger equation for the envelope function via the finite element method. The modifications undergone by the spectrum due to the changes in the conical structure geometry (radius and apical angle) as well as in the position of the donor atom are discussed. With the information regarding electron states the linear optical absorption coefficient associated with transition between confined energy levels is evaluated and its features are discussed. The comparison of results obtained within the considered model with available experimental data in GaAs truncated-whisker-like quantum dots shows very good agreement. Besides, our simulation leads to identify the lowest energy photoluminescence peak as donor-related, instead of being associated to acceptor atoms, as claimed after experimental measurement (Hiruma et al. (1995) [14]). Also, a checking of our numerical approach is performed by comparing with analytical solutions to the problem of a spherical cone-shaped GaN with infinite confinement and donor impurity located at the cone apex. Coincidence is found to be remarkable.

Biosynthesis of CdS Quantum Dots Mediated by Volatile Sulfur Compounds Released by Antarctic Pseudomonas fragi.

Previously we reported the biosynthesis of intracellular cadmium sulfide quantum dots (CdS QDs) at low temperatures by the Antarctic strain Pseudomonas fragi GC01. Here we studied the role of volatile sulfur compounds (VSCs) in the biosynthesis of CdS QDs by P. fragi GC01. The biosynthesis of nanoparticles was evaluated in the presence of sulfate, sulfite, thiosulfate, sulfide, cysteine and methionine as sole sulfur sources. Intracellular biosynthesis occurred with all sulfur sources tested. However, extracellular biosynthesis was observed only in cultures amended with cysteine (Cys) and methionine (Met). Extracellular nanoparticles were characterized by dynamic light scattering, absorption and emission spectra, energy dispersive X-ray, atomic force microscopy, transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Purified QDs correspond to cubic nanocrystals of CdS with sizes between 2 and 16 nm. The analysis of VSCs revealed that P. fragi GC01 produced hydrogen sulfide (H2S), methanethiol (MeSH) and dimethyl sulfide (DMS) in the presence of sulfate, Met or Cys. Dimethyl disulfide (DMDS) was only detected in the presence of Met. Interestingly, MeSH was the main VSC produced in this condition. In addition, MeSH was the only VSC for which the concentration decreased in the presence of cadmium (Cd) of all the sulfur sources tested, suggesting that this gas interacts with Cd to form nanoparticles. The role of MeSH and DMS on Cds QDs biosynthesis was evaluated in two mutants of the Antarctic strain Pseudomonas deceptionensis M1T: megL - (unable to produce MeSH from Met) and mddA - (unable to generate DMS from MeSH). No biosynthesis of QDs was observed in the megL - strain, confirming the importance of MeSH in QD biosynthesis. In addition, the production of QDs in the mddA - strain was not affected, indicating that DMS is not a substrate for the biosynthesis of nanoparticles. Here, we confirm a link between MeSH production and CdS QDs biosynthesis when Met is used as sole sulfur source. This work represents the first report that directly associates the production of MeSH with the bacterial synthesis of QDs, thus revealing the importance of different VSCs in the biological generation of metal sulfide nanostructures.

Enhancing the energy spectrum of graphene quantum dot with external magnetic and Aharonov-Bohm flux fields.

In this paper, we have to apply the Dirac-Weyl equation to find the analytical energy eigenvalues of the graphene quantum dot interacting in the presence of AB-flux field and external magnetic field. We find that the energy eigenvalue of the graphene quantum dot decreases with both magnetic and AB-flux field but the effect of AB-flux field is more dominant. By ameliorating the intensity of the AB-flux field and keeping the magnetic field constant, the quantum-dot states entangled to produce Landau Levels. We show that besides using the graphene sheet and external magnetic field, the Aharonov-Bohm AB-flux field could as well be used to manipulate the carriers state energies in graphene.

In vitro tracking of phospholipase A2 from snake venom conjugated with magic-sized quantum dots.

Phospholipases A2 represent a family of enzymes with important application in medicine. However, direct tracking is difficult due to the absence of a stable, effective and specific marker for these enzymes. Magic-sized quantum dots (MSQDs) are inorganic semiconducting nanocrystals with unique physical properties. They have the ability to conjugate to proteins, making them excellent markers for biological systems. In this work, we labelled phospholipase A2 from Bothrops alternatus snake venom with Cadmium selenide (CdSe)/cadmium sulphate (CdS) MSQDs-a biocompatible and luminescent probe-. Bioconjugation was confirmed using infrared spectra and fluorescence microscopy, which demonstrated that the CdSe/CdS MSQDs interact with phospholipase A2 without interfering with its activity. This probe may be an important tool for the elucidation of many biological mechanisms, because it allows the pathway of phospholipase A2 to be tracked from its entry through the plasma membrane until its incorporation into the nucleus of myoblasts.

