Sequential reaction intermediates in aliphatic C-H bond functionalization initiated by a bis(mu-oxo)dinickel(III) complex

The reaction of [Ni2(OH)2(Me2-tpa)2]2+ (1) (Me2-tpa = bis(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) with H2O2 causes oxidation of a methylene group on the Me2-tpa ligand to give an N-dealkylated ligand and oxidation of a methyl group to afford a ligand-based carboxylate and an alkoxide as the final oxidation products. A series of sequential reaction intermediates produced in the oxidation pathways, a bis(mu-oxo)dinickel(III) ([Ni2(O)2(Me2-tpa)2]2+ (2)), a bis(mu-superoxo)dinickel(II) ([Ni2(O2)2(Me2-tpa)2]2+ (3)), a (mu-hydroxo)(mu-alkylperoxo)dinickel(II) ([Ni2(OH)(Me2-tpa)(Me-tpa-CH2OO)]2+ (4)), and a bis(mu-alkylperoxo)dinickel(II) ([Ni2(Me-tpa-CH2OO)2]2+ (5)), was isolated and characterized by various physicochemical measurements including X-ray crystallography, and their oxidation pathways were investigated. Reaction of 1 with H2O2 in methanol at -40 degrees C generates 2, which is extremely reactive with H2O2, producing 3. Complex 2 was isolated only from disproportionation of the superoxo ligands in 3 in the absence of H2O2 at -40 degrees C. Thermal decomposition of 2 under N2 generated an N-dealkylated ligand Me-dpa ((6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine) and a ligand-coupling dimer (Me-tpa-CH2)2. The formation of (Me-tpa-CH2)2 suggests that a ligand-based radical Me-tpa-CH2* is generated as a reaction intermediate, probably produced by H-atom abstraction by the oxo group. An isotope-labeling experiment revealed that intramolecular coupling occurs for the formation of the coupling dimer. The results indicate that the rebound of oxygen to Me-tpa-CH2* is slower than that observed for various high-valence bis(mu-oxo)dimetal complexes. In contrast, the decomposition of 2 and 3 in the presence of O2 gave carboxylate and alkoxide ligands, respectively (Me-tpa-COO- and Me-tpa-CH2O-), instead of (Me-tpa-CH2)2, indicating that the reaction of Me-tpa-CH2* with O2 is faster than the coupling of Me-tpa-CH2* to generate ligand-based peroxyl radical Me-tpa-CH2OO*. Although there is a possibility that the Me-tpa-CH2OO* species could undergo various reactions, one of the possible reactive intermediates, 4, was isolated from the decomposition of 3 under O2 at -20 degrees C. The alkylperoxo ligands in 4 and 5 can be converted to a ligand-based aldehyde by either homolysis or heterolysis of the O-O bond, and disproportionation of the aldehyde gives a carboxylate and an alkoxide via the Cannizzaro reaction.     

Stabilization of High‐Valence Ruthenium with Silicotungstate Ligands: Preparation,Structural Characterization,and Redox Studies of Ruthenium(III)‐Substituted α‐Keggin‐Type Silicotungstates with Pyridine Ligands, [SiW11O39RuIII(Py)]5−

Ruthenium(III)‐substituted α‐Keggin‐type silicotungstates with pyridine‐based ligands, [SiW₁₁O₃₉Ru^III(Py)]^5?, (Py: pyridine ( 1 ), 4‐pyridine‐carboxylic acid ( 2 ), 4,4′‐bipyridine ( 3 ), 4‐pyridine‐acetamide ( 4 ), and 4‐pyridine‐methanol ( 5 )) were prepared by reacting [SiW₁₁O₃₉Ru^III(H₂O)]^5? with the pyridine derivatives in water at 80 °C and then isolated as their hydrated cesium salts. These compounds were characterized using cyclic voltammetry (CV), UV/Vis, IR, and ¹H NMR spectroscopy, elemental analysis, titration, and X‐ray absorption near‐edge structure (XANES) analysis (Ru K‐edge and L₃‐edge). Single‐crystal X‐ray analysis of compounds 2 , 3 , and 4 revealed that Ru^III was incorporated in the α‐Keggin framework and was coordinated by pyridine derivatives through a Ru? N bond. In the solid state, compounds 2 and 3 formed a dimer through π? π interaction of the pyridine moieties, whereas they existed as monomers in solution. CV indicated that the incorporated Ru^III–Py was reversibly oxidized into the Ru^IV–Py derivative and reduced into the Ru^II–Py derivative.     

Doping light emitters into metal-organic frameworks

Space division with red cubes: Doping metal-organic frameworks with another metal component gives a further opportunity to tune their properties. Recent work successfully introduced europium into the inorganic nodes of frameworks. Although the doping element does not affect the framework topology, highly improved emissive performance was measured thanks to the intrinsic red emission of europium.     

Application of a new microcantilever biosensor resonating at the air-liquid interface for direct insulin detection and continuous monitoring of enzymatic reactions

Here we describe the application of a recently developed high-resolution microcantilever biosensor resonating at the air-liquid interface for the continuous detection of antigen-antibody and enzyme-substrate interactions. The cantilever at the air-liquid interface demonstrated 50% higher quality factor and a 5.7-fold increase in signal-to-noise-ratio (SNR) compared with one immersed in the purified water. First, a label-free detection of a low molecular weight protein (insulin, 5.8 kDa) in physiological concentration was demonstrated. The liquid facing side of the cantilever was functionalized by coating its surface with insulin antibodies, while the opposite side was exposed to air. The meniscus membrane at the micro-slit around the cantilever sustained the liquid in the microchannel. After optimizing the process of surface functionalization, the resonance frequency shift was successfully measured for insulin solutions of 0.4, 2.0, and 6.3 ng ml(-1). To demonstrate additional application of the device for monitoring enzymatic protein degradation, the liquid facing microcantilever surface was coated with human recombinant SOD1 (superoxide dismutase 1) and exposed to various concentrations of proteinase K solution, and the kinetics of the SOD1 digestion was continuously monitored. The results showed that it is a suitable tool for sensitive protein detection and analysis.     

