This paper reported a one-step synthesis of Ag2S/Ag@MoS2 nanocomposites and its applications in the surface-enhanced Raman scattering (SERS) detection and photocatalytic degradation of organic pollutants. The nanocomposites were well characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammograms (CV), the Brunauer-Emmett-Teller (BET), and Fourier transforms infrared spectra (FTIR). The AgNPs were uniformly dispersed on the MoS2 nanosheets and the particle size of the AgNPs was about 10–30 nm. These Ag2S/Ag@MoS2 nanocomposites offered sensitive SERS signals for the detection of R6G with the limit of detections as low as 10?10 M. The photocatalytic activity of the composite catalyst was studied by the degradation of methylene blue (MB) dye under light illumination. The apparent rate constant of MB degradation for the obtained catalyst could reach 6.6?×?10?2 min?1, indicating that the novel Ag2S/Ag@MoS2 nanocomposites can be explored for organic pollutant’s detection and degradation.
The most important limitation for boron neutron capture therapy of cancer is the selective accumulation of boron compounds in tumor tissues in significant quantities. In this paper, we describe the possibility to use magnetic Ni/Fe nanotubes as carriers for boron delivery. Carborane derivatives containing 10 and 21 boron atoms per molecule were immobilized on Ni/Fe nanotubes by covalent and ionic interactions. Magnetic properties of NTs were investigated by Mössbauer spectroscopy. Structure, element, chemical composition, and morphology of obtained magnetic nanotubes were studied by XRD, SEM-EDA, and FTIR spectroscopy. Results indicate success immobilization of carborane derivatives on Ni/Fe nanotubes and great potential to use them as carriers for boron neutron cancer therapy of cancer.
Dendritic Pt–Cu nanoparticles were synthesized by a facile one-step method with the help of surfactant Brij58 at room temperature, and we also studied the effects of different Pt–Cu ratios on the morphology and size of nanoparticles. In addition, we further tuned the morphology of the Pt–Cu nanostructures by introducing bromide ions, eventually leading to the appearance of some tripod-like structures. Compared with dendritic Pt–Cu and commercial Pt black, these tripod-like Pt–Cu nanostructures exhibited higher electrocatalytic activity and CO tolerance for catalyzing methanol oxidation.
Silver nanoparticles (AgNPs) have been intensively studied for several purposes including therapeutic applications in cancer. When prepared with tryptophan and photoreduction, silver nanoparticles (TrpAgNPs) become an alternative to conventional anticancer drugs. In this study, the anticancer activity of synthesized TrpAgNPs against MCF-7 breast cancer cells was evaluated, and the inhibitory concentration (IC50) was found to be ~3.4 mg/mL. Since the protoporphyrin IX (PPIX) concentrations in tumor cells are elevate compared to normal cells, the PPIX-TrpAgNP interaction was studied to investigate if it could contribute for cell apoptosis. The investigation was performed using PPIX solution (0.9 μg/mL) with different TrpAgNP concentrations (from 0 to 13 mg/mL). PPIX was characterized by UV-Vis spectroscopy, steady-state and time-resolved fluorescence spectroscopy. The results have shown that the presence of spherical TrpAgNps with 16-nm diameter quench the PPIX fluorescence intensity. This quenching is strongly dependent on the concentration of the TrpAgNPs, and it is caused by a combination of a static and a dynamic process. The chemical binding leads to oxidation of tryptophan and formation of kynurenine, observed in the emission spectra around 470 nm. The strong reduction of the PPIX fluorescence decay lifetime with nanoparticle increasing concentration confirms the quenching processes due to charge transfer from the excited PPIX states to the resonant silver states. The present study confirms the anticancer activity of TrpAgNPs on the human breast cancer cell line (MCF-7) in vitro and indicates that PPIX-AgNP interaction could contribute with MCF-7 apoptosis.
The molecular dynamics simulation (MD) was carried out to investigate the mechanical properties of pristine polymethylmethacrylate (PMMA) and the composites of PMMA mixed with the silver nanoparticles (PMMA/AgNPs) at two AgNP weight fractions at 0.60 and 1.77 wt%. From the stress–strain profiles by the tensile process, it can be seen that the improvement on Young’s modulus is insignificant at these lower AgNP fractions. The tensile strength of pristine PMMA can be slightly improved by the embedded AgNPs at 1.77 wt%, because the local density and strength of PMMA in the vicinity of AgNP surface within about 8.2 Å are improved. For the temperature effect on the mechanical properties of pristine PMMA and PMMA/AgNP composite, the Young’s moduli and strength of pristine PMMA and PMMA/AgNP composite significantly decrease at temperatures of 450 and 550 K, which are close to the predicted melting temperature of pristine PMMA about 460 K. At these temperatures, the PMMA materials become more ductile and the AgNPs within the PMMA matrix display higher mobility than those at 300 K. When the tensile strain increases, the AgNPs tend to get closer and the fracture appears at the PMMA part, leading to the close values of Young’s modulus and ultimate strength for pristine PMMA and PMMA/AgNP composite at 450 and 550 K.