Stimulation of Cysteine-Coated CdSe/ZnS Quantum Dot Luminescence by meso-Tetrakis (p-sulfonato-phenyl) Porphyrin.

Interaction between porphyrins and quantum dots (QD) via energy and/or charge transfer is usually accompanied by reduction of the QD luminescence intensity and lifetime. However, for CdSe/ZnS-Cys QD water solutions, kept at 276 K during 3 months (aged QD), the significant increase in the luminescence intensity at the addition of meso-tetrakis (p-sulfonato-phenyl) porphyrin (TPPS4) has been observed in this study. Aggregation of QD during the storage provokes reduction in the quantum yield and lifetime of their luminescence. Using steady-state and time-resolved fluorescence techniques, we demonstrated that TPPS4 stimulated disaggregation of aged CdSe/ZnS-Cys QD in aqueous solutions, increasing the quantum yield of their luminescence, which finally reached that of the fresh-prepared QD. Disaggregation takes place due to increase in electrostatic repulsion between QD at their binding with negatively charged porphyrin molecules. Binding of just four porphyrin molecules per single QD was sufficient for total QD disaggregation. The analysis of QD luminescence decay curves demonstrated that disaggregation stronger affected the luminescence related with the electron-hole annihilation in the QD shell. The obtained results demonstrate the way to repair aged QD by adding of some molecules or ions to the solutions, stimulating QD disaggregation and restoring their luminescence characteristics, which could be important for QD biomedical applications, such as bioimaging and fluorescence diagnostics. On the other hand, the disaggregation is important for QD applications in biology and medicine since it reduces the size of the particles facilitating their internalization into living cells across the cell membrane.

Magnetocaloric Effect in an Antidot: The Effect of the Aharonov-Bohm Flux and Antidot Radius.

In this work, we report the magnetocaloric effect (MCE) for an electron interacting with an antidot, under the effect of an Aharonov-Bohm flux (AB-flux) subjected to a parabolic confinement potential. We use the Bogachek and Landman model, which additionally allows the study of quantum dots with Fock-Darwin energy levels for vanishing antidot radius and AB-flux. We find that AB-flux strongly controls the oscillatory behaviour of the MCE, thus acting as a control parameter for the cooling or heating of the magnetocaloric effect. We propose a way to detect AB-flux by measuring temperature differences.

Alzheimer's Disease and Parkinson's Disease: A Review of Current Treatment Adopting a Nanotechnology Approach.

Neurodegenerative disorders (NDDs) are characterized by the progressive loss of structure or neuron function, often associated with neuronal death. Treatments for neurodegenerative diseases only address symptoms without having any disease-modifying effect but serious side effects. Currently, there is no effective treatment for NDDs. This is due to the poor flow of drugs to the blood-barrier brain (BBB) which does not allow macromolecules like proteins and peptides to pass through it. Targeted drug delivery to the central nervous system (CNS) for the diagnosis and treatment of NDDs, such as Alzheimer's disease (AD), is restricted due to the limitations posed by the BBB as well as opsonization by plasma proteins in the systemic circulation and peripheral side-effects. Nanotechnology thereby presents a broad approach for transporting molecules through the BBB, thus allowing the entry of substances acting directly on the site affected by the disease. The aim of this review is to outline current strategies in nanotechnology for treating Alzheimer's and Parkinson's diseases.

Composition-Tunable Optical Properties of Zn x Cd(1 - x)S Quantum Dot-Carboxymethylcellulose Conjugates: Towards One-Pot Green Synthesis of Multifunctional Nanoplatforms for Biomedical and Environmental Applications.

