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The bending strength of silicon nitride (Si3N4) plays a vital role in its application and is influenced by various process factors. Current experimental methods for investigating Si3N4 ceramics exhibiting low efficiency and high cost are incapable of systematically analysing the effect of process factors on the bending strength of Si3N4 ceramics and quantitatively predicting the optimum process parameters. In this study, machine learning (ML) approaches based on extreme gradient boosting (XGBoost) were applied to predict and analyse the bending strength of Si3N4 ceramics. Because the classification model of XGBoost is easily interpretable, the factors affecting the bending strength could be quantitatively evaluated. The current model can provide a suitable order of adding sintering additives to obtain excellent bending strength in Si3N4 ceramics. Although this study focuses on the bending strength of Si3N4 ceramics, the new approach reported herein is applicable for the in silico design and analysis of other ceramic materials.

The status of oxygen impurity in β-Si3N4 lattice and its impact on β-Si3N4 phonon spectrum were studied using the first principle calculation based on density functional theory. The dependence of in silico thermal conductivity of β-Si3N4 upon lattice oxygen was quantitatively addressed. This study also confirms that rare-earth La doping has a pinning effect on oxygen, which underlies, in mechanism, for the increase of thermal conductivity of β-Si3N4 ceramic by restraining oxygen diffusion inside β-Si3N4 lattice. The theoretical prediction above is consistent in trend with the reported experimental results. In addition, in silico modulus values of β-Si3N4 ceramic were also revealed declined with increasing oxygen impurity.

Early diagnosis of diseases by contrast-enhanced magnetic resonance imaging (MRI) using iron oxide superparamagnetic nanoparticles (IOSNPs) has been extensively investigated due to the good biocompatibility of modified IOSNPs. However, the low magnetic sensitivity of IOSNPs still inflicts a certain limitation on their further application. In this study, we employed first-principles calculations based on spin-polarized density functional theory (SDFT) to find the optimal dysprosium-doped scheme for improving the magnetic sensitivity of IOSNPs. Elicited from the optimal doping scheme, we synthesized a sort of ultrasmall γ-iron oxide superparamagnetic nanoparticle by a special phase transfer-coprecipitation method. The appropriately Dy-doped γ-IOSNPs coated with short-chain polyethylene glycol are small in hydrodynamic size and highly dispersed with effectively improved superparamagnetism for enhancing T2-weighted MRI relaxivity, which is well consistent with the SDFT prediction. The measured spin-spin relaxivity r2 is 123.2 s-1 mM-1, nearly double that of the pure γ-IOSNPs (67.8 s-1 mM-1) and substantially surpassing that of both clinically-approved T2 contrast agents Feridex and Resivist. The low dysprosium doping does not induce notable nanotoxicity for IOSNPs, but contributes sufficiently to their high relaxation performance instead, which endows the Dy-doped γ-IOSNPs with high potential as a better T2-weighted MRI contrast medium. Both the method and the nanomagnets reported in this study are expected to promote studies on designing and preparing high-performance MRI contrast agents as well as computational materials.

We report the magneto-electric behavior of a dual-modality biomedical nanoprobe, a ternary nanosystem consisting of gold and gadolinia clusters and water molecules, with the effect of both nanoclusters on the structural and electronic properties of water. The hydrogen-oxygen bond lengths and angles as well as electronic charges of water molecules surrounding both nanoclusters were calculated using Hubbard U corrected density functional theory aided by molecular dynamics approach. The calculations reveal existence of a magneto-electric interaction between gold and gadolinium oxide nanoclusters, which influences the physical properties of surrounding water remarkably. A broader (narrower) distribution of H O bond lengths (H O H bond angles) was observed at the presence of either gold or gadolinia nanoclusters. The presence of Gd6O9 cluster leads to the larger charges of neighbour oxygen atoms. The distribution of oxygen atom charges becomes border when both Gd6O9 and A u 13 clusters coexist. Ab initio calculation provides a feasible approach to explore the most essential interactions among functional components of a multimodal nanoprobe applied in aqueous environment.

