Study of the structure and electronic state of thiolate-protected gold clusters by means of 197Au Mössbauer spectroscopy

We have investigated the structures and electronic states of a series of glutathionate-protected Au clusters, Au _n (SG) _m with n = 10 ? ～55, using ¹⁹⁷Au Mössbauer spectroscopy, which allows us to probe the local environment of the constituent Au atoms via isomer shift (IS) and quadrupole splitting (QS). The spectral profile abruptly changes on going from Au₂₂(SG)₁₇ to Au₂₅(SG)₁₈, then it smoothly changes to that of Au～₅₅(SG)_m. However, the spectral profile dramatically changes on going from Au～₅₅(SG)_m to the dodecanethiolate-protected Au cluster with average diameter of 2 nm. The ¹⁹⁷Au Mössbauer spectra of glutathionate-protected Au clusters and dodecanethiolate-protected Au clusters were successfully analyzed on the basis of the structure and electronic state of Au₂₅(SG)₁₈.     

Study on charge transfer interaction and valence state of layered perovskite-type mixed valence complex [NH3(CH2) n NH3]2[(AuII2)(AuIIII4)(I3)2] (n = 7, 8), by means of 197Au Mössbauer spectroscopy

Cs₂[Au^I X ₂][Au^III X ₄](X = Cl, Br, and I) is well known for the three-dimensional perovskite-type gold mixed valence system. Recently, layered perovskite-type gold mixed valence complexes, [NH₃(CH₂) _n NH₃]₂[(Au^II₂)(Au^IIII₄)(I₃)₂] (n = 7 and 8), have been synthesized. We have investigated the relationship between the structural dimensionality and the Au^I–Au^III charge transfer interaction for Cs₂[Au^II₂][Au^IIII₄] and [NH₃(CH₂) _n NH₃]₂[(Au^II₂)(Au^IIII₄)(I₃)₂] (n = 7 and 8) by means of ¹⁹⁷Au Mössbauer spectroscopy.     

Mechanism of the NO2 conversion to NO2- in an alkaline solution.

The reaction of NO2 and NaOH aqueous solution at room temperature was studied for elucidating the behavior of gaseous NO2 in an alkaline solution. Experimental runs related to NO2 absorption have been carried out in various pH solutions. The nitrite and nitrate ions formed in these absorption solutions were quantitatively analyzed. In the case of pH 5-12, both of the nitrite and nitrate ions were formed simultaneously. On the other hand, only the nitrite ion was formed when the pH of the absorption solution was higher than 13. In this paper, a new reaction mechanism was proposed to explain the selective formation of nitrite ion in the 10 M alkaline solution. In order to confirm the new reaction mechanism, H2(18)O was used as part of the absorption solution for detecting oxygen gas production. The amounts of reaction products: (18)O(18)O, (18)O(16)O and (16)O(16)O, were quantitatively determined. It was confirmed that the new reaction proceeds mainly in the 10 M alkaline solution.     

Electronic Properties of Low-Dimensional Ternary Copper Chal-Cogenides A-Cu-X (A˭Na,K, Rb,Cs; X˭S,Se)

Abstract

Electronic properties of Na₃Cu₄S₄, K₃Cu₈S₆, Rb₃Cu₈S₆, Rb₃Cu₈Se₆, KCu₃S₂, and CsCu₃S₂ are discussed on the basis of the measurements of resistivity and thermopower.     

Three‐Step Spin State Transition and Hysteretic Proton Transfer in the Crystal of an Iron(II) Hydrazone Complex

A proton–electron coupling system, exhibiting unique bistability or multistability of the protonated state, is an attractive target for developing new switchable materials based on proton dynamics. Herein, we present an iron(II) hydrazone crystalline compound, which displays the stepwise transition and bistability of proton transfer at the crystal level. These phenomena are realized through the coupling with spin transition. Although the multi‐step transition with hysteresis has been observed in various systems, the corresponding behavior of proton transfer has not been reported in crystalline systems; thus, the described iron(II) complex is the first example. Furthermore, because proton transfer occurs only in one of the two ligands and π electrons redistribute in it, the dipole moment of the iron(II) complexes changes with the proton transfer, wherein the total dipole moment in the crystal was canceled out owing to the antiferroelectric‐like arrangement.     

Diameter and Refractive Index of a Cylindrical Thread Determined by Scattered Light Pattern

We have devised a method of determining the optimal value of both the refractive index n and the diameter D of a transparent cylinder by the scattering intensity pattern over a wide range of scattering angle. We have shown that the method is stable to small variations of data for the sample with D#x2272;10#x03BB; (wavelength) and could specifically determine the parameters of a spider#x0027;s thread as n = 1.520 (#x2212;0.033, #x002B;0.033), D=0.564 (#x2212;0.009, #x002B;0.011)#x03BC;m for #x03BB; = 632.8 nm.     

Photodynamic Therapy for Cancer Cells Using Metal-Halide Lamps

New metal-halide lamps were developed and their effect on the efficiency of photodynamic therapy (PDT) for cancer cells, murine thymic lymphoma cells (EL-4), was investigated. 5-Aminolevulinic acid-induced protoporphyrin IX was used as a photosensitizer. The metal-halide lamps were made by introducing sodium iodide (Na lamp), lithium iodide (Li lamp), and sodium iodide-lithium iodide mixture (Na-Li lamp) into their discharge tubes. These lamps emitted light in the range of 550 to 750 nm and had specific emission peaks at 580 and 600 nm for the Na lamp, 580, 610, and 680 nm for the Li lamp, and 580, 610, and 675 nm for the Na-Li lamp. Changes in the survival rate of EL-4 with increasing irradiation time indicated that PDT efficiency of the lamps increased in the order Li lamp < Na lamp < Na-Li lamp. We also found that a dark interval during irradiation of the light with the Na-Li lamp enhanced PDT efficiency.     

Sol-gel synthesis and dilute magnetism of nano MgO powder doped with Fe

Mg oxides doped with 1 % ⁵⁷Fe were prepared by a sol-gel method, and annealed at various temperatures. Nano-size Mg oxides were characterized by Mössbauer spectrometry, magnetization and XRD measurements. The crystalline size of MgO increases with increase of annealing temperature. Samples annealed at 600 °C and 800 °C gave only doublet peaks of paramagnetic Fe³⁺ in Mössbauer spectra although Fe³⁺ doping into MgO induced a distorted structure and showed weak ferromagnetism. It is considered that the magnetic property is due to defect induced magnetism by doping Fe³⁺ into MgO. For a sample heated at 1000 °C, it is found from low temperature Mössbauer spectra that Fe³⁺ species are located at the core and shell of fine MgFe₂O₄ grains and diluted in MgO matrix.