A mechanoluminescent material, ZnS:Mn,Li, with enhanced brightness for visualizing dental occlusion.

Mechanoluminescent materials are characterized by high luminescence intensity, high repeatability, no external voltage activation, and a good linear relationship between stress and mechanoluminescence intensity within a certain range. Therefore, mechanoluminescent materials have attracted increasing attention from researchers in the fields of stress sensing, encryption and anti-counterfeiting, structural health monitoring, energy-saving lighting, intelligent wearable devices, and other fields. In this study, ZnS:Mn powders with different Mn2+ ratios and different ion doping were synthesized by a high-temperature solid-phase reaction, and the synthesis of various materials was characterized. Then, the optimal mechanoluminescence effect of the ZnS:1%Mn,1%Li material was obtained. The photoluminescence intensity of ZnS:1%Mn,1%Li was 16.7 times higher than that of the sample without doping with Li+, and the mechanoluminescence intensity was 1.64 times higher. Finally, polyethylene terephthalate (PET) film was combined with ZnS:Mn,Li mechanoluminescent powders to prepare flexible three-layer composite film. Based on this, a feasible strategy for the detection of temporomandibular disorders was proposed. The composite film is easy to use, economical, and safe, and has good mechanoluminescent performance, which has potential application value in the field of occlusal force detection and visualization.

Impact of luminescent-ion doping on the crystallographic and photo-physical properties of the CaMoO4 nanoparticles.

Luminescent lanthanide (Ln3+ = Pr, Nd, Sm, Eu, and Tb)-ions doped calcium molybdate(CaMoO4) nanoparticles(NPs) were prepared by the polyol wet-chemical route. X-ray diffraction (XRD) pattern of all samples showed the formation of a single-phase scheelite type tetragonal structure with an average crystalline size over 21.6-33.4 nm. Thermal stability was evaluated to study the surface-anchored functional groups by weight loss measurement. Fourier transform infrared (FTIR) spectra were recorded to identify the adsorbed functional groups. Aqueous dispersibility and colloidal stability were recorded with the help of the UV/visible absorption spectra. These nanocrystals formed semi-transparent colloidal solutions after being evenly disseminated in aqueous media. The doping of the luminescent ions significantly affects the crystal structure and photoluminescence (PL) properties of the CaMoO4:Ln3+ NPs. In a comparative analysis of the absorption spectra, bandgap, Raman-active modes, and luminescent properties, they were greatly influenced by altering the dopant ion due to the variation in the atomic radius of the element. The doping of smaller atomic radius Ln3+-ions distorts the unit cell, and, subsequently, bond angle/length alters the symmetry of the host crystal. The distorted crystal lattice affects the crystalline, size, lattice parameter, band gap values, Raman active vibrational modes, and luminescent efficiency. The distorted crystal structure of the host lattices facilitates the movement of the oxygen vacancies through charge transfer, resulting in efficiently suppressed emission efficiency.Graphical abstract.

Novel ruthenium-doped vanadium carbide/polymeric nanohybrid sensor for acetaminophen drug detection in human blood.

