Subincanadines A-C,novel quaternary indole alkaloids from Aspidosperma subincanum

Three novel quaternary indole alkaloids with an unprecedented 1-azoniatricyclo[4.3.3.0(1,5)]undecane moiety, subincanadines A-C (1-3), as well as two new indole alkaloids with a 1-azabicyclo[5.2.2]undecane moiety, subincanadines D (4) and E (5), and a new indole alkaloid with a 1-azabicyclo[4.3.1]decane moiety, subincanadine F (6), have been isolated from the barks of Aspidosperma subincanum Mart, and the structures of 1-6 and the stereochemistry of 1-3 were elucidated by spectroscopic data and chemical means.     

Rattling in the Quadruple Perovskite CuCu3V4O12

Of particular interest is a peculiar motion of guest atoms or ions confined to nanospace in cage compounds, called rattling. While rattling provides unexplored physical properties through the guest–host interactions, it has only been observed in a very limited class of materials. Herein, we introduce an A‐site‐ordered quadruple perovskite, CuCu₃V₄O₁₂, as a new family of cage compounds. This novel AA′₃B₄O₁₂‐type perovskite has been obtained by a high‐pressure synthesis technique and structurally characterized to have cubic Im$\bar 3$ symmetry with an ionic model of Cu²⁺Cu²⁺₃V⁴⁺₄O₁₂. The thermal displacement parameter of the A‐site Cu²⁺ ion is as large as U_iso≈0.045 Ų at 300 K, indicating its large‐amplitude thermal oscillations in the oversized icosahedral cages. Remarkably, the presence of localized phonon modes associated with rattling of the A‐site Cu²⁺ ion manifests itself in the low‐temperature specific heat data. This work sheds new light on the structure–property relations in perovskites.     

Drastic difference in the photo-driven hydrogenation reactions of ruthenium complexes containing NAD model ligands

Successful control of photo-driven NAD(+)/NADH type hydrogenation reactions in ruthenium complexes has been accomplished by using a new NAD(+) model ligand with modulated distortion of the ligand taking advantage of the substituent effect.     

Organometallic compounds : XII. stereochemical interconversion reactions between 1,1′−bis(α-hydroxyalkyl)ferrocenes and 7-oxa[3]ferrocenophanes

Meso and racemic isomers of 1,1′-bis(α-hydroxyalkyl)ferrocene derivatives, and trans and cis isomers of 7-oxa[3]ferrocenophanes have been isolated. The configurations of these isomers have been determined both by spectroscopy and from their reaction behavior. It has been found that the ring-closure and ring-opening interconversion reactions between 1,1′-bis(α-hydroxyalkyl)ferrocenes and 7-oxa[3]ferrocenophanes are stereospecific. PMR spectra of the diols and ethers have been examined at 100 MHz in CF₃COOH, and the existence of α-[1′-(α-hydroxyalkyl)ferrocenyl]carbonium ions has been demonstrated in this acid. A mechanism for the various interconversion reactions is proposed on the basis of their stereospecific reactivity and from the PMR spectra of the carbonium ions.     

Sequential injection chemiluminescence immunoassay for nonionic surfactants by using magnetic microbeads

A rapid and sensitive immunoassay based on a sequential injection analysis (SIA) using magnetic microbeads for the determination of alkylphenol polyethoxylates (APnEOs) is described. An SIA system was constructed from a syringe pump, a switching valve, a flow-through type immunoreaction cell equipped with a photon counting unit and a neodymium magnet. Magnetic beads, to which an anti-APnEOs monoclonal antibody was immobilized, were used as a solid support in an immunoassay. The introduction, trapping and release of the magnetic beads in and from the immunoreaction cell were controlled by means of a neodymium magnet and adjusting the flow of a carrier solution. The immunoassay was based on an indirect competitive immunoreaction of an anti-APnEOs monoclonal antibody immobilized on the magnetic beads with a sample APnEOs and a horseradish peroxidase (HRP)-labeled APnEOs in the same sample solution, and was based on the subsequent chemiluminscence reaction of HRP on the magnetic microbeads with a luminol solution containing hydrogen peroxide and p-iodophenol. The anti-APnEOs antibody was immobilized on the magnetic microbeads by coupling the antibody with the magnetic beads after activation of a carboxylate moiety on the surface of the magnetic beads that had been coated with a polylactic acid film. The antibody immobilized magnetic beads were introduced in the immunoreaction cell and trapped in it by the neodymium magnet, which was equipped beneath the immunoreaction cell. An APnEOs sample solution containing the HRP-labeled APnEOs at a constant concentration, and a luminol solution containing hydrogen peroxide and p-iodophenol were sequentially introduced into the immunoreaction cell, according to an SIA programmed sequence. Chemiluminescence emission was monitored by means of a photon counting unit located at the upper side of the immunoreaction cell by collecting the emitted light with a lens. A typical sigmoidal calibration curve was obtained, when the logarithm of the concentration of APnEOs was plotted against the chemiluminescence intensity as the number of photons in 100 ms using standard APnEOs sample solutions at various concentrations (0–1000 ppb) under optimum conditions. The lower detection limit defined as IC₈₀ is ca 10 ppb. The time required for analysis is less than 15 min per a sample. The present method was successfully applied to the determination of APnEOs in river water.     

