Hydrothermal synthesis, characterization and Raman studies of Eu activated Gd2O3 nanorods

Eu³⁺ (8 mol%) activated gadolinium oxide nanorods have been prepared by hydrothermal method without and with surfactant, cityl trimethyl ammonium bromide (CTAB). Powder X-ray diffraction (PXRD) studies reveal that the as-formed product is in hexagonal Gd(OH)₃:Eu phase and subsequent heat treatment at 350 and 600 °C transforms the sample to monoclinic GdOOH:Eu and cubic Gd₂O₃:Eu phases, respectively. The structural data and refinement parameters for cubic Gd₂O₃:Eu nanorods were calculated by the Rietveld refinement. SEM and TEM micrographs show that as-obtained Gd(OH)₃:Eu consists of uniform nanorods in high yield with uniform diameters of about 15 nm and lengths of about 50-150 nm. The temperature dependent morphological evolution of Gd₂O₃:Eu without and with CTAB surfactant was studied. FTIR studies reveal that CTAB surfactant plays an important role in converting cubic Gd₂O₃:Eu to hexagonal Gd(OH)₃:Eu. The strong and intense Raman peak at 489 cm⁻¹ has been assigned to A_g mode, which is attributed to the hexagonal phase of Gd₂O₃. The peak at ∼360 cm⁻¹ has been assigned to the combination of F_g and E_g modes, which is mainly attributed to the cubic Gd₂O₃ phase. The shift in frequency and broadening of the Raman modes have been attributed to the decrease in crystallite dimension to the nanometer scale as a result of phonon confinement.     

Effects of charge storage dielectric thickness on hybrid gadolinium oxide nanocrystal and charge trapping nonvolatile memory

The characteristics of hybrid gadolinium oxide nanocrystal (Gd₂O₃-NC) and gadolinium oxide charge trapping (Gd₂O₃-CT) memories were investigated with different Gd₂O₃ film thickness. By performing the rapid thermal annealing on Gd₂O₃ films with different thickness, the Gd₂O₃-NCs with the diameter of 6–9 nm for charge storage, surrounded by the amorphous Gd₂O₃ (α-Gd₂O₃) layer, were formed. The α-Gd₂O₃ layer was considered to be the charge trapping layer, resulting in the large memory window of Gd₂O₃-NC/CT memories with thick Gd₂O₃ film. The charge trapping energy level of the Gd₂O₃-NCs and α-Gd₂O₃ layer was extracted to be 0.16 and 0.45 eV respectively by using the temperature-dependent retention measurement. Further, after a 10⁶ program/erase cycling operation, the memory with thin Gd₂O₃ film can be predicted to sustain a 94% memory window of the first cycling one while the memory with thick Gd₂O₃ film suffered from a 30% charge loss because of the traps within the α-Gd₂O₃ layer. The Gd₂O₃ film thickness of 10 nm was optimized to exhibit superior performances of the Gd₂O₃-NC/CT memory, which can be applied into the nonvolatile memory.     

Synthesis and characterization of gadolinium nanostructured materials with potential applications in magnetic resonance imaging,neutron-capture therapy and targeted drug delivery

Two Gadolinium nanostructured materials, Gd₂(OH)₅NO₃ nanoparticles and Gd(OH)₃ nanorods, were synthesized and extensively characterized by various techniques. In addition to the potential use of Gd₂(OH)₅NO₃ in magnetic resonance imaging (MRI) and Neutron-capture therapy (NCT) application, it could also be used in targeted drug delivery. An antibiotic (nalidixic acid), two amino acids (aspartic and glutamic acid), a fatty acid and a surfactant (SDS) were intercalated in the nanoparticles. The surface of the nanoparticles was modified with folic acid in order to be capable of targeted delivery to folate receptor expressing sites, such as tumor human cells.     