The use of advanced electroactive catalysts enhances the performance of electrochemical biosensors in real-time biomonitoring and has received much attention owing to its excellent physicochemical and electrochemical possessions. In this work, a novel biosensor was developed based on the electrocatalytic activity of functionalized vanadium carbide (VC) material, including VC@ruthenium (Ru), VC@Ru-polyaniline nanoparticles (VC@Ru-PANI-NPs) as non-enzymatic nanocarriers for the fabrication of modified screen-printed electrode (SPE) to detect acetaminophen in human blood. As-prepared materials were characterized using SEM, TEM, XRD, and XPS techniques. Biosensing was carried out using cyclic voltammetry and differential pulse voltammetry techniques and has revealed imperative electrocatalytic activity. A quasi-reversible redox method of the over-potential of acetaminophen increased considerably compared with that at the modified electrode and the bare SPE. The excellent electrocatalytic behaviour of VC@Ru-PANI-NPs/SPE is attributed to its distinctive chemical and physical properties, including rapid electron transfer, striking á´«-á´« interface, and strong adsorptive capability. This electrochemical biosensor exhibits a detection limit of 0.024 µM, in a linear range of 0.1-382.72 µM with a reproducibility of 2.45 % relative standard deviation, and a good recovery from 96.69 % to 105.59 %, the acquired results ensure a better performance compared with previous reports. The enriched electrocatalytic activity of this developed biosensor is mainly credited to its high surface area, better electrical conductivity, synergistic effect, and abundant electroactive sites. The real-world utility of the VC@Ru-PANI-NPs/SPE-based sensor was ensured via the investigation of biomonitoring of acetaminophen in human blood samples with satisfactory recoveries.

Facile synthesized NaGdF4 :Yb,Er peanut-shaped, highly biocompatible, colloidal upconversion nanospheres.

A facile method was used for the synthesis of peanut-shaped very emissive NaGdF4 :Yb, Er upconversion nanospheres (UCNSs) at lower temperatures with uniform size distribution. Crystallographic structure, phase purity, morphology, thermal robustness, biocompatibility, colloidal stability, surface chemistry, optical properties, and luminesce properties were explored by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), zeta potential, thermogravimetric/differential thermal analysis (TGA/DTA), Fourier-transform infrared (FTIR), ultraviolet (UV)-visible and photoluminescence spectroscopic tools. XRD pattern verified the construction of a single-phase, highly-crystalline NaGdF4 phase with a hexagonal structure. Peanut-shaped morphology of the sample was obtained from SEM micrographs which were validated from high-resolution TEM images, to have an equatorial diameter of 170 to 200 nm and a length of 220 to 230 nm, with irregular size, monodispersed, porous structure, and rough surface of the particles. The positive zeta potential value exhibited good biocompatibility along with high colloidal stability as observed from the absorption spectrum. The prepared UCNSs revealed high dispersibility, irregular size peanut-shaped morphology, rough surface, good colloidal stability, and excellent biocompatibility in aqueous media. A hexagonal phase NaGdF4 doped with ytterbium (Yb) and erbium (Er) UCNSs revealed the characteristics of highly dominant emissions located at 520-525, 538-550, and 659-668 nm corresponding to the 2 H11/2 → 4 I15/2 , 4 S3/2 → 4 I15/2 , and 4 F9/2 → 4 I15/2 transition of Er3+ ions, respectively, as a result of energy transfer from sensitizer Yb3+ ion to emitter Er3+ ion.

Physiochemical characterization of highly biocompatible, and colloidal LaF3:Yb/Er upconversion nanoparticles.

Highly colloidal upconversion nanoparticles (UCNPs) were synthesized at low temperatures by the thermal decomposition process. The structure, morphology, crystallinity, surface chemistry, and optical properties were systematically optimized and studied through various spectroscopic techniques. X-ray diffraction (XRD) patterns have shown the formation of single-phase, highly purified, well-crystalline, hexagonal LaF3 NPs, while the TEM micrographs show small, irregular sizes, spherically shaped, and aggregated polycrystalline UCNPs with an average crystalline size of about 8-15 nm. The Negative Zeta Potential value exhibits good biocompatibility of the UCNPs, which supports the idea that surface-anchored hydroxyl groups facilitate the stabilization of the NPs in aqueous media, as well as enhance biomolecules' tagging efficiency. The absorption spectrum, Zeta Potential, and hydrodynamic size that were measured in aqueous media illustrate excellent dispersibility, colloidal stability, biocompatibility, and cytotoxicity character of the UCNPs. Zeta potential and MTT assay studies illustrated high biocompatibility, it could be due to the surface-anchored hydroxyl groups. The nanoproduct demonstrates an excellent UC luminescence spectrum (i.e., prominent green emission 4S3/2 → 4I/15/2) upon irradiation by the 980-nm laser diode. TEM micrographs, further, revealed that this optically active material with aqueous sensitivities, porous crystal structure, and excellent UCNPs, could be a favorable candidate for potential photonics-based bio-related applications.

