Thiourea-catalyzed nucleophilic addition of TMSCN and ketene silyl acetals to nitrones and aldehydes

The effect of hydrogen bonding between nitrones and urea derivatives in the nucleophilic addition reaction was examined. Thioureas bearing an electron-withdrawing group on an aromatic ring, behave like Lewis acid to promote the addition of TMSCN and ketene silyl acatals to various nitrones and aldehydes. Presumed interaction between nitrones and thioureas was supported by NMR experiments.     

Graphite furnace atomic absorption spectrometric determination of ruthenium in iron meteorites

A procedure for the determination of ruthenium in iron meteorites involves its oxidation to RuO₄ by sodium periodate in hydrochloric acid and extraction of the tetroxide into chloroform. Various parameters of the method were studied: sample dissolution, optimum amount of oxidant, shaking time, distribution ratio and stability of the complex. The relative standard deviation assessed from replicate analyses of the North Chile iron meteorite was 6.6%. There are no certified standards for iron meteorites, but the value of 20.0 μg g^? obtained for this meteorite compares well with a reported abundance of 19.3 μg g^?1 obtained by radiometric neutron-activation analysis (RNAA). The analysis of 15 meteorites that had previously been analysed by RNAA gave values averaging 11% below those reported by the latter method, but within the standard deviation of the RNAA data. It is considered that the present method is a more practical alternative to RNAA for the determination of ruthenium in iron meteorites.     

Use of potassium-form cation-exchange resin as a conductimetric enhancer in ion-exclusion chromatography of aliphatic carboxylic acids

In this study, a cation-exchange resin (CEX) of the K⁺-form, i.e., an enhancer resin, is used as a postcolumn conductimetric enhancer in the ion-exclusion chromatography of aliphatic carboxylic acids. The enhancer resin is filled in the switching valve of an ion chromatograph; this valve is usually used as a suppressor valve in ion-exchange chromatography. An aliphatic carboxylic acid (e.g., CH₃COOH) separated by a weakly acidic CEX column of the H⁺-form converts into that of the K⁺-form (e.g., CH₃COOK) by passing through the enhancer resin. In contrast, the background conductivity decreases because a strong acid (e.g., HNO₃) with a higher conductimetric response in an eluent converts into a salt (e.g., KNO₃) with a lower conductimetric response. Since the pH of the eluent containing the resin enhancer increases from 3.27 to 5.85, the enhancer accelerates the dissociations of analyte acids. Consequently, peak heights and peak areas of aliphatic carboxylic acids (e.g., acetic acid, propionic acid, butyric acid, and valeric acid) with the enhancer resin are 6.3-8.0 times higher and 7.2-9.2 times larger, respectively, than those without the enhancer resin. Calibrations of peak areas for injected analytes are linear in the concentration range of 0.01-1.0 mM. The detection limits (signal-to-noise ratio = 3) range from 0.10 μM to 0.39 μM in this system, as opposed to those in the range of 0.24-7.1 μM in the separation column alone. The developed system is successfully applied to the determination of aliphatic carboxylic acids in a chicken droppings sample.     

Dendritic effects on the ordered assembly and the interfacial one-electron oxidation of redox-active dendron-functionalized gold nanoparticles

A higher generation dendron with a long-alkyl chain thiol (DA2-SH) induced the formation of nanoparticles with a small core with quite a narrow size distribution (1.5 +/- 0.1 nm), the self-assembly of one-dimensional arrays of these gold nanoparticles (DA2-Au), and the stabilization for the formation of the radical cation of the phenothiazine of DA2-Au nanoparticles from the interfacial one-electron oxidation of the nanoparticles with NOBF4.     

Adaptive echolocation sounds of insectivorous bats, Pipistrellus abramus, during foraging flights in the field

Echolocation pulses emitted by wild Pipistrellus abramus were investigated while foraging for insects in the field. Similar to other European pipistrelles, the frequency structure during foraging varied. During the search phase, the bats emitted long shallow frequency-modulated pulses 9-11 ms in duration, whereas the maximum pulse duration of the bats approaching a large target wall in the laboratory was 3 ms. No significant difference was observed between decreases in the interpulse interval during these two approach flights. It is concluded that the bats use a long quasi-constant frequency pulse to find a weak echo from a small prey target.     

Ring-Opened Hemiporphyrazines: Helical Molecules Exhibiting Circularly Polarized Luminescence

We designed and synthesized a new type of small helical molecule exhibiting intense circularly polarized luminescence (CPL) ( 1_2H ) by modifying a 20π-electron hemiporphyrazine with a large transition magnetic dipole moment. The hemiporphyrazine ring was opened and one additional pyridine unit was introduced, resulting in an overlap of two pyridine rings. X-ray structure analysis confirmed that 1_2H and its zinc complex ( 1_Zn ) adopt a helical geometry. A racemic mixture of 1_Zn was resolved into two enantiomers ((P)- and (M)- 1_Zn ), which exhibited CPL with a high luminescence dissymmetry factor (g_lum) value of ±2.1×10⁻². The origin of the large g_lum value was rationalized by means of DFT calculations. Helical structures could be formed in a diastereoselective manner by covalently attaching chiral units to the skeleton ( 1’_2H and 1’_Zn ). 1_Zn was found to possess chiral recognition ability for amines.     

