Hexakis(2,4,6-triisopropylphenylsilsesquioxane)

Hexasilsesquioxanes bearing bulky Tip (2,4,6-triisopropylphenyl) groups were synthesized and the structure was determined. The X-ray crystal analysis revealed that the enantiomer pair originating from the restricted rotation of the bulky Tip groups was included in the single lattice. In solution, evidence for the rapid interconversion of both enantiomers was encountered in ¹H NMR. Thus, variable temperature NMR indicated peak broadeningupon warming the sample, with a coalescence temperature of 38 ° C. Kinetic parameters of the rotation were also calculated.     

Analysis of Light Propagation in a Realistic Head Model by a Hybrid Method for Optical Brain Function Measurement

Near infrared spectroscopy (NIRS) is used to measure the change in blood volume and oxygenation in the brain cortex induced by functional brain activation. The development of an adequate model to calculate light propagation in the head is very important because the light is strongly scattered in the tissue and this causes ambiguity in the volume of tissue interrogated with a source–detector pair of the NIRS instrument. In this study, a two-dimensional realistic head model is generated from a MRI scan of a human adult head. The light propagation in the head model is calculated by the hybrid Monte Carlo–diffusion method to obtain the change in detected intensity caused by a focal absorption change in the grey matter or in the white matter to discuss the relationship between the depth of the activated region and the sensitivity of the NIRS signal. The sensitivity to the activated region in the white matter steeply decreases with an increase of the depth of the activated region because the spatial sensitivity profile is mainly confined to the grey matter. The contribution of the focal brain activity to the NIRS signal is determined by not only the depth of the activated region from the head surface but also the depth of the activated region from the brain surface.     

Laser flash photolysis of carboxymethylcellulose in an aqueous solution

Laser flash photolysis with excitation at 248 nm was used to study photochemically derived changes of carboxymethylcellulose (CMC) in aqueous solutions. Transient absorption spectra of solutions after photolysis revealed a broad band with a maximum of approximately 720 nm, which could be ascribed to the signal of the hydrated electron. The interaction of the hydrated electron with CMC was slow (<10⁷ dm³ mol^?1 s^?1), but the OH radical, formed by the decomposition of H₂O₂, reacted with CMC at a high rate constant (9.5–11.0 × 10⁸ dm³ mol^?1 s^?1). The rate constant of the reactions of CMC with hydroxyl radicals depended on the conformation of the macromolecules, which was determined by the pH of the solution. Transient absorption was recorded at a wavelength shorter than 370 nm for CMC solutions photolyzed in the presence of H₂O₂. As a result of OH attack, long‐lived radicals were formed on CMC. The recombination of macroradicals led to the formation of crosslinking bonds between side‐chain groups, and as a result of it an insoluble gel arose in low‐pH solutions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 505–518, 2005     

Waveform Measurement of Ultra-Short Optical Pulses Based on Two-Photon Absorption in Si-Image Sensor

We demonstrate a novel waveform mesurement system of ultra-short optical pulses based on the two-photon absorption process in a Si-image sensor. Using an interferometer with a tilt mirror in the reference path, the relative time difference between the signal and reference pulses is spatially distributed on the Si-image sensor, so the intensity auto-correlation is monitored as an image at a time without using moving parts. This system can create or remove an interference fringe pattern overlapped on the auto-correlation image by controlling the polarization states of the laser pulse, which is useful for measuring the crossing angle between the signal and reference beams as well as avoiding contamination of the interference fringe into the auto-correlation image. We successfully measured optical pulses less than 100 fs from a fiber ring laser with a temporal resolution of 0.4 fs. The obtained waveform agreed well with that observed with a conventional second harmonic generation (SHG) based auto-correlator.     

Coverage centralities for temporal networks

Structure of real networked systems, such as social relationship, can be modeled as temporal networks in which each edge appears only at the prescribed time. Understanding the structure of temporal networks requires quantifying the importance of a temporal vertex, which is a pair of vertex index and time. In this paper, we define two centrality measures of a temporal vertex based on the fastest temporal paths which use the temporal vertex. The definition is free from parameters and robust against the change in time scale on which we focus. In addition, we can efficiently compute these centrality values for all temporal vertices. Using the two centrality measures, we reveal that distributions of these centrality values of real-world temporal networks are heterogeneous. For various datasets, we also demonstrate that a majority of the highly central temporal vertices are located within a narrow time window around a particular time. In other words, there is a bottleneck time at which most information sent in the temporal network passes through a small number of temporal vertices, which suggests an important role of these temporal vertices in spreading phenomena.     

Nonpolar isosteres of damaged DNA bases: effective mimicry of mutagenic properties of 8-oxopurines

A substantial fraction of mutations that arise in the cell comes from oxidative damage to DNA bases. Oxidation of purine bases at the 8-position, yielding 8-oxo-G and 8-oxo-A, results in conformational changes (from anti to syn) that cause miscoding during DNA replication. Here we describe the synthesis and biophysical and biochemical properties of low-polarity shape mimics of 8-oxopurines, and we report that these new analogues exhibit remarkable mimicry of the mutagenic properties of the natural damaged bases. A 2-chloro-4-fluoroindole nucleoside (1) was designed as an isosteric analogue of 8-oxo-dG, and a 2-chloro-4-methylbenzimidazole nucleoside (2) as a mimic of 8-oxo-dA. The nucleosides were prepared by reaction of the parent heterocycles with Hoffer's chlorodeoxyribose derivative. Structural studies of the free nucleosides 1 and 2 revealed that both bases are oriented syn, thus mimicking the conformation of the oxopurine nucleosides. Suitably protected phosphoramidite derivatives were prepared for incorporation into synthetic DNAs, to be used as probes of DNA damage responses, and 5'-triphosphate derivatives (3 and 4) were synthesized as analogues of damaged nucleotides in the cellular nucleotide pool. Base pairing studies in 12-mer duplexes showed that 1 and 2 have low affinity for polar pairing partners, consistent with previous nonpolar DNA base analogues. However, both compounds pair with small but significant selectivity for purine partners, consistent with the idea that the syn purine geometry leads to pyrimidine-like shapes. Steady-state kinetics studies of 1 and 2 were carried out with the Klenow fragment of Escherichia coli DNA Pol I (exo-) in single-nucleotide insertions. In the DNA template, the analogues successfully mimicked the mutagenic behavior of oxopurines, with 1 being paired selectively with adenine and 2 pairing selectively with guanine. The compounds showed similar mutagenic behavior as nucleoside triphosphate analogues, being preferentially inserted opposite mutagenic purine partners. The results suggest that much of the mutagenicity of oxopurines arises from their shapes in the syn conformation rather than from electrostatic and hydrogen-bonding effects. The new analogues are expected to be generally useful as mechanistic probes of cellular responses to DNA damage.