Catalytic performance of the Ce-doped LaCoO3 perovskite nanoparticles.

A series of La1-xCexCoO3 perovskite nanoparticles with rhombohedral phases was synthesized via sol-gel chemical process. X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), Electron Diffraction Spectroscopy (EDS), Thermogravimetric Analysis (TGA), UV-Vis spectroscopy, Fourier Transform Infrared spectra (FTIR), Nitrogen Adsorption/desorption Isotherm, Temperature Program Reduction/Oxidation (TPR/TPO), X-ray Photoelectron Spectroscopy (XPS) techniques were utilized to examine the phase purity and chemical composition of the materials. An appropriate doping quantity of Ce ion in the LaCoO3 matrix have reduced the bond angle, thus distorting the geometrical structure and creating oxygen vacancies, which thus provides fast electron transportation. The reducibility character and surface adsorbed oxygen vacancies of the perovskites were further improved, as revealed by H2-TPR, O2-TPD and XPS studies. Furthermore, the oxidation of benzyl alcohol was investigated using the prepared perovskites to examine the effect of ceria doping on the catalytic performance of the material. The reaction was carried out with ultra-pure molecular oxygen as oxidant at atmospheric pressure in liquid medium and the kinetics of the reaction was investigated, with a focus on the conversion and selectivity towards benzaldehyde. Under optimum reaction conditions, the 5% Ce doped LaCoO3 catalyst exhibited enhanced catalytic activity (i.e., > 35%) and selectivity of > 99%, as compared to the other prepared catalysts. Remarkably, the activity of catalyst has been found to be stable after four recycles.

Highly Water-Soluble Luminescent Silica-Coated Cerium Fluoride Nanoparticles Synthesis, Characterizations, and In Vitro Evaluation of Possible Cytotoxicity.

A coprecipitation process was utilized for the preparation of terbium fluoride nanocrystals by cerium fluoride. Silica was used to modify the surface of these core/shell nanocrystals. The synthesized CeF3:Tb@LaF3 and CeF3:Tb@LaF3@SiO2 nanoparticles (NPs) were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV/vis spectrophotometry, and photoluminescence spectrophotometry. XRD patterns showed resolved reflection planes with broad widths, confirming the nanocrystalline nature of the CeF3:Tb@LaF3@SiO2 NPs. Fourier transform infrared spectra clearly revealed a uniform, smooth silica layer encapsulating the luminescent seed core and confirmed the polycrystalline nature of the CeF3:Tb@LaF3@SiO2 NPs. The TEM result showed an average crystalline size of 18 nm, which illustrated good agreement with the XRD results. The results of photoluminescence spectrophotometry confirmed the doping of terbium ions in the CeF3 crystal lattice. The cytotoxicity results of the MTT assay showed that CeF3:Tb@LaF3@SiO2 NPs have minimum toxicity with respect to CeF3:Tb@LaF3 NPs and the control drug dasatinib on HT-29 and HepG2 cell lines. Moreover, results of inverted microscopy confirmed the nontoxic and biocompatible nature of CeF3:Tb@LaF3@SiO2 NPs. These findings show that CeF3:Tb@LaF3@SiO2 NPs are promising candidates for applications in biomedical science in the future, such as bioimaging, biolabeling, biodetection or bio-probing, labeling of cells and tissue, drug delivery, cancer therapy, and multiplexed analysis.

Optically active neodymium hydroxide surface-functionalized mesoporous silica micro-cocoons for biomedical applications.

Neodymium hydroxide (Nd(OH)3)-surface modified mesoporous silica micro-cocoon microstructures were prepared using a facile single-step sol-gel chemical process. XRD revealed the semi-crystalline nature of the as-prepared materials. TEM and SEM micrographs exhibited highly monodisperse, non-aggregated, typical ordered mesoporous, and irregular sized cocoon-shaped micro-structures with a narrow size distribution. Optical properties, that were examined in the aqueous media, revealed a high colloidal stability and the formation of a semi-transparent colloidal solution. The colloidal solution of Nd(OH)3-surface functionalized micro-structures revealed well characteristics absorption bands of Nd3+ ions in the visible region. thus validating the successful coating of SiO2@Nd(OH)3 layer over the surface silica forming core-shell structures. Zeta potential, 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium) bromide, and neutral red uptake assays were applied in a dose-dependent manner to investigate the biocompatibility and toxic potential of the designed cocoon-shaped microstructures. Both the assays and the high zeta potential value demonstrated good cell viability even at high concentrations and hydrophilic conditions, indicating excellent biocompatibility and non-toxicity. These highly hydrophilic, optically active, mesoporous, biocompatible, and non-toxic cocoon-shaped microstructures could be potentially suitable candidates for optical bio-probes and drug delivery applications.

Mitigation of acyl-homoserine lactone (AHL) based bacterial quorum sensing, virulence functions, and biofilm formation by yttrium oxide core/shell nanospheres: Novel approach to combat drug resistance.

The present study evaluated the efficacy of Y2O3:Tb (core) and Y2O3:Tb@SiO2 nanospheres (core/shell NSs) against virulence functions regulated by quorum sensing (QS) and biofilm formation in pathogenic bacteria. Scanning electron microscope (SEM) images were used to study the size, shape, and morphology. The images clearly displayed spherical shaped, mono-dispersed particles with narrow size distribution and an average grain size of 110-130 nm. The chemical composition of the samples was determined by using energy dispersive X-ray (EDX) and X-ray photoelectron spectroscopy (XPS). We determined the impact of core and core/shell NSs on QS using sensor strains of Chromobacterium violaceum CVO26 and Pseudomonas aeruginosa PAO1 in a comparative study. Sub-MICs of core and core/shell NSs substantially suppressed QS-controlled violacein production in C. violaceum. Similar concentration-dependent effect of sub-MICs of synthesized core and core/shell NSs was observed in the QS-regulated virulence functions (elastase, total protease, pyocyanin production, swarming motility, and exopolysaccharide production) in PAO1. A concentration-dependent decrease (14-60%) was recorded in the biofilm forming capability of PAO1, upon treatment with core and core/shell NSs. Moreover, core/shell NSs were more effective in inhibiting biofilm at higher tested concentrations as compared to core-NSs. The synthesized NSs demonstrated significantly impaired attachment of cells to the microtiter plate indicating that NSs target biofilm inhibition at the attachment stage. Based on these results, we predict that core and core/shell NSs may be an alternative to combat the threat of drug-resistant pathogenic bacteria.

Toxicity response of highly colloidal, bioactive, monodisperse SiO2@ Pr(OH)3 hollow microspheres.

In a facile synthesis, highly colloidal, bioactive Pr(OH)3-encapsulated silica microspheres (PSMSs) with an average diameter of 500-700 nm were successfully prepared via a sol-gel process followed by heat treatment. The phase formation, morphology, surface and optical properties of the as-synthesized PSMSs were characterized by various techniques including X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope (TEM), N2-adsorption-desorption, energy dispersive X-ray (EDX) analysis, Fourier transform infrared (FTIR) and UV/vis spectroscopy. The PSMSs were semi-amorphous or ultra-small in size, highly dispersible in water, mesoporous, irregular in size and spherical in shape. The SEM images show a well-ordered broad nanoporous structure which is preserved after coating with Pr(OH)3 molecules, demonstrating interaction between the optically active Pr3+ ion and silanol (Si-OH) groups via hydrogen bonding. Optical spectra show well-resolved weak intensity 4f-4f absorption transitions in the visible region of the Pr3+ ion, indicating successful grafting of the Pr(OH)3 layer. Toxicity was measured by MTT and NRU assays to determine potential toxicity. Cell viability was suppressed with increasing dosage of PSMSs, but showed greater than 55% cell viability at a concentration of 200 µg/mL, resulting in low toxicity. Due to its high aqueous dispersibility, optical activity, excellent biocompatibility and low toxic nature, it could be a favorable material for biomedical and drug delivery applications.

