Bulk and nanoparticle powders of LaCoO3 (LCO) were synthesized and their magnetic and structural properties were studied using SQUID magnetometry and neutron diffraction. The bulk and large nanoparticles exhibit weak ferromagnetism (FM) below T ≈ 85 K and a crossover from strong to weak antiferromagnetic (AFM) correlations near a transition expressed in the lattice parameters, To≈40 K. This crossover does not occur in the smallest nanoparticles; instead, the magnetic behavior is predominantly ferromagnetic. The amount of FM in the nanoparticles depends on the amount of Co3O4 impurity phase, which induces tensile strain on the LCO lattice. A core-interface model is introduced, with the core region exhibiting the AFM crossover and with FM in the interface region near surfaces and impurity phases.

Bulk La(w)CoO(3) particles with w = 1.1, 1.0, 0.9, 0.8, and 0.7 were synthesized using starting materials with varying molar ratios of La(2)O(3) and Co(3)O(4). The resulting particles are characterized as LaCoO(3) crystals interfaced with a crystalline Co(3)O(4) phase. X-ray and neutron scattering data show little effect on the average structure and lattice parameters of the LaCoO(3) phase resulting from the Co(3)O(4) content, but magnetization data indicate that the amount of Co(3)O(4) strongly affects the ferromagnetic ordering at the interfaces below TC ≈ 89 K. In addition to ferromagnetic long-range order, LaCoO(3) exhibits antiferromagnetic behavior with an unusual temperature dependence. The magnetization for fields 20 Oe ⩽ H ⩽ 5 kOe is fit to a combination of a power law ((T - TC)/TC)(β) behavior representing the ferromagnetic long-range order and sigmoid-convoluted Curie-Weiss-like behavior representing the antiferromagnetic behavior. The critical exponent β = 0.63 ± 0.02 is consistent with 2D (surface) ordering. Increased Co(3)O(4) correlates well to increased ferromagnetism. The weakening of the antiferromagnetism below T ≈ 40 K is a consequence of the lattice reaching a critical rhombahedral distortion as T is decreased for core regions far from the Co(3)O(4) interfaces. We introduce a model that describes the ferromagnetic behavior of the interface regions and the unusual antiferromagnetism of the core regions.

Lead halide perovskites are strong candidates for high-performance low-cost photovoltaics, light emission, and detection applications. A hot-phonon bottleneck effect significantly extends the cooling time of hot charge carriers, which thermalize through carrier-optic phonon scattering, followed by optic phonon decay to acoustic phonons and finally thermal conduction. To understand these processes, we adjust the lattice dynamics independently of electronics by changing isotopes. We show that doubling the mass of hydrogen in methylammonium lead iodide by replacing protons with deuterons causes a large 20 to 50% softening of the longitudinal acoustic phonons near zone boundaries, reduces thermal conductivity by ~50%, and slows carrier relaxation kinetics. Phonon softening is attributed to anticrossing with the slowed libration modes of the deuterated molecules and the reduced thermal conductivity to lowered phonon velocities. Our results reveal how tuning the organic molecule dynamics enables control of phonons important to thermal conductivity and the hot-phonon bottleneck.

Background and purpose

Recent advances in molecular techniques have characterized distinct subtypes of diffuse intrinsic pontine gliomas. Our aim was the identification of MR imaging correlates of these subtypes.

Materials and methods

Initial MRIs from subjects with diffuse intrinsic pontine gliomas recruited for a prospective clinical trial before treatment were analyzed. Retrospective imaging analyses included FLAIR/T2 tumor volume, tumor volume enhancing, the presence of cyst and/or necrosis, median, mean, mode, skewness, kurtosis of ADC tumor volume based on FLAIR, and enhancement at baseline. Molecular subgroups based on EGFR and MGMT mutations were established. Histone mutations were also determined (H3F3A, HIST1H3B, HIST1H3C). Univariate Cox proportional hazards regression was used to test the association of imaging predictors with overall and progression-free survival. Wilcoxon rank sum, Kruskal-Wallis, and Fisher exact tests were used to compare imaging measures among groups.

Results

Fifty patients had biopsy and MR imaging. The median age at trial registration was 6 years (range, 3.3-17.5 years); 52% were female. On the basis of immunohistochemical results, 48 patients were assigned to 1 of 4 subgroups: 28 in MGMT-/epidermal growth factor receptor (EGFR)-, 14 in MGMT-/EGFR+, 3 in MGMT+/EGFR-, and 3 in MGMT+/EGFR+. Twenty-three patients had histone mutations in H3F3A, 8 in HIST1H3B, and 3 in HIST1H3C. Enhancing tumor volume was near-significantly different across molecular subgroups (P = .04), after accounting for the false discovery rate. Tumor volume enhancing, median, mode, skewness, and kurtosis ADC T2-FLAIR/T2 were significantly different (P ≤ .048) between patients with H3F3A and HIST1H3B/C mutations.

Conclusions

MR imaging features including enhancement and ADC histogram parameters are correlated with molecular subgroups and mutations in children with diffuse intrinsic pontine gliomas.