Photochemical control of molecular assembly formation in a catanionic surfactant system

Photochemical control of vesicle disintegration and reformation in aqueous solution was examined using a mixture of 4-butylazobenzene-4'-(oxyethyl)trimethylammonium bromide (AZTMA) as the photoresponsive cationic surfactant and sodium dodecylbenzenesulfonate (SDBS) as the anionic surfactant. Spontaneous vesicle formation was found in a wide-ranging composition of the trans-AZTMA/SDBS system. AZTMA molecules constituting vesicles underwent reversible trans-cis photoisomerization when irradiated with ultraviolet and visible light. Transmission electron microscopy observations using the freeze-fracture technique (FF-TEM) showed that UV light irradiation caused the vesicles to disintegrate into coarse aggregates and visible light irradiation stimulated the reformation of vesicles (normal control). A detailed investigation of the phase state and the effects of UV and visible light irradiation on the AZTMA/SDBS system with the use of electroconductivity, dynamic/static light scattering, and surface tension measurements and FF-TEM observations revealed that in the AZTMA-rich composition (AZTMA/SDBS 9:1) a micellar solution before light irradiation became a vesicular solution after UV light irradiation and visible light irradiation allowed the return to a micellar solution (reverse control). Thus, we could photochemically control the disintegration (normal control) and reformation (reverse control) of vesicles in the same system.     

Confocal microscopic evaluation of mixing performance for three-dimensional microfluidic mixer

We developed a confocal microscopic method for a quantitative evaluation of the mixing performance of a three-dimensional microfluidic mixer. We fabricated a microfluidic baker's transformation (MBT) mixer as a three-dimensional passive-type mixer for the efficient mixing of solutions. Although the MBT mixer is one type of ideal mixers, it is hard to evaluate its mixing performance, since the MBT mixer is based on several cycles of complicated three-dimensional microchannel structures. We applied the method developed here to evaluate the mixing of water and a fluorescein isothiocyanate (FITC; diffusion coefficient, 4.9 × 10(-10) m(2) s(-1)) solution by the MBT mixer. This method enables us to capture vertical section images for the fluid distributions of FITC and water at different three-dimensional microchannel structures of the MBT device. These images are in good agreement with those of mixing images based on numerical simulations. The mixing ratio could be calculated by the fluorescence intensity at each pixel of the vertical section image; complete mixing is recognized by a mixing ratio of more than 90%. The mixing ratios are measured at different cycles of the MBT mixer by changing the flow rate; the mixing performance is evaluated by comparisons with the mixing ratio of the straight microchannel without the MBT mixer.     

Inhibition assay of yeast cell walls by plasmon resonance Rayleigh scattering and surface-enhanced Raman scattering imaging

We report on plasmon resonance Rayleigh scattering (PRRS) and surface enhanced Raman scattering (SERS) imaging for inhibition assay of yeast cell walls. This assay reveals that the proteins having alkali sensitive linkage bound to β1,3 glucan frameworks in cell walls are involved in SERS activity. The result is further confirmed by comparison of genetically modified cells and wild type cells. Finally, we find that PRRS and SERS spots do not appear on cell walls when daughter cells are enough smaller than parent ones, but appear when size of daughter cells are comparable to parent cells. This finding indicates the relationship between expression of the proteins that generate SERS spots and cell division. These results demonstrate that PRRS and SERS imaging can be a convenient and sensitive method for analysis of cell walls.     

Zwitterionic heterogemini surfactants containing ammonium and carboxylate headgroups 2: aggregation behavior studied by SANS, DLS, and cryo-TEM

