Myxofibrosarcoma: Outcomes, Prognostic Factors, and Role of Neoadjuvant Radiation Therapy.

Purpose: Myxofibrosarcoma (MFS) is a subtype of soft tissue sarcoma with a highly infiltrative growth pattern that leads to a higher risk of inadvertent positive surgical margins and local relapse. Poorly defined tumor margins also pose a challenge for radiation therapy (RT) planning, in terms of treatment volumes and administration of pre- versus postoperative RT. This study aims to evaluate local control and patterns of recurrence in patients with MFS treated with neoadjuvant RT followed by definitive surgical excision. Methods and Materials: Multiple institutional databases were retrospectively searched for patients diagnosed with MFS between 2013 and 2021 who were exclusively treated with preoperative RT followed by definitive surgery at our institution. The endpoints of the study were defined as local tumor recurrence, distant metastasis, and death after the date of definitive surgery. Results: Forty-nine patients met the inclusion criteria and were included in the final study. The median age at diagnosis was 67 years, and 71% of patients were male. The tumor was superficially located in 63% of patients, and the mean tumor size at presentation was 7.8 cm. All patients received neoadjuvant RT and completed their planned course of treatment. Neoadjuvant chemotherapy was administered in 22% of patients. Inadvertent excision (IE) before definitive treatment was performed in 25 patients (51%), 84% of which had superficially located tumors. All margins were assessed using frozen section analysis at the time of definitive surgery, and 100% of patients had negative surgical margins, with 25% having no residual tumor. With a median follow-up of 4.7 years, the 5-year local control rate was 87%, and 5-year overall survival was 98%. Tumor depth was associated with distant metastasis (P < .01). Conclusions: Despite the infiltrative nature of MFS, preoperative RT followed by definitive surgical excision, especially in the setting of a reliable frozen section margin analysis, was associated with excellent local control.

Samarium-Activated La2Hf2O7 Nanoparticles as Multifunctional Phosphors.

Recent developments in the field of designing novel nanostructures with various functionalities have pushed the scientific world to design and develop high-quality nanomaterials with multifunctional applications. Here, we propose a new kind of doped metal oxide pyrochlore nanostructure for solid-state phosphor, X-ray scintillator, and optical thermometry. The developed samarium-activated La2Hf2O7 (LHOS) nanoparticles (NPs) emit a narrow and stable red emission with lower color temperature and adequate critical distance under near-UV and X-ray excitations. When the LHOS NPs are exposed to an energetic X-ray beam, the Sm3+ ions situated at the symmetric environment get excited along with those located at the asymmetric environment, which results in a low asymmetry ratio of Sm3+ under radioluminescence compared to photoluminescence. High activation energy and adequate thermal sensitivity of the LHOS NPs highlight their potential as a thermal sensor. Our results indicate that these Sm3+-activated La2Hf2O7 NPs can serve as a multifunctional UV, X-ray, and thermographic phosphor.

Thermally Induced Disorder-Order Phase Transition of Gd2Hf2O7:Eu3+ Nanoparticles and Its Implication on Photo- and Radioluminescence.

Crystal structure has a strong influence on the luminescence properties of lanthanide-doped materials. In this work, we have investigated the thermally induced structural transition in Gd2Hf2O7 (GHO) using Eu3+ ions as the spectroscopic probe. It was found that complete phase transition from the disordered fluorite phase (DFP) to the ordered pyrochlore phase (OPP) can be achieved in GHO with the increase of annealing temperature from 650 → 1100 → 1300 °C. OPP is the more stable structural form for the GHOE nanoparticles (NPs) annealed at a higher temperature based on the energy calculation by density functional theory (DFT). The asymmetry ratio of the GHOE-650 NPs was the highest, whereas the quantum yield, luminescence intensity, and lifetime values of the GHOE-1300 NPs were the highest. Emission intensity of Eu3+ ions increases significantly with the phase transition from the DFP to OPP phase and is attributed to the higher radiative transition rate (281 s-1) of the 5D0 level of the Eu3+ ion in the environment with relatively lower symmetry (C 2v ) because of the increase of crystal size. As the structure changes from DFP to OPP, radioluminescence showed tunable color change from red to orange. The Eu3+ local structure obtained from DFT calculation confirmed the absence of inversion symmetry in the DFP structure, which is consistent with the experimental emission spectra and Stark components. We also elucidated the host to dopant optical energy transfer through density of states calculations. Overall, our current studies present important observations for the GHOE NPs: (i) thermally induced order-disorder phase transition, (ii) change of point group symmetry around Eu3+ ions in the two phases, (iii) high thermal stability, and (iv) tunability of radioluminescent color. This work provides fundamental understanding of the relationship between the crystal structure and photophysical properties of lanthanide-doped materials and helps design a strategy for advanced optoelectronic materials.