The effect of interaction of low-index atomic planes, (100), (110), and (111) terminating CdSe platelet nanocrystals is examined using molecular dynamics (MD) simulations. Asymmetry of the environment of atoms at the end surface layers leads to anisotropic deformation of the cubic lattice and to a relative shift of Cd and Se sub-lattices. Interference of distortions of the crystal lattice originating at the terminal surfaces leads to changes of symmetry of the CdSe lattice in the whole sample volume. In the models, 2–3 nm thick, for all types of surfaces under examination, the initial cubic lattice symmetry gets lost in the whole sample volume.
The results of molecular dynamics (MD) simulations of CdSe crystals terminated by low-index atomic planes, (100), (110) and (111), are presented. The effect of the crystal termination on the atomic arrangement (interatomic distances) at the surface and underneath the surface is examined. It is shown that the crystal lattice is distorted in lateral and normal directions to the depth of up to about 2 nm from the surface. The exact characteristic of the changes of interatomic distances is specific to the type of the atomic plane terminating the crystal lattice. At some surfaces, the very last monoatomic layer loses the long-range ordering and becomes quasi amorphous. The atoms group into randomly distributed pairs or short linear groups.
Nitrilimine cycloadditions to ethylenes, acetylenes, and activated nitriles have been exploited in the presence of catalytic amounts of oleic-acid-coated iron oxide nanoparticles (diameter?=?11.9?±?1.0 nm). The reactions were fully regioselective with monosubstituted ethylenes and ethyl cyanoformiate, while mixtures of cycloadducts were obtained in the presence of methyl propiolate. The intervention of iron oxide nanoparticles allowed carrying out the cycloadditions at milder conditions compared to the metal-free thermal processes. A labile intermediate has been proposed to explain this behavior.
Graphical abstract Nitrilimine cycloadditions to ethylenes, acetylenes, and activated nitriles have been exploited in the presence of catalytic amounts of oleic-acid-coated iron oxide nanoparticles.
This work uses linear and looped RGDfV sequences attached to the surface of small (1.8 nm in diameter) gold nanoparticles (AuNPs) to enhance the radiosensitizating effects of Cilengitide, a cyclic RGDf (NMe)V pentapeptide that targets αvβ3 integrin which is overexpressed in certain cancers. Following synthesis and purification, the AuNPs were evaluated in vitro against HUVEC, H460, and MCF7 cells in clonogenic assays using a 137Cs irradiator. Untargeted AuNPs induced no significant dose enhancement factors (DEFs) in any of the cell types when compared to radiation treatment alone, whereas all evaluated AuNPs functionalized with targeting peptides performed at least as well as controls (irradiation after Cilengitide treatment). The observed DEFs also suggest that cyclizing the linear peptides into more spatially constrained, looped structures may facilitate target binding. These greater dose enhancements merit future in vivo studies of drug-AuNP conjugates to assess the ability of the nanostructures to provide an improved therapeutic benefit over treatment with drug candidates and radiation alone.
In this study, two different synthetic methods in aqueous solution are presented to tune the optical properties of CdTe and CdSe semiconductor nanoparticles. Additionally, the influence of different temperatures, pressures, precursor ratios, surface ligands, bases, and core components in the synthesis was investigated with regard to the particle sizes and optical properties. As a result, a red shift of the emission and absorption maxima with increasing reaction temperature (100 to 220°C), pressure (1 to 25 bar), and different ratios of core components of alloyed semiconductor nanoparticles could be observed without a change of the particle size. An increase in particle size from 2.5 to 5 nm was only achieved by variation of the mercaptocarboxylic acid ligands in combination with the reaction time and used base. To get a first hint on the cytotoxic effects and cell uptake of the synthesized quantum dots, in vitro tests mesenchymal stem cells (MSCs) were carried out.
In recent years, two-dimensional confined catalysis, i.e., the enhanced catalytic reactions in confined space between metal surface and two-dimensional overlayer, makes a hit and opens up a new way to enhance the performance of catalysts. In this work, graphdiyne overlayer was proposed as a more excellent material than graphene or hexagonal boron nitride for two-dimensional confined catalysis on Pt(111) surface. Density functional theory calculations revealed the superiority of graphdiyne overlayer originates from the steric hindrance effect which increases the catalytic ability and lowers the reaction barriers. Moreover, with the big triangle holes as natural gas tunnels, graphdiyne possesses higher efficiency for the transit of gaseous reactants and products than graphene or hexagonal boron nitride. The results in this work would benefit future development of two-dimensional confined catalysis.
