A pH-responsive carboxylic β-1,3-glucan polysaccharide for complexation with polymeric guests

The helix-forming nature of β-1,3-glucan polysaccharides is a characteristic that has potential for producing gene carriers, bio-nanomaterials and other chiral nanowires. Herein, carboxylic curdlan (CurCOOH) bearing the β-1,3-polyglucuronic acid structure was successfully prepared from β-1,3-glucan polysaccharide curdlan (Cur) by one-step oxidation using a 4-acetamido-TEMPO/NaClO/NaClO(2) system as the oxidant. The resulting high-molecular-weight CurCOOH was proved to bear the 6-COOH group in 100% purity. The optical rotatory dispersion (ORD) spectra indicated that the obtained CurCOOH behaves as a water-soluble single-strand in various pH aqueous media. This advantage has allowed us to use CurCOOH as a polymeric host to form various macromolecular complexes. For example, complexation of CurCOOH with single-walled carbon nanotubes (SWNTs) resulted in a water-soluble one-dimensional architecture, which formed a dispersion in aqueous solution that was stable for several months, and much more stable than SWNTs complexes of the similar negatively-charged polyacrylic acid (PAA) and polymethacrylic acid (PMAA). It was shown that in the complex, SWNTs are effectively wrapped by a small amount of CurCOOH, enabling them to avoid electrostatic repulsion. This pH-responsive CurCOOH formed a very stable complex with cationic water-soluble polythiophenes (PT-1), which was stabilized not only by the hydrophobic interaction but also by the electrostatic attraction between trimethylammonium cations in PT-1 and dissociated anionic COO(-) groups in CurCOOH. The included PT-1 became CD-active only in the neutral to basic pH region, and the positive Cotton effect suggested that the conjugated main chain is twisted in the right-handed direction. We also found that CurCOOH can interact with polycytidylic acid (poly(C)) only under high NaCl concentrations, the binding and release of which could be controlled by a change in the salt concentration. We believe, therefore, that CurCOOH bearing a dissociable COOH group can act as a new potential polymeric host to construct novel polymeric complexes applicable for gene carriers, biosensors, chiral polymer assemblies, etc.     

Creation of chiral thixotropic gels through a crown-ammonium interaction and their application to a memory-erasing recycle system

A unique class of oligothiophene-based organogelator bearing two crown ethers at both ends was synthesized. This compound could gelatinize several organic solvents, forming one-dimensional fibrous aggregates. From the observation of circular dichroism, it was confirmed that the helical handedness of the fibrous assembly is controllable by the chirality of 1,2-bisammonium guests, thus suggesting that one guest molecule bridges two gelator molecules through the crown-ammonium interaction. Interestingly, we have found that such chirality is created by thermal gelation, whereas it disappears by thixotropic gelation. The new finding implies that the present organogel system is applicable as a reversible switching memory device, featuring memory creation by a heat mode and memory erasing by a mechanical mode.     

Excited state hydrogen transfer in fluorophenol.ammonia clusters studied by two-color REMPI spectroscopy

Two-color (1 + 1') REMPI mass spectra of o-, m- and p-fluorophenol.ammonia (1 ration) clusters were measured with a long delay time between excitation and ionization lasers. The appearance of NH(4)(NH(3))(n-1)(+) with 100 ns delay after exciting the S(1) state is a strong indication of generation of long-lived species via S(1). In analogy with the phenol.ammonia clusters, we conclude that an excited state hydrogen transfer reaction occurs in o-, m- and p-fluorophenol.ammonia clusters. The S(1)-S(0) transition of o-, m- and p-fluorophenol.ammonia (1 : 1) clusters were measured by the (1 + 1') REMPI spectra, while larger (1 ration) cluster (n = 2-4) were observed by monitoring the long-lived NH(4)(NH(3))(n-1) clusters action spectra. The vibronic structures of m- and p-fluorophenol.ammonia clusters are assigned based on vibrational calculations in S(0). The o-fluorophenol.ammonia (1 : 1) cluster shows an anharmonic progression that is analyzed by a one-dimensional internal rotational motion of the ammonia molecule. The interaction between the ammonia molecule and the fluorine atom, and its change upon electronic excitation are suggested. The broad action spectra observed for the o-fluorophenol.ammonia (1 : n) cluster (n>== 2) suggest the excited state hydrogen transfer is faster than in m- and p-fluorophenol.ammonia clusters. The different reaction rates between o-, m- and p-fluorophenol.ammonia clusters are found from comparison between the REMPI and action spectra.     

Vibrational overtone spectroscopy of phenol and its deuterated isotopomers

We have measured the OH- and OD-stretching fundamental and overtone spectra of phenol and its deuterated isotopomers under jet-cooled conditions using nonresonant ionization detection spectroscopy and vapor-phase infrared (IR) and near-infrared (NIR) spectra at room temperature using conventional and photoacoustic spectroscopy. The OH- and OD-stretching bands in the jet-cooled spectra are about 1-10 cm(-1) wide and generally show a few Lorentzian shaped peaks. The bands in the room-temperature spectra have widths of 20-30 cm(-1) and display clear rotational profiles. The band profiles in the jet-cooled spectra arise mostly from nonstatistical intramolecular vibrational redistribution (IVR) with specific coupling to "doorway" states, which are likely to involve CH- and CD-stretching vibrations. The transition dipole moment that determines the rotational structure is found to rotate significantly from the fundamental to the third overtone and is not directed along the OH(D) bond. We use these calculated transition dipole moments to simulate the rotational structure. We determine the rotational temperature in the jet-cooled spectra to be about 0.5 K. Anharmonic oscillator local mode calculations of frequencies and intensities of the OH- and OD-stretching transitions are compared with our measured results. The calculated intensities are in good agreement with the absolute intensities obtained from conventional spectroscopy and with the relative intensities obtained from the room-temperature laser spectroscopy.     

