Coordination polymer thin film heterostructures of the Prussian blue analogue Ni(II)b[Cr(III)(CN)6](0.7)·nH2O (NiCr-PBA) and the 3D Hofmann-like spin crossover compound Fe(azpy)[Pt(CN)4]·xH2O {azpy = 4,4'-azopyridine} have been developed, and spin transition properties have been characterized via SQUID magnetometry and Raman spectroscopy. The magnetic response of the ferromagnetic NiCr-PBA layer (T(c) ≈ 70 K) can be altered by inducing the LIESST effect (light-induced excited spin state trapping) in the coupled paramagnetic Fe(II) spin crossover material. Whereas an increase in magnetization is measured for the single-phase Fe(azpy)[Pt(CN)4]·xH2O, a decrease in magnetization is observed for the heterostructure. These results indicate the LIESST effect alone cannot account for the sign and magnitude of the magnetization change in the heterostructure, but the temperature profile of the magnetization shows that significant changes in the NiCr-PBA network are correlated to the spin state of the Hofmann-like SCO network.

Oxidized cytochrome c oxidase can now be prepared either to react rapidly (fast) or to react slowly (slow) with cyanide [Baker, G.M., Noguchi, M., & Palmer, G. (1987) J. Biol. Chem. 262, 595-604]. Slow oxidized cytochrome c oxidase is also characterized by an integer spin g = 12 EPR signal which is absent in the fast form. The saturation magnetization of two samples of both forms of cytochrome oxidase has been studied at four applied magnetic fields (0.3125, 1.25, 2.5, and 5.0 T) over a temperature range from 2 to 200 K using a superconducting susceptometer. The saturation magnetization data of the two preparations are readily distinguished. The data for the coupled cytochrome a3: CuB site of both preparations are most simply interpreted as exhibiting S = 2 paramagnetism with D = +13 cm-1 for the fast and D = -7 cm-1 for the slow forms, respectively. However, there is some indication that the fast form is a mixture of both S = 2 and S = 1 paramagnetic species while the slow form is only S = 2.

Phosphate glasses incorporating large concentrations of Eu 3+ ions are of interest for optical applications as their distinct red-emitting character resists deterioration with increasing Eu 3+ content. Still, the low propensity for concentration quenching in these is not well understood, and thus evaluations linking structural, thermal, and optical properties with Eu 3+ content are desired. In this work, 50P 2 O 5 -(50 − x)BaO-xEu 2 O 3 (x = 0, 1, 2, 4, 6 mol %) glasses pertinent to photonics were prepared by melt-quenching and further scrutinized with regards to the composition−structure−property relationship. A comprehensive experimental investigation was carried out encompassing density and basic physical properties, X-ray diffraction (XRD), Raman scattering, dilatometry, differential scanning calorimetry (DSC), optical absorption, and photoluminescence (PL) spectroscopy with emission decay analysis. The data from six techniques are in strong agreement with the existence of a critical Eu 2 O 3 concentration which divides the studied concentration range into two sections: (1) lower concentrations, up to about 2.5 (±0.1) mol %, with predominantly long-range (LR) effects of the modifier electrostatic field and (2) higher dopant concentrations, with predominantly short-range (SR) effects of the modifier field. The authors propose that LR interactions lead to shortening of the P-tetrahedral chains, while the SR interactions are expressed in increasing the covalent character of the bonds between the nonbridging oxygens and Eu 3+ ions. Concentration correlations between diverse macroscopic data sets, such as densitometry, dilatometry, Raman scattering, calorimetry, and PL, concur synergistically, elucidating the microscopic physical LR−SR interplay between glass network former and the cationic electrostatic field of the modifiers.

An in situ optical microspectroscopy study of the surface plasmon resonance (SPR) evolution of Ag nanoparticles (NPs) embedded in thick SiO(2) films deposited on soda-lime glass has been conducted during thermal processing in air. The temperature and time dependences of the SPR were analyzed in the context of Mie extinction and crystal growth theories and were discussed along with consideration of oxidation processes and film/substrate physicochemical interactions. At relatively high temperatures, Ag NPs were indicated to grow first through a diffusion-based process and subsequently via Ostwald ripening. At lower temperatures, an initial decrease in Ag particle size was indicated due to oxidation, followed by NP diffusion-based growth. The growth and oxidation stages appeared temperature and time dependent, allowing for the tuning of material properties. The product of Ag NP oxidation was revealed by photoluminescence spectroscopy performed ex situ as single Ag(+) ions. The oxidative effect of the air atmosphere on Ag NPs was shown to be ultimately circumvented by the thick nanocomposite film. The phenomenon was explained on the basis of the displacement of the Ag/Ag(+) redox equilibrium toward Ag NP stability after ion migration toward the substrate being self-constrained. In addition, the current spectroscopic approach has been proposed for estimating the activation energy for silver diffusion in the SiO(2) matrix.

No abstract

No abstract

Silver nanoparticle (NP) precipitation in a meltquenched aluminophosphate glass matrix has been studied and compared for 8 mol% and 4 mol% concentrations of both Ag 2 O and SnO dopants. The assessment is carried out by monitoring the plasmonic evolution of glass-embedded Ag NPs in real time during thermal treatments by in situ optical microspectroscopy and complemented by transmission electron microscopy and X-ray diffraction characterization. The time variation in the surface plasmon resonance of Ag NPs is analyzed in the framework of Mie extinction theory in connection with nanocrystal precipitation in the supersaturated solid solutions. For the higher concentration of silver and tin, nucleation and growth processes were distinguished, which appeared to be temperature-and time-dependent. Hence, favorable conditions were induced for the precipitation of a large amount of small NPs in the system. On the other hand, the nucleation and growth stages were not well separated in time for the lower concentration of dopants, resulting in Ag NPs of a broad size range. However, such less-concentrated nanocomposite allowed for the precipitation of NPs much larger than those observed for the 8% doped glass. Varying the degree of supersaturation in the system has been established as an important means for the tuning of material optical properties for photonic (nanoplasmonic) applications.

No abstract