Helix-Sense-Selective Synthesis of Right- and Left-Handed Helical Luminescent Poly(diphenylacetylene)s with Memory of the Macromolecular Helicity and Their Helical Structures.

Symmetrically substituted poly(diphenylacetylene) (PDPA) bearing carboxy pendants was found to fold into a one-handed helix upon thermal annealing with nonracemic amines in water accompanied by chiral amplification of the helicity. The induced right- or left-handed helical PDPA was retained (memorized) after complete removal of the chiral amines, thus producing a one-handed helical circularly polarized luminescent PDPA in a helix-sense-selective manner. The helical PDPA with static helicity memory is tolerant toward modification of carboxy pendants, providing functional PDPAs with an optical activity solely due to macromolecular helicity. The PDPA and its derivatives before and after the one-handed helicity induction and its subsequent memory of the helicity exhibited well-resolved very simple 1H and 13C NMR and Raman spectra whose spectral patterns are virtually identical independent of the helical sense bias. On the basis of the 1H and 13C NMR, IR, Raman, and vibrational and electronic circular dichroism spectral measurement results combined with theoretical calculations, the key structural features (cis or trans and cisoid or transoid) of the PDPA as well as its helix inversion barrier and absolute handedness (right- or left-handed helix) and helix-sense excess of the one-handed helical PDPA and its derivatives with static helicity memory were determined. As a result, almost complete right- and left-handed helical cis-transoidal PDPAs with 98% helix-sense excess were successfully obtained using noncovalent helicity induction and memory strategy.

Complementary double-stranded helical oligomers bearing achiral bifunctional groups that catalyze asymmetric aldol reaction.

Two novel chiral dimer and trimer strands composed of m-terphenyl groups linked through p-diethynylbenzene units with the chiral amidine group and achiral piperazine group introduced at the terminus or center of the strands, respectively, and its complementary achiral carboxylic acid dimer and trimer were synthesized. The complementary chiral/achiral strands form an excess-handed double-helical structure as supported by intense split-type Cotton effects in the absorption regions of the conjugated backbones biased by the chiral amidinium-carboxylate salt bridges. The double-helical trimer was found to catalyze the direct aldol reaction of cyclohexanone with 4-nitrobenzaldehyde and produce the products with a moderate enantioselectivity despite the fact that the catalytically active bifunctional piperazine/carboxylic acid pair introduced in the middle is achiral, indicating the key role of the one-handed double-helical framework for supramolecular bifunctional organocatalysis.

Direct Detection of Hardly Detectable Hidden Chirality of Hydrocarbons and Deuterated Isotopomers by a Helical Polyacetylene through Chiral Amplification and Memory.

We report the first direct chirality sensing of a series of chiral hydrocarbons and isotopically chiral compounds (deuterated isotopomers), which are almost impossible to detect by conventional optical spectroscopic methods, by a stereoregular polyacetylene bearing 2,2'-biphenol-derived pendants. The polyacetylene showed a circular dichroism due to a preferred-handed helix formation in response to the hardly detectable hidden chirality of saturated tertiary or chiroptical quaternary hydrocarbons, and deuterated isotopomers. In sharp contrast to the previously reported sensory systems, the chirality detection by the polyacetylene relies on an excess one-handed helix formation induced by the chiral hydrocarbons and deuterated isotopomers via significant amplification of the chirality followed by its static memory, through which chiral information on the minute and hidden chirality can be stored as an excess of a single-handed helix memory for a long time.

Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions.

In this review, we describe the recent advances in supramolecular helical assemblies formed from chiral and achiral small molecules, oligomers (foldamers), and helical and nonhelical polymers from the viewpoints of their formations with unique chiral phenomena, such as amplification of chirality during the dynamic helically assembled processes, properties, and specific functionalities, some of which have not been observed in or achieved by biological systems. In addition, a brief historical overview of the helical assemblies of small molecules and remarkable progress in the synthesis of single-stranded and multistranded helical foldamers and polymers, their properties, structures, and functions, mainly since 2009, will also be described.

Accuracy Verification of Respiratory-gated Radiotherapy that Combines the Respiration-Monitoring Device and Respiratory-gated System.

The purpose of this study is to evaluate the mechanical accuracy of a respiratory-gated radiation system that combines the Linear Indicator-equipped Abches respiration-monitoring device and the Varian Real-time Position Management system (LI-RPM system). This combined configuration, implemented for the first time in Japan, was compared with the stand-alone Varian RPM system (RPM system). The delay times, dose profiles, and output waveforms of the LI-RPM and RPM systems were evaluated using a self-produced dynamic phantom. The delay times for the LI-RPM and RPM systems were both 0.1 s for 4 s and 8 s test periods. The corresponding output waveform correlation factors (R2) for the 4 s and 8 s test periods were 0.9981 and 0.9975, respectively. No difference was observed in the dose profiles of the two systems. Thus, the present results indicate that the proposed LI-RPM combined respiratory-gated radiation system has similar properties to the RPM system. However, it offers several advantages in terms of its versatility, including its alignment assistance capabilities for non-coplanar treatments.

Switchable enantioseparation based on macromolecular memory of a helical polyacetylene in the solid state.