Redox reaction in two-dimensional porous coordination polymers based on ferrocenedicarboxylates

A series of 1,1'-ferrocenedicarboxylate-based two-dimensional porous coordination polymers were synthesized by incorporating different diamine co-ligands. These compounds immobilized on electrodes, exhibited reversible redox reactions, arising from ferrocenyl moiety.     

Hydrothermal and solid-state transformation of ruthenium-supported Keggin-type heteropolytungstates [XW11O39{Ru(II)(benzene)(H2O)}]n- (X = P (n = 5), Si (n = 6), Ge (n = 6)) to ruthenium-substituted Keggin-type heteropolytungstates

A new pathway for the preparation of mono-ruthenium (Ru)(iii)-substituted Keggin-type heteropolytungstates with an aqua ligand, [PW(11)O(39)Ru(iii)(H(2)O)](4-) (1a), [SiW(11)O(39)Ru(iii)(H(2)O)](5-) (1b) and [GeW(11)O(39)Ru(iii)(H(2)O)](5-) (1c), using [Ru(ii)(benzene)Cl(2)](2) as a Ru source was described. Compounds 1a-1c were prepared by reacting [XW(11)O(39)](n-) (X = P, Si and Ge) with [Ru(ii)(benzene)Cl(2)](2) under hydrothermal condition and were isolated as caesium salts. Ru(benzene)-supported heteropolytungstates, [PW(11)O(39){Ru(ii)(benzene)(H(2)O)}](5-) (2a), [SiW(11)O(39){Ru(ii)(benzene)(H(2)O)}](6-) (2b) and [GeW(11)O(39){Ru(ii)(benzene)(H(2)O)}](6-) (2c), were first produced in the reaction media, and then transformed to 1a, 1b and 1c, respectively, under hydrothermal conditions. Calcination of Ru(benzene)-supported heteropolytungstates, 2a, 2b and 2c, in the solid state produced mixtures of 1a, 1b and 1c with CO (carbon monoxide)-coordinated complexes, [PW(11)O(39)Ru(ii)(CO)](5-) (4a), [SiW(11)O(39)Ru(ii)(CO)](6-) (4b) and [GeW(11)O(39)Ru(ii)(CO)](6-) (4c), respectively. From comparison of their catalytic activities in water oxidation reaction, it was indicated that ruthenium should be incorporated in the heteropolytungstate in order to promote catalytic activity.     

Adsorption and disruption of lipid bilayers by nanoscale protein aggregates

Nanoparticles taken into biological systems can have biological impacts through their interactions with cell membranes, accompanied by protein adsorption onto the nanoparticle surfaces, forming a so-called protein corona. Our current research aims to demonstrate that nanoscale protein aggregates behave like such nanoparticles with regard to the interaction with lipid membranes. In this study, the adsorption and disruption of the lipid membranes by protein aggregates were investigated using amyloid fibrils and nanoscale thermal aggregates of lysozyme. Both types of protein aggregates had disruptive effects on the negatively charged liposomes, similar to polycationic nanoparticles. Interestingly, adsorption of liposomes on the amyloid fibrils preceding disruption occurred even if the net charge of the liposome was zero, suggesting the importance of hydrophobic interactions in addition to electrostatic interactions. The results of the present study provide new insights into the biological impacts of nanoparticles in vivo.     

Proton acceleration to 40 MeV using a high intensity, high contrast optical parametric chirped-pulse amplification/Ti:sapphire hybrid laser system

Using a high-contrast (10(10):1) and high-intensity (10(21) W/cm(2)) laser pulse with the duration of 40 fs from an optical parametric chirped-pulse amplification/Ti:sapphire laser, a 40 MeV proton bunch is obtained, which is a record for laser pulse with energy less than 10 J. The efficiency for generation of protons with kinetic energy above 15 MeV is 0.1%.     

NanoPARCEL: a method for controlling cellular behavior with external light

We developed a simple preparation procedure for the protein encapsulated nanoparticle and used the nanoparticle for spatiotemporal activity control of various proteins. We succeeded in the local protein activation within cells by light using the nanoparticle.     

Tensile and Tensile-Mode Fatigue Testing of Microscale Specimens in Constant Humidity Environment

A tensile and tensile-mode-fatigue tester has been developed for testing microscale specimens in high humidity environments in order to investigate the fracture mechanisms of microelectromechanical materials. A humidity control system was installed on a tensile-mode fatigue tester equipped with an electrostatic force grip. A specimen and a griping device were inserted into a small chamber and the humidity was controlled by air flow from a temperature and humidity chamber. The humidity stability was within ±2%RH for humidities in the range 25–90%RH for eight hours of testing. Fatigue tests were performed on single-crystal silicon (SCS) specimens in constant humidity environments and laboratory air for up to 10⁶ cycles. The gauge length, width, and thickness of the SCS specimens were 100 or 500 μm, 13.0 μm, and 3.3 μm, respectively. The average tensile strength was 3.68 GPa in laboratory air; this value decreased in high humidity environments. Fatigue failure was observed during cyclic loading at stresses lower than the average strength. A reduction in the fatigue strength was observed at high relative humidities. Different fracture origins and fracture behaviors were observed in tensile tests and fatigue tests, which indicates that the water vapor in air affects the fatigue properties of SCS specimens.