Specifications of a neutron exposure accelerator system for biological effects experiments (NASBEE) in NIRS

We developed a neutron irradiation facility, neutron exposure accelerator system for biological effect experiments (NASBEE) for biological studies in National Institute of Radiological Sciences, Japan. Irradiation field of 2 MeV average neutrons generated by a Be(d–n)B reaction is established. Dose uniformity of 240 mm in diameter irradiation field is producible within ±2.5% with a dose rate of 0.87 Gy/h at sample target distance of 1170 mm. Two irradiation rooms, a specific pathogen-free (SPF) conditioned one and a conventional, are now available. Irradiation protocols for in vitro experiments are now established and demonstrated by obtaining a relative biological effectiveness (RBE) of cell inactivation measured to be 3.54 with 10% survival dose (D₁₀).     

Low-temperature heat capacity of triangle antiferromagnetic molecular clusters K12[(VO)3(SbW9O33)2]·15H2O and K12[(VO)3(BiW9O33)2]·29H2O

Energy level diagrams have been determined for two molecular clusters, K₁₂[(VO)₃(SbW₉O₃₃)₂]·15H₂O and K₁₂[(VO)₃(BiW₉O₃₃)₂]·29H₂O, by low-temperature heat capacity measurements down to 85 mK under magnetic field strengths up to 9 T. Both compounds exhibit a broad heat capacity peak dependent upon the magnetic field, which can be explained by the thermal excitation in the magnetic energy levels. A detailed analysis based on the numerical calculation reveals that the spin-spin interaction between the V⁴⁺ ions includes a Dzyaloshinskii-Moriya interaction.     

Effect of chloroform on complexation and chiral aggregation of bilirubin-bovine serum albumin at heptane/water interface

The effect of chloroform on the chiroselective reaction between bilirubin (BR) and bovine serum albumin (BSA) at the interface between a heptane phase (including CHCl(3)) and an aqueous phase was investigated by means of the absorption and circular dichroism (CD) spectroscopies combined with a centrifugal liquid membrane (CLM) method, and a CLM microscopic fluorescence spectroscopy as well. The observed absorption, CD and fluorescence spectra disclosed the interfacial complexation process of BR with BSA for the first time, suggesting further aggregation of the BR-BSA complex at the interface. It was noticed more that, due to the formation of the chiral aggregates of BR-BSA complex, the interfacial CD signal of M(-) conformation of BR was appeared gradually. However, higher content of CHCl(3) in the organic phase, resulting in the increase in fluorescence intensity, evidently affected the formation of the aggregates of the complex at the interface. The addition of extra CHCl(3) to the interfacial aggregates induced temporal inversion of CD sign of BR, which should be caused by the local structural change of BSA brought about by the specific solvation of CHCl(3).     

Effect of a carboxyl group on the chemiluminescent reaction of tris(2,2′-bipyridine)ruthenium(III) with aliphatic amines

The effect of a carboxyl group beside nitrogen of aliphatic amines on the tris(2,2′-bipyridine)ruthenium(III), Ru(bpy)₃³⁺, chemiluminescent reaction was examined. It has been shown that a carboxylate anion promotes the chemiluminescent reaction at a lower pH and then the aliphatic amines with this substituent can be sensitively detected compared with corresponding aliphatic amines without this substituent. Based on this finding, preliminary studies on simultaneous determination of 4-hydroxyproline, N-methylglycine, N-methylalanine, proline, and pipecolic acid in human serum have been performed using isocratic reversed-phase ion-pair high-performance liquid chromatography (HPLC) with electrogenerated Ru(bpy)₃³⁺ chemiluminescent detection. The detection limits (signal-to-noise ratio of 3) with the proposed method were 3.0, 12, 2.7, 4.6, and 10 nM for 4-hydroxyproline, N-methylglycine, N-methylalanine, proline, and pipecolic acid, respectively.     

A fluorous tag-bound fluorescence derivatization reagent, F-trap pyrene, for reagent peak-free HPLC analysis of aliphatic amines

We have developed a novel pre-column fluorescence derivatization reagent for amines, F-trap pyrene. This reagent comprises a fluorescent pyrene moiety, an amine-reactive Marshall linker, and a fluorophilic perfluoroalkyl group known as fluorous tag. When the reagent reacts with aliphatic amines and amino acids to give fluorescent derivatives, the fluorous tag in the reagent is eliminated simultaneously. Therefore, excess unreacted reagents in the derivatization reaction solution still have the fluorous tag and could be removed by fluorous solid-phase extraction selectively before high-performance liquid chromatography (HPLC) analysis. By using this reagent, 13 kinds of aliphatic amine (C₂–C₁₆) derivatives can be separated within 40 min by reversed-phase HPLC with gradient elution. In this chromatogram, unreacted reagents peak at around 28 min, greatly decrease after fluorous solid-phase extraction, and do not interfere with the quantification of each amine. The detection limits (S/N = 3) for examined aliphatic amines are 3.6–25 fmol per 20 μL injection. We have also applied this reagent successfully to the amino acid analysis.