In the chromatographic separation of enantiomers the order of elution is determined by the strength of diasteromeric interactions between the components of the mixture and a chiral stationary phase. For analytical purposes, it is ideal to have the minor component elute first, whereas in the preparative mode a faster elution of the major component is desirable. Here we describe a stationary phase constructed from a polyacetylene that bears 2,2'-bisphenol-derived side chains in which chirality can be switched in the solid state prior to use. Both the macromolecular helicity of the polymer backbone and the axial chirality of the side chains can be switched in the solid state by interaction with a chiral alcohol, but importantly are maintained after removal of the chiral alcohol because of a memory effect. The chiral stationary phase thus prepared was used to separate the enantiomers of trans-stilbene oxide with the enantiomer elution order determined by the preseparation treatment.

Dosimetric properties and clinical application of an a-Si EPID for dynamic IMRT quality assurance.

Dosimetric properties of an amorphous silicon electronic portal imaging device (EPID) for verification of intensity-modulated radiation therapy (IMRT) were investigated as a replacement for conventional verification tools. The portal dosimetry system of Varian's EPID (aS1000) has an integrated image mode for portal dosimetry (PD). The source-to-imager distance was 105 cm, and there were no extra buildup materials on the surface of the EPID in this study. Several dosimetric properties were examined. For clinical dosimetry, the dose distributions of dynamic IMRT beams for prostate cancer (19 patients, 97 beams) were measured by EPID and compared with the results of ionization chamber (IC) measurements. In addition, pretreatment measurements for prostate IMRT (50 patients, 309 beams) were performed by EPID and were evaluated by the gamma method (criterion: 3 mm/3 %). The signal-to-monitor unit ratio of PD showed dose dependence, indicating ghosting effects. Tongue-and-groove effects were observed as a result of the dose difference in the measured EPID images. The results of PD for clinical IMRT beams were in good agreement with the predicted dose image with average values of 1.37 and 0.25 for γ (max) and γ (ave), respectively. The point doses of PD were slightly, but significantly, higher than the results of IC measurements (p < 0.05 paired t test). However, this small difference seems clinically acceptable. This portal dosimetry system is useful as a rapid and convenient verification tool for dynamic IMRT.

Dosimetric properties of radiophotoluminescent glass detector in low-energy photon beams.

PURPOSE: A radiophotoluminescent glass rod dosimeter (RGD) has recently become commercially available. It is being increasingly used for dosimetry in radiotherapy to measure the absorbed dose including scattered low-energy photons on the body surface of a patient and for postal dosimetry audit. In this article, the dosimetric properties of the RGD, including energy dependence of the dose response, reproducibly, variation in data obtained by the RGD for each energy, and angular dependence in low-energy photons, are discussed. METHODS: An RGD (GD-301, Asahi Techno Glass Corporation, Shizuoka, Japan) was irradiated with monochromatic low-energy photon beams generated by synchrotron radiation at Photon Factory, High Energy Accelerator Research Organization (KEK). The size of GD-301 was 1.5 mm in diameter and 8.5 mm in length and the active dose readout volume being 1 mm diameter and 0.6 mm depth located 0.7 mm from the end of the detector. The energy dependence of the dose response and reproducibility and variation were investigated for RGDs irradiated with a plastic holder and those irradiated without the plastic holder. Response of the RGD was obtained by not only conventional single field irradiation but also bilateral irradiation. Angular dependence of the RGD was measured in the range of 0°-90° for 13, 17, 40, and 80 keV photon beams by conventional single field irradiation. RESULTS: The dose responses had a peak at around 40 keV. For the energy range of less than 25 keV, all dose response curves steeply decreased in comparison with the ratio of mass energy absorption coefficient of the RGD to that of air. As for the reproducibility and variation in data obtained by the RGD, the coefficient of variance increased with decrease in photon energy. Furthermore, the variation for bilateral irradiation was less than that for single field irradiation. Regarding angular dependence of the RGD, for energies of 13 and 17 keV, the response decreased with increase in the irradiation angle, and the minimum values were 93.5% and 86%, respectively. CONCLUSIONS: Our results showed the dosimetric properties of the RGD, including the energy dependence of the dose response, reproducibly, variation, and angular dependence in low-energy photons and suggest that the accuracy of the absorbed dose in low-energy photons is affected by the readout method and the distribution of radiophotoluminescence centers in the RGD.

Helical polymer brushes with a preferred-handed helix-sense triggered by a terminal optically active group in the pendant.

Helical polymer brushes with a preferred-handed helix-sense composed of a poly(phenylacetylene) backbone and poly(phenyl isocyanate) pendants are synthesized. The helix-sense of the backbone is effectively controlled by the helical chirality of the pendants, which is triggered by an optically active group introduced at the pendant terminal.

Visual comparisons between Cherenkov radiation from water and fluorescence from a scintillator.

A system for observing blue light of Cherenkov radiation was constructed using a Co-60 gamma-ray irradiation unit. However, there was some doubt that the observed light was not Cherenkov light, but scintillation. Therefore, the radiation from water was compared with that from a scintillator. The difference between both luminosities was examined using photographs taken in a dark irradiation room with mirrors and a camera. The radiation from the scintillator was much stronger than that from water. The differences between luminosities of the light radiated in the beam direction, at right angles to the beam and in the reverse beam direction were examined for both radiations. The luminosity from water showed very definite anisotropy, while that from the scintillator was almost isotropic. Furthermore, the light radiated in the beam direction from water was the strongest, and the strengths of the light radiated in the three directions from the scintillator were almost equivalent to each other. It was confirmed that the radiation from water irradiated by Co-60 gamma-rays was indeed Cherenkov light. The anisotropy of the radiated Cherenkov light and the isotropy of the scintillation were clearly observed in the photographs.