Uniform and well-crystallized tetragonal NaGd(MoO 4 ) 2 nanocrystals with the morphology of nanocubes were synthesized via a modified hydrothermal synthesis method with oleic acid as complexing agent. The as-synthesized NaGd(MoO 4 ) 2 nanocubes were characterized by means of powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy and selected area electron diffraction respectively. The side-length of the NaGd(MoO 4 ) 2 nanocubes is about 100–150 nm. The SAED pattern indicates highly crystalline nature of the NaGd(MoO 4 ) 2 nanocubes. The effect of Na 2 MoO 4 contents on the formation of NaGd(MoO 4 ) 2 nanocrystals is investigated. A possible growth mechanism of NaGd(MoO 4 ) 2 nanocubes is deduced based on time-dependent morphology evolution and XRD analysis. Down-shifting/upconversion photoluminescence properties of NaGd(MoO 4 ) 2 : Eu 3+ , Tb 3+ and Yb 3+ /Er 3+ nanocubes are investigated in detail. Furthermore, the energy transfer mechanism for upconversion luminescence in NaGd(MoO 4 ) 2 : Yb 3+ /Er 3+ nanocubes is investigated on the basis of energy level scheme and the excitation power dependence of upconversion luminescence intensities.

We report the hyperfine couplings and chemical shifts of water protons in a typical NMR-photonic dual-modality nanoprobe that consists of gadolinium oxide and gold nanoclusters surrounded by water molecules, which have been addressed through density functional theory (DFT). The DFT calculation of the ternary system provide a feasible approach not only to explore the intriguing interactions among functional components of a multimodal nanoprobe applied in aqueous environment, but also to interpret the underlying mechanism for enhancement of modality that is too complicated to be addressed by a phenomenological approach of the conventional NMR theory.

We propose a novel and efficient F− anion doping strategy for enhancing upconversion luminescence in upconversion nanophosphors. NaGd(MoO4)2:Yb3+/Er3+ nanophosphors doped with different F− contents are synthesized hydrothermally. Rietveld refinement results obtained from X-ray diffraction data indicate that the Gd–O bond length decreases and the O–Gd–O bond angle varies with increasing F− content, resulting in augmented local crystal field strength and distorted local site symmetry of the dopant lanthanide sites. Judd–Ofelt analysis suggests that the calculated radiative quantum efficiency of the 4S3/2 level and the radiative branching ratio of 4S3/2 → 4I15/2 transition in F−-doped NaGd(MoO4)2:Yb3+/Er3+ nanophosphors are much greater than those in F− anion-free samples. It is inferred that F− anion doping helps to reduce the nonradiative transition probabilities based on the luminescence dynamics. Rietveld refinement results and Judd–Ofelt analysis confirm jointly that doping of interstitial F− anions could enhance local crystal field strength with odd parity and modify site symmetry of the lanthanide activator ions, leading to enhanced radiative transitions and inhibited nonradiative transitions. A maximum of 17-fold enhancement of total emission intensity is found in NaGd(MoO4)2:Yb3+/Er3+/F− nanophosphors compared with F− anion-free counterparts. The proposed F− anion doping strategy provides an alternative approach for enhancing upconversion luminescence efficiency and could be extended to other inorganic upconversion nanomaterials.

The development of upconversion nanoparticles (UCNs) for theranostics application is a new strategy toward the accurate diagnosis and efficient treatment of cancer. Here, magnetic and fluorescent lanthanide-doped gadolinium oxide (Gd2O3) UCNs with bright upconversion luminescence (UCL) and high longitudinal relaxivity (r1) are used for simultaneous magnetic resonance imaging (MRI)/UCL dual-modal imaging and photodynamic therapy (PDT). In vitro and in vivo MRI studies show that these products can serve as good MRI contrast agents. The bright upconversion luminescence of the products allows their use as fluorescence nanoprobes for live cells imaging. We also utilized the luminescence-emission capability of the UCNs for the activation of a photosensitizer to achieve significant PDT results. To the best of our knowledge, this study is the first use of lanthanide-doped Gd2O3 UCNs in a theranostics application. This investigation provides a useful platform for the development of Gd2O3-based UCNs for clinical diagnosis, treatment, and imaging-guided therapy of cancer.

