A novel anthracene-based fluorescent colorimetric sensor for the simple naked-eye diagnosis of methylmalonic aciduria

A novel molecular sensor using anthracene bearing two amidopyridines emits blue fluorescence in the presence of succinic acid and green fluorescence in the presence of malonic acid, and its fluorescence intensity increased upon binding. Using this molecular sensor, we succeeded in detecting the difference of one carbon atom between succinic acid and malonic acid with the naked-eye. Furthermore, when methylmalonic acid was dissolved in urine to provide a model system for methylmalonic aciduria, the fluorescence changed from blue to green, and methylmalonic acid was successfully detected with the naked-eye.     

Water-soluble supramolecular porphyrin dimer: self-organization of mono(imidazolyl)-substituted Zn porphyrin to a special-pair type dimer in water

Tris(4-carboxylphenyl)-mono(N-methylimidazolyl)-substituted Zn porphyrin was synthesized as a precursor for a water-soluble supramolecular porphyrin dimer. The dimer formation was performed in a NaHCO₃ aq solution (pH 8.4) and phosphate buffer solutions (pH 7.4-9.0). The split Soret bands of Zn porphyrin observed in the absorption spectra clearly showed self-organization to a special-pair type slipped cofacial dimer via metal coordination of imidazole even in water.     

Determination of Ubiquinone in Blood by High-Performance Liquid Chromatography with Post-Column Fluorescence Derivatization Using 2-Cyanoacetamide

It was shown that ubiquinone (CoQ₁₀) and ubiquinol (CoQ₁₀H₂) produce fluorescence products under alkaline conditions when reacted with 2-cyanoacetamide. The reaction mixture from CoQ₁₀ gave fluorescence with excitation and emission maximum wavelengths at 442 nm and 549 nm, respectively. This reaction was considered to proceed via Craven’s reaction. Moreover, 2-cyanoacetamide was shown to be a useful reagent for high-performance liquid chromatography (HPLC) with post-column fluorescence derivatization of CoQ₁₀ and CoQ₁₀H₂ in blood. CoQ₁₀ showed a linear response in the range of 0.32–1276 ng, and the detection limit (S/N = 3) was 0.16 ng. Moreover, the sample pretreatment by deproteinization and extraction of CoQ₁₀ and CoQ₁₀H₂ from plasma using 1-propanol with potassium formate was effective for excellent separation of CoQ₁₀ and CoQ₁₀H₂ from other fluorescent substances in the blood. This simple and rapid pretreatment was considered to minimize the oxidation of CoQ₁₀H₂. On the other hand, CoQ₁₀ and CoQ₁₀H₂ in plasma samples obtained by finger prick were detected, as in venous blood obtained by venipuncture. Our method involving the simple and rapid collection of plasma by finger prick and sample pretreatment is thought to be applicable for the determination of CoQ₁₀H₂/total CoQ₁₀ ratio as a biomarker of oxidative stress.     

Role of Ti 3d carriers in mediating the ferromagnetism of Co∶TiO2 anatase thin films

We study the surface and bulk electronic structure of the room-temperature ferromagnet Co∶TiO(2) anatase films using soft- and hard-x-ray photoemission spectroscopy with probe sensitivities of ～1 and ～10 nm, respectively. We obtain direct evidence of metallic Ti(3+) states in the bulk, which get suppressed to give a surface semiconductor, thus indicating the difference in electronic structure between surface and bulk. X-ray absorption and resonant photoemission spectroscopy reveal Ti(3+) electrons at the Fermi level (E(F)) and high-spin Co(2+) electrons occurring away from E(F). The results show the importance of the charge neutrality condition: Co(2+)+V(O)(2-)+2Ti(4+)?Co(2+)+2Ti(3+) (V(O) is oxygen vacancy), which gives rise to the elusive Ti 3d carriers mediating ferromagnetism via the Co 3d-O 2p-Ti 3d exchange interaction pathway of the occupied orbitals.     