Geometry of deformed exponential families: Invariant,dually-flat and conformal geometries

An information-geometrical foundation is established for the deformed exponential families of probability distributions. Two different types of geometrical structures, an invariant geometry and a flat geometry, are given to a manifold of a deformed exponential family. The two different geometries provide respective quantities such as deformed free energies, entropies and divergences. The class belonging to both the invariant and flat geometries at the same time consists of exponential and mixture families. Theq$q$-families are characterized from the viewpoint of the invariant and flat geometries. The q$q$-exponential family is a unique class that has the invariant and flat geometries in the extended class of positive measures. Furthermore, it is the only class of which the Riemannian metric is conformally connected with the invariant Fisher metric.     

Targeted sonodynamic therapy using protein-modified TiO2 nanoparticles

Our previous study suggested new sonodynamic therapy for cancer cells based on the delivery of titanium dioxide (TiO₂) nanoparticles (NPs) modified with a protein specifically recognizing target cells and subsequent generation of hydroxyl radicals from TiO₂ NPs activated by external ultrasound irradiation (called TiO₂/US treatment). The present study first examined the uptake behavior of TiO₂ NPs modified with pre-S1/S2 (model protein-recognizing hepatocytes) by HepG2 cells for 24 h. It took 6 h for sufficient uptake of the TiO₂ NPs by the cells. Next, the effect of the TiO₂/US treatment on HepG2 cell growth was examined for 96 h after the 1 MHz ultrasound was irradiated (0.1 W/cm², 30 s) to the cells which incorporated the TiO₂ NPs. Apoptosis was observed at 6 h after the TiO₂/US treatment. Although no apparent cell-injury was observed until 24 h after the treatment, the viable cell concentration had deteriorated to 46% of the control at 96 h. Finally, the TiO₂/US treatment was applied to a mouse xenograft model. The pre-S1/S2-immobilized TiO₂ (0.1 mg) was directly injected into tumors, followed by 1 MHz ultrasound irradiation at 1.0 W/cm² for 60 s. As a result of the treatment repeated five times within 13 days, tumor growth could be hampered up to 28 days compared with the control conditions.     

Reverse Engineering Analysis of the High-Temperature Reversible Oligomerization and Amyloidogenicity of PSD95-PDZ3

PSD95-PDZ3, the third PDZ domain of the post-synaptic density-95 protein (MW 11 kDa), undergoes a peculiar three-state thermal denaturation (N ↔ I_n ↔ D) and is amyloidogenic. PSD95-PDZ3 in the intermediate state (I) is reversibly oligomerized (RO: Reversible oligomerization). We previously reported a point mutation (F340A) that inhibits both ROs and amyloidogenesis and constructed the PDZ3-F340A variant. Here, we “reverse engineered” PDZ3-F340A for inducing high-temperature RO and amyloidogenesis. We produced three variants (R309L, E310L, and N326L), where we individually mutated hydrophilic residues exposed at the surface of the monomeric PDZ3-F340A but buried in the tetrameric crystal structure to a hydrophobic leucine. Differential scanning calorimetry indicated that two of the designed variants (PDZ3-F340A/R309L and E310L) denatured according to the two-state model. On the other hand, PDZ3-F340A/N326L denatured according to a three-state model and produced high-temperature ROs. The secondary structures of PDZ3-F340A/N326L and PDZ3-wt in the RO state were unfolded according to circular dichroism and differential scanning calorimetry. Furthermore, PDZ3-F340A/N326L was amyloidogenic as assessed by Thioflavin T fluorescence. Altogether, these results demonstrate that a single amino acid mutation can trigger the formation of high-temperature RO and concurrent amyloidogenesis.     

Does Chiral Sensitivity of a Structure Depend on the Metal Core? Alkali Ion Complexes of Cyclo(Tyr-Tyr)

Alkali metal complexes of cyclic dipeptide cyclo Tyr-Tyr have been studied under cryogenic ion trap conditions. Their structure was obtained by combining Infra-Red Photo-Dissociation (IRPD) and quantum chemical calculations. The structural motif strongly depends on the relative chirality of the tyrosine residues. For residues of identical chirality, the cation interacts with one amide oxygen and one of the aromatic rings only; the distance between the aromatic rings does not change with the nature of the metal. In contrast, for residues of opposite chirality, the metal cation is located in between the two aromatic rings and interacts with both of them. The distance between the two aromatic rings strongly depends on the metal. Electronic spectra obtained by Ultra Violet Photodissociation (UVPD) spectroscopy and analysis of the UV photo-fragments shed light on the excited state deactivation processes, which depend on both the chirality of the residue and that of the metal ion core. Na⁺ stands out by the presence of low-lying charge transfer states resulting in the broadening of the electronic spectrum.