Mechanistic study of asymmetric Michael addition of malonates to enones catalyzed by a primary amino acid lithium salt

A mechanistic study was carried out for the asymmetric Michael addition reaction of malonates to enones catalyzed by a primary amino acid lithium salt to elucidate the origin of the asymmetric induction. A primary β-amino acid salt catalyst, O-TBDPS β-homoserine lithium salt, exhibited much higher enantioselectivity than that achieved with the corresponding catalysts derived from α- and γ-amino acids for this reaction. Detailed studies of the transition states with DFT calculations revealed that the lithium cation and carboxylate group of the β-amino acid salt catalyst have important roles in achieving high enantioselectivity in the Michael addition reaction of malonates to enones.     

Improvement of TiO2/Dye/Electrolyte Interface Conditions by Positional Change of Alkyl Chains in Modified Panchromatic Ru Complex Dyes

A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation.     

在粗糙表面上用液晶空间光调制器进行振动测量

为实现在一段时间内连续实时观测振动物体的全息干涉图形,采用覆盖铝箔的喇叭作为振动物体,利用铝箔原有未经特殊处理表面反射的漫反射光成像,并用光寻址液晶空间光调制器(Liquid crystal-sparial lightmodulator,LC-SLM)作为全息记录载体,来实现振动测量。实验中采用时间平均干涉测量法,得到了不同振动频率下物体的干涉图形。同时在连续改变振动物体的振动频率时,可以清晰地观察到物体振动全息干涉图形的变化过程,即近实时的全息干涉图形。     

Experimental investigation of amplitude death in delay-coupled double-scroll circuits with randomly time-varying network topology

Nonlinear Dynamics - The present study experimentally investigates amplitude death in delay-coupled double-scroll circuits with a time-varying network topology that randomly changes at a regular...     

Protective Effect of Ferulic Acid against Hydrogen Peroxide Induced Apoptosis in PC12 Cells

Ferulic Acid (FA) is a highly abundant phenolic phytochemical which is present in plant tissues. FA has biological effects on physiological and pathological processes due to its anti-apoptotic and anti-oxidative properties, however, the detailed mechanism(s) of function is poorly understood. We have identified FA as a molecule that inhibits apoptosis induced by hydrogen peroxide (H₂O₂) or actinomycin D (ActD) in rat pheochromocytoma, PC12 cell. We also found that FA reduces H₂O₂-induced reactive oxygen species (ROS) production in PC12 cell, thereby acting as an anti-oxidant. Then, we analyzed FA-mediated signaling responses in rat pheochromocytoma, PC12 cells using antibody arrays for phosphokinase and apoptosis related proteins. This FA signaling pathway in PC12 cells includes inactivation of pro-apoptotic proteins, SMAC/Diablo and Bad. In addition, FA attenuates the cell injury by H₂O₂ through the inhibition of phosphorylation of the extracellular signal-regulated kinase (ERK). Importantly, we find that FA restores expression levels of brain-derived neurotrophic factor (BDNF), a key neuroprotective effector, in H₂O₂-treated PC12 cells. As a possible mechanism, FA increases BDNF by regulating microRNA-10b expression following H₂O₂ stimulation. Taken together, FA has broad biological effects as a neuroprotective modulator to regulate the expression of phosphokinases, apoptosis-related proteins and microRNAs against oxidative stress in PC12 cells.     

Application of nanoscale packed capillary liquid chromatography (75 μm id) and capillary zone electrophoresis/electrospray ionization mass spectrometry to the analysis of macrolide antibiotics

Nanoscale separation techniques, nanoscale packed capillary columns (75 μm id), and capillary zone electrophoresis (CZE), on-line with electrospray mass spectrometry (ESI/MS), were applied to the separation of a series of ten macrolide antibiotics. Both techniques use sub-microliter-per-minute flow rates through the analytical column and therefore require an electrospray probe that incorporates coaxial sheath flow. Positive ion electrospray mass spectra of these compounds yielded mainly protonated molecules. Fragmentation to yield structurally significant fragment ions was achieved by collision-induced dissociation (CID) at increased skimmer voltages. Separations were achieved using both techniques, with CZE/ESI/MS showing improved peak shapes and detection limits combined with faster analysis times. Nanoscale packed capillary columns provided better chromatographic resolution and was less susceptible to peak broadening caused by overloading of the analytes.     

High-Affinity Ratiometric Fluorescence Probe Based on 6-Amino-2,2′-Bipyridine Scaffold for Endogenous Zn2+ and Its Application to Living Cells

Zinc is an essential trace element involved in many biological activities; however, its functions are not fully understood. To elucidate the role of endogenous labile Zn²⁺, we developed a novel ratiometric fluorescence probe, 5-(4-methoxyphenyl)-4-(methylsulfanyl)-[2,2′-bipyridin]-6-amine (6 (rBpyZ)) based on the 6-amino-2,2′-bipyridine scaffold, which acts as both the chelating agent for Zn²⁺ and the fluorescent moiety. The methoxy group acted as an electron donor, enabling the intramolecular charge transfer state of 6 (rBpyZ), and a ratiometric fluorescence response consisting of a decrease at the emission wavelength of 438 nm and a corresponding increase at the emission wavelength of 465 nm was observed. The ratiometric probe 6 (rBpyZ) exhibited a nanomolar-level dissociation constant (K_d = 0.77 nM), a large Stokes shift (139 nm), and an excellent detection limit (0.10 nM) under physiological conditions. Moreover, fluorescence imaging using A549 human lung adenocarcinoma cells revealed that 6 (rBpyZ) had good cell membrane permeability and could clearly visualize endogenous labile Zn²⁺. These results suggest that the ratiometric fluorescence probe 6 (rBpyZ) has considerable potential as a valuable tool for understanding the role of Zn²⁺ in living systems.     

A method to determine effective metamaterial properties based on stratified metafilms

Metamaterials’ properties may be quantified through the assignment of bulk material parameters such as magnetic permeability and electric permittivity. These assignments rely on the assumption that metamaterials are effective media, in this context meaning that their electromagnetic properties are independent of the sample size. This assumption is not always valid, particularly for metafilms, the surface equivalents of metamaterials. However, metamaterials comprised of numerous metafilm and dielectric layers can be uniquely characterized in the effective medium approximation when all aspects of the metamaterial are properly integrated. We present a simple model based on stratified systems to illustrate this fact. The model further assists in the interpretation of novel metamaterial behaviors and offers a rapid and accurate method to determine the functionality of bulk metamaterial-based devices.     

Electron spin torque in atoms

The spin torque and zeta force, which govern spin dynamics, are studied by using monoatoms in their steady states. We find nonzero local spin torque in transition metal atoms, which is in balance with the counter torque, the zeta force. We show that d-orbital electrons have a crucial effect on these torques. Nonzero local chirality density in transition metal atoms is also found, though the electron mass has the effect to wash out nonzero chirality density. Distribution patterns of the chirality density are the same for Sc–Ni atoms, though the electron density distributions are different.