Physico-chemical properties and catalytic activity of the sol-gel prepared Ce-ion doped LaMnO3 perovskites.

Ce-doped LaMnO3 perovskite ceramics (La1-xCexMnO3) were synthesized by sol-gel based co-precipitation method and tested for the oxidation of benzyl alcohol using molecular oxygen. Benzyl alcohol conversion of ca. 25-42% was achieved with benzaldehyde as the main product. X-ray diffraction (XRD), thermogravimetric analysis (TGA), BET surface area, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (H2-TPR), temperature-programmed oxidation (O2-TPO), FT-IR and UV-vis spectroscopic techniques were used to examine the physiochemical properties. XRD analysis demonstrates the single phase crystalline high purity of the perovskite. The Ce-doped LaMnO3 perovskite demonstrated reducibility at low-temperature and higher mobility of surface O2-ion than their respective un-doped perovskite. The substitution of Ce3+ ion into the perovskite matrix improve the surface redox properties, which strongly influenced the catalytic activity of the material. The LaMnO3 perovskite exhibited considerable activity to benzyl alcohol oxidation but suffered a slow deactivation with time-on-stream. Nevertheless, the insertion of the A site metal cation with a trivalent Ce3+ metal cation led to an enhanced in catalytic performance because of atomic-scale interactions between the A and B active site. La0.95Ce0.05MnO3 catalyst demonstrated the excellent catalytic activity with a selectivity of 99% at 120 °C.

Preparation, characterizations and in vitro cytotoxic activity of nickel oxide nanoparticles on HT-29 and SW620 colon cancer cell lines.

Despite the extensive implication of nickel oxide nanoparticles (NiO-NPs) in different fields such as biomedical science and industrial manufacturing, their effect on human cancer cells has not been elucidated. In this study, we report a simple process for the preparation of NiO-NPs. X-ray diffraction and transmission electron microscopy were used to characterize the surface architecture and dimension of the synthesized NiO-NPs. The average diameter of the NiO-NPs was approximately 20-25 nm. We used two human colon cancer cell lines, HT-29 and SW620, to assess the nanoparticles' cytotoxicity. The MTT assay showed that the NiO-NPs reduced cell viability of HT-29 and SW620 cell lines. The results of inverted microscopy showed the highest cytotoxic activity with 600 µg/ml concentration of NiO-NPs on HT-29 cells. Western blot assay showed the downregulation of anti-apoptotic Bcl2 and Bcl-xL proteins in HT-29 cells treated with NiO-NPs. Moreover the results demonstrated the induction of PARP (Cleaved) in NiO-NPs treated HT-29 cells which are considered the marker of apoptosis. The NiO-NPs were not demonstrated bactericidal effect on six different bacterial strains tested, implying that the NiO-NPs may not perturb the human normal gut microbiome. The results have showed the promising application of the NiO-NPs in management of cancer in near future.

Mesoporous multi-silica layer-coated Y2O3:Eu core-shell nanoparticles: Synthesis, luminescent properties and cytotoxicity evaluation.