Quantum dots (QDs) are colloidal semiconductor nanocrystals with unique properties that can be engineered by controlling the nanoparticle size and chemical composition by doping and alloying strategies. However, due to their potential toxicity, augmenting their biocompatibility is yet a challenge for expanding to several biomedical and environmentally friendly applications. Thus, the main goal of this study was to develop composition-tunable and biocompatible Zn x Cd1 - x S QDs using carboxymethylcellulose polysaccharide as direct capping ligand via green colloidal aqueous route at neutral pH and at room temperature for potential biomedical and environmental applications. The ternary alloyed QDs were extensively characterized using UV-vis spectroscopy, photoluminescence spectroscopy (PL), transmission electron microscopy (TEM), X-ray diffraction (XRD), electron energy loss spectroscopy (EELS), and X-ray photoelectrons spectroscopy (XPS). The results indicated that Zn x Cd(1 - x)S QDs were surface stabilized by carboxymethylcellulose biopolymer with spherical morphology for all composition of alloys and narrow sizes distributions ranging from 4 to 5 nm. The XRD results indicated that monophasic ternary alloyed Zn x Cd1 - x S nanocrystals were produced with homogenous composition of the core as evidenced by EELS and XPS analyses. In addition, the absorption and emission optical properties of Zn x Cd1 - x S QDs were red shifted with increasing the amount of Cd2+ in the alloyed nanocrystals, which have also increased the quantum yield compared to pure CdS and ZnS nanoparticles. These properties of alloyed nanomaterials were interpreted based on empirical model of Vegard's law and chemical bond model (CBM). As a proof of concept, these alloyed-QD conjugates were tested for biomedical and environmental applications. The results demonstrated that they were non-toxic and effective fluorophores for bioimaging live HEK293T cells (human embryonic kidney cells) using confocal laser scanning fluorescence microscopy. Moreover, these conjugates presented photocatalytic activity for photodegradation of methylene blue used as model organic industrial pollutant in water. Hence, composition-tunable optical properties of ternary Zn x Cd1 - x S (x = 0-1) fluorescent alloyed QDs was achieved using a facile eco-friendly aqueous processing route, which can offer promising alternatives for developing innovative nanomaterials for applications in nanomedicine and environmental science and technology.

Photoelectrochemical determination of tert-butylhydroquinone in edible oil samples employing CdSe/ZnS quantum dots and LiTCNE.

A novel photoelectrochemical sensor was developed for determination of tert-butyl-hydroquinone (TBHQ) in edible vegetable oils, based on CdSe/ZnS core-shell quantum dots sensitized with lithium tetracyanoethylenide (LiTCNE). The CdSe/ZnS/LiTCNE photoelectrochemical sensor presented a TBHQ photocurrent about 13-fold higher and a charge transfer resistance 62-fold lower than observed for a CdSe/ZnS sensor. The photoelectrochemical sensor showed selectivity to TBHQ, with a high photocurrent for this antioxidant compared to the photocurrent responses for other phenolic antioxidants. The CdSe/ZnS/LiTCNE photoelectrochemical sensor presented a linear range from 0.6 to 250µmolL-1, sensitivity of 0.012µALµmol-1, and a limit of detection of 0.21µmolL-1 for TBHQ, under optimized experimental conditions. The sensor was successfully employed in the analysis of edible oil samples, with recoveries of between 98.25% and 99.83% achieved.

One-step multiplexed detection of foodborne pathogens: Combining a quantum dot-mediated reverse assaying strategy and magnetic separation.

A rapid and multiplexed immunosensor was developed based on a quantum dot (QD)-reverse assaying strategy (RAS) and immuno-magnetic beads (IMBs) for one-step and simultaneous detection of Escherichia coli O157: H7 and Salmonella. In a conventional QD-based immunosensor, the fluorescence signal of the "IMBs-target-QD" immunoconjugate is directly used as the assaying readout. However, the fluorescence signal is affected by IMBs due to light scattering and the "IMBs-target-QD" immunoconjugate needs multiple washing and re-suspension steps. To address these problems, we use the surplus QD-antibody conjugate as signal readout in the RAS, which prevents interference from the IMBs, increases the fluorescence signal, and avoids complex operations. Compared with conventional QD-based immunosensor, the sensitivity of QD-RSA immunosensor for detection of Escherichia coli O157: H7 has been improved fifty-fold, and whole analysis procedure can be finished within 1h. Therefore, this RSA strategy is promising for improving the performance of QD-based immunosensors and could greatly broaden their applications.

Coupling effects on photoluminescence of exciton states in asymmetric quantum dot molecules.

We present a theoretical study of photoluminescence from exciton states in InAs/GaAs asymmetric dot pairs, where interdot coupling is reached via magnetic field in the Faraday configuration. Electronic structure is obtained by finite element calculations, and Coulomb effects are included using a perturbative approach. According to our simulated spectra, bright excited states may become optically accessible at low temperatures in hybridization regimes where intermixing with the ground state is achieved. Our results show effective magnetic control on the energy, polarization and intensity of emitted light, and suggest these coupled nanostructures as relevant candidates for implementation of quantum optoelectronic devices.