Facile synthesis of an ambient stable pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion: from serendipity to design

The stability of singly or multiply negatively charged π-conjugated organic compounds is greatly influenced by their electronic delocalization. Herein, we report a strategic methodology for isolation of a mysterious compound. The isolated compounds, a pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion, were highly stable under ambient conditions due to high delocalization of the negative charge over multiple electron deficient C N groups and pyrene π-scaffolds and allowed purification by column chromatography. To our knowledge, this is the first report on TCNE type reductive condensation of malononitrile involving pyrene di- and tetraone and formation of pyrenopyrrole. All compounds were characterized by spectroscopic methods and X-ray crystallography. A UV-vis spectroscopic study shows an intense low energy absorption band with a large absorption coefficient (ε).

An ambient stable pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion have been isolated and characterized, showing a low energy intense absorption band with the absorption coefficient reaching 7.1 × 10⁴ dm³ mol⁻¹ cm⁻¹.     

Competitive Assay for Theophylline Based on an Abasic Site‐Containing DNA Duplex Aptamer and a Fluorescent Ligand

A fluorescence assay for theophylline, one of the common drugs for acute and chronic asthmatic conditions, has been developed based on an abasic site‐containing DNA duplex aptamer (AP aptamer) in combination with an abasic site‐binding fluorescent ligand, riboflavin. The assay is based on the competitive binding of theophylline and riboflavin at the abasic (AP) site of the AP aptamer. In the absence of theophylline, riboflavin binds to the receptor nucleotide opposite the AP site, which leads to fluorescence quenching of the riboflavin. Upon addition of theophylline, competitive binding occurs between theophylline and riboflavin, which results in an effective fluorescence restoration due to release of riboflavin from the AP site. From an examination of the optimization of the AP aptamers, the complex of riboflavin with a 23‐mer AP aptamer (5′‐TCT GCG TCC AGX GCA ACG CAC AC‐3′/5′‐GTG TGC GTT GCC CTG GAC GCA GA‐3′; X : the AP site (Spacer C3, a propylene residue)) possessing cytosine as a receptor nucleotide was found to show a selective and effective fluorescence response to theophylline; the limit of detection for theophylline was 1.1 μM . Furthermore, fluorescence detection of theophylline was successfully demonstrated with high selectivity in serum samples by using the optimized AP aptamer and riboflavin.     

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.     

基于散射实验极化靶的2.5T/1.3K的动态核极化(DNP)系统的开发

动态核极化法(Dynamic Nuclear Polarization, DNP)是利用热平衡下的电子在磁场中的高自旋极化率转移到原子核自旋的技术,从而极大的提高原子核自旋极化率。多种动态极化靶材料已广泛的用于自旋物理散射实验。本文介绍一种简单实用,共同开发的日本山形大学DNP系统,包括超导磁场,氦4蒸发恒冷器,微波系统以及NMR核磁共振检测系统,测得中子靶材料氘带丁醇(D-butanol)中氘核的极化率在2.5T/1.3K达到+6.5%。     

Complete description of invariant Einstein metrics on the generalized flag manifold SO(2n)/U(p)?× U(n ? p)

We find the precise number of non-K?hler SO(2n)-invariant Einstein metrics on the generalized flag manifold M = SO(2n)/U(p)×U(n−p) with n ≥ 4 and 2 ≤ p ≤ n−2. We use an analysis on parametric systems of polynomial equations and we give some insight towards the study of such systems. We also examine the isometric problem for these Einstein metrics.     

Scanning ion conductance microscopy for imaging biological samples in liquid: a comparative study with atomic force microscopy and scanning electron microscopy

The present study was designed to show the applicability of scanning ion conductance microscopy (SICM) for imaging different types of biological samples. For this purpose, we first applied SICM to image collagen fibrils and showed the usefulness of the approach-retract scanning (ARS)/hopping mode for such samples with steep slopes. Comparison of SICM images with those obtained by AFM revealed that the ARS/hopping SICM mode can probe the surface topography of collagen fibrils and chromosomes at nanoscale resolution under liquid conditions. In addition, we successfully imaged cultured HeLa cells, with 15 μm in height by ARS/hopping SICM mode. Because SICM can obtain non-contact (or force-free) images, delicate cellular projections were visualized on the surface of the fixed cell. SICM imaging of live HeLa cells further demonstrated its applicability to study the morphological dynamics associated with biological processes on the time scale of minutes under liquid conditions. We further applied SICM for imaging the luminal surface of the trachea and succeeded in visualizing the surface of both ciliated and non-ciliated cells. These SICM images were comparable with those obtained by scanning electron microscopy. Although the dynamic mode of AFM provides better resolution than the ARS/hopping mode of SICM in some samples, only the latter can obtain contact-free images of samples with steep slopes, rendering it an important tool for observing live cells as well as unfixed or fixed soft samples with complicated shapes. Taken together, we demonstrate that SICM imaging, especially using an ARS/hopping mode, is a useful technique with unique capabilities for imaging the three-dimensional topography of a range of biological samples under physiologically relevant aqueous conditions.     

Ultracontractivity for Markov Semigroups and Quasi-Stationary Distributions

We prove the existence and uniqueness of quasi-stationary distributions for symmetric Markov processes. In particular, we show that if its Markov semigroup is intrinsic ultracontractive, then there exists a unique quasi-stationary distribution. We apply our results to one-dimensional diffusion processes.     

Effect of temporal resolution on the estimation of left ventricular function by cardiac MR imaging

The aim of this study was to investigate the effect of temporal resolution on the estimation of left ventricular (LV) function by cardiac magnetic resonance (MR) imaging using a steady-state free precession (SSFP) sequence. Left ventricular function was assessed by cine MR imaging using a segmented SSFP sequence in 10 healthy volunteers. Views per segment (VPS) were set at 8 and 20, resulting in high and low true temporal resolution, respectively. Irrespective of VPS, images were reconstructed at 40 cardiac phases, providing high apparent temporal resolution. Data were analyzed using 40, 20 and 10 phases to simulate different apparent temporal resolutions. Increasing the cardiac phases used for analysis slightly decreased mean end-systolic volume (ESV) and slightly increased mean ejection fraction (EF). No substantial difference in estimates of end-diastolic volume (EDV) was found between VPSs of 8 and 20. Imaging with a VPS of 20 yielded a larger ESV and smaller EF than imaging with a VPS of 8 when 40 phases were used. In conclusion, low true temporal resolution causes overestimation of ESV and underestimation of EF. Improvement of apparent temporal resolution mildly reduces but does not eliminate the errors caused by low true temporal resolution.     

Computer-Generated Holograms Based on the Three-Dimensional Fourier Spectrum

A method to synthesize a computer-generated hologram (CGH) of real-existing objects from projection images is proposed. Different from other similar methods, our method enables the synthesis of a CGH with only one-dimensional (1-D) mechanical scanning of the objects. Our method is connected with the three-dimensional (3-D) Fourier spectrum of the objects by the 3-D central slice theorem (CST). Two efficient recording techniques for projection images and numerical experiments to verify our principle is discussed. A comparison between the two techniques is also presented from the viewpoint of diffraction efficiency. © 2005 The Optical Society of Japan     

Parallel Implementation of Successive Convex Relaxation Methods for Quadratic Optimization Problems

As computing resources continue to improve, global solutions for larger size quadrically constrained optimization problems become more achievable. In this paper, we focus on larger size problems and get accurate bounds for optimal values of such problems with the successive use of SDP relaxations on a parallel computing system called Ninf (Network-based Information Library for high performance computing).