Masato Sumita

β-Cyclodextrin-crosslinked alginate gel for patient-controlled drug delivery systems: regulation of host–guest interactions with mechanical stimuli

Macroscopic mechanical force has attracted much attention as an existing yet novel energy source for modification of molecular interactions and molecular reactivity. Although various molecular level phenomena have been controlled by using macroscopic mechanical forces, control of host-guest inclusion has not been a research target. Here we report a novel controlled release system triggered by a mechanical stimulus. Release of ondansetron (ODN), an anti-emetic drug, from a designer hydrogel composed of a β-cyclodextrin (CyD) derivative and alginate (AL) can be controlled by mild mechanical compressions that mimic operation by a patients hand. ODN is released in response to mechanical compressions by changing the inclusion ability of CyD moieties, which may be conformationally distorted, and/or suppressed stabilization of the inclusion complex when an external stress is applied. It is revealed that the release can be induced even by the slight conformational restriction for β-CyD due to the mechanical stimulus. This controlled release technology provides a novel dosing strategy enabling on-demand administration of medicines through a mechanical stimulus generated intentionally by the patient.

Nanoporous Carbon Sensor with Cage-in-Fiber Structure: Highly Selective Aniline Adsorbent toward Cancer Risk Management

Carbon nanocage-embedded nanofibrous film works as a highly selective adsorbent of carcinogen aromatic amines. By using quartz crystal microbalance techniques, even ppm levels of aniline can be repetitively detected, while other chemical compounds such as water, ammonia, and benzene give negligible responses. This technique should be applicable for high-throughput cancer risk management.

Protonated Carboxyl Anchor for Stable Adsorption of Ru N749 Dye (Black Dye) on a TiO2 Anatase (101) Surface

We have investigated the adsorption stability of ruthenium N749 dye [black dye (BD)], a highly efficient dye for dye-sensitized solar cells (DSCs), through protonated and deprotonated carboxyl group anchors on a TiO2 anatase (101) surface by using first-principles calculations. Geometry optimizations of the surface system with a supercell and the UV-visible spectrum calculation of the optimized dye structure were carried out. Among the configurations with one and two anchors, the BD adsorption anchored with one protonated carboxyl group was found to be the most stable, in contrast to most previous reports. Hydrogen bonding between the proton retained in BD and the surface oxygen is responsible for the stability of the protonated anchor. We confirmed that the calculated UV-visible spectrum of the most stable dye structure shows the best consistency with the experimental data. It is also demonstrated that the electronic density of states largely depends on the proton position. This novel aspect of adsorption via a protonated carboxyl anchor gives a new perspective for interfacial electronic processes of DSCs.

Micrometer-level naked-eye detection of caesium particulates in the solid state

Abstract Large amounts of radioactive material were released from the Fukushima Daiichi nuclear plant in Japan, contaminating the local environment. During the early stages of such nuclear accidents, iodine I-131 (half-life 8.02 d) is usually detectable in the surrounding atmosphere and bodies of water. On the other hand, in the long-term, soil and water contamination by Cs-137, which has a half-life of 30.17 years, is a serious problem. In Japan, the government is planning and carrying out radioactive decontamination operations not only with public agencies but also non-governmental organizations, making radiation measurements within Japan. If caesium (also radiocaesium) could be detected by the naked eye then its environmental remediation would be facilitated. Supramolecular material approaches, such as host–guest chemistry, are useful in the design of high-resolution molecular sensors and can be used to convert molecular-recognition processes into optical signals. In this work, we have developed molecular materials (here, phenols) as an optical probe for caesium cation-containing particles with implementation based on simple spray-on reagents and a commonly available fluorescent lamp for naked-eye detection in the solid state. This chemical optical probe provides a higher spatial resolution than existing radioscopes and gamma-ray cameras.

