A Ru(I) metalloradical that catalyzes nitrene coupling to azoarenes from arylazides

Unusual N-N coupling of aryl azides to yield azoarenes is demonstrated by the Ru(I) metalloradical, [SiP(iPr)(3)]Ru(N(2)) (4) ([SiP(iPr)(3)] = (2-iPr(2)PC(6)H(4))(3)Si(-)). The yield of the azoarene is dependent on the substituent on the aryl azide, and the reaction is catalytic for p-methoxy and p-ethoxy phenyl azides, while no azoarene is observed for p-trifluoromethylphenyl azide. Studies aimed at probing the viability of a bimolecular coupling mechanism of metal imide species, as shown in the related [SiP(iPr)(3)]Fe system, have led to the isolation of several structurally unusual complexes including the ruthenium(IV) imide, 7-OMe, as well as the Ru(II) azide adduct 8-OMe. One electron reduction of 7-OMe complex led to the isolation of the formally Ru(III) imide complex, [SiP(iPr)(3)]Ru(NAr) (Ar = p-MeOC(6)H(4), 5-OMe). EPR spectroscopy on 5-OMe suggests that the complex is electronically similar to the previously reported imide complex, [SiP(iPr)(3)]Ru(NAr) (Ar = p-CF(3)C(6)H(4,)5-CF(3)), and features radical character on the NAr moiety, but to a greater degree. The stability of 5-OMe establishes that bimolecular coupling of 5-OMe is kinetically inconsistent with the reaction. Further studies rule out mechanisms in which 5-OMe reacts directly with free aryl azide or a transient Ru(I) azide adduct. Together, these studies show that 5-OMe is likely uninvolved in the catalytic cycle and demonstrates the influence of the metal center on the mechanism of reaction. Instead, we favor a mechanism in which free aryl nitrene is released during the catalytic cycle and combines with itself or with free aryl azide to yield the azoarene.     

Intermolecular Radical Reaction of O,Se-Acetals Generated via Seleno-Pummerer Rearrangement

A new general protocol for the synthesis of O,Se-acetals using the seleno-Pummerer reaction has been developed, and their radical-based two- and three-component coupling reactions were studied. The three-component coupling employed the O,Se-acetal, cyclopentenone, and an allylstannane derivative, and enabled stereoselective installations of α-acyloxy alkyl and functionalized allyl groups to generate the 2,3-trans-disubstituted cyclopentanone in a single operation. The obtained highly functionalized structure was used as an intermediate for facile assembly of the zedoarondiol carboskeleton.     

Cyano-bridged Mn(III)-M(III) single-chain magnets with M(III)=Co(III), Fe(III), Mn(III), and Cr(III)

A series of isostructural cyano-bridged Mn(III)(h.s.)-M(III)(l.s.) alternating chains, [Mn(III)(5-TMAMsalen)M(III)(CN)(6)]?4H(2)O (5-TMAMsalen(2-)=N,N'-ethylenebis(5-trimethylammoniomethylsalicylideneiminate), Mn(III)(h.s.)=high-spin Mn(III), M(III)(l.s.)=low-spin Co(III), Mn-Co; Fe(III), Mn-Fe; Mn(III), Mn-Mn; Cr(III), Mn-Cr) was synthesized by assembling [Mn(III)(5-TMAMsalen)](3+) and [M(III)(CN)(6)](3-). The chains present in the four compounds, which crystallize in the monoclinic space group C2/c, are composed of an [-Mn(III)-NC-M(III)-CN-] repeating motif, for which the -NC-M(III)-CN- motif is provided by the [M(III)(CN)(6)](3-) moiety adopting a trans bridging mode between [Mn(III)(5-TMAMsalen)](3+) cations. The Mn(III) and M(III) ions occupy special crystallographic positions: a C(2) axis and an inversion center, respectively, forming a highly symmetrical chain with only one kind of cyano bridge. The Jahn-Teller axis of the Mn(III)(h.s.) ion is perpendicular to the N(2)O(2) plane formed by the 5-TMAMsalen tetradentate ligand. These Jahn-Teller axes are all perfectly aligned along the unique chain direction without a bending angle, although the chains are corrugated with an Mn-N(axis) -C angle of about 144°. In the crystal structures, the chains are well separated with the nearest inter-chain M???M distance being relatively large at 9?? due to steric hindrance of the bulky trimethylammoniomethyl groups of the 5-TMAMsalen ligand. The magnetic properties of these compounds have been thoroughly studied. Mn-Fe and Mn-Mn display intra-chain ferromagnetic interactions, whereas Mn-Cr is characterized by an antiferromagnetic exchange that induces a ferrimagnetic spin arrangement along the chain. Detailed analyses of both static and dynamic magnetic properties have demonstrated without ambiguity the single-chain magnet (SCM) behavior of these three systems, whereas Mn-Co is merely paramagnetic with S(Mn)=2 and D/k(B)=-5.3?K (D being a zero-field splitting parameter). At low temperatures, the Mn-M compounds with M=Fe, Mn, and Cr display remarkably large M versus H hysteresis loops for applied magnetic fields along the easy magnetic direction that corresponds to the chain direction. The temperature dependence of the associated relaxation time for this series of compounds systematically exhibits a crossover between two Arrhenius laws corresponding to infinite-chain and finite-chain regimes for the SCM behavior. These isostructural hetero-spin SCMs offer a unique series of alternating [-Mn-NC-M-CN-] chains, enabling physicists to test theoretical SCM models between the Ising and Heisenberg limits.     