It is well known that when nanoparticles (NPs) are exposed to biological fluid, it results into formation of nanoparticle protein corona, which has been the subject of extensive studies for the development of targeted drug delivery. In this work, we demonstrated the dynamic light scattering, fluorescence, and UV-visible spectroscopy as quantitative and qualitative tools to monitor adsorption of BSA protein onto silver nanoparticles (AgNPs). The adsorption resulted in significant gradual increase in average hydrodynamic radius of BSA-AgNP corona from 24 to 35 nm and its attainment of equilibrium point (saturation) that correlated with albumin concentration enables condition for bound and unbound protein adsorption to be interpreted. Using DLS, the dissociation constant (KD) was obtained for soft corona to be 2.09?±?0.30 μM. The UV-visible and fluorescence spectroscopy results were correlated with DLS. Loss of percent helicity in secondary structure of adsorbed BSA was monitored in both coronas as compared to native protein. Both coronas were found to be biocompatible with RBC membrane. Further, the results of adsorption isotherm model were used to validate the multilayer formation of albumin protein on silver nanoparticles. The obtained results would be relevant in the drug design development for tumor-targeted therapy.
A novel strategy to synthesize photoluminescent silicon nanocrystals (SiNCs) from a reaction between tetraethylorthosilicate (TEOS) and trimethyl-hexadecyl-ammonium borohydride (CTABH4) in organic solvent is presented. The formation reaction occurs spontaneously at room temperature in homogeneous phase. The produced silicon nanocrystals are characterized by using their photoluminescent properties and via HRTEM. In addition, theoretical calculations of the optical absorption spectrum of silicon quantum dots in vacuum with different sizes and surface moieties were performed in order to compare with the experimental findings. The new chemical reaction is simple and can be implemented to produce silicon nanocrystal with regular laboratory materials by performing easy and safe procedures.
Despite advancements in treatment of infectious diseases, opportunistic pathogens continue to pose a worldwide threat. Identifying a source of infection/inflammation is often challenging which highlights the need of improved diagnostic agents. Using a model of local S. aureus infection, here we evaluated the potential of betamethasone or dexamethasone loaded in poly (lactic acid) nanoparticles and radiolabeled with 99mTc to detect an infection/inflammation site in vivo. A betamethasone and dexamethasone nanoparticles (NPs) with 200 and 220 nm in size, respectively, were created with a 98% 99mTc radiolabeling efficiency. When injected in infected mice, betamethasone NPs presented a higher accumulation in the infected hind paw in comparison with dexamethasone NPs. Our results suggest that this nanosystem may be a valid nanoradiopharmaceutical for the detection of inflammation/infection foci in vivo.
Water dispersible boron nanoparticles have great potential as materials for boron neutron capture therapy of cancer and magnetic resonance imaging, if they are prepared on a large scale with uniform size and shape and hydrophilic modifiable surface. We report the first method to prepare spherical, monodisperse, water dispersible boron core silica shell nanoparticles (B@SiO2 NPs) suitable for aforementioned biomedical applications. In this method, 40 nm elemental boron nanoparticles, easily prepared by mechanical milling and carrying 10-undecenoic acid surface ligands, are hydrosilylated using triethoxysilane, followed by base-catalyzed hydrolysis of tetraethoxysilane, which forms a 10-nm silica shell around the boron core. This simple two-step process converts irregularly shaped hydrophobic boron particles into the spherically shaped uniform nanoparticles. The B@SiO2 NPs are dispersible in water and the silica shell surface can be modified with primary amines that allow for the attachment of a fluorophore and, potentially, of targeting moieties.
In this study, a tumor-targeting poly(d, l-lactic-co-glycolic acid) (PLGA) loaded “off-on” fluorescent probe nanoparticle (PFN) delivery system was developed to evaluate the region of tumor by off-on fluorescence. The biodegradability of the nanosize PFN delivery system readily released the probe under tumor acidic conditions. The probe with good biocompatibility was used to monitor the intracellular glutathione (GSH) of cancer cells and selectively localize to mitochondria for tumor imaging. The incorporated tumor-targeting probe was based on the molecular photoinduced electron transfer (PET) mechanism preventing fluorescence (“off” state) and could be easily released under tumor acidic conditions. However, the released tumor-targeting fluorescence probe molecule was selective towards GSH with high selectivity and an ultra-sensitivity for the mitochondria of cancer cells and tissues significantly increasing the probe molecule fluorescence signal (“on” state). The tumor-targeting fluorescence probe showed sensitivity to GSH avoiding interference from cysteine and homocysteine. The PFNs could enable fluorescence-guided cancer imaging during cancer therapy. This work may expand the biological applications of PFNs as a diagnostic reagent, which will be beneficial for fundamental research in tumor imaging.
