Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

Evaluation of measurement uncertainty in the elemental analysis of sintered silicon carbide using laser ablation in liquid—inductively coupled plasma mass spectrometry with external calibration and isotope dilution

Accreditation and Quality Assurance - The goal of this study was to evaluate the uncertainty of elemental analytical methods that use laser ablation in liquid (LAL) as a pretreatment. After LAL...     

Polyether-bridged bis(tert-butyl nitroxide) paramagnetic hosts showing receptor ability to calcium(II) and barium(II) ions

The title compounds, Ph2bNO and Ph3bNO, were designed as a biradical paramagnetic host, and their chelation ability was confirmed by inclusion of a size-matched alkaline-earth metal ion. The crystal structures of [Ca(hfac)₂(Ph2bNO)] and [Ba(hfac)₂(Ph3bNO)] were determined, where Hhfac stands for 1,1,1,5,5,5-hexafluoropentane-2,4-dione. The solution electron paramagnetic resonance spectra showed switching behavior. Five lines were found for Ph3bNO and charecterized as the hyperfine splitting due to the two nitrogen atoms. After addition of barium(II) ion, the spectrum turned to be three lines. Removal of the barium ion recovered the five line pattern. The present system can be regarded as a reversible magnetic-coupling switch by means of a supramolecular technique.     

The intramolecular Morita-Baylis-Hillman-type alkylation reaction

From the initial development of a homologous Morita-Baylis-Hillman reaction utilizing epoxides as electrophiles, the method was expanded to enable the exclusively organocatalyzed intramolecular allylation of enones and to develop the intramolecular MBH-type alkylation of activated alkenes. We successfully utilized both enones and unsaturated thioesters as the activated alkene component. This work, carried out using stoichiometric amounts of the trialkylphosphine, gave an array of functionalized five- and six-membered carbocycles in high yields. With the cycloalkylation of enones and thioesters, conditions that allowed the use of substoichometric amounts of the phosphine catalyst were developed. As a result both five- and six-membered rings can be formed efficiently with little to no loss in yield upon comparison to yields obtained when stoichiometric amounts of trialkylphosphines were employed. We isolated, for the first time, an MBH-type intermediate exhibiting unprecedented trans geometry of the phosphonium salt and acyl group.     

On energy estimates for second order hyperbolic equations with Levi conditions for higher order regularity

We consider energy estimates for second order homogeneous hyperbolic equations with time dependent coefficients. The property of energy conservation, which holds in the case of constant coefficients, does not hold in general for variable coefficients; in fact, the energy can be unbounded as t → ∞ in this case. The conditions to the coefficients for the generalized energy conservation (GEC), which is an equivalence of the energy uniformly with respect to time, has been studied precisely for wave type equations, that is, only the propagation speed is variable. However, it is not true that the same conditions to the coefficients conclude (GEC) for general homogeneous hyperbolic equations. The main purpose of this paper is to give additional conditions to the coefficients which provide (GEC); they will be called as C ^k -type Levi conditions due to the essentially same meaning of usual Levi condition for the well-posedness of weakly hyperbolic equations.     

Generalised energy conservation law for wave equations with variable propagation speed

We investigate the long time behaviour of the L²-energy of solutions to wave equations with variable speed of propagation. The novelty of the approach is the combination of estimates for higher order derivatives of the coefficient with a stabilisation property.     

Modification and limitations of the Livinghouse catalytic Pauson-Khand reaction

The difficult and impractical purification of Co₂(CO)₈ is not necessary in the catalytic thermal Pauson-Khand reaction previously described by Livinghouse.     

Complexity of Body Movements during Sleep in Children with Autism Spectrum Disorder

Recently, measuring the complexity of body movements during sleep has been proven as an objective biomarker of various psychiatric disorders. Although sleep problems are common in children with autism spectrum disorder (ASD) and might exacerbate ASD symptoms, their objectivity as a biomarker remains to be established. Therefore, details of body movement complexity during sleep as estimated by actigraphy were investigated in typically developing (TD) children and in children with ASD. Several complexity analyses were applied to raw and thresholded data of actigraphy from 17 TD children and 17 children with ASD. Determinism, irregularity and unpredictability, and long-range temporal correlation were examined respectively using the false nearest neighbor (FNN) algorithm, information-theoretic analyses, and detrended fluctuation analysis (DFA). Although the FNN algorithm did not reveal determinism in body movements, surrogate analyses identified the influence of nonlinear processes on the irregularity and long-range temporal correlation of body movements. Additionally, the irregularity and unpredictability of body movements measured by expanded sample entropy were significantly lower in ASD than in TD children up to two hours after sleep onset and at approximately six hours after sleep onset. This difference was found especially for the high-irregularity period. Through this study, we characterized details of the complexity of body movements during sleep and demonstrated the group difference of body movement complexity across TD children and children with ASD. Complexity analyses of body movements during sleep have provided valuable insights into sleep profiles. Body movement complexity might be useful as a biomarker for ASD.     

Catalyst precursors for the catalytic Pauson-Khand reaction

Dicobalt hexacarbonyl complexes of enynes serve as Co₂(CO)₈ surrogates for the intramolecular Pauson-Khand cycloaddition. Enynes with polar functional groups allow for easy separation of the catalyst cyclopentenone by-product (acid or base wash, silica gel plug column) from the desired cyclopentenone.