Glycosylated quantum dots as fluorometric nanoprobes for trehalase.

Trehalase is an important enzyme in the metabolic cascades of many organisms, catalysing the hydrolysis of the disaccharide trehalose. Herein we describe the first examples of fluorometric nanoprobes for detection of trehalase, based on trehalose-functionalised quantum dots (QDs). QDs cross-linked with trehalose form aggregates, which are released upon enzymatic cleavage of the trehalose glycosidic bond proportionally to the enzyme concentration, offering a unique and efficient approach for specific sensing of this biologically important enzyme.

Microbe-Based Sensor for Long-Term Detection of Urine Glucose.

The development of a reusable and low-cost urine glucose sensor can benefit the screening and control of diabetes mellitus. This study focused on the feasibility of employing microbial fuel cells (MFC) as a selective glucose sensor for continuous monitoring of glucose levels in human urine. Using MFC technology, a novel cylinder sensor (CS) was developed. It had a quick response time (100 s), a large detection range (0.3-5 mM), and excellent accuracy. More importantly, the CS could last for up to 5 months. The selectivity of the CS was validated by both synthetic and actual diabetes-negative urine samples. It was found that the CS's selectivity could be significantly enhanced by adjusting the concentration of the culture's organic matter. The CS results were comparable to those of a commercial glucose meter (recovery ranged from 93.6% to 127.9%) when the diabetes-positive urine samples were tested. Due to the multiple advantages of high stability, low cost, and high sensitivity over urine test strips, the CS provides a novel and reliable approach for continuous monitoring of urine glucose, which will benefit diabetes assessment and control.

Amino-Functionalized Mesoporous Silica Nanoparticle-Encapsulated Octahedral Organoruthenium Complex as an Efficient Platform for Combatting Cancer.

In the process of synthesis of a new drug, as important as the drug itself is the formulation used, because the same compound can present a very different efficacy depending on how it is administered. In this work, we demonstrate how the antitumor capacity of a new octahedral organoruthenium complex, [Ru(ppy-CHO)(phen)2][PF6] is affected by its encapsulation in different types of mesoporous silica nanoparticles. The interactions between the Ru complex and the silica matrix and how these interactions are affected at two different pHs (7.4 and 5.4, mimicking physiological and endolysosomal acidic conditions, respectively) have been studied. The encapsulation has also been shown to affect the induction of apoptosis and necrosis and progression of the cell cycle compared to the free drug. The encapsulation of the Ru complex in nanoparticles functionalized with amino groups produced very high anticancer activity in cancer cells in vitro, especially against U87 glioblastoma cells, favoring cellular internalization and significantly increasing the anticancer capacity of the initial non-encapsulated Ru complex.

Magneto-Fluorescent Microbeads for Bacteria Detection Constructed from Superparamagnetic Fe3O4 Nanoparticles and AIS/ZnS Quantum Dots.

The efficient and sensitive detection of pathogenic microorganisms in aqueous environments, such as water used in medical applications, drinking water, and cooling water of industrial plants, requires simple and fast methods suitable for multiplexed detection such as flow cytometry (FCM) with optically encoded carrier beads. For this purpose, we combine fluorescent Cd-free Ag-In-S ternary quantum dots (t-QDs) with fluorescence lifetimes (LTs) of several hundred nanoseconds and superparamagnetic Fe3O4 nanoparticles (SPIONs) with mesoporous CaCO3 microbeads to a magneto-fluorescent bead platform that can be surface-functionalized with bioligands, such as antibodies. This inorganic bead platform enables immuno-magnetic separation, target enrichment, and target quantification with optical readout. The beads can be detected with steady-state and time-resolved fluorescence microscopy and flow cytometry (FCM). Moreover, they are suited for readout by time gated emission. In the following, the preparation of these magneto-fluorescent CaCO3 beads, their spectroscopic and analytic characterization, and their conjugation with bacteria-specific antibodies are presented as well as proof-of-concept measurements with Legionella pneumophila including cell cultivation and plating experiments for bacteria quantification. Additionally, the possibility to discriminate between the long-lived emission of the LT-encoded capture and carrier CaCO3 beads and the short-lived emission of the dye-stained bacteria with time-resolved fluorescence techniques and single wavelength excitation is demonstrated.

Circular Dichroism Spectroscopy as a Powerful Tool for Unraveling Assembly of Chiral Nonluminescent Aggregates of Photosensitizer Molecules on Nanoparticle Surfaces.

Recent developments in nanoscience and nanotechnology significantly help improve the properties of traditional materials. A striking example of this is the formation of hybrid nanostructures based on nanoparticles and photosensitizer molecules, the potential range of applications of which extends from photovoltaics to biomedicine. However, the creation of new and effective hybrid nanomaterials of this form inevitably entails new challenges, one of which is a common and critical problem of aggregation of both nanoparticles and photosensitizer molecules. Therefore, a fundamental challenge is to determine the presence of these aggregates, which will produce a significant step toward creating a new generation of materials and devices of broad-spectrum applicability. Here we report on the key role of circular dichroism spectroscopy as a tool to detect the formation of nonluminescent aggregates of chlorin e6, a second-generation photosensitizer, in a hybrid nanostructure with ZnS:Mn quantum dots. These aggregates are active acceptors of photoexcitation energy from quantum dots and limit the photophysical properties of the whole nanostructure. It has been established that circular dichroism spectroscopy reveals the presence of nonluminescent molecule aggregates at chlorin e6 concentrations of ∼10-6 mol/L, which compares very favorably to absorption spectroscopy which does not show any direct indications of aggregation up to ∼10-5 mol/L. This result demonstrates the promise and importance of using circular dichroism spectroscopy in the study of organic/inorganic hybrid nanostructures.

Intraband optical activity of semiconductor nanocrystals.

Here we review our three recently developed analytical models describing the intraband optical activity of semiconductor nanocrystals, which is induced by screw dislocations, ionic impurities, or irregularities of the nanocrystal surface. The models predict that semiconductor nanocrystals can exhibit strong optical activity upon intraband transitions and have large dissymmetry of magnetic-dipole absorption. The developed models can be used to interpret experimental circular dichroism spectra of nanocrystals and to advance the existing techniques of enantioseparation, biosensing, and chiral chemistry.

Dislocation-induced chirality of semiconductor nanocrystals.

Optical activity is a common natural phenomenon, which occurs in individual molecules, biomolecules, biological species, crystalline solids, liquid crystals, and various nanosized objects, leading to numerous important applications in almost every field of modern science and technology. Because this activity can hardly be altered, creation of artificial active media with controllable optical properties is of paramount importance. Here, for the first time to the best of our knowledge, we theoretically demonstrate that optical activity can be inherent to many semiconductor nanowires, as it is induced by chiral dislocations naturally developing during their growth. By assembling such nanowires in two- or three-dimensional periodic lattices, one can create optically active quantum supercrystals whose activity can be varied in many ways owing to the size quantization of the nanowires' energy spectra. We believe that this research is of particular importance for the future development of semiconducting nanomaterials and their applications in nanotechnology, chemistry, biology, and medicine.

Intrinsic Chirality of CdSe/ZnS Quantum Dots and Quantum Rods.

A new class of chiral nanoparticles is of great interest not only for nanotechnology, but also for many other fields of scientific endeavor. Normally the chirality in semiconductor nanocrystals is induced by the initial presence of chiral ligands/stabilizer molecules. Here we report intrinsic chirality of ZnS coated CdSe quantum dots (QDs) and quantum rods (QRs) stabilized by achiral ligands. As-prepared ensembles of these nanocrystals have been found to be a racemic mixture of d- and l-nanocrystals which also includes a portion of nonchiral nanocrystals and so in total the solution does not show a circular dichroism (CD) signal. We have developed a new enantioselective phase transfer technique to separate chiral nanocrystals using an appropriate chiral ligand and obtain optically active ensembles of CdSe/ZnS QDs and QRs. After enantioselective phase transfer, the nanocrystals isolated in organic phase, still capped with achiral ligands, now display circular dichroism (CD). We propose that the intrinsic chirality of CdSe/ZnS nanocrystals is caused by the presence of naturally occurring chiral defects.

Blood biocompatibility of surface-bound multi-walled carbon nanotubes.

Blood clots when it contacts foreign surfaces following platelet activation. This can be catastrophic in clinical settings involving extracorporeal circulation such as during heart-lung bypass where blood is circulated in polyvinyl chloride tubing. Studies have shown, however, that surface-bound carbon nanotubes may prevent platelet activation, the initiator of thrombosis. We studied the blood biocompatibility of polyvinyl chloride, surface-modified with multi-walled carbon nanotubes in vitro and in vivo. Our results show that surface-bound multi-walled carbon nanotubes cause platelet activation in vitro and devastating thrombosis in an in vivo animal model of extracorporeal circulation. The mechanism of the pro-thrombotic effect likely involves direct multi-walled carbon nanotube-platelet interaction with Ca(2+)-dependant platelet activation. These experiments provide evidence, for the first time, that modification of surfaces with nanomaterials modulates blood biocompatibility in extracorporeal circulation.