第一性原理模拟U在Gd2Zr2O7烧绿石中的固溶

采用第一性原理密度泛函理论模拟U在Gd₂Zr₂O₇烧绿石中的固溶,在低浓度U掺杂时,Gd₂Zr₂O₇烧绿石保持烧绿石结构;随着U掺杂浓度增加,Gd₂(Zr_{2-y}U_y)O₇和(Gd_{2-y}U_y)Zr₂O₇体系的晶格常数发生线性变化．计算结果表明,由于总能较低,U原子更偏向于替代无序换位后Gd₂Zr₂O₇晶格中B位的Gd原子．     

Reduced magnetic moment of gadolinium in the oxyde and the sulphate

It is found that in Gd₂O₃, Gd_0.5Y_1.5O₃ and Gd₂(SO)₃ · 8H₂O both the effective paramagnetic moment and the saturation moment of the gadolinium ion are reduced 1.5–2% with respect to 7.95 μ_B and 7.01μ_B, respectively.     

Sol-hydrothermally derived gadolinium oxide (Gd2O3) nanorods and tamarind-like shape evolution under 80 MeV C6+ ion impact

The present work highlights swift heavy ion irradiation-induced shape evolution of gadolinium oxide (Gd₂O₃) nanorods synthesized via a sol-hydrothermal route. Upon dispersing Gd₂O₃ nanorods in the polyvinyl alcohol matrix, thin solid films were cast on borosilicate glass substrates. The films were then exposed to 80?MeV carbon-ion irradiation, while fluence was varied in the range of 1×10¹¹–3×10¹²?ions/cm². The post analyses were carried out by using X-ray diffraction, high resolution transmission electron microscopy (TEM) and Raman spectroscopy studies. An apparently observable shortening of length (L) and diameter (D) of the nanorods can be revealed through the TEM imaging analyses. Moreover, while exhibiting an aspect ratio (L/D) between 3.3 and 4.7, the nanorods were found to exist in the form of bunching at higher fluences. The irradiation-induced tamarind-like shape evolution at higher fluences was attributed to the overlapping of ion impacts on certain regions of the nanorods. The most intense Raman active peak of the pristine sample located at ～360?cm^?1 was seen to experience blue-shifting (～375?cm^?1) when irradiated at the highest fluence (～3×10¹²?ions/cm²). An altered shape evolution of a thermally and mechanically stable oxide system by the energetic ion impact would bring in new insights as regards construction of surface patterns and their potential use in miniaturized devices.     

Nonlinear optical microscopy for drug delivery monitoring and cancer tissue imaging

A multimodal nonlinear optical microscope that combines coherent anti‐Stokes Raman scattering (CARS), two‐photon excitation fluorescence (TPEF), second‐harmonic generation (SHG) and sum‐frequency generation (SFG) was developed and applied to image breast cancer tissue and MCF‐7 cells as well as monitoring anticancer drug delivery in live cells. TPEF imaging showed that drugs are preferentially localized in the cytoplasm and the nuclear envelope in resistant cells. Moreover, the extracellular matrix was observed by TPEF signals arising from elastin's autofluorescence and SHG signals from collagen fibrils in breast tissue sections. Additionally, CARS signals arising from proteins and (PO₂)⁻ allowed identification of tumors. Label‐free imaging with chemical contrast of significant components of cancer cells and tissue suggests the potential of multimodal nonlinear optical microscopy for early detection and diagnosis of cancer. Copyright © 2010 John Wiley & Sons, Ltd.     