Neuron phase shift adaptive to time delay in locomotor control

Based on neurophysiological evidence, theoretical studies have shown that walking can be generated by mutual entrainment of oscillations of a central pattern generator (CPG) and a body. However, it has also been shown that the time delay in the sensorimotor loop destabilizes mutual entrainment, and results in the failure to walk. Recently, it has been reported that if (a) the neuron model used to construct the CPG is replaced by physiologically faithful neuron model (Bonhoeffer–Van der Pol type) and (b) the mechanical impedance of the body (muscle viscoelasticity) is controlled depending on the angle between two legs, the phase relationship between CPG activity and body motion could be flexibly locked according to the loop delay and, therefore, mutual entrainment can be stabilized. That is, locomotor control adaptive to the loop delay can emerge from the coupling between CPG and body. Here, we call this mechanism flexible-phase locking. In this paper, we construct a system of coupled oscillators as a simplified model of a walking system to theoretically investigate the mechanism of flexible-phase locking, and to analyze the simplified model. The analysis suggests that the following are required as the essential mechanism: (i) an asymptotically stable limit cycle of the coupling system of CPG and body and (ii) a sign difference between afferent and efferent coupling coefficients.     

The Memetic Tree-based Genetic Algorithm and its application to Portfolio Optimization

We introduce a Memetic system to solve the application problem of Financial Portfolio Optimization. This problem consists of selecting a number of assets from a market and their relative weights to form an investment strategy. These weights must be optimized against a utility function that considers the expected return of each asset, and their co-variance; which means that as the number of available assets increases, the search space increases exponentially. Our method introduces two new concepts that set it apart from previous evolutionary based approaches. The first is the Tree-based Genetic Algorithm (GA), a recursive representation for individuals which allows the genome to learn information regarding relationships between the assets, and the evaluation of intermediate nodes. The second is the hybridization with local search, which allows the system to fine-tune the weights of assets after the tree structure has been decided. These two innovations make our system superior than other representations used for multi-weight assignment of portfolios.     

Two-dimensional networks based on Mn4 complex linked by dicyanamide anion: from single-molecule magnet to classical magnet behavior

Three two-dimensional (2D) network compounds based on Mn(III)/Mn(II) tetranuclear single-molecule magnets (SMMs) connected by dicyanamide (dcn-) linkers have been synthesized: [Mn4(hmp)4(Hpdm)2(dcn)2](ClO4)2 x 2 H2O x 2 MeCN (2), [Mn4(hmp)4Br2(OMe)2(dcn)2] x 0.5 H2O x 2 THF (3), [Mn4(hmp)6(dcn)2](ClO4)2 (4), where Hhmp and H2pdm are 2-hydroxymethylpyridine and pyridine-2,6-dimethanol, respectively. The [Mn4]/dcn- system appears very versatile, but enables its chemistry to be rationalized by a fine-tune of the synthetic conditions. The double cuboidal [Mn4] unit is preserved in the whole family of compounds, despite strong modifications of its Mn(II) coordination sphere. The chemical control of the coordination number of dcn- on the Mn(II) sites has been the key to obtain the following series of compounds: a discrete cluster, [Mn4(hmp)6(NO3)2(dcn)2] x 2 MeCN (1), 2D networks (2, 3, and 4), and the previously reported 3D compound, [Mn4(hmp)4(mu3-OH)2][Mn(II)(dcn)6] x 2 MeCN x THF. Direct current magnetic measurements show that both Mn2+-Mn3+ and Mn3+-Mn3+ intra-[Mn4] magnetic interactions are ferromagnetic leading to an S(T) = 9 ground state for the [Mn4] unit. Despite the very similar 2D lattices in 2-4, the two kinds of orientation of the [Mn4] unit (i.e., angle variations between the two easy axes) lead to different magnetic properties ranging from SMM behavior for 2 and 1 to a long-range canted antiferromagnetic order for 4. Compound 3 is more complicated as the magnetic measurements strongly suggest the presence of a canted antiferromagnetic order below 2.1 K, although the magnetization slow relaxation is simultaneously observed. Heat capacity measurements confirm the long-range magnetic order in 4, while in 3, the critical behavior is frozen by the slow relaxation of the anisotropic [Mn4] units.     

In situ and ex situ observations of the growth dynamics of single perylene nanocrystals in water

The growth dynamics of fluorescent perylene nanocrystals, which are fabricated by the reprecipitation method, was investigated using in situ and ex situ single-particle fluorescence measurements. A red shift in the emission maxima as the aging time increased was observed by single-particle fluorescence spectral measurements. The number and size of the nanocrystals increased with the increasing aging time in water. It was concluded that the metastable intermediates, such as clusters and initial nanoparticles, are relevant for the early stages of nucleation and growth of the perylene nanocrystals.     

Two new 15-deoxycimigenol-type and three new 24-epi-cimigenol-type glycosides from Cimicifuga Rhizome

Two new 15-deoxycimigenol-type (1, 2) and three new 24-epi-cimigenol-type glycosides (3-5) were isolated from Cimicifuga Rhizome, and the structures were elucidated on the basis of spectroscopic data including 2D NMR spectra and chemical evidence. The two new 15-deoxycimigenol-type glycosides were the first cimigenol-type glycosides lacking a hydroxyl group at C-15.