Estimation of dye configuration from conventional chiroptical spectra of porphyrin integrates: combination of exciton theory with Monte Carlo molecular structural simulation

Dye integrates (arrays and aggregates) are the subject of current interest in photochemical devices. However, they are in general not suitable for X-ray crystallography because of their poor crystallinity. Here, we improved a simple method of estimating dye configurations in porphyrin integrates from their visible absorption (AB) and circular dichroism (CD) spectra. For this purpose, we calculate the dipolar and optical rotatory strengths of an integrate on the basis of the exciton theory for a given porphyrin configuration, generate the theoretical AB and CD spectra of the dye integrate using a phenomenological line shape function, a Voigt function with an adjustable line width, and optimize the configuration by minimizing the square sum (S) of the difference between the observed and calculated spectra. We adopted two optimization methods to achieve a least-squares fit between the calculated and observed spectra: the Metropolis Monte Carlo (MC) method, which incorporates S into the molecular force-field energy as a constraint, and the quasi-Newton (QN) method, which numerically minimizes S and uses no molecular force field. To check the feasibility of these methods, we simulated the AB and CD spectra of Tr?ger's base and meso-meso-linked porphyrins using the QN program, then compared the dye configurations with their X-ray structures. The calculated dye configuration of Tr?ger's base porphyrin is sufficiently in agreement with that of the X-ray structure (RMSD=0.21 A for the ZnS4 center), whereas that of meso-meso-linked porphyrin was not. These results were discussed in terms of charge transfer between two porphyrins. Finally, we applied the QN and MC methods to the structural estimation of a newly prepared peptide-linked bis(porphyrin) Boc-(PorZn,S)2-OBut. The best configurations estimated by these two methods were sufficiently in agreement with each other.     

Echo-intensity compensation in echolocating bats (Pipistrellus abramus) during flight measured by a telemetry microphone

An onboard microphone (Telemike) was developed to examine changes in the basic characteristics of echolocation sounds of small frequency-modulated echolocating bats, Pipistrellus abramus. Using a dual high-speed video camera system, spatiotemporal observations of echolocation characteristics were conducted on bats during a landing flight task in the laboratory. The Telemike allowed us to observe emitted pulses and returning echoes to which the flying bats listened during flight, and the acoustic parameters could be precisely measured without traditional problems such as the directional properties of the recording microphone and the emitted pulse, or traveling loss of the sound in the air. Pulse intensity in bats intending to land exhibited a marked decrease by 30 dB within 2 m of the target wall, and the reduction rate was approximately 6.5 dB per halving of distance. The intensity of echoes returning from the target wall indicated a nearly constant intensity (-42.6 +/- 5.5 dB weaker than the pulse emitted in search phase) within a target distance of 2 m. These findings provide direct evidence that bats adjust pulse intensity to compensate for changes in echo intensity to maintain a constant intensity of the echo returned from the approaching target at an optimal range.     

A protocol for searching the most probable phase‐retrieved maps in coherent X‐ray diffraction imaging by exploiting the relationship between convergence of the retrieved phase and success of calculation

Coherent X‐ray diffraction imaging (CXDI) is a technique for visualizing the structures of non‐crystalline particles with size in the submicrometer to micrometer range in material sciences and biology. In the structural analysis of CXDI, the electron density map of a specimen particle projected along the direction of the incident X‐rays can be reconstructed only from the diffraction pattern by using phase‐retrieval (PR) algorithms. However, in practice, the reconstruction, relying entirely on the computational procedure, sometimes fails because diffraction patterns miss the data in small‐angle regions owing to the beam stop and saturation of the detector pixels, and are modified by Poisson noise in X‐ray detection. To date, X‐ray free‐electron lasers have allowed us to collect a large number of diffraction patterns within a short period of time. Therefore, the reconstruction of correct electron density maps is the bottleneck for efficiently conducting structure analyses of non‐crystalline particles. To automatically address the correctness of retrieved electron density maps, a data analysis protocol to extract the most probable electron density maps from a set of maps retrieved from 1000 different random seeds for a single diffraction pattern is proposed. Through monitoring the variations of the phase values during PR calculations, the tendency for the PR calculations to succeed when the retrieved phase sets converged on a certain value was found. On the other hand, if the phase set was in persistent variation, the PR calculation tended to fail to yield the correct electron density map. To quantify this tendency, here a figure of merit for the variation of the phase values during PR calculation is introduced. In addition, a PR protocol to evaluate the similarity between a map of the highest figure of merit and other independently reconstructed maps is proposed. The protocol is implemented and practically examined in the structure analyses for diffraction patterns from aggregates of gold colloidal particles. Furthermore, the feasibility of the protocol in the structure analysis of organelles from biological cells is examined.