具有介孔结构的MnSiO3@Fe3O4@C纳米粒子的制备以及作为pH响应的T1-T2*双模MRI造影剂的研究应用

本文通过一个简单的、温和的方案制备了平均尺寸为120 nm,介孔结构的纳米粒子MnSiO₃@Fe₃O₄@C. 粒子的细胞毒性微小,可以用作T₁-T₂^*双模MRI造影剂. 酸性条件下MnSiO₃@Fe₃O₄@C释放出大量的Mn²⁺缩短T₁弛豫时间,提高成像分辨率. 超顺磁性的Fe₃O₄可以增强T₂对比成像,检测病变组织. 类似于肿瘤微环境/细胞器的酸性PBS(pH=5.0)中Mn²⁺的释放率达到31.66%,约为中性条件(pH=7.4)下的7倍. 释放的Mn²⁺通过内吞作用被细胞摄取,经肾脏排出,细胞毒性实验表明,MnSiO₃@Fe₃O₄@C具有低的细胞毒性,即使高浓度的200 ppm MnSiO₃@Fe₃O₄@C对HeLa细胞的毒性也相对较小. 对荷瘤小鼠静脉注射定量MnSiO₃@Fe₃O₄@C后,可以观察到一个快速增强的对比成像,给药24 h后,T₁MRI信号显著增强,达到132%,而T₂信号则明显降低至53.8%,活体MR成像证明了MnSiO₃@Fe₃O₄@C可以同时作为阳性和阴性造影剂. 此外,得益于介孔MnSiO₃优秀的酸敏感性,MnSiO₃@Fe₃O₄@C可以作为一种潜在的药物载体,实现肿瘤的诊疗一体化.     

Thermo and photoluminescence properties of Eu activated hexagonal, monoclinic and cubic gadolinium oxide nanorods

Different phases of Eu³⁺ activated gadolinium oxide (Gd (OH)₃, GdOOH and Gd₂O₃) nanorods have been prepared by the hydrothermal method with and without cityl trimethyl ammonium bromide (CTAB) surfactant. Cubic Gd₂O₃:Eu (8 mol%) red phosphor has been prepared by the dehydration of corresponding hydroxide Gd(OH)₃:Eu after calcinations at 350 and 600 °C for 3 h, respectively. When Eu³⁺ ions were introduced into Gd(OH)₃, lattice sites which replace the original Gd³⁺ ions, a strong red emission centered at 613 nm has been observed upon UV illumination, due to the intrinsic Eu³⁺ transition between ⁵D₀ and ⁷F configurations. Thermoluminescence glow curves of Gd (OH)₃: Eu and Gd₂O₃:Eu phosphors have been recorded by irradiating with gamma source (⁶⁰CO) in the dose range 10-60 Gy at a heating rate of 6.7 °C sec⁻¹. Well resolved glow peaks in the range 42-45, 67-76, 95-103 and 102-125 °C were observed. When γ-irradiation dose increased to 40 Gy, the glow peaks were reduced and with increase in γ-dose (50 and 60 Gy) results the shift in first two glow peak temperatures at about 20 °C and a new shouldered peak at 86 °C was observed. It is observed that there is a shift in glow peak temperatures and variation in intensity, which is mainly attributed to different phases of gadolinium oxide. The trapping parameters namely activation energy (E), order of kinetics (b) and frequency factor were calculated using peak shape and the results are discussed.     

Preparation and characterization of Gd2O3:Eu rods by surfactant assemblies—microwave heating

Gd₂O₃:Eu³⁺ rods were successfully obtained by microwave heating the as-prepared substance, which templated by surfactant assemblies of gadolinium hydroxide and europium hydroxide, formed in a reaction between Gd(NO₃)₃-Eu(NO₃)₃ and urea. Transmission electron microscopy (TEM) characterizations indicated that the synthesized rods with an averaging diameter of 100-150 nm and agglomerates slightly. Powder X-ray diffraction (XRD) results indicated that the resultant rods were cubic Gd₂O₃. The luminescent of Gd₂O₃:Eu³⁺ rods were investigated by photoluminescence (PL). Upon excitation with 257 and 277 nm, respectively, Gd₂O₃:Eu³⁺ rods show a strong red emission line at around 611 nm. Furthermore, this novel method required a very short heating time, thus reducing the energy consumption.     