A self-contained polymeric 2-DE chip system for rapid and easy analysis

We developed a polymeric 2-DE chip system. The chip consisted of an IEF region, an SDS-PAGE region, a valveless connection port, and a sample introduction port. A "junction structure" as a valveless connection port, which allowed separating and connecting the first- and second-dimensional gels, was fabricated between their regions. A "solution inlet" as a sample introduction port was fabricated to perform the liquid and sample introductions without solution leakage. Simultaneous sample monitoring was performed using the on-chip detection system. The performances of the system were demonstrated using commercially available proteins as a standard specimen and tissue-extracted proteins as the real samples. All procedures were employed without any movement of relocation part. This new 2-D separation system realized improved labor-intensive operations and a reduced experimental time.     

OXIDATION OF RIBOSE MOIETY OF ADENOSINE INDUCED BY IRRADIATION OF NEAR-UV LIGHT IN THE PRESENCE OF IRON(III) CHLORIDE

Abstract— Irradiation of near-UV light in the presence of FeCl₃ caused oxidation of adenosine with concomitant reduction of Fe(III) under either aerobic or anaerobic atmosphere. Major photoproducts were adenine and adenosine-5'-aldehyde, showing that oxidation took place mostly at the ribose moiety of adenosine. Detailed study showed that the reaction proceeded by the light absorption due to Fe(III) at 300-350 nm.     

Synthesis and characterization of A4[Re6Q8L6]@SiO2 red-emitting silica nanoparticles based on Re6 metal atom clusters (A = Cs or K, Q = S or Se, and L = OH or CN)

Metal atom clusters constitute very promising candidates as luminophores for applications in biotechnology because they are nanosized entities offering robust luminescence in the near-infrared field (NIR). However, they cannot be used as prepared for biological applications because of potential toxic effects and quenching of the clusters' luminescence in aqueous media, and they therefore need to be dispersed in a biocompatible matrix. We describe herein the encapsulation of octahedral rhenium clusters, denoted as A(4)[Re(6)Q(8)L(6)] (A = Cs or K, Q = S or Se, and L = OH or CN), in silica nanoparticles by a water-in-oil microemulsion process, paying particular attention to the clusters' stability. The obtained A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles are 30 nm in size with good monodispersity and a perfectly spherical shape, as shown by scanning electron microscopy (SEM). The presence of cluster units inside the silica matrix was evidenced by scanning transmission electron microscopy in annular dark-field mode (ADF-STEM). From the point of view of their optical properties, the A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles show red and NIR emission under UV excitation, even when dispersed in water. The evolution of the structural and luminescence properties of clusters before and after encapsulation was followed by Raman and photoluminescence spectroscopy.     

Formation of double helix self-assembled monolayers of ethynylhelicene oligomer disulfides on gold surfaces

Optically active ethynylhelicene pentamers and hexamers linked by disulfide bonds were synthesized. They formed self-assembled monolayers (SAMs) with double helix structure on gold surfaces, which were analyzed by infrared reflection-absorption spectroscopy (IR-RAS), quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and circular dichroism (CD). Double helix SAMs could be formed on gold surfaces either from double helices or random coils in solution. The double helices on the surface were more stable than in solution. This result suggested the presence of strong intercomplex interactions between double helix complexes on the surface.