Magnetic nanoparticles to recover cellular organelles and study the time resolved nanoparticle-cell interactome throughout uptake.

Nanoparticles in contact with cells and living organisms generate quite novel interactions at the interface between the nanoparticle surface and the surrounding biological environment. However, a detailed time resolved molecular level description of the evolving interactions as nanoparticles are internalized and trafficked within the cellular environment is still missing and will certainly be required for the emerging arena of nanoparticle-cell interactions to mature. In this paper promising methodologies to map out the time resolved nanoparticle-cell interactome for nanoparticle uptake are discussed. Thus silica coated magnetite nanoparticles are presented to cells and their magnetic properties used to isolate, in a time resolved manner, the organelles containing the nanoparticles. Characterization of the recovered fractions shows that different cell compartments are isolated at different times, in agreement with imaging results on nanoparticle intracellular location. Subsequently the internalized nanoparticles can be further isolated from the recovered organelles, allowing the study of the most tightly nanoparticle-bound biomolecules, analogous to the 'hard corona' that so far has mostly been characterized in extracellular environments. Preliminary data on the recovered nanoparticles suggest that significant portion of the original corona (derived from the serum in which particles are presented to the cells) is preserved as nanoparticles are trafficked through the cells.

Multishell Silver Indium Selenide-Based Quantum Dots and Their Poly(methyl methacrylate) Composites for Application in Red-Light-Emitting Diodes.

In this work, the production of novel multishell silver indium selenide quantum dots (QDs) shelled with zinc selenide and zinc sulfide through a multistep synthesis precisely designed to develop high-quality red-emitting QDs is explored. The formation of the multishell nanoheterostructure significantly improves the photoluminescence quantum yield of the nanocrystals from 3% observed for the silver indium selenide core to 27 and 46% after the deposition of the zinc selenide and zinc sulfide layers, respectively. Moreover, the incorporation of the multishelled QDs in a poly(methyl methacrylate) (PMMA) matrix via in situ radical polymerization is investigated, and the role of thiol ligand passivation is proven to be fundamental for the stabilization of the QDs during the polymerization step, preventing their decomposition and the relative luminescence quenching. In particular, the role of interface chemistry is investigated by considering both surface passivation by inorganic zinc chalcogenide layers, which allows us to improve the optical properties, and organic thiol ligand passivation, which is fundamental to ensuring the chemical stability of the nanocrystals during in situ radical polymerization. In this way, it is possible to produce silver-indium selenide QD-PMMA composites that exhibit bright red luminescence and high transparency, making them promising for potential applications in photonics. Finally, it is demonstrated that the new silver indium selenide QD-PMMA composites can serve as an efficient color conversion layer for the production of red light-emitting diodes.

Expanding the Horizons of Machine Learning in Nanomaterials to Chiral Nanostructures.

Machine learning holds significant research potential in the field of nanotechnology, enabling nanomaterial structure and property predictions, facilitating materials design and discovery, and reducing the need for time-consuming and labor-intensive experiments and simulations. In contrast to their achiral counterparts, the application of machine learning for chiral nanomaterials is still in its infancy, with a limited number of publications to date. This is despite the great potential of machine learning to advance the development of new sustainable chiral materials with high values of optical activity, circularly polarized luminescence, and enantioselectivity, as well as for the analysis of structural chirality by electron microscopy. In this review, an analysis of machine learning methods used for studying achiral nanomaterials is provided, subsequently offering guidance on adapting and extending this work to chiral nanomaterials. An overview of chiral nanomaterials within the framework of synthesis-structure-property-application relationships is presented and insights on how to leverage machine learning for the study of these highly complex relationships are provided. Some key recent publications are reviewed and discussed on the application of machine learning for chiral nanomaterials. Finally, the review captures the key achievements, ongoing challenges, and the prospective outlook for this very important research field.

Chiroptically active quantum nanonails.