Core–Shell Bi2Se3@mSiO2‐PEG as a Multifunctional Drug‐Delivery Nanoplatform for Synergistic Thermo‐Chemotherapy with Infrared Thermal Imaging of Cancer Cells

Thermo‐chemotherapy combining photothermal therapy (PTT) with chemotherapy has become a potent approach for antitumor treatment. In this study, a multifunctional drug‐delivery nanoplatform based on polyethylene glycol (PEG)‐modified mesoporous silica‐coated bismuth selenide nanoparticles (referred to as Bi₂Se₃@mSiO₂‐PEG NPs) is developed for synergistic PTT and chemotherapy with infrared thermal (IRT) imaging of cancer cells. The product shows no/low cytotoxicity, strong near‐infrared (NIR) optical absorption, high photothermal conversion capacity, and stability. Utilizing the prominent photothermal effect, high‐contrast IRT imaging and efficient photothermal killing effect on cancer cells are achieved upon NIR laser irradiation. Moreover, the successful mesoporous silica coating of the Bi₂Se₃@mSiO₂‐PEG NPs cannot only largely improve the stability but also endow the NPs high drug loading capacity. As a proof‐of‐concept model, doxorubicin (DOX) is successfully loaded into the NPs with rather high loading capacity (≈50.0%) via the nanoprecipitation method. It is found that the DOX‐loaded NPs exhibit a bimodal on‐demand pH‐ and NIR‐responsive drug release property, and can realize effective intracellular drug delivery for chemotherapy. The synergistic thermo‐chemotherapy results in a significantly higher antitumor efficacy than either PTT or chemotherapy alone. The work reveals the great potential of such core–shell NPs as a multifunctional drug‐delivery nanosystem for thermo‐chemotherapy.     

Eu<Superscript>3+</Superscript> As a Luminescent Probe for Studying the Structure of R<Subscript>2</Subscript>O<Subscript>3</Subscript> Materials (R = Y,Eu, and Gd)

Spectra of Eu³⁺ in various dielectric matrices (Gd₂O₃:Eu³⁺, Y₂O₃:Eu³⁺, Eu₂O₃, and mSiO₂/Gd₂O₃:Eu³⁺ mesoporous particles) are studied by local cathodoluminescence. The results allowed identification of the local environment of Er³⁺ ions in amorphous samples and detection of the monoclinic Eu₂O₃ phase impurity in samples with yttrium oxide. The cathodoluminescence spectra of chemically pure Y₂O₃, Eu₂O₃, and Gd₂O₃ are recorded. Conclusions about the structural features of the materials are made and confirmed by other methods (XRD and EPMA).     

Synthesis of rare earth hydroxide nanorods by room temperature reaction of oxide precursors with water

In this study, solid state chemical reaction of anhydrous chloride precursors with Na₂CO₃ has been used to manufacture composite powders of nanocrystalline rare earth oxide grains embedded within a matrix of NaCl. Subsequent washing of these powders with deionised water resulted in removal of the NaCl matrix and hydration of the oxide nanoparticles. In the case of Nd₂O₃ and Sm₂O₃, the hydration process yielded hydroxide nanorods. In contrast, washing of the Gd₂O₃ yielded a powder consisting of irregularly shaped nanoparticles of Gd₂O₃ and GdOOH. Analysis using high resolution transmission electron microscopy revealed that the Nd₂O₃ and Sm₂O₃ nanorods were not single crystals but were composed of crystalline subunits with a common á 0001 ñ \left\langle {0001} \right\rangle growth direction. The results obtained in this study demonstrate that rare earth hydroxide nanorods can be synthesised from oxide precursors without the need for hydrothermal processing at elevated temperature and pressure.     

Gadolinium oxide high-k gate dielectrics prepared by anodic oxidation

The growth and properties of gadolinium oxide (Gd₂O₃) films prepared by anodic oxidation were investigated. Uniform Gd₂O₃ thin film with good oxide quality was obtained. The X-ray diffraction (XRD) pattern of the Gd₂O₃ films showed that they had a poly-crystalline structure. The dielectric constants of Gd₂O₃ films oxidized at 30 and 60 V are 9.4 and 12.2, respectively. The equivalent oxide thickness (EOT) of the Gd₂O₃ stacked oxide is in the range of 5.8-9.4 nm. The MOS capacitor with Gd₂O₃ exhibits interesting electrical properties. Longer oxidation time reduced the leakage current density for 30 V anodic oxidation but increased the leakage current density for 60 V anodic oxidation. This work reveals that Gd₂O₃ could also be an alternative dielectric for Si substrate and therefore, might pave the way to fabricate CMOS devices in the future.     

