Analysis of dislocation images in X-ray topography of protein crystals: tetragonal hen egg-white lysozyme crystals

Dislocation images in X-ray topography of protein crystals such as tetragonal hen egg-white lysozyme crystals were analyzed. Not only extinction but also double contrast of dislocation images are clearly observed on the X-ray topographs. It should be noted that the observed image widths of the dislocation contrasts are much less than those calculated on the basis of the kinematical theory in X-ray topography, which has been successfully applied for inorganic crystals and organic crystals of small molecules so far. Moreover, in tetragonal HEW lysozyme crystals, the rocking curve widths of the perfect crystal related to the kinematical theory are less than the measured ones by two orders of magnitude. This discrepancy is consistent with that in the image width of the dislocation contrast. From this correlation, it is suggested that the larger rocking curve width, or higher mosaicity, is mainly responsible for the observed image width in the grown crystals.     

A versatile scaffold for facile synthesis of fluorescent cyano-substituted stilbenes

Here we report the facile derivatization of a cyano-substituted stilbene into higher π-extended analogues. The cyano-substituted stilbene, which serves as a synthetic scaffold, has a bromo group and a formyl group on its 4- and 4′-position of the phenylene rings and thus readily undergoes selective transformation into other functional groups using various simple organic reactions. The resultant π-conjugated molecules that contain a cyano-substituted stilbene skeleton exhibit fluorescence in solution and in the solid state.     

Prolate and Oblate Shape Coexistence in 188Pt

A standard in-beam γ-spectroscopy experiment for ¹⁸⁸Pt is performed via the¹⁷⁶Yb(¹⁸O, 6n) reaction at beam energies of 88 and 95MeV, and the level scheme for ¹⁸⁸Pt is established. Prolate and oblate shape coexistence has been demonstrated to occur in ¹⁸⁸Pt by applying the projected shell model. The rotation alignment of i_13/2 neutrons drives the yrast sequence changingsuddenly from prolate to oblate shape at angular momentum 10h, indicating likely a new type of shape phase transition along the yrast line in ¹⁸⁸Pt.     

Construction of a High‐Mannose‐Type Glycan Library by a Renewed Top‐Down Chemo‐Enzymatic Approach

A comprehensive method for the construction of a high‐mannose‐type glycan library by systematic chemo‐enzymatic trimming of a single Man9‐based precursor was developed. It consists of the chemical synthesis of a non‐natural tridecasaccharide precursor, the orthogonal demasking of the non‐reducing ends, and trimming by glycosidases, which enabled a comprehensive synthesis of high‐mannose‐type glycans in their mono‐ or non‐glucosylated forms. It employed glucose, isopropylidene, and N‐acetylglucosamine groups for blocking the A‐, B‐, and C‐arms, respectively. After systematic trimming of the precursor, thirty‐seven high‐mannose‐type glycans were obtained. The power of the methodology was demonstrated by the enzymatic activity of human recombinant N‐acetylglucosaminyltransferase‐I toward M7–M3 glycans, clarifying the substrate specificity in the context of high‐mannose‐type glycans.     

Development of a Millimeter-Wave Electron-Spin-Resonance Measurement System for Ultralow Temperatures and Its Application to Measurements of Copper Pyrazine Dinitrate

We have developed a millimeter-wave electron-spin-resonance (ESR) measurement system using a ³He-⁴He dilution refrigerator for the ultralow-temperature range below 1 K. The currently available frequency range is 125–130 GHz. This system is based on a Fabry-Pérot-type resonator (FPR) that is composed of two mirrors. The frequency can be changed by adjusting the distance between the mirrors using a piezoelectric actuator installed at the bottom of the resonator. A homodyne detection system with an InSb detector is built into the low-temperature section of the ³He-⁴He dilution refrigerator; this system provides high sensitivity. Using this system, we performed ESR measurements on a Heisenberg quantum-spin chain—copper pyrazine dinitrate, Cu(C₄H₄N₂)(NO₃)₂—over the temperature range from 6.6 down to 0.25 K. The ESR lines change continuously with decreasing temperature. Our results suggest that the ESR spectrum of copper pyrazine dinitrate may be useful as a temperature sensor for the very low-temperature range.     

Dynamic nuclear self-polarization of Ⅲ-Ⅴ semiconductors

Ⅲ-Ⅴ semiconductors exhibit dynamic nuclear self-polarization (DYNASP) owing to the contact hyperfine interaction (HFI) between optically excited conduction electrons and lattice nuclei.In the self-polarization process at a low temperature,electron spin state and the nuclear polarization (magnetization) exchange a positive feedback,increasing energy splitting of the conduction electron states,thereby a large nuclear polarization.This phenomenon was theoretically predicted previously for conduction electrons excited linearly and elliptically polarized light.The polarization of the conduction electrons was represented by a parameter α in a formula for nuclear polarization (Eq.(9) in Ref.[1]);however,the effect of external magnetic fields on the nuclear polarization was not considered.Therefore,this study introduces this effect by further extending the previous studies.Herein,α'represents the combination of the effects of elliptically polarized electrons and an external magnetic field,which is used in the equations presented in previous studies.When α'=0,a large nuclear polarization is obtained below critical temperature Tc,but no polarization occurs above Tc.When α'＞ 0,the nuclear polarization is enhanced above Tc.Below Tc,the nuclear polarization follows a hysteresis curve when α'is partially manipulated by adjusting the degree of the polarization of the exciting laser.     

Temperature-controlled photosensitization properties of benzophenone-conjugated thermoresponsive copolymers

We previously found that a copolymer, poly(NIPAM- co-BP), consisting of N-isopropylacrylamide (NIPAM) and benzophenone (BP) units, behaves as a photosensitizer showing temperature-controlled oxygenation activity by singlet oxygen ( (1)O 2) in water ( J. Am. Chem. Soc. 2006, 128, 8751-8753 ). This polymer shows a heat-induced oxygenation enhancement at <20 degrees C, while showing suppression at >20 degrees C. This is driven by a heat-induced phase transition of the polymer from coil to micelle and then to globule state, controlling the stability and diffusion of (1)O 2 and the location of substrate. In the present work, effects of polymer concentration and BP content of the polymer on the oxygenation activity were studied at 5-35 degrees C. Increase in the polymer concentration leads to activity decrease at >20 degrees C due to strong polymer aggregation, suppressing incident light absorption of the BP units. With a decrease in BP content of the polymer, heat-induced oxygenation enhancement at <20 degrees C is more pronounced because formation of small size micelles accelerates (1)O 2 oxygenation. The obtained findings reveal that the polymer with low BP content, when used at high concentration, shows clear-cut off- on- off activity change against the temperature window: very low activity at <5 degrees C and >25 degrees C, and very high activity at middle temperature range.     

Temperature-controlled changeable oxygenation selectivity by singlet oxygen with a polymeric photosensitizer

A polymeric photosensitizer, poly(NIPAM-co-RB), consisting of N-isopropylacrylamide and rose bengal units, demonstrates a temperature-controlled changeable oxygenation selectivity by singlet oxygen in water.