Interconvertible multiple photoluminescence color of a gold(i) isocyanide complex in the solid state: solvent-induced blue-shifted and mechano-responsive red-shifted photoluminescence

In this study, we report the interconvertible tetracolored solid state photoluminescence of gold(i) isocyanide complex 2 upon various external stimuli through solid state structural changes. Soaking complex 2 in acetone yields blue emission as a result of the formation of 2B. The subsequent removal of acetone yields 2G through a crystal-to-crystal phase transition, which exhibits green emission. This green-emitting solid 2G exhibits stepwise emission color changes to yellow and then to orange upon mechanical stimulation by ball-milling, which corresponds to the formation of 2Y and 2O, respectively. 2B could be recovered upon the addition of acetone to 2G, 2Y, and 2O. Thus, these four emitting solid states of 2 can be switched between repeatedly by means of acetone soaking and the application of mechanical stimulation. Importantly, single crystal and powder X-ray diffraction (PXRD) studies fully show the detailed molecular arrangements of 2B, 2G, and 2Y. This is the first mechanochromic compound to show interconvertible four color emission in the solid state. We also present the first example of using PXRD measurements and the Rietveld refinement technique for the structural analysis of a ground powder in a luminescence mechanochromism study. We obtained complete molecular-level structural information of the crystalline states of 2B, 2G, 2Y, and 2O. In comparison with a more solvophobic analogue 1, we suggest that the weak interaction of 2 with acetone in the solid state would allow a solvent inclusion/release mode, which is an important structural factor for the unprecedented multicolor mechanochromic luminescence.     

Structural analysis of alanine tripeptide with antiparallel and parallel beta-sheet structures in relation to the analysis of mixed beta-sheet structures in Samia cynthia ricini silk protein fiber using solid-state NMR spectroscopy

The structural analysis of natural protein fibers with mixed parallel and antiparallel beta-sheet structures by solid-state NMR is reported. To obtain NMR parameters that can characterize these beta-sheet structures, (13)C solid-state NMR experiments were performed on two alanine tripeptide samples: one with 100% parallel beta-sheet structure and the other with 100% antiparallel beta-sheet structure. All (13)C resonances of the tripeptides could be assigned by a comparison of the methyl (13)C resonances of Ala(3) with different [3-(13)C]Ala labeling schemes and also by a series of RFDR (radio frequency driven recoupling) spectra observed by changing mixing times. Two (13)C resonances observed for each Ala residue could be assigned to two nonequivalent molecules per unit cell. Differences in the (13)C chemical shifts and (13)C spin-lattice relaxation times (T(1)) were observed between the two beta-sheet structures. Especially, about 3 times longer T(1) values were obtained for parallel beta-sheet structure as compared to those of antiparallel beta-sheet structure, which could be explicable by the difference in the hydrogen-bond networks of both structures. This very large difference in T(1) becomes a good measure to differentiate between parallel or antiparallel beta-sheet structures. These differences in the NMR parameters found for the tripeptides may be applied to assign the parallel and antiparallel beta-sheet (13)C resonances in the asymmetric and broad methyl spectra of [3-(13)C]Ala silk protein fiber of a wild silkworm, Samia cynthia ricini.     

X-ray magnetic circular dichroism at rare-earth L23 absorption edges in various compounds and alloys

Theoretical interpretations of X-ray magnetic circular dichroism (XMCD) at rare-earth (called R hereafter) L₂₃ absorption edges are reviewed using differing models, depending on the material under investigation. In the first chapter, we present an overview of recent developments for XMCD in XAS with a few general remarks, especially at R atom absorption edges. In Section 2, we first describe basic mechanism of XMCD at L₂₃ edges of R systems, and then we essentially discuss two examples of XMCD spectra in: (i) R₂Fe₁₄B metallic compounds, with the help of a cluster model, and (ii) RFe₂ Laves-phase compounds, using a tight-binding approximation for R 5d and Fe 3d conducting states. A good agreement between theory and experiment for R₂Fe₁₄B suggests that a cluster model provides a valuable method to quantitatively calculate XMCD spectra of R systems, even with quite complicated atomic arrangements. For RFe₂ systems the XMCD spectral shape, especially for the L₂ edge of heavy R elements, is more complicated than those of R₂Fe₁₄B systems, and this is explained by the competition of some different XMCD mechanisms. In Section 3, we focus on special series of Ce systems, related to XAS and XMCD studies at the Ce L₂₃ edges. Two clearly differing cases are interpreted: (i) A well localized 4f¹ system, i.e. CeRu₂Ge₂; (ii) A less localized 4f¹ system, i.e. CeFe₂, with a 3d partner. Then, from a more experimental point of view, we investigate the influence of substitution on the low temperature properties of CePd₃ compounds, i.e. Ce(_Pd1-xMnx)3$\mathrm{Ce}({\mathrm{Pd}}_{1-x}{\mathrm{Mn}}_x{)}_3$ alloys where x   is about 0.03, giving rise to (_CePd3)8Mn$({\mathrm{CePd}}_3{)}_8\mathrm{Mn}$ ordered structure. We give another example: Ce(_Pd1-xNix)3$\mathrm{Ce}({\mathrm{Pd}}_{1-x}{\mathrm{Ni}}_x{)}_3$ alloys with x taken up to about 0.25. Also the Ce L₂₃ XMCD signal measured in pure CePd₃ demonstrates that in the Ce based dense Kondo materials, only the 4f¹ channel yields a magnetic response.     