Responsible nanotechnology development

Chelated gadolinium ions, e.g., Gd-DTPA, are today used clinically as contrast agents for magnetic resonance imaging (MRI). An attractive alternative contrast agent is composed of gadolinium oxide nanoparticles as they have shown to provide enhanced contrast and, in principle, more straightforward molecular capping possibilities. In this study, we report a new, simple, and polyol-free way of synthesizing 4?C5-nm-sized Gd₂O₃ nanoparticles at room temperature, with high stability and water solubility. The nanoparticles induce high-proton relaxivity compared to Gd-DTPA showing r ₁ and r ₂ values almost as high as those for free Gd³⁺ ions in water. The Gd₂O₃ nanoparticles are capped with acetate and carbonate groups, as shown with infrared spectroscopy, near-edge X-ray absorption spectroscopy, X-ray photoelectron spectroscopy and combined thermogravimetric and mass spectroscopy analysis. Interpretation of infrared spectroscopy data is corroborated by extensive quantum chemical calculations. This nanomaterial is easily prepared and has promising properties to function as a core in a future contrast agent for MRI.     

Application of the model-free approach to the study of non-isothermal decomposition of un-irradiated and γ-irradiated hydrated gadolinium acetylacetonate

The non-isothermal decomposition of unirradiated and γ-irradiated hydrated gadolinium acetylacetone with 10² kGy γ-ray absorbed dose was carried out in air and in nitrogen atmospheres and in the temperature range of 25–1000°C. The results indicate that gadolinium acetylacetonate decomposes through four main decomposition steps leading to the formation of intermediate products whose chemical structure is independent of the gas atmosphere applied and on the investigated absorbed dose. The final product at 820°C was found to be Gd₂O₃ irrespective of the gas atmosphere and the irradiation conditions. The non-isothermal data were analyzed using linear Flynn–Wall–Ozawa and non-linear Vyazovkin (VYZ) iso-conversional methods. The results of the application of these free models on the present kinetic data showed that the activation energy, E_a is independent of α in a very wide conversion range (0.1–0.9) indicating that the decomposition process is controlled by a unique kinetic model. The results of the model-fitting analysis showed that the decomposition course of the four decomposition steps of hydrated gadolinium acetylacetone was controlled by the D₃ Jander diffusion model. Pure phase of Gd₂O₃ nanoparticles was obtained by thermal oxidation of γ-irradiated GdAcAc.3 H₂O at 800°C for 6 h. X-ray diffraction, transmission electron microscopy (TEM) and atomic force microscopy (AFM) techniques were employed for characterization of the as-synthesized nanoparticles. This is the first attempt to prepare Gd₂O₃ nanoparticles by solid-state thermal decomposition of γ-irradiated hydrated gadolinium acetylacetone.     

Biosynthesis and magnetic properties of mesoporous Fe3O4 composites

Magnetic Fe₃O₄ materials with mesoporous structure are synthesized by co-precipitation method using yeast cells as a template. The X-ray diffraction (XRD) pattern indicates that the as-synthesized mesoporous hybrid Fe₃O₄ is well crystallized. The Barrett-Joyner-Halenda (BJH) models reveal the existence of mesostructure in the dried sample which has a specific surface area of 96.31 m²/g and a pore size distribution of 8-14 nm. Transmission electron microscopy (TEM) measurements confirm the wormhole-like structure of the resulting samples. The composition and chemical bonds of the Fe₃O₄/cells composites are studied by Fourier transform infrared (FT-IR) spectroscopy. Preliminary magnetic properties of the mesoporous hybrid Fe₃O₄ are characterized by a vibrating sample magnetometer (VSM). The magnetic Fe₃O₄/cells composites with mesoporous structure have potential applications in biomedical areas, such as drug delivery.     