Influence of ordering change on the optical and thermal properties of inflation polyethylene films

Changes of thermal diffusivity inside femtosecond laser-structured volumes as small as few percent were reliably determined (with standard deviation less than 1%) with miniaturized sensors. An increase of thermal diffusivity of a crystalline high-density polyethylene (HDPE) inflation films by 10-20% from the measured (1.16 ± 0.01) × 10⁻⁷ m² s⁻¹ value in regions not structured by femtosecond laser pulses is considerably larger than that of non-crystalline polymers, 0-3%. The origin of the change of thermal diffusivity are interplay between the laser induced disordering, voids’ formation, compaction, and changes in molecular orientation. It is shown that laser structuring can be used to modify thermal and optical properties. The birefringence and infrared spectroscopy with thermal imaging of CH₂ vibrations are confirming inter-relation between structural, optical, and thermal properties of the laser-structured crystalline HDPE inflation films. Birefringence modulation as high as Δn ∼ ± 1 × 10⁻³ is achieved with grating structures.     

Practical techniques for a three‐dimensional FEM analysis of incompressible fluid flow contained with slip walls and a downstream tube bundle

Two practical techniques are proposed in this paper to simulate a flow contained in a plenum with a downstream tube bundle under a PC environment. First, a technique to impose slip wall conditions on smooth‐faced planes and sharp edges is proposed to compensate for the mesh coarseness relative to boundary layer thickness. In particular, a new type of Poisson equation is formulated to simultaneously satisfy both such velocity boundary conditions on walls and the incompressibility constraint. Second, a numerical model for a downstream tube bundle is proposed, where hydraulic resistance in a tube is imposed as a traction boundary condition on a fluid surface contacting the tube bundle end. The effectiveness of the techniques is numerically demonstrated in the application to a flow in a condenser water box. Copyright © 2001 John Wiley & Sons, Ltd.     

A new positive‐definite regularization of incompressible Navier–Stokes equations discretized with Q1/P0 finite element

A new regularization method is proposed for the Galerkin approximation of the incompressible Navier–Stokes equations with Q1/P0 element, by newly introducing a square‐type linear form into the variational divergence‐free constraint regularized with the global pressure jump (GPJ) method. The addition of the square‐type linear form is intended to eliminate the hydrostatic pressure mode appearing in confined flows, and to make the discretized matrix positive definite and then non‐singular without the pressure pegging trick. Effects of the free parameters for the regularization on the solutions are numerically examined with a 2‐D driven cavity flow problem. Furthermore, the convergences in the conjugate gradient iteration for the solution of the pressure Poisson equation are compared among the mixed method, the GPJ method and the present method for both leaky and non‐leaky 3‐D driven cavity flows. Finally, the non‐leaky 3‐D cavity flows at different Re numbers are solved to compare with the literature data and to demonstrate the accuracy of the proposed method. Copyright © 2003 John Wiley & Sons, Ltd.     

On streamline diffusion arising in Galerkin FEM with predictor/multi‐corrector time integration

In the present paper, the author shows that the predictor/multi‐corrector (PMC) time integration for the advection–diffusion equations induces numerical diffusivity acting only in the streamline direction, even though the equations are spatially discretized by the conventional Galerkin finite element method (GFEM). The transient 2‐D and 3‐D advection problems are solved with the PMC scheme using both the GFEM and the streamline upwind/Petrov Galerkin (SUPG) as the spatial discretization methods for comparison. The solutions of the SUPG‐PMC turned out to be overly diffusive due to the additional PMC streamline diffusion, while the solutions of the GFEM‐PMC were comparatively accurate without significant damping and phase error. A similar tendency was seen also in the quasi‐steady solutions to the incompressible viscous flow problems: 2‐D driven cavity flow and natural convection in a square cavity. Copyright © 2002 John Wiley & Sons, Ltd.     

A projection method of estimation for a subfamily of exponential families

Summary This paper is concerned with estimation for a subfamily of exponential-type, which is a parametric model with sufficient statistics. The family is associated with a surface in the domain of a sufficient statistic. A new estimator, termed a projection estimator, is introduced. The key idea of its derivation is to look for a one-to-one transformation of the sufficient statistic so that the subfamily can be associated with a flat subset in the transformed domain. The estimator is defined by the orthogonal projection of the transformed statistic onto the flat surface. Here the orthogonality is introduced by the inverse of the estimated variance matrix of the statistic on the analogy of Mahalanobis's notion (1936,Proc. Nat. Inst. Sci. Ind.,2, 49–55). Thus the projection estimator has an explicit representation with no iterations. On the other hand, the MLE and classical estimators have to be sought as numerical solutions by some algorithm with a choice of an initial value and a stopping rule. It is shown that the projection estimator is first-order efficient. The second-order property is also discussed. Some examples are presented to show the utility of the estimator.