Molten-Salt Synthesis of Complex Metal Oxide Nanoparticles.

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. Here, we introduce the molten-salt synthesis (MSS) method for making metal oxide nanomaterials. Advantages over other methods include its simplicity, greenness, reliability, scalability, and generalizability. Using pyrochlore lanthanum hafnium oxide (La2Hf2O7) as a representative, we describe the MSS protocol for the successful synthesis of complex metal oxide nanoparticles (NPs). Furthermore, this method has the unique ability to produce NPs with different material features by changing various synthesis parameters such as pH, temperature, duration, and post-annealing. By fine-tuning these parameters, we are able to synthesize highly uniform, non-agglomerated, and highly crystalline NPs. As a specific example, we vary the particle size of the La2Hf2O7 NPs by changing the concentration of the ammonium hydroxide solution used in the MSS process, which allows us to further explore the effect of particle size on various properties. It is expected that the MSS method will become a more popular synthesis method for nanomaterials and more widely employed in the nanoscience and nanotechnology community in the upcoming years.

Correlating Structure and Luminescence Properties of Undoped and Eu3+-Doped La2Hf2O7 Nanoparticles Prepared with Different Coprecipitating pH Values through Experimental and Theoretical Studies.

Understanding the structure-property relationship and optimizing properties of phosphors for use in lighting and scintillation fields is an important materials challenge. In this work, we investigated the effects of the pH value of the coprecipitating solution adjusted by the concentration of NH4OH(aq) on the structure and optical properties of the obtained La2Hf2O7 nanoparticles (NPs). The obtained NPs stabilize in the ideal pyrochlore structure, but the extent of ordering increased with an increase in the pH value used. The NPs prepared at pH = 12.1 displayed the best optical performance owing to the balance of the crystallinity, agglomeration, and surface defects. On the basis of density functional theory (DFT) calculations, the origin of violet-blue emission in undoped La2Hf2O7 NPs was attributed to defect states in the electronic band gap arising due to oxygen defects. For the La2Hf2O7:Eu3+ NPs, the Eu3+ dopants possess low symmetry and their occupancy is more favorable at the LaO8 site. DFT calculations further justify the complete host-to-dopant energy transfer and origin of the most intense red emission observed experimentally. Understanding the interplay of the experimental and theoretical results thus is a very useful general approach for improving the efficiency of luminescent materials.

Effect of Molten Salt Synthesis Processing Duration on the Photo- and Radioluminescence of UV-, Visible-, and X-ray-Excitable La2Hf2O7:Eu3+ Nanoparticles.

Ln3+-ion-doped nanomaterials possess excellent properties because of their high color purity, longer excited state lifetime, narrow emission, and large Stokes shifts. In this work, we studied the correlation between the luminescence properties of La2Hf2O7:Eu3+ pyrochlore nanoparticles (NPs) synthesized by a molten salt synthesis (MSS) method at a relatively low temperature and several MSS processing durations (from 1 to 12 h). We synthesized these NPs with different sizes just by changing the MSS processing time without subjecting to high temperature. Raman spectroscopy confirmed the stabilization of the ideal pyrochlore structure of the La2Hf2O7:Eu3+ NPs at various MSS processing durations. The synthesized NPs exhibited bright red emission under UV, visible, and X-ray excitations, highlighting their potential applications as a red phosphor and scintillator. As the MSS processing time was increased from 1 to 12 h, a spectral change in the position of the charge transfer state in the La2Hf2O7:Eu3+ NPs was observed. The sample processed by the MSS with a duration of 3 h exhibited the highest luminescence intensity, which was attributed to its optimum crystals with least surface defects and less agglomeration. The obtained results strongly and unambiguously indicate the brighter side of this new type of pyrochlore-based NPs in the fast growing field of solid-state lighting and scintillator materials.