Redox Reaction Mechanisms with Non-triiodide Mediators in Dye-Sensitized Solar Cells by Redox Potential Calculations

We investigate reaction mechanisms of the redox mediators in dye-sensitized solar cells through systematic calculations of redox potentials of possible cobalt complexes and iodides in acetonitrile solution by use of the thermodynamic cycle method with continuum solvent model. The calculated redox potentials were in good agreement with the experimental values, although the experimentalists used different reference electrodes. The maximum open circuit voltage (VOC) of the mediators calculated in this work indicate that the I2(•-)/2I(-) and I2/I2(•-) as well as the net I2/2I(-) redox reactions can dominate at both photoanode and counter-electrode.

Calorimetric and dielectric study of organic ferroelectrics, phenazine-chloranilic acid, and its bromo analog

The heat capacities of single crystals of organic ferroelectric complexes phenazine-chloranilic acid (Phz-H(2)ca) and phenazine-bromanilic acid (Phz-H(2)ba) were measured. At temperatures below those of the reported ferroelectric phase transitions, heat capacity anomalies due to successive phase transitions were found in both complexes. Excess entropies involved in the low-temperature successive phase transitions are much larger than those due to the ferroelectric phase transitions. The temperature dependence of the complex dielectric constants showed the existence of multiple dielectric relaxation modes in both complexes and their deuterated analogs (Phz-D(2)ca and Phz-D(2)ba). We discuss the possibility of concerted hopping of neighboring protons within a hydrogen-bonded chain while taking into account the one-dimensional nature of the chain.

Calorimetric study of glass transition in molecular liquids consisting of globular associates: dicyclorohexylmethanol and tricyclohexylmethanol.

Heat capacities of liquids and liquid-quenched glasses (LQGs) of dicyclorohexylmethanol (DCHM) and tricyclohexylmethanol (TCHM) were measured by adiabatic calorimetry. Upon cooling the liquid compounds, they undergo glass transitions around 250 and 265 K, respectively. Temperature dependence of the FT-IR spectrum of TCHM liquid showed the gradual formation of dimers in the supercooled state with decreasing temperature. The magnitude of heat capacity jump at glass transition is discussed through a comparison with other low-molecular mass LQG. Combining the present results with previous heat capacity results on crystalline TCHM, residual entropies of LQG and standard thermodynamic quantities are established for both compounds.

Neat liquid consisting of hydrogen-bonded tetramers: dicyclohexylmethanol.

Nonmonotonous temperature dependence was detected in the heat capacity and dielectric constant of the title compound in the liquid state. A coherent analysis of FT-IR spectra, heat capacity, and dielectric constants shows that the neat liquid at low temperatures consists of closed (square) tetramers via H-bonds.

Characterization of the hyperline of D1/D0 conical intersections between the maleic acid and fumaric acid anion radicals

The cation and anion radicals of symmetrical 1,2-disubstituted ethylenes are expected to have a symmetry-allowed conical intersection (CI) between the ground doublet state (D0) and the lowest excited doublet state (D1) near a 90°-twisted geometry. By the complete active space self-consistent field method, we characterized the hyperline formed by D1/D0 CIs between the anion radicals of maleic acid (cis) and fumaric acid (trans). An implication of the results for the known one-way cis→trans photoisomerization of the maleic acid anion radical and other related ion radicals is presented.

Calorimetric Study of Correlated Disordering in [Hdamel]2[CuII(tdpd)2]·2THF Crystal

The heat capacity of [Hdamel]2[Cu(II)(tdpd)2] x 2 THF was measured from 6 to 250 K by adiabatic calorimetry. There are four heat anomalies around 150 K associated with disordering in the orientation of the uncoordinated THF molecules and in the conformation of the out-of-plane allyl groups of [Hdamel](+) units. The total entropy of transition was determined to be 19.8 J K(-1) mol(-1), less than the 4R ln 2 (R = gas constant) expected from the crystal structure at room temperature. The smallness of the total entropy change on phase transitions proves the presence of the strong motional correlation between the adjacent allyl groups. The calorimetric conclusion agreed with the crystal structure at 200 K re-examined in this study.