Anchoring of alkyl chain molecules on oxide surface using silicon alkoxide

Chemical states of the interfaces between octadecyl-triethoxy-silane (ODTS) molecules and sapphire surface were measured by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) using synchrotron soft X-rays. The nearly self-assembled monolayer of ODTS was formed on the sapphire surface. For XPS and NEXAFS measurements, it was elucidated that the chemical bond between silicon alkoxide in ODTS and the surface was formed, and the alkane chain of ODTS locates upper side on the surface. As a result, it was elucidated that the silicon alkoxide is a good anchor for the immobilization of organic molecules on oxides.     

Picosecond optical switching of a 1.5 μm active birefringent optical fiber loop filter using 1.3 μm control optical pulses and a 1.3 μm semiconductor optical amplifier

Less than 100ps, polarization-independent switching operation of an active birefringent optical fiber loop filter using 1.3 μm control optical pulses as well as a 1.3 μm semiconductor optical amplifier (SOA) has been demonstrated. In the proposed SOA-based active birefringent filter operating at 1.55 μm wavelength, 1.3 μm SOA is employed to control the polarization-mode dispersion in the loop part. By injecting 1.3 μm ps gain-switched optical control pulses into the SOA, 1.5 μm input signals can be switched from the transmission port to the reflection port with less than 100 ps rise time.     

Mapping of the cationic starch adsorbed on pulp fibers by ToF-SIMS

Cationic starch (CS) is routinely used in the papermaking process to improve the dry strength or printability of paper. The effectiveness depends on the distribution of the starch on the pulp fiber, and in this study, time-of-flight secondary ion mass spectrometry was used to investigate this distribution. The characteristic peak at 58m/z was applied to map the CS. Based on the imaging analysis of the handsheets with the CS as an internal additive, the distribution of CS became more uniform with decreasing freeness. The amount of adsorbed CS increased with increasing fiber length and was lower on vessels than on other fibers. These results were related to fibrillation. From the analysis of handsheets with CS as an external additive, the penetration depth of the starch into base paper increased with decreases in the sizing degree of the base paper.     

A glass capillary microelectrode based on capillarity and its application to the detection of L-glutamate release from mouse brain slices.

A new glass capillary microelectrode for L-glutamate is described using pulled glass capillaries (tip size, approximately 12.5 microm) with a very small volume (approximately 2 microl) of inner solution containing glutamate oxidase (GluOx) and ascorbate oxidase. The operation of the electrode is based on capillary action that samples L-glutamate into the inner solution. The enzyme reaction by GluOx generates hydrogen peroxide that is detected at an Os-gel-HRP polymer modified Pt electrode in a three-electrode configuration. The amperometric response behavior of the electrode was characterized in terms of the capillarity, response time, sensitivity and selectivity for measurements of L-glutamate. The currents at 0 V vs. Ag/AgCl increased linearly with the L-glutamate concentration from 10 to 150 microM for in vitro and in situ calibrations. The response was highly selective to L-glutamate over ascorbate, dopamine, serotonin and other amino acids. The detection of L-glutamate in the extracellular fluids of different regions of mouse hippocampal slices under stimulation of KCl was demonstrated.     

Real-time monitoring of <Emphasis Type="SmallCaps">L</Emphasis>-glutamate release from mouse brain slices under ischemia with a glass capillary-based enzyme electrode

Real-time monitoring of L-glutamate release from various neuronal regions of mouse hippocampal slices under ischemia (a glucose-free hypoxia condition) is described. A glass capillary microelectrode with a tip size of ∼10 μm containing a very small volume (∼2 μL) of a solution of glutamate oxidase (GluOx) and ascorbate oxidase was used. First, the amperometric response behavior of the electrode at 0 V versus Ag/AgCl was characterized with a standard glutamate solution in terms of continuous measurements, effect of oxygen, viscosity of solution and concentration dependence. The electrode was applied to the real-time monitoring of L-glutamate released from different neuronal regions of acute hippocampal slices submerged in a hypoxia solution. The time-resolved amounts of L-glutamate released at various neuronal regions (CA1, CA3 and DG) of mouse hippocampal slices were quantified and compared with the reported L-glutamate fluxes using difference-image analysis during ischemia.     

Molecular interactions between phospholipids and mangostin in a lipid bilayer

Molecular interactions between phospholipids and mangostin in a lipid bilayer have been investigated in terms of the maximum additive concentration (MAC) of mangostin in liposomes, the surface potential, particle size, microscopic-viscosity and microscopic-polarity of liposomes, and the permeability of glucose. The mangostin used is a natural product extract: 1,3,6-trihydroxy-7-methoxy-2,8-bis(3-methyl-2-butenyl)-9-xanthenenone.

The MAC of mangostin was fairly dependent upon the nature of the liposomes (uncharged, negatively charged or positively charged). Solubilization of mangostin in the liposomal bilayer resulted in both an increase in the negative charge on the liposomal surface, strenghthening the state of the bilayer membrane, and a depression in the release of the glucose involved. Mangostin was found to temporarily stabilize the liposomal bilayer, although the bilayer membrane is still unstable in the long run.