In recent years, extensive research efforts have been dedicated to the investigation of CdSe/CdS-based quantum-confined nanostructures, driven by their distinctive properties. The morphologies of these nanostructures have been shown to directly affect their properties, an area which has proven to be an important field of study. Herein, we report a new morphology of CdSe/CdS core-shell heterostructures in the form of a 'nanonail' - a modified nanorod-like morphology, in which a distinctive triangular head can be observed at one end of the structure. In-depth studies of this morphology reveal a material with tuneable rod length and width, as well as exceptional photoluminescent properties. Following this, we have demonstrated the ability to induce chiroptical activity via ligand exchange, revealing the important role of the specific morphology, shell thickness and chiral ligand concentration in the effect of ligand induced chirality. In addition, the cellular uptake and cytotoxicity of obtained chiral nanostructures were evaluated on human lung-derived A549 cancer cells, revealing a significant enantioselectivity in biological activity. Finally, analysis on monolayers of the material demonstrate the complete absence of FRET processes. Overall, this CdSe/CdS heterostructure is another tuneable morphology of a very important nanomaterial, one which shows great advantages and a range of potential applications.

Boron Nitride Nanosheet-Magnetic Nanoparticle Composites for Water Remediation Applications.

The combination of 0D nanoparticles with 2D nanomaterials has attracted a lot of attention over the last years due to the unique multimodal properties of resulting 0D-2D nanocomposites. In this work, we developed boron nitride nanosheets (BNNS) functionalized with manganese ferrite magnetic nanoparticles (MNPs). The functionalization process involved attachment of MNPs to exfoliated BNNS by refluxing the precursor materials in a polyol medium. Characterization of the produced BNNS-MNP composites was carried out using powder X-ray diffraction, transmission electron microscopy, vibrating sample magnetometry, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The adhesion of MnFe2O4 magnetic nanoparticles onto the BNNS remained unaffected by repeated sonication and heating in a furnace at 400 °C, underscoring the robust nature of the formed bond. FTIR spectra and XPS deconvolution confirmed the presence of strong bonding between BNNS and the MNPs. Membranes were fabricated from the BNNS and the BNNS-MnFe2O4 nanocomposites for evaluating their efficiency in removing the methylene blue dye pollutant. The membranes have been characterized by scanning electron microscopy, Brunauer-Emmett-Teller surface area analysis, and mercury intrusion porosimetry. The effectiveness of dye removal was monitored using ultraviolet-visible spectroscopy. The BNNS-MnFe2O4 nanocomposite membranes exhibited enhanced MB capture compared to membranes made from pure BNNS alone. The recyclability assessment of BNNS-MnFe2O4 demonstrated exceptional performance, retaining 92% efficiency even after eight cycles. These results clearly demonstrate the high potential of these magnetic nanocomposites as reusable materials for water filtration membranes. Furthermore, the introduction of magnetic functionality as part of the membrane brings an exciting opportunity for in situ magnetic heating of the membrane, which shall be explored in future work.

Efficient quenching of TGA-capped CdTe quantum dot emission by a surface-coordinated europium(III) cyclen complex.

Extremely efficient quenching of the excited state of aqueous CdTe quantum dots (QDs) by photoinduced electron transfer to a europium cyclen complex is facilitated by surface coordination to the thioglycolic acid capping ligand. The quenching dynamics are elucidated using steady-state emission and picosecond transient absorption.

Magnetic core-shell nanoparticles for drug delivery by nebulization.

BACKGROUND: Aerosolized therapeutics hold great potential for effective treatment of various diseases including lung cancer. In this context, there is an urgent need to develop novel nanocarriers suitable for drug delivery by nebulization. To address this need, we synthesized and characterized a biocompatible drug delivery vehicle following surface coating of Fe3O4 magnetic nanoparticles (MNPs) with a polymer poly(lactic-co-glycolic acid) (PLGA). The polymeric shell of these engineered nanoparticles was loaded with a potential anti-cancer drug quercetin and their suitability for targeting lung cancer cells via nebulization was evaluated. RESULTS: Average particle size of the developed MNPs and PLGA-MNPs as measured by electron microscopy was 9.6 and 53.2 nm, whereas their hydrodynamic swelling as determined using dynamic light scattering was 54.3 nm and 293.4 nm respectively. Utilizing a series of standardized biological tests incorporating a cell-based automated image acquisition and analysis procedure in combination with real-time impedance sensing, we confirmed that the developed MNP-based nanocarrier system was biocompatible, as no cytotoxicity was observed when up to 100 µg/ml PLGA-MNP was applied to the cultured human lung epithelial cells. Moreover, the PLGA-MNP preparation was well-tolerated in vivo in mice when applied intranasally as measured by glutathione and IL-6 secretion assays after 1, 4, or 7 days post-treatment. To imitate aerosol formation for drug delivery to the lungs, we applied quercitin loaded PLGA-MNPs to the human lung carcinoma cell line A549 following a single round of nebulization. The drug-loaded PLGA-MNPs significantly reduced the number of viable A549 cells, which was comparable when applied either by nebulization or by direct pipetting. CONCLUSION: We have developed a magnetic core-shell nanoparticle-based nanocarrier system and evaluated the feasibility of its drug delivery capability via aerosol administration. This study has implications for targeted delivery of therapeutics and poorly soluble medicinal compounds via inhalation route.