Unique incorporation behavior of amino acid-type surfactant into phospholipid vesicle membrane

The incorporation behavior of some anionic surfactants, including amino acid-type surfactants, on phospholipid vesicles was investigated. This was done by measuring the release of a vesicle-entrapped fluorescence probe and the scattered light intensities of vesicle particles in the surfactant solution as a function of surfactant concentration and time. Sodium dodecyl sulfate, sodium dodecanesulfonate, sodium dodecanoyl sarcosinate, and sodium dodecanoyl glutamate were employed in this study. All surfactants ruptured the phospholipid vesicle at around each critical micelle concentration by mixed micelle formation with phospholipid. While leakage of the fluorescence probe took place at a very low concentration in the sulfate- or sulfonate-type surfactant systems, it occurred at the concentration just below the CMC in the amino acid-type surfactant systems. Kinetic analysis of the release of the probe from the vesicles showed that the former surfactants adsorbed independently and homogeneously onto the phospholipid vesicles, while the latter surfactants were cooperatively incorporated.     

Scattering characteristics of a beam mode in dielectric-slab optical waveguide

Scattering of the light beam propagating through a dielectric-slab optical waveguide occurs due to refractive index inhomogeneities of the thin film region and due to boundary irregularities of the filmsubstrate and the film-air interfaces. The quantity and direction of the scattered light are evaluated by means of a perturbation method together with the use of a stationary phase method, for a variety of correlation lengths and variances and the thin film thicknesses. The results show that for a slab waveguide of t/=10.0,t and being the thickness of thin film and the wavelength of light, the effect of refractive index inhomogeneities is pronounced in comparison with that of waveguide wall irregularities. In this case, therefore, the scattering pattern is determined mainly by the correlation length of refractive index inhomogeneities.     

One-pot multistep synthesis of 4-acetoxy-2-amino-3-arylbenzofurans from 1-aryl-2-nitroethylenes and cyclohexane-1,3-diones

[reaction: see text] A novel method for synthesizing 4-acetoxy-2-amino-3-arylbenzofurans (4) from 1-aryl-2-nitroethylenes (1) and cyclohexane-1,3-diones (2) is described. The method features one-pot operation of a solution of 1 and 2 in THF with catalytic Et3N (rt, 12 h) followed with Ac2O, Et3N, and DMAP (rt, 5 h), although the process consists of 13 elementary reactions.     

Ce(iv)-centered charge-neutral perovskite layers topochemically derived from anionic [CeTa2O7]− layers

Layered perovskites have been extensively investigated in many research fields, such as electronics, catalysis, optics, energy, and magnetics, because of the fascinating chemical properties that are generated by the specific structural features of perovskite frameworks. Furthermore, the interlayers of these structures can be chemically modified through ion exchange to form nanosheets. To further expand the modification of layered perovskites, we have demonstrated an advance in the new structural concept of layered perovskite “charge-neutral perovskite layers” by manipulating the perovskite layer itself. A charge-neutral perovskite layer in [Ce^IVTa₂O₇] was synthesized through a soft chemical oxidative reaction based on anionic [Ce^IIITa₂O₇]⁻ layers. The Ce oxidation state for the charge-neutral [Ce^IVTa₂O₇] layers was found to be tetravalent by X-ray absorption fine structure (XAFS) analysis. The atomic arrangements were determined through scattering transmission electron microscopy and extended XAFS (EXAFS) analysis. The framework structure was simulated through density functional theory (DFT) calculations, the results of which were in good agreement with those of the EXAFS spectra quantitative analysis. The anionic [Ce^IIITa₂O₇]⁻ layers exhibited optical absorption in the near infrared (NIR) region at approximately 1000 nm, whereas the level of NIR absorption decreased in the [Ce^IVTa₂O₇] charge-neutral layer due to the disappearance of the Ce 4f electrons. In addition, the chemical reactivity of the charge-neutral [Ce^IVTa₂O₇] layers was investigated by chemical reduction with ascorbic acid, resulting in the reduction of the [Ce^IVTa₂O₇] layers to form anionic [Ce^IIITa₂O₇]⁻ layers. Furthermore, the anionic [Ce^IIITa₂O₇]⁻ layers exhibited redox activity which the Ce in the perovskite unit can be electrochemically oxidized and reduced. The synthesis of the “charge-neutral” perovskite layer indicated that diverse features were generated by systematically tuning the electronic structure through the redox control of Ce; such diverse features have not been found in conventional layered perovskites. This study could demonstrate the potential for developing innovative, unique functional materials with perovskite structures.

This study proposed a new layer modification technique, “layer charge control”, for layered perovskites, and the structures of the obtained charge neutral [CeTa₂O₇] perovskite sheet were characterized theoretically and experimentally.     

Chirally autocatalytic reaction performed in highly supersaturated conditions

Spontaneous chiral asymmetry generation, which is the preferential production of one enantiomer in a non‐chiral environment by chiral autocatalysis, could be observed in a preparation of a octahedral cobalt complex, cis‐[CoBr(NH₃)(en)₂]Br₂. A concentration fluctuation in a far‐from‐equilibrium chemical system will grow if the rate of local autocatalytic production of a compound in a small volume overcomes its loss due to diffusion. In a chirally autocatalytic system, this phenomenon could produce a large variation in the enantiomeric excess. In a reaction that produces the cobalt complex, the reaction rate was found to increase in the highly supersaturated solution of the product. In supersaturated solutions, before crystals of the solute have nucleated, embryos, which are the clusters of the solute, are formed. Ternary water‐solubility isotherm of each enantiomer of the cobalt complex suggests that each embryo consists of one exclusive enantiomer. Each chiral cluster, which could be regarded as polymeric material, thus formed in a highly supersaturated solution, may act as catalyst for the production of the same enantiomer. Life is a far‐from‐equilibrium self‐organized polymeric system in which chiral symmetry is broken. This reaction system is thus a model for the generation and amplification of chiral asymmetry in polymeric materials; it provides some insight in to the mechanisms that might have produced the observed biomolecular homochirality.