Metallo-meso-5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrins (metallo-TPPSs), such as ZnTPPS, have been widely used as photosensitizers. However, their vulnerability to photodegradation significantly limits their applications. In this contribution, we demonstrate a method to enhance the photostability of metallo-TPPSs while retaining photoactivity via encapsulation inside cores of complex micelles. Poly(ethylene glycol)-b-poly(4-vinylpyridine) (PEG-b-P4VP) and metallo-TPPSs can form complex micelles in acidic solution through electrostatic interactions and then undergo axial coordination with the pyridine moieties of PEG-b-P4VP when the pH is adjusted to 7.4. In this way, metallo-TPPSs are entrapped in the hydrophobic, compact micellar cores, which effectively prevents photodegradation of the metallo-TPPSs that would otherwise occur in aqueous solution. In addition, the photodebromination of 2,3-dibromo-3-phenylpropionic acid (DPP) sensitized with ZnTPPS has been used as a model reaction to study the photosensitive activity of ZnTPPS entrapped in complex micelles. The entrapped ZnTPPSs exhibit pronounced activity and have much higher efficiency and faster photosensitive reaction rates than free ZnTPPS.     

Pseudo helix-sense-selective polymerisation of achiral substituted acetylenes

Pseudo helix-sense-selective polymerisation of a wide range of achiral substituted acetylenes having dynamic covalent bonds has been realised to yield static one-handed helical polymers without any other chiral moieties.     

Oligonucleotide-templated reactions for sensing nucleic acids

Oligonucleotide-templated reactions are useful for applying nucleic acid sensing. Various chemistries for oligonucleotide-templated reaction have been reported so far. Major scientific interests are focused on the development of signal amplification systems and signal generation systems. We introduce the recent advances of oligonucleotide-templated reaction in consideration of the above two points.     

Fast and facile dissolution of cellulose with tetrabutylphosphonium hydroxide containing 40 wt% water

Tetrabutylphosphonium hydroxide containing 40 wt% water dissolved 20 wt% cellulose at the final concentration within 5 minutes under mild stirring at 25 °C.     

Photochemical dynamics of indolylmaleimide derivatives

On-the-fly nonadiabatic ab initio molecular dynamics simulations have been carried out for three anionic species of indolylmaleimides (3-(1H-3-indolyl)-2,5-dihydro-1H-2,5-pyrroledione, IM) to clarify the mechanisms of photochemical reactions. The results are obtained for (i) a monovalent anion with a deprotonated indole NH group (IM(-)'), (ii) a monovalent anion with a deprotonated maleimide NH group (IM(-)') and (iii) a divalent anion with doubly deprotonated indole and the maleimide NH groups (IM(2-)). Quantum chemical calculations are treated at the three state averaged complete-active space self-consistent field level for 6 electrons in 5 orbitals with the cc-pVDZ basis set (CAS (6, 5) SCF/cc-pVDZ). Molecular dynamics simulations are performed with electronically nonadiabatic transitions included using the Zhu-Nakamura version of the trajectory surface hopping (ZN-TSH) method. It is found that the nonadiabatic transitions occur accompanied by the stretching and shrinking motions of the N(7)-C(8) bond in the case of IM(-)' and the C(11)-N(12) bond in IM(2-) rather than the twisting motion of the dihedral angle. We also found that the ultrafast S(2)→ S(1) nonadiabatic transitions occur through the conical intersection (CoIn) right after photoexcitation to S(2) in IM(-)' and IM(2-). Furthermore, the S(1)→ S(0) nonadiabatic transitions are found to take place in IM(-)'. It is concluded that IM(2-) would mainly contribute to the photoemission, because the S(1)← S(0) and S(2)← S(0) transitions of IM(-)' are dipole-forbidden transitions and, moreover, IM(2-) is found to be the only species to stay in the S(1) state without non-radiative decay.     

A peroxide-bridged imidazole dimer formed from a photochromic naphthalene-bridged imidazole dimer

2,4,5-Triphenylimidazole (lophine) is known as the first chemiluminescence substrate, and its oxidized derivative, the 2,4,5-triphenylimidazolyl radical, corresponds to the coloured species in the photochromic reaction of hexaarylbiimidazole (HABI). We report the first direct observation of the O(2) adduct of the imidazolyl radical that forms the end-on peroxide-bridged imidazole dimer. The ring-opening reaction of the peroxide-bridged imidazole dimer leading to the formation of an N-benzoylbenzamidine derivative supports the presence of the 4,5-epidioxide of lophine as a reaction intermediate of its chemiluminescence.