Mesoporous multi-layered silica-coated luminescent Y2O3:Eu nanoparticles (NPs) were prepared by a urea-based decomposition process, and their surfaces were gradually modified with nanoporous and mesoporous silica layers using modified sol-gel methods. The synthesized luminescent core-shell NPs were characterized thoroughly to investigate their structural, morphological, thermal, optical, photo luminescent properties and their surface chemistry. The morphology of the core NPs were nearly spherical in shape and were nano-sized grains. The observed luminescent efficiency of the mesoporous multi-layered silica-coated luminescent core NPs was gradually reduced because of bond formation between the Y2O3:Eu core and the amorphous silica shell via YOSiOH bridges on the surface of the NPs; the bonds suppressed the non-radiative transition pathways. Biocompatibility tests on Human breast cancer cells using the 3­(4,5­Dimethylthiazol­2­yl)­2,5­diphenyltetrazolium bromide and lactate dehydrogenase assays indicated that the core-shell NPs were non-toxic even at high concentrations. The mesoporous SiO2 layer played a key role in perfecting the solubility, biocompatibility, and non-toxicity of the NPs. The zeta potential, surface chemistry (Fourier transform infrared spectroscopy), and optical absorption spectral analyses revealed the high hydrophilicity of the as-prepared core-shell NPs because of the active surface-functionalized silanol (SiOH) groups, which could potentially offer many exciting opportunities in photonic-based biomedical applications.

Aqueous dispersible green luminescent yttrium oxide:terbium microspheres with nanosilica shell coating.

Tb-doped Y2O3 microspheres (MSs) were prepared via a homogeneous thermal degradation process at a low temperature and then coated with a nanosilica shell (Y2O3:Tb@SiO2) using a sol-gel process. The core MSs were highly crystalline and spherical with a porous surface, single cubic phase, and particle size of 100-250 nm. Transmission electron microscopy (TEM) images clearly showed the spherical shape of the as-prepared core MSs, which were fully covered with a thick and mesoporous nanosilica shell. Fourier transform infrared (FTIR) spectra displayed the well-resolved infrared absorption peaks of silica (SiO, SiOSi, etc.), confirming the presence of the silica surface coating. The core MSs retained their spherical shape even after heat treatment and subsequent silica surface coating. It was observed that the core/shell MSs are easily dispersible in aqueous media and form a semi-transparent colloidal solution. Ultraviolet/visible and zeta potential studies were tested to prove the changes in the surface chemistry of the as-designed core/shell MSs and compare with their core counterpart. The growth of the amorphous silica shell not only increased the particle size but also enhanced remarkably the solubility and colloidal stability of the MSs in aqueous media. The strongest emission lines originating from the characteristic intra-shell 4f-4f electronic transitions of Tb ions were quenched after silica layer deposition, but the MSs still showed strong green (5D4 → 7F5 at 530-560 nm as most dominant) emission efficiency, which indicates great potential in fluorescent bio-probes. The emission intensity is discussed in relation to the quenching mechanism induced by surface silanol (Si-OH) groups, particle size, and surface charge.

Effect of Surface Functionalization on Structural and Optical Properties of Luminescent LaF3:Sm Nanoparticles.

Samarium (Sm3+)-doped LaF3 nanoparticles (NPs) subsequently encapsulated with inert crystalline LaF3 and amorphous silica layers were prepared by polyol and sol-gel chemical process, respectively. These surface modified core/shell/SiO2-nanostructured were characterized by X-ray diffraction (XRD), FE-transmission electron microscopy (TEM), thermal analysis, FTIR, UV/Vis absorption, bang gap energy and photoluminescence spectroscopy. The FETEM, EDX and FTIR spectral studies clearly revealed that the silica layer has been formed surrounding the core-NPs. Comparative spectral analysis indicated that core/shell/SiO2-NPs revealed high solubility in aqueous and non-aqueous solvents. The decrease in band gap energy after surface growth of an inert LaF3 and silica shells is directly correlated to the increase in grain size. On comparing the emission intensity, a significant enhancement was observed after inert layer coating, whereas, it suppress after silica encapsulation due to the non-radiative transitions. The increase luminescent intensity after inert shell growth indicates that a significant amount of non-radiative centers existing on the surface of core/shell nanoparticles can be eliminated by the shielding effect of LaF3 shells. These observed results indicate that the as-prepared core/shell/SiO2-NPs could be highly useful in broad photonic based applications such as optical sensor/optical bio-probe and light emitting diode.

Highly biocompatible, monodispersed and mesoporous La(OH)3:Eu@mSiO2 core-shell nanospheres: Synthesis and luminescent properties.

Monodispersed La(OH)3:Eu nanospheres(core-NSs) were synthesized by urea-based homogeneous co-precipitation process, where mesoporous silica layer was coated over the surface of luminescent La(OH)3:Eu core-NSs. The XRD data exhibit the high crystalline, single hexagonal-shaped La(OH)3:Eu core and silica modified La(OH)3:Eu@mSiO2 (core-shell) NSs. Monodispersibility, spherical shaped, high surface area and mesoporosity were identified by TEM analysis and were further confirmed by BET analysis. The as-synthesized samples are highly soluble in aqueous media at ambient conditions. Spectroscopic analyses were also carried out to examine the impact of surface modification on structural, surface chemistry, optical and luminescence behavior of the as-designed silica coated core-shell NSs. The emission spectral study revealed that the luminescence intensity of magnetic-dipole transition (590 nm, 5D0 → 7F1) is dominant with respect to electric-dipole (614 nm, 5D0 → 7F2) transition. The high crystallinity of the hydroxide products supports the existence of good photoluminescence intensity, a good indication for their future use in detection of biomacromolecules through hypersensitive emission (614 nm, 5D0 → 7F2) transition. Excellent biocompatibility, cell viability and good luminescence properties suggested that the as-prepared core-shell NSs are an ideal candidate for luminescence biolabeling/bioimaging and as an optical bio-probe.

Silica-modified luminescent LaPO4 :Eu@LaPO4 @SiO2 core/shell nanorods: Synthesis, structural and luminescent properties.

Monoclinic-type tetragonal LaPO4 :Eu (core) and LaPO4 :Eu@LaPO4 (core/shell) nanorods (NRs) were successfully prepared using a urea-based co-precipitation process under ambient conditions. An amorphous silica layer was coated around the luminescent core/shell NRs via the sol-gel process to improve their solubility and colloidal stability in aqueous and non-aqueous media. The prepared nano-products were systematically characterized by X-ray diffraction pattern, transmission electron microscopy, energy dispersive X-ray analysis, and FTIR, UV/Vis, and photoluminescence spectroscopy to examine their phase purity, crystal phase, surface chemistry, solubility and luminescence characteristics. The length and diameter of the nano-products were in the range 80-120 nm and 10-15 nm, respectively. High solubility of the silica-modified core/shell/Si NRs was found for the aqueous medium. The luminescent core NRs exhibited characteristic excitation and emission transitions in the visible region that were greatly affected by surface growth of insulating LaPO4 and silica layers due to the multiphonon relaxation rate. Our luminescence spectral results clearly show a distinct difference in intensities for core, core/shell, and core/shell/Si NRs. Highly luminescent NRs with good solubility could be useful candidates for a variety of photonic-based biomedical applications.

In-vitro cytotoxicity and cellular uptake studies of luminescent functionalized core-shell nanospheres.

Monodispersed luminescent functionalized core-shell nanospheres (LFCSNs) were successfully synthesized and investigated for their cyto-toxic effect on human liver hepatocellular carcinoma cell line (HepG2 cells) by adopting MTT, DNA Ladder, TUNEL assay and qPCR based gene expressions through mRNA quantifications. The TUNEL and DNA ladder assays suggested an insignificant apoptosis in HepG2 cells due to the LFCSNs treatment. Further, the qPCR results also show that the mRNA expressions of cell cycle checkpoint gene p53 and apoptosis related gene (caspase-9) was up-regulated, while the antiapoptotic gene BCl-2 and apoptosis related genes FADD and CAS-3 (apoptosis effecter gene) were down-regulated in the LFCSNs treated cells. The nanospheres that were loaded into the cells confirm their intracellular uptake by light and fluorescent spectro-photometry and microscopy imaging analysis. The loaded nanospheres demonstrate an absolute resistance to photo-bleaching, which were applied for dynamic imaging to real-time tracking in-vitro cell migratory activity for continuous 24 and 48 h durations using a time-lapsed fluorescent microscope. These properties of LFCSNs could therefore promote applications in the area of fluorescent protein biolabeling and drug-delivery.

Evaluation of in vitro cytotoxicity, biocompatibility, and changes in the expression of apoptosis regulatory proteins induced by cerium oxide nanocrystals.

Cerium oxide nanocrystals (CeO2-NCs) exhibit superoxide dismutase and catalase mimetic activities. Based on these catalytic activities, CeO2-NCs have been suggested to have the potential to treat various diseases. The crystalline size of these materials is an important factor that influences the performance of CeO2-NCs. Previous reports have shown that several metal-based nanocrystals, including CeO2-NCs, can induce cytotoxicity in cancer cells. However, the underlying mechanisms have remained unclear. To characterize the anticancer activities of CeO2-NCs, several assays related to the mechanism of cytotoxicity and induction of apoptosis has been performed. Here, we have carried out a systematic study to characterize CeO2-NCs phase purity (X-ray diffraction), morphology (electron microscopy), and optical features (optical absorption, Raman scattering, and photoluminescence) to better establish their potential as anticancer drugs. Our study revealed anticancer effects of CeO2-NCs in HT29 and SW620 colorectal cancer cell lines with half-maximal inhibitory concentration (IC50) values of 2.26 and 121.18 µg ml-1, respectively. Reductions in cell viability indicated the cytotoxic potential of CeO2-NCs in HT29 cells based on inverted and florescence microscopy assessments. The mechanism of cytotoxicity confirmed by estimating possible changes in the expression levels of Bcl2, BclxL, Bax, PARP, cytochrome c, and ß-actin (control) proteins in HT29 cells. Down-regulation of Bcl2 and BclxL and up-regulation of Bax, PARP, and cytochrome c proteins suggested the significant involvement of CeO2-NCs exposure in the induction of apoptosis. Furthermore, biocompatibility assay showed minimum effect of CeO2-NCs on human red blood cells.

Physiochemical properties of greatly enhanced photoluminescence of aqueous dispersible upconversion CaF2:Yb/Er nanoparticles.

Crystal phase morphological structure and optical properties of the as-prepared upconversion CaF2:Yb/Er(core) and sequential coating of an inert crystalline material and silica layers surrounding the seed core-nanoparticles (NPs) were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), optical absorption, FTIR spectroscopy and upconversion photoluminescence spectroscopy. Owing to the unique properties of CaF2 host matrix, we realized their practical applications in biomedical science to improve the upconversion luminescence property and aqueous dispersibility. The surface coating on the seed core particles will significantly influence the structural, optical band gap energy and upconversion luminescence properties. These NPs were well-dispersed in aqueous and non-aqueous solvents to form clear colloidal solutions. The colloidal solutions of three samples show a characteristic optical absorption band in UV/Visible region. As a result, optical band gap gradually decreases after sequential growth of the inert shell and amorphous silica due to an increase in the crystalline size. Comparative upconversion luminescence analysis showed that after inert shell growth, the upconversion intensity was greatly improved, and such an improvement was found to arise from efficient suppression of surface-related deactivation from the core nanocrystals. Interestingly, growth of an inert (CaF2) shell over the seed core NPs shows intense upconversion emission lines under 980 nm NIR laser excitation, highlighting their promising applications, such as multi-analyte biolabels, staining, displays and other photonic based technological applications.