Precise control and consecutive modulation of spin transition temperature using chemical migration in porous coordination polymers

Precise control of spin transition temperature (T(c)) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[Pt(II)(CN)(4)]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T(c)(up) = 304 K and T(c)(down) = 284 K) and its iodine adduct {Fe(pz)[Pt(II/IV)(CN)(4)(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt(II), raised the T(c) by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe(pz)[Pt(CN)(4)(I)(n)]} (1-In; n = 0.0-1.0), which resulted in consecutive modulation of T(c) in the range 300-400 K while maintaining the hysteresis width. Furthermore, it was demonstrated that iodine migration in the solid mixture was triggered by the spin transition of 1-I. The magnetically bistable porous framework decorating guest interactive open-metal-site in the pore surface makes it possible to modulate T(c) ad arbitrium through unique postsynthetic method using iodine migration.     

Tigloylshikonin, a new minor Shikonin derivative, from the roots and the commercial root extract of lithospermum erythrorhizon

Tigloylshikonin, a new shikonin derivative esterified with tiglic acid ((E)-2-methylbut-2-enoic acid), was isolated as a minor pigment from a food colorant "Shikon color," a commercial root extract from Lithospermum erythrorhizon SIEBOLD et ZUCCARINI. The structure of tigloylshikonin was elucidated using (1)H, (13)C, the difference nuclear Overhauser effect (NOE), and 2D NMR techniques. Its stereochemistry was determined by chiral-phase HPLC analysis. Tigloylshikonin was also found in the roots of L. erythrorhizon, which indicated that this new shikonin derivative is a typical component of naphthoquinone pigments in the roots of L. erythrorhizon.     

Synthesis and X-ray crystal structure of a difunctionalized pillar[5]arene at A1/B2 positions by in situ cyclization and deprotection

The reaction of 1,4-dimethoxybenzene and paraformaldehyde using AlBr(3) yields multiple-deprotected pillar[5]arenes. A1/B2 di-deprotected pillar[5]arene can be isolated by silica gel chromatography and washing procedures. The X-ray structure and polymerization of the A1/B2 di-deprotected pillar[5]arene are reported.     

Analysis of repeated impacts on a steel rod with visco-plastic material behavior

In machine dynamics impacts are usually common phenomena, resulting from collisions of moving bodies. Even low velocity impacts might produce high stresses in the contact region, which result in inelastic deformation. Thereby, visco-plastic materials, such as steel, show a significant increase of the yield stress with the strain rate. In machine dynamics repeated collisions occur, resulting in repeated impacts on a previously deformed contact area. Then, inelastic deformation and the resulting residual stresses produced by previous impacts have an influence on the behavior of the following impacts. Thus, the impact behavior varies with the number of impacts. This paper presents a numerical and experimental evaluation of repeated impacts with identical impact velocity up to 3 m/s, whereby the deformation history of the contact area, due to previous impacts, is included. The approach is applied to longitudinal impacts of an elastic steel sphere on a steel rod with distinct visco-plastic material behavior which is identified by Split Hopkinson Pressure Bar tests. A Finite Element analysis and experimental verification using two Laser-Doppler-Vibrometers are performed. It is shown that for an accurate impact simulation the FE model must include the visco-plastic material behavior of the steel. Further it is found that the maximal contact force, the rebound velocity and the coefficient of restitution increase with the number of impacts, while the contact duration decreases with the number of impacts. After several impacts these quantities show saturation to a constant value, indicating no significant additional inelastic deformation in the later impacts. Further, the residual stress distribution, the maximal von Mises stress distribution and the local deformation at the contact point are evaluated and a characteristic force-deformation diagram is obtained. Finally, an analysis is performed to describe the relation between maximal force and remaining crater at the contact point.     

Comment on an anomalous mean free path of heed for plasmon excitation

Several possibilities to interpret an anomalous mean free path of HEED for plasmon excitation are discussed. It is pointed out that more detail analysis in experiments should be necessary to conclude such anomaly.