Nanoparticle-based drug delivery: case studies for cancer and cardiovascular applications.

Nanoparticles (NPs) comprised of nanoengineered complexes are providing new opportunities for enabling targeted delivery of a range of therapeutics and combinations. A range of functionalities can be included within a nanoparticle complex, including surface chemistry that allows attachment of cell-specific ligands for targeted delivery, surface coatings to increase circulation times for enhanced bioavailability, specific materials on the surface or in the nanoparticle core that enable storage of a therapeutic cargo until the target site is reached, and materials sensitive to local or remote actuation cues that allow controlled delivery of therapeutics to the target cells. However, despite the potential benefits of NPs as smart drug delivery and diagnostic systems, much research is still required to evaluate potential toxicity issues related to the chemical properties of NP materials, as well as their size and shape. The need to validate each NP for safety and efficacy with each therapeutic compound or combination of therapeutics is an enormous challenge, which forces industry to focus mainly on those nanoparticle materials where data on safety and efficacy already exists, i.e., predominantly polymer NPs. However, the enhanced functionality affordable by inclusion of metallic materials as part of nanoengineered particles provides a wealth of new opportunity for innovation and new, more effective, and safer therapeutics for applications such as cancer and cardiovascular diseases, which require selective targeting of the therapeutic to maximize effectiveness while avoiding adverse effects on non-target tissues.

Ligand induced chirality in In2S3 nanoparticles.

Chiral inorganic nanostructures have attracted a lot of attention over the last few years. Here we report the first observation of chirality in indium sulfide nanoparticles, which have been produced by a co-precipitation reaction in the presence of cysteine as a chiral agent. The process resulted in the production of spherical nanoparticles with an average diameter of around 3.6 nm. Circular dichroism spectroscopy of the nanoparticles showed an intense chiroptical signal corresponding to the indium sulfide excitonic transition, confirming the successful transfer of chirality to the In2S3 inorganic matrix. Nuclear magnetic resonance analysis of a colloidal solution of the nanoparticles demonstrated critical evidence of chemisorption of the chiral ligand on the surface of the nanoparticles and revealed a characteristic fast chemical exchange between the ligand chemisorbed on the surface of the nanoparticles and the free ligand in solution. Finally, the effect of the chiral ligand's structure on the transfer of chirality was investigated, with consideration of other amino acid ligands, and the critical role of the thiolate group in the optimisation of the chiral transfer was observed. This research is expected to stimulate further development and applications of new chiral semiconductor nanomaterials.

Boron Nitride Nanosheets Functionalized with Fe3O4 and CoFe2O4 Magnetic Nanoparticles for Nanofiltration Applications.

Nanofiltration (NF) is one of the emerging technologies that is very promising for water purification among many other applications. 2D boron nitride (BN) based nanomaterials are excellent building blocks for NF membranes. In our work, BN nanosheets (BNNS) have been functionalized with magnetic nanoparticles (MNPs) to form BNNS-MNP nanocomposites. It was found that the nanocomposites are stable with the MNPs giving very good coverage with both magnetite and cobalt ferrite MNPs and showing good attachment and stability to sonication. These nanocomposites have been tested for removal of methylene blue (MB) dye and MNPs from water. BNNS-magnetite nanocomposites showed higher removal efficiency of the MB from water than the corresponding pure BNNS, while the BNNS-cobalt ferrite removal efficiency was slightly less than the pure BNNS. The BNNS-cobalt ferrite material was regenerated by burning off the MB and recycled to show the recyclability of this material. The BNNS membranes were tested for filtration of 14 ± 4 nm magnetite MNPs and were found to capture 100% of the nanoparticles with no MNPs left in the filtrate. Thus, we have developed magnetic nanocomposite membranes, which have demonstrated great potential for water remediation. We believe that this research opens up promising ways for production of 2D nanocomposite materials with multiple applications.

Chirality in luminescent Cs3Cu2Br5 microcrystals produced via ligand-assisted reprecipitation.

Herein we report new chiral luminescent Cs3Cu2Br5 needle-like microcrystals and the analysis of their optical properties and the effect of the ligand structure on the transfer of chirality.