Programming supramolecular peptide materials by modulating the intermediate steps in the complex assembly pathway: Implications for biomedical applications

Self-assembling peptides form a prominent class of supramolecular materials with in general good biocompatibility. To afford better control over the material properties, tremendous progress has been made in studying the supramolecular organization of the peptide assemblies. This knowledge has helped us to understand the correlation between the molecular structure of the peptide building blocks and the properties of the supramolecular products. However, peptide self-assembly consists of a complex pathway rather than a spontaneous thermodynamic process. This implies that the outcome of the self-assembly is critically governed by the assembly pathway. Here, we are going to discuss how peptide self-assembly can be modulated at the intermediate steps in the self-assembly pathway. The focus will be to demonstrate this engineering approach on the example of zero-dimensional/one-dimensional nanostructure selectivity over the β-sheet assembly pathway. In addition, we provide examples of biomedical applications of such steered peptide assemblies in the field of drug delivery and tissue engineering.     

Three-Step Spin State Transition and Hysteretic Proton Transfer in the Crystal of an Iron(II) Hydrazone Complex

A proton–electron coupling system, exhibiting unique bistability or multistability of the protonated state, is an attractive target for developing new switchable materials based on proton dynamics. Herein, we present an iron(II) hydrazone crystalline compound, which displays the stepwise transition and bistability of proton transfer at the crystal level. These phenomena are realized through the coupling with spin transition. Although the multi-step transition with hysteresis has been observed in various systems, the corresponding behavior of proton transfer has not been reported in crystalline systems; thus, the described iron(II) complex is the first example. Furthermore, because proton transfer occurs only in one of the two ligands and π electrons redistribute in it, the dipole moment of the iron(II) complexes changes with the proton transfer, wherein the total dipole moment in the crystal was canceled out owing to the antiferroelectric-like arrangement.     

Microwave surface impedance measurements of LiFeAs,LiFe(As,P) and FeSe1−xTex single crystals

We study microwave surface impedance measurements of LiFeAs, LiFe(As,P) and FeSe_1?xTe_x single crystals. The in-plane penetration depths of LiFeAs and LiFe(As,P) depend on temperature exponentially at low temperatures, which is a strong indication that these two materials have the nodeless superconducting gap. The temperature dependence of the superfluid density indicates that LiFeAs and LiFe(As,P) are multi-gap superconductors with at least two isotropic gaps. In FeSe_1?xTe_x, on the other hand, the quadratic temperature dependence of the in-plane penetration depth appears, which indicates the existence of some sort of quasiparticle excitations. In addtion, the real part of the microwave conductivity exhibits a large enhancement below T_c in all three materials, which results from the increase of the quasiparticle relaxation time, τ, below T_c.     

Controlling stereoselectivity of solid-state photoreactions by co-crystal formation

An external heavy-atom effect in crystals was found to influence the reaction path of the photocyclization of cyclohexenones drastically, and that was successfully applied to control the cis-trans stereochemistry of the reaction by making co-crystals of heavy-atom containing and non-containing analogues in various ratios.     

Solid-state photochromism of chromenes: enhanced photocoloration and observation of unstable colored species at low temperatures

Solid-state photochromism of benzopyrans and naphthopyrans (chromenes) was investigated in the temperature range between 300 and 80 K. Variable-temperature diffuse reflectance spectroscopy of microcrystalline powders showed that the extent of photocoloration was greatly enhanced at low temperatures. All the chromenes examined exhibited solid-state photochromism at low temperatures, even when they showed little or no photocoloration at room temperature. The solid-state photochromic properties of the chromenes were quite similar to those reported for analogous photochromic compounds of spiropyrans and spirooxazines, which indicates that these classes of compounds are generally photochromic even in the solid state. Photobleaching reactions of the colored merocyanine forms proceeded at low temperatures through the formation of a colorless intermediate, instead of directly resuming the original closed form. In addition to two stable planar merocyanine forms, which are usually observed in the photochromic reactions in solution, photoreactions at low temperatures allowed us to observe unstable colored species, which were tentatively assigned as nonplanar cisoid forms, and were stabilized in the solid state at low temperatures.     

Catalytic reactions on neutral Rh oxide clusters more efficient than on neutral Rh clusters

Gas phase catalytic reactions involving the reduction of N(2)O and oxidation of CO were observed at the molecular level on isolated neutral rhodium clusters, Rh(n) (n = 10-28), using mass spectrometry. Sequential oxygen transfer reactions, Rh(n)O(m-1) + N(2)O → Rh(n)O(m) + N(2) (m = 1, 2, 3,…), were monitored and the rate constant for each reaction step was determined as a function of the cluster size. Oxygen extraction reactions by a CO molecule, Rh(n)O(m) + CO → Rh(n)O(m-1) + CO(2) (m = 1, 2, 3,…), were also observed when a small amount of CO was mixed with the reactant N(2)O gas. The rate constants of the oxygen extraction reactions by CO for m ≥ 4 were found to be two or three orders of magnitude higher than the rate constants for m ≤ 3, which indicates that the catalytic reaction proceeds more efficiently when the reaction cycles turn over around Rh(n)O(m) (m ≥ 4) than around bare Rh(n). Rhodium clusters operate as more efficient catalysts when they are oxidized than non- or less-oxidized rhodium clusters, which is consistent with theoretical and experimental studies on the catalytic CO oxidation reaction on a rhodium surface.     

Measurement of the hyperfine structure of antihydrogen in a beam

A measurement of the hyperfine structure of antihydrogen promises one of the best tests of CPT symmetry. We describe an experiment planned at the Antiproton Decelerator of CERN to measure this quantity in a beam of slow antihydrogen atoms.     

Abe homotopy classification of topological excitations under the topological influence of vortices

Topological excitations are usually classified by the nth homotopy group πn. However, for topological excitations that coexist with vortices, there are cases in which an element of πn cannot properly describe the charge of a topological excitation due to the influence of the vortices. This is because an element of πn corresponding to the charge of a topological excitation may change when the topological excitation circumnavigates a vortex. This phenomenon is referred to as the action of π₁ on πn. In this paper, we show that topological excitations coexisting with vortices are classified by the Abe homotopy group κn. The nth Abe homotopy group κn is defined as a semi-direct product of π₁ and πn. In this framework, the action of π₁ on πn is understood as originating from noncommutativity between π₁ and πn. We show that a physical charge of a topological excitation can be described in terms of the conjugacy class of the Abe homotopy group. Moreover, the Abe homotopy group naturally describes vortex-pair creation and annihilation processes, which also influence topological excitations. We calculate the influence of vortices on topological excitations for the case in which the order parameter manifold is Sn/K, where Sn is an n-dimensional sphere and K is a discrete subgroup of SO(n+1). We show that the influence of vortices on a topological excitation exists only if n is even and K includes a nontrivial element of O(n)/SO(n).     

Mössbauer study of Fe3+/Fe2+ ratio in amphiboles to search correlation with hydrogen isotope fractionation

New intense muon beams with flux several orders of magnitude higher than at present muon facilities would allow many novel experimental studies that were until now statistically not feasible. The investigation of the nuclear properties of short-lived nuclei using muonic atom spectroscopy would become possible. A feasibility study at RIKEN-RAL muon facility using the cold hydrogen film method to produce radioactive muonic atoms is in progress. A new surface ionization type ion source was recently installed to expand the variety of available ions. Encouraging experimental results were obtained with stable alkaline-earth and rare-earth isotope ions implanted in solid deuterium films. The latest results are reported in this paper.