Uniform and well-crystallized NaGd(MoO4)2: Yb3+/Er3+ microcrystals with tetragonal plate morphology were synthesized by a facile hydrothermal method. The structure and phase purity of the samples were identified by powder XRD analysis. The steady-state and transient luminescence spectra were measured and analyzed. Under 980 nm excitation, intense green luminescence at 531 and 553 nm, and red luminescence at 657 and 670 nm were observed. The optimum doping concentrations for Yb3+ and Er3+ are determined to be 20% and 1% in NaGd(MoO4)2 tetragonal plate microcrystals. With increasing Yb3+ doping concentrations, the total integral emission intensities increase first and then decrease. The red/green intensity ratio of NaGd(MoO4)2: Yb3+/Er3+ microcrystals increases from 0.4 to 1.0 with the increase in Yb3+ concentrations. Based on the energy level diagram, the energy-transfer mechanisms are investigated in detail according to the double logarithmic plot of upconversion intensities versus pump powers. The energy-transfer mechanisms for green and red upconversion luminescence are ascribed to two-photon processes at lower Yb3+ concentrations, and involve high-Yb3+-induced one-photon processes at higher Yb3+ concentrations. For the red upconversion luminescence, energy back-transfer process, that is, 4S3/2 (Er3+) + 2F7/2 (Yb3+) → 4I13/2 (Er3+) + 2F5/2 (Yb3+), is dominant at higher Yb3+ concentrations. Theoretical model of the energy-transfer mechanisms based on rate equations is established, which agrees well with the experimental results.

Herein, hollow-structured Gd2O3:RE3+/Yb3+ (RE = Er, Ho, Tm) nanoparticles (NPs) were prepared via a urea-based chemical coprecipitation method followed by subsequent calcination and etching. Under 980 nm near-infrared (NIR) irradiation, upconversion (UC) emission gains the highest intensity of red, green and blue peaks for Gd2O3:Er3+/Yb3+, Gd2O3:Ho3+/Yb3+ and Gd2O3:Tm3+/Yb3+ NPs respectively. The corresponding fluorescence in-cell images exhibit bright visible light. The continuous color-tunable UC emission of each spectrum was investigated by increasing the concentration of the sensitizer Yb3+ ions from 0 to 20 mol% with the most intense red, green and blue emission achieved. The structure, morphology, components and magnetic property of Gd2O3:Ho3+/Yb3+ NPs were investigated intensively. The results show that the NPs possess a distinctly hollow structure and uniform spherical shape, and are well-crystallized and highly monodispersed with a mean diameter of 118 nm. Due to the designed hollow structure which is of benefit to water contact of a large number of Gd3+ on the surface, the measured T1 relaxivity of the NPs is nearly 5 times larger than the relaxivity of the commercial gadolinium diethylenetriaminepentaacetate (Gd-DTPA). The relaxation enhancement in the hollow-structured Gd2O3:RE3+/Yb3+ (RE = Er, Ho, Tm) NPs is addressed in the framework of Solomon–Bloembergen–Morgan theory. The biocompatibility studies in 293 and HeLa cells indicate that the hollow NPs have no observable cytotoxicity at a concentration up to 200 μg ml−1. All these results demonstrate that the hollow-structured nanocomposite has the potential to be developed into a safe and highly efficient magnetic resonance and fluorescence nanoprobe for in-cell molecular imaging of cancer.

The longitudinal surface plasmon resonance of light-irradiated gold nanorods (Au NRs) is generated to enhance the local electric fields of Au NR-based nano-dumbbells (NDs), tailored specifically by coating mesoporous silica at two poles of Au NRs and embedding photosensitizer indocyanine green (ICG) into the mesopores. The assembled NDs possess a superior uniformity and water dispersity with a strong plasmonic absorption around 800 nm. Time-domain finite-difference calculations indicate that the enhanced local electric field of NDs is predominantly distributed in the dumbbells at two poles of Au NRs, which improves the photonic performance of ICG significantly. Illuminated by an 800 nm laser, the fabricated NDs demonstrate an enhanced combination of photothermal and photodynamic effects in comparison to either Au NRs or ICG alone. Synergistic damaging of photothermal and photodynamic combination to nasopharyngeal carcinoma cells has been corroborated experimentally, thus causing substantial cell death under a lower incident near-infrared laser power. This study concludes that the plasmonic NDs combined synergistically with efficient photothermal and photodynamic effects are highly promising in cancer therapy.

Gadolinium oxide-based core-shelled nanoparticles have recently emerged as novel magnetic resonance imaging contrast agents for high relaxivity and tumor targeting. However, their relaxivity enhancement mechanism has not yet been clearly understood. We prepared highly dispersible and uniform core-shell structured nanoparticles by encapsulating silica spheres (90 nm in diameter) with gadolinium oxide shells of different thicknesses (from 1.5 nm to 20 nm), and proved experimentally that the shell thickness has an inverse effect on relaxivity. The core-shelled nanoparticles are of a larger relaxivity than the commercial contrast agent Gd-DTPA, with an enhancement from 1.8 to 7.3 times. Based on the Solomon-Bloembergen-Morgan theory which is usually adopted for interpreting the relaxation changes of water protons in Gd3+ chelates, we introduced a shielding ansatz of nanoshells and derived a concise formula specifically to correlate the relaxivity of this sort of core-shelled nanoparticles with the shell thickness directly. The formula calculation is well consistent with the experimental results, and the formula can be generally applied to evaluate the relaxation enhancement underlying the high relaxivity of any core-shelled nanoparticle. Furthermore, the core-shelled nanoparticles possess a negligible nanotoxicity according to the in vitro cytotoxicity and in vivo histopathology and hematology assays. The enhanced signals of in vivo tumor-targeted magnetic resonance imaging indicate that the ultrathin gadolinium oxide nanoshells may function as a potential candidate for advanced positive contrast agents in further clinical applications.

Multifunctional nanoprobes, due to their unique nanocomposite structures, have prominent advantages that combine multimodal imaging of a tumor with photothermal therapy. However, they remain a challenge for constructing nanostructures via conventional approaches due to the peculiar environmental sensitivity of each component. Here, we report the design and synthesis of Gd-based nanoparticle-tailored gold nanorods with distinctive core–shell and dumbbell nanoarchitectures (NAs) by a specific synthesis technology. The prepared NAs possess a tunable particle size of 80–120 nm in length and 50–90 nm in diameter, which are suitable for cellular uptake and passive targeting of a tumor. The formation of two distinct heterostructures and their underlying mechanism were studied through systematic investigations on the controllable synthesis process. The as-prepared nanoprobes possess an ultrahigh longitudinal relaxivity (r1) of 22.69 s−1 mM−1 and thus a significant magnetic resonance imaging signal enhancement has been observed in mice tumors. The NAs, especially the dumbbell type, show a vivid two-photon cell imaging and a remarkable photothermal conversion efficiency owing to their superior longitudinal surface plasmon resonance. Both in vitro cytotoxicity and in vivo immunotoxicity assays give substantial evidence of excellent biocompatibility attained in the NAs. The development of multifunctional targeting nanoprobes in this study could provide guidance for tailored design and controllable synthesis of heterostructured nanocomposites utilized for multimodal imaging and photothermal therapy of cancer.

We report a class of multi-functional core–shell nanoarchitectures, consisting of silica nanospheres as the core and Gd2O3:Dy3+ nanocrystals as the ultra-thin shell, that enable unique multi-color living cell imaging and remarkable in vivo magnetic resonance imaging. These types of targeted cell imaging nanoarchitectures can be used as a variety of fluorescence nanoprobes due to the multi-color emissions of the Gd2O3:Dy3+ nanophosphor. We also proposed a strategy of modulating core–shell structure design to achieve an enhanced magnetic resonance contrast ability of Gd2O3 nanoagents, and the classical Solomon–Bloembergen–Morgan theory was applied to explicate the mechanism underlying the enhancement. The as-synthesized ligand-free nanomaterial possesses a suitable particle size for cellular uptake as well as avoiding penetrating the blood–brain barrier with good water-solubility, stability, dispersibility and uniformity. The extremely low cytotoxicity and favorable biocompatibility obtained from in vitro and in vivo bioassays of the as-designed nanoparticles indicate their excellent potential as a candidate for functioning as a targeted nanoprobe.

We report the impact of a PEGylated GNR on the structure of latent membrane protein 1 (LMP1) binding to tumor necrosis factor receptor (TNFR)-associated factor 3 (TRAF3) using molecular dynamics simulation. Focusing on the anisotropy of a GNR validated by experiment and finite-difference time-domain (FDTD) calculation, this study addressed three typical scenarios of LMP1-TRAF3 with a PEGylated GNR. The structure of LMP1-TRAF3 backbone, specifically the individual LMP1, changes with a PEGylated GNR included, and the variation is more significant along longitudinal axis than its transversal counterpart. Moreover, a heating-up GNR gains a more salient variation of LMP1 structure.

Nanoprobes for combined optical and magnetic resonance imaging have tremendous potential in early cancer diagnosis. Gold nanoparticles (AuNPs) co-doped with Gd2O3 mesoporous silica nanocomposite (Au/Gd@MCM-41) can produce pronounced contrast enhancement for T1 weighted image in magnetic resonance imaging (MRI). Here, we show the remarkably high sensitivity of Au/Gd@MCM-41 to the human poorly differentiated nasopharyngeal carcinoma (NPC) cell line (CNE-2) using fluorescence lifetime imaging (FLIM). The upconversion luminescences from CNE-2 and the normal nasopharyngeal (NP) cells (NP69) after uptake of Au/Gd@MCM-41 show the characteristic of two-photon-induced-radiative recombination of the AuNPs. The presence of the Gd3+ ion induces a much shorter luminescence lifetime in CNE-2 cells. The interaction between AuNPs and Gd3+ ion clearly enhances the optical sensitivity of Au/Gd@MCM-41 to CNE-2. Furthermore, the difference in the autofluorescence between CNE-2 and NP69 cells can be efficiently demonstrated by the emission lifetimes of Au/Gd@MCM-41 through the Forster energy transfers from the endogenous fluorophores to AuNPs. The results suggest that Au/Gd@MCM-41 may impart high optical resolution for the FLIM imaging that differentiates normal and high-grade precancers.

Pure tetragonal phase, uniform and well-crystallized sodium gadolinium molybdate (NaGd(MoO4)2) nanocrystals with diverse morphologies, e.g. nanocylinders, nanocubes and square nanoplates have been selectively synthesized via oleic acid-mediated hydrothermal method. The phase, structure, morphology and composition of the as-synthesized products are studied. Contents of both sodium molybdate and oleic acid of the precursor solutions are found to affect the morphologies of the products significantly and oleic acid plays a key role in the morphology-controlled synthesis of NaGd(MoO4)2 nanocrystals with diverse morphologies. Growth mechanism of NaGd(MoO4)2 nanocrystals is proposed based on time-dependent morphology evolution and X-ray diffraction analysis. Morphology-dependent down-shifting photoluminescence properties of NaGd(MoO4)2: Eu3+ nanocrystals and upconversion photoluminescence properties of NaGd(MoO4)2: Yb3+/Er3+ and Yb3+/Tm3+ nanoplates are investigated in detail. Charge transfer band in the down-shifting excitation spectra shows a slight blue-shift and the luminescence intensities and lifetimes of Eu3+ are decreased gradually with the morphology of the nanocrystals varying from nanocubes to thin square nanoplates. Upconversion energy transfer mechanisms of NaGd(MoO4)2: Yb3+/Er3+, Yb3+/Tm3+ nanoplates are proposed based on the energy level scheme and power dependence of upconversion emissions. Thermometric properties of NaGd(MoO4)2: Yb3+/Er3+ nanoplates are investigated and the maximum sensitivity is determined to be 0.01333 K−1 at 285 K.