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.     

D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

Proton conductivity of phosphoric acid derivative of fullerene

The proton conductive property of methano [60] fullerene diphosphoric acid has been investigated under various humidity conditions at the temperature range between 15 and 45 °C. It shows proton conductivity as high as 10⁻² S cm⁻¹ at 25 °C under relative humidity of 95%. Thermal analyses including TG–DTA and thermal desorption mass spectroscopy (TDS) confirm that the compound is thermally stable up to 200 °C. Proton conduction of the compound depends very much on humidity or water content. The logarithmic conductivity at 25 °C is increased linearly with increasing relative humidity. The activation energy (E_a) estimated from the slope of log(σT) vs. 1/T is decreased from 1.08 to 0.52 eV, as the relative humidity is increased from 40% to 75%. The humidity dependence of conductivity is discussed in the light of the observed hydration isotherm.     

Intake of different chemical species of dietary arsenic by the japanese,and their blood and urinary arsenic levels

We calculated the intake of each chemical species of dietary arsenic by typical Japanese, and determined urinary and blood levels of each chemical species of arsenic. The mean total arsenic intake by 35 volunteers was 195±235 (15.8-1039) μg As day^?1, composed of 76% trimethylated arsenic (TMA), 17.3% inorganic arsenic (As_i), 5.8% dimethylated arsenic (DMA), and 0.8% monomethylated arsenic (MA): the intake of TMA was the largest of all the measured species. Intake of As_i characteristically and invariably occurred in each meal. Of the intake of As_i, 45-75% was methylated in vivo to form MA and DMA, and excreted in these forms into urine. The mean measured urinary total arsenic level in 56 healthy volunteers was 129±92.0 μg As dm^?3, composed of 64.6% TMA, 26.7% DMA, 6.7% As_i and 2.2% MA. The mean blood total arsenic level in the 56 volunteers was 0.73±0.57 μg dl^?1, composed of 73% TMA, 14% DMA and 9.6% As_i. The urinary TMA levels proved to be significantly correlated with the whole-blood TMA levels (r = 0.376; P<0.01).     

A precision measurement of the hyperfine structure of87Sr+

The ground state hyperfine splitting of⁸⁷Sr⁺ was measured with a precision of 1×10^–8. The experiments were performed with an RF ion trap connected to an ISOL (isotope separator on-line), where all the possible transitions between Zeeman sublevels were observed by a laser-microwave double resonance method. The magnetic dipole hyperfine constant was determined to beA=–1 000 473.673 (11) kHz.     

Fluorescent humic substances–arsenic complex in well water in areas where blackfoot disease is endemic in Taiwan

The relationship between the four components, (1) fluorescence intensity, (2) arsenic concentration, (3) pH and (4) total dissolved solids, (TDS) measured in well waters from areas in Taiwan where blackfoot disease (BFD) is endemic was studied, as well as the relationships between the four degrees of BFD and each of the above four symptomatic components, in order to evaluate the etiological factors of BFD more progressively. The following 95% confidence intervals were obtained in well water samples (n = 1189): fluorescence intensity, 26.837–32.570; arsenic concentration, 0.103–0.127 mg dm^?3; pH, 7.466–7.519; and TDS 733.063–801.647 mg dm^?3. Fluorescence intensities of the four degrees of BFD were not all the same (F = 64.54, P < 0.001), and nor were arsenic concentrations (F = 72.03, P < 0.001), pH values (F = 7.30, P < 0.001), nor TDS values (F = 10.76, P < 0.001). In addition, multiple comparisons indicate that the higher the epidemical degree, the higher the fluorescence intensities, arsenic concentrations and pH values become; however, such a relationship is not found for TDS values. Moreover, the fluorescence intensities have positive linear correlations with arsenic concentrations (r = 0.49, P < 0.001), pH (r = 0.25, P < 0.001), and TDS (r = 0.18, P < 0.001), as do the arsenic concentrations with pH (r = 0.22, P < 0.001). Of the four epidemical degree groups, pairs are not significantly different from one another in correlation coefficients between fluorescence intensity and arsenic concentration, which implies a steady relationship between fluorescent compounds and arsenic. We conclude that fluorescent compounds in well water, as possible etiological factors of BFD, are closely related to arsenic along with pH and TDS values in the areas where BFD is endemic. In addition, we infer that a complex is formed by fluorescent compounds, arsenic and other metals.     

Spin structure and weak ferromagnetism of Mn3Sn

The compound Mn₃Sn shows an interesting magnetic behavior. A triangular screw spin structure has been observed below 250 K, whose period is independent of temperature. The screw structure is sensitive to heat treatment, alloy composition and impurity content.     

A compact optical heterodyne interferometer by optical integration and its application

A compact high-resolution optical heterodyne interferometer combining a two-frequency light module and a minute optical system is described. The light module, which generates two independent frequencies of light, is fabricated by proton exchange method on LiNbO₃ substrate. We report an experiment evaluating measurement accuracy using a micro-displacement measurement system which incorporates this interferometer. Results of the experiment with a standard thickness sample show high thermal stability with maximum measurement error of 1.8 nm at a temperature from 19°C to 33°C. The system was used to measure the hysteresis of a piezoelectric element for displacements of several nm, thereby making it possible to analyze the system quantitatively in practice.