B1-to-B2 structural transitions in rock salt intergrowth structures

The rock salt (B1) structure of binary oxides or chalcogenides transforms to the CsCl (B2) structure under high pressure, with critical pressures P(s) depending on the cation to anion size ratio (R(c)/R(a)). We investigated structural changes of A(2)MO(3) (A = Sr, Ca; M = Cu, Pd) comprising alternate 7-fold B1 AO blocks and corner-shared MO(2) square-planar chains under pressure. All of the examined compounds exhibit a structural transition at P(s) = 29-41 GPa involving a change in the A-site geometry to an 8-fold B2 coordination. This observation demonstrates, together with the high pressure study on the structurally related Sr(3)Fe(2)O(5), that the B1-to-B2 transition generally occurs in these intergrowth structures. An empirical relation of P(s) and the R(c)/R(a) ratio for the binary system holds well for the intergrowth structure also, which means that P(s) is predominantly determined by the rock salt blocks. However, a large deviation from the relation is found in LaSrNiO(3.4), where oxygen atoms partially occupy the apical site of the MO(4) square plane. We predict furthermore the occurrence of the same structural transition for Ruddlesden-Popper-type layered perovskite oxides (AO)(AMO(3))(n), under higher pressures. For investigating the effect on the physical properties, an electrical resistivity of Sr(2)CuO(3) is studied.     

Generalized Lax-Milgram theorem in Banach spaces and its application to the elliptic system of boundary value problems

We generalize the well-known Lax-Milgram theorem on the Hilbert space to that on the Banach space. Suppose that ${a(\cdot, \cdot)}$ is a continuous bilinear form on the product ${X\times Y}$ of Banach spaces X and Y, where Y is reflexive. If null spaces N _X and N _Y associated with ${a(\cdot, \cdot)}$ have complements in X and in Y, respectively, and if ${a(\cdot, \cdot)}$ satisfies certain variational inequalities both in X and in Y, then for every ${F \in N_Y^{\perp}}$ , i.e., ${F \in Y^{\ast}}$ with ${F(\phi) = 0}$ for all ${\phi \in N_Y}$ , there exists at least one ${u \in X}$ such that ${a(u, \varphi) = F(\varphi)}$ holds for all ${\varphi \in Y}$ with ${\|u\|_X \le C\|F\|_{Y^{\ast}}}$ . We apply our result to several existence theorems of L ^r -solutions to the elliptic system of boundary value problems appearing in the fluid mechanics.     

Sequential charge separation in two axially linked phenothiazine-aluminum(III) porphyrin-fullerene triads

New supramolecular triads (PTZpy→AlPor-C(60), TPTZpy→AlPor-C(60)), containing aluminum(III) porphyrin (AlPor), fullerene (C(60)), and phenothiazine (phenothiazine = PTZ, 2-methylthiophenothaizine = TPTZ) have been constructed. In these triads the fullerene and phenothiazine units are bound axially to opposite faces of the porphyrin plane via covalent and coordination bonds, respectively. The ground- and excited-state properties of the triads and reference dyads are studied using steady-state and time-resolved spectroscopic techniques. The time-resolved data show that photoexcitation results in charge separation from the excited singlet state of the porphyrin to the C(60) unit, generating (Donor)py→AlPor(?+)-C(60)(?-), Donor = PTZ and TPTZ. A subsequent hole shift from the porphyrin to phenothiazine generates the charge-separated state (Donor)(?+)py→AlPor-C(60)(?-). The lifetime of the charge separation exhibits a modest increase from 39 ns in the absence of the donor to 100 ns in PTZpy→AlPor-C(60) and 83 ns in TPTZpy→AlPor-C(60). These lifetimes are discussed in terms of the electronic coupling between phenothiazine, the porphyrin, and C(60).     

Immunological Evaluation of Co‐Assembling a Lipidated Peptide Antigen and Lipophilic Adjuvants: Self‐Adjuvanting Anti‐Breast‐Cancer Vaccine Candidates

Co‐assembling vaccines composed of a lipidated HER2‐derived antigenic CH401 peptide and either a lipophilic adjuvant, Pam₃CSK₄, α‐GalCer, or lipid A 506, were evaluated as breast cancer vaccine candidates. This vaccine design was aimed to inherit both antigen multivalency and antigen‐specific immunostimulation properties, observed in reported self‐adjuvanting vaccine candidates, by using self‐assembly and adjuvant‐conjugated antigens. Under vaccination concentrations, respective lipophilic adjuvants underwent co‐assembly with lipidated CH401, which boosted the anti‐CH401 IgG and IgM production. In particular, α‐GalCer was responsible for the most significant immune activation. Therefore, the newly developed vaccine design enabled the optimization of adjuvants against the antigenic CH401 peptide in a simple preparatory manner. Overall, the co‐assembling vaccine design opens the door for efficient and practical self‐adjuