Development of a zinc ion-selective luminescent lanthanide chemosensor for biological applications

Detection of chelatable zinc (Zn(2+)) in biological studies has attracted much attention recently, because chelatable Zn(2+) plays important roles in many biological systems. Lanthanide complexes (Eu(3+), Tb(3+), etc.) have excellent spectroscopic properties for biological applications, such as long luminescence lifetimes of the order of milliseconds, a large Stoke's shift of >200 nm, and high water solubility. Herein, we present the design and synthesis of a novel lanthanide sensor molecule, [Eu-7], for detecting Zn(2+). This europium (Eu(3+)) complex employs a quinolyl ligand as both a chromophore and an acceptor for Zn(2+). Upon addition of Zn(2+) to a solution of [Eu-7], the luminescence of Eu(3+) is strongly enhanced, with high selectivity for Zn(2+) over other biologically relevant metal cations. One of the important advantages of [Eu-7] is that this complex can be excited with longer excitation wavelengths (around 340 nm) as compared with previously reported Zn(2+)-sensitive luminescent lamthanide sensors, whose excitation wavelength is at too high an energy level for biological applications. The usefulness of [Eu-7] for monitoring Zn(2+) changes in living HeLa cells was confirmed. This novel Zn(2+)-selective luminescent lanthanide chemosensor [Eu-7]should be an excellent lead compound for the development of a range of novel luminescent lanthanide chemosensors for biological applications.     

Pseudo Approximation Algorithms with Applications to Optimal Motion Planning

We introduce a technique for computing approximate solutions to optimization problems. If $X$ is the set of feasible solutions, the standard goal of approximation algorithms is to compute $x\in X$ that is an $\varepsilon$-approximate solution in the following sense: $$d(x) \leq (1+\varepsilon)\, d(x^*),$$ where $x^* \in X$ is an optimal solution, $d\colon\ X\rightarrow {\Bbb R}_{\geq 0}$ is the optimization function to be minimized, and $\varepsilon>0$ is an input parameter. Our approach is first to devise algorithms that compute pseudo $\varepsilon$-approximate solutions satisfying the bound $$d(x) \leq d(x_R^*) + \varepsilon R,$$ where $R>0$ is a new input parameter. Here $x^*_R$ denotes an optimal solution in the space $X_R$ of $R$-constrained feasible solutions. The parameter $R$ provides a stratification of $X$ in the sense that (1) $X_R \subseteq X_{R}$ for $R < R$ and (2) $X_R = X$ for $R$ sufficiently large. We first describe a highly efficient scheme for converting a pseudo $\varepsilon$-approximation algorithm into a true $\varepsilon$-approximation algorithm. This scheme is useful because pseudo approximation algorithms seem to be easier to construct than $\varepsilon$-approximation algorithms. Another benefit is that our algorithm is automatically precision-sensitive. We apply our technique to two problems in robotics: (A) Euclidean Shortest Path (3ESP), namely the shortest path for a point robot amidst polyhedral obstacles in three dimensions, and (B) $d_1$-optimal motion for a rod moving amidst planar obstacles (1ORM). Previously, no polynomial time $\varepsilon$-approximation algorithm for (B) was known. For (A), our new solution is simpler than previous solutions and has an exponentially smaller complexity in terms of the input precision.     

Ruthenium catalyzed addition reaction of carboxylic acid across olefins without beta-hydride elimination

The cationic ruthenium catalyst (Cp*RuCl2)2/AgOTf/Ligand promotes the addition reaction of carboxylic acids across olefins without beta-hydride elimination.     

Determination of distance of intra-molecular hydrogen bonding in (Ala-Gly)15 with silk I form after removal of the effect of MAS frequency in REDOR experiment

It is important to know the structure of silk I (Bombyx mori silk structure before spinning in the solid state) in order to understand the mechanism of fiber formation at the atomic level. In this study, 15N-dephased, 13C-observe REDOR has been carried out to determine the atomic distance of intra-molecular hydrogen bond between the 13C=O carbon of the 14th Gly residue and the 15N nitrogen of the 17th Ala residue of (AG)(6)A[1-13C]GAG[15N]AG(AG)(6) with silk I form after removal of the effect of MAS frequency on the re-coupling. The distance was determined to be 4.3A, which confirmed the intra-molecular hydrogen bonding formation between these two atomic sites.     

60]fullerenoacetyl chloride as a versatile precursor for fullerene derivatives: efficient ester formation with various alcohols

[reaction: see text] [60]Fullerenoacetyl chloride, one of the reactive derivatives of [60]fullerenoacetic acid, was isolated and identified for the first time. This acid chloride was easily synthesized in good yield from tert-butyl [60]fullerenoacetate through two steps. In the presence of 4-(dimethylamino)pyridine as a base, the acid chloride smoothly reacted with various alcohols under mild conditions to give the corresponding esters including [60]fullerene-biomolecule hybrids in moderate to high yields.     

Some Geometry of the Cone of Nonnegative Definite Matrices and Weights of Associated X2 Distribution

Consider the test problem about matrix normal mean M with the null hypothesis M = O against the alternative that M is nonnegative definite. In our previous paper (Kuriki (1993, Ann. Statist., 21, 1379–1384)), the null distribution of the likelihood ratio statistic has been given in the form of a finite mixture of ² distributions referred to as X² distribution. In this paper, we investigate differential-geometric structure such as second fundamental form and volume element of the boundary of the cone formed by real nonnegative definite matrices, and give a geometric derivation of this null distribution by virtue of the general theory on the X² distribution for piecewise smooth convex cone alternatives developed by Takemura and Kuriki (1997, Ann. Statist., 25, 2368–2387).     

On the Eigenstates of the Elliptic Calogero–Moser Model

It is known that the trigonometric Calogero–Sutherland model is obtained by the trigonometric limit (–1) of the elliptic Calogero–Moser model, where (1, ) is a basic period of the elliptic function. We show that for all square-integrable eigenstates and eigenvalues of the Hamiltonian of the Calogero–Sutherland model, if exp(2–1) is small enough then there exist square-integrable eigenstates and eigenvalues of the Hamiltonian of the elliptic Calogero–Moser model which converge to the ones of the Calogero–Sutherland model for the 2-particle and the coupling constant l is positive integer cases and the 3-particle and l=1 case. In other words, we justify the regular perturbation with respect to the parameter exp(2–1). With some assumptions, we show analogous results for N-particle and l is positive integer cases.     

High-temperature protonic motion and low-temperature lattice deformation in one-dimensional hydrogen-bonded molecular chain in tetramethylpyrazine–chloranilic acid (1:1)

Recent theoretical advances have identified several computational algorithms that can be implemented utilizing quantum information processing (QIP), which gives an exponential speedup over the corresponding (known) algorithms on conventional computers. QIP makes use of the counter-intuitive properties of quantum mechanics, such as entanglement and the superposition principle. Unfortunately it has so far been impossible to build a practical QIP system that outperforms conventional computers. Atomic ions confined in an array of interconnected traps represent a potentially scalable approach to QIP. All basic requirements have been experimentally demonstrated in one and two qubit experiments. The remaining task is to scale the system to many qubits while minimizing and correcting errors in the system. While this requires extremely challenging technological improvements, no fundamental roadblocks are currently foreseen.     

Correlation between proton transfer and 35Cl NQR frequency as well as molecular geometry of chloranilic acid in co‐crystals with some organic bases

Proton transfer in hydrogen‐bonded organic co‐crystals of chloranilic acid with some organic bases was investigated by nuclear quadrupole resonance (NQR) spectroscopy. The ³⁵Cl NQR frequencies of chloranilic acid molecule as well as ¹⁴N NQR frequencies of the organic base molecule were measured with the conventional pulse methods as well as double‐resonance methods, respectively. The extent of proton transfer in the O···H···N hydrogen bond was estimated from Townes–Dailey analysis of the ¹⁴N NQR parameters. The ³⁵Cl NQR frequency and molecular geometry of chloranilic acid are correlated to the extent of proton transfer in the protonation process of the organic base molecule. It is shown that the hydrogen bond affects the π‐electron system of chloranilic acid. Geometry dependence of the O···H···N hydrogen bond, i.e. the H? N valence bond order versus the hydrogen‐bond geometry correlation is also discussed. Copyright © 2010 John Wiley & Sons, Ltd.