Graphical abstract The tumor-bearing mice were injected intravenously through the tail with the PFNs; after injection, the PFNs can accumulate to tumor region via the EPR effect. The PFNs can prolong blood circulation time and easily degraded under tumor acidic conditions to release an off-on probe in tumor, and the probe can target glutathione of mitochondria, making probe fluorescence enhanced largely (“on” state).
Addition reaction between C60 and ethylenediamine occurred at room temperature in an ambient condition. C60-ethylenediamine adduct particles were prepared by mixing toluene solutions of C60 and ethyelenediamine. Average diameter of the C60-ethylenediamine adduct particles was changed non-linearly according to the reaction time, which were observed using transmission electron microscopy. Early stage of the reaction, the diameter of the adduct particles was changed from about 250 to about 430 nm. Then, the size of the adduct particles was converged to about 300 nm. During this addition reaction, the crystalline sizes of adduct particles were constant about 2–3 nm, regardless of the sizes of the adduct particles, which were determined by X-ray diffraction measurement.
The recognition of tumor markers in living cancer cells has attracted increasing interest. In the present study, the turn-on fluorescence probe was designed based on the fluorescence of thiolated chitosan-coated CdTe QDs (CdTe/TCS QDs) quenched by hyaluronan, which could provide the low background signal for sensitive cellular imaging. This system is expected to offer specific recognition of CD44 receptor over other substances owing to the specific affinity of hyaluronan and CD44 receptor (~8–9 kcal/mol). The probe is stable in aqueous and has little toxicity to living cells; thus, it can be utilized for targeted cancer cell imaging. The living lung cancer cell imaging experiments further demonstrate its value in recognizing cell-surface CD44 receptor with turn-on mode. In addition, the probe can be used to recognize and differentiate the subtypes of lung cancer cells based on the difference of CD44 expression on the surface of lung cancer cells. And, the western blot test further confirmed that the expression level of the CD44 receptor in lung cancer cells is different. Therefore, this probe may be potentially applied in recognizing lung cancer cells with higher contrast and sensitivity and provide new tools for cancer prognosis and therapy.
Graphical abstract ? Hyaluronan functionalizing sulfhydryl chitosan-coated CdTe QDs were designed as a “turn-on” fluorescence probe for recognizing cancer cells. ? The fabricating probe is based on the high affinity of hyaluronan and CD44 receptor for specific recognition of CD44 receptor in lung cancer cell. ? The probe can be used to recognize and differentiate the subtypes of lung cancer cells based on the difference of CD44 expression on the surface of lung cancer cells. ? The probe showed the lower background signal than that of always-on nanoprobes avoiding the non-specific adsorption on the surface of the normal cells.
Carbon-coated ZnFe2O4 spheres with sizes of ~110–180 nm anchored on graphene nanosheets (ZF@C/G) are successfully prepared and applied as anode materials for lithium ion batteries (LIBs). The obtained ZF@C/G presents an initial discharge capacity of 1235 mAh g?1 and maintains a reversible capacity of 775 mAh g?1 after 150 cycles at a current density of 500 mA g?1. After being tested at 2 A g?1 for 700 cycles, the capacity still retains 617 mAh g?1. The enhanced electrochemical performances can be attributed to the synergetic role of graphene and uniform carbon coating (~3–6 nm), which can inhibit the volume expansion, prevent the pulverization/aggregation upon prolonged cycling, and facilitate the electron transfer between carbon-coated ZnFe2O4 spheres. The electrochemical results suggest that the synthesized ZF@C/G nanostructures are promising electrode materials for high-performance lithium ion batteries.
A novel nano-size MnxOy/clinoptilolite catalyst of high activity for propane-SCR reaction of NOx at low temperatures has been synthesized by a hydrothermal method in a temperature range of 80–180 °C. The optimum synthesis temperature resulting in maximum NOx conversion was 150 °C. An optimum manganese oxide loading of 0.2 wt.% results in the best catalytic behavior (71% NOx conversion). All catalysts exhibited an optimal propane-SCR reaction temperature of 200 °C. The optimum catalyst produces no detectable CO (GHSV 27,000 h) at 200 °C. Manganese in the optimum catalyst exists as Mn2+ (37.8%), Mn3+ (14.2%), and Mn4+ (48%).
Graphical abstract Flake-like manganese oxide nanostructures (indicated by an arrow in the TEM picture) next to the clinoptilolite zeolite sheet-like crystals result in a promising low-temperature propane-selective catalytic reduction of NOx.