Processes of the excitation energy migration and transfer in Ce-doped alkali gadolinium phosphates studied with time-resolved photoluminescence spectroscopy technique

Spectral-kinetic characteristics of Gd³⁺ and Ce³⁺ luminescence from a series of Ce³⁺-doped alkali gadolinium phosphates of MGdP₄O₁₂ type (M=Li, Na, Cs) have been studied within 4.2-300 K temperature range using time-resolved luminescence spectroscopy techniques. The processes of energy migration along the Gd³⁺ sub-lattice and energy transfer between the Gd³⁺ and Ce³⁺ ions have been investigated. Peculiarities of these processes have been compared for MGdP₄O₁₂ phosphate hosts with different alkali metal ions. A contribution of different levels from the ⁶P_j multiplet of the lowest Gd³⁺ excited state into the energy migration and transfer processes has been clarified. The phonon-assisted occupation of high-energy ⁶P_{5/2, 3/2} levels by Gd³⁺ in the excited ⁶P_j state has been revealed as a shift of Gd³⁺⁶P_j→⁸S_7/2 emission into the short-wavelength spectral range upon the temperature increase. The relaxation of excited Gd³⁺ via phonon-assisted population of Gd³⁺⁶P_5/2 level (next higher one to the lowest excited ⁶P_7/2) is supposed to be responsible for the rise in probability of energy migration within the Gd³⁺ sub-lattice initiating the Gd³⁺→Ce³⁺ energy transfer at T<150 K, whereas further intensification of Gd³⁺→Ce³⁺ energy transfer at T>150 K is explained by the increase in probability of Gd³⁺ relaxation into the highest ⁶P_3/2 level of the ⁶P_j multiplet. An efficient reversed Ce³⁺→Gd³⁺ energy transfer has been revealed for the studied phosphates at 4.2 K.     

Custom NIR Imaging of New Up-Conversion Multimodal Gadolinium Oxysulfide Nanoparticles

Up-conversion (UC) nanoparticles (NPs) appear as promising probes for easy, cost-effective, and efficient in vivo imaging. In this paper, a new kind of UCNPs is proposed: Gd₂O₂S:Yb³⁺/Tm³⁺ for multimodal bioimaging, exhibiting a strong fluorescent emission in the near-infrared range (802 nm) when excited at 980 nm. The in vivo fluorescence detection of such NPs is made possible by the development of a dedicated custom-made imaging system. However, the high sensitivity of the techniques is counterbalanced with a limited resolution which highlights the necessity of combining different approaches to gather as much vital information as possible. The presence of a large amount of gadolinium also confers interesting contrasting properties both in magnetic resonance imaging (MRI) and computed tomography (CT) that could be advantageously exploited in the context of multimodal in vivo imaging. In this study, the UC emission properties and energy transfer processes of this new nanoprobe are reported. The detectability of the UCNPs is exhibited using the custom-made imaging system in different tissues (skin, muscle, kidney, liver, brain), depths (different anatomical localization), and species (rat and mouse), punctually and chronically. Last, promising multimodal bioimaging results are presented in UC, MRI, and CT, showing a relatively low detection threshold.     

Anomalous conductivity and microstructure in gadolinium doped ceria prepared from nano-sized powder

The temperature and the oxygen partial pressure dependences of the electron and hole conductivities were measured by the dc polarization method using a Hebb–Wagner's ion blocking cell for Gd_0.2Ce_0.8O_1.9 polycrystalline bodies with grain size of 0.5 μm prepared by sintering of nano-sized powder. A significant enrichment of gadolinium was observed in the vicinity of the grain boundary by TEM/EDS analyses. The electron conductivity were comparable with those of conventional Gd_0.2Ce_0.8O_1.9 polycrystalline body with grain size of 2 μm, and it followed p(O₂)^− 1/4 dependence at temperatures T = 973–1273 K. However, the observed hole conductivity was higher than that of conventional Gd_0.2Ce_0.8O_1.9, and it did not follow p(O₂)^1/4 dependence. This anomalous p(O₂) dependence disappeared after the sample was treated at T = 1773 K for 38 h and grain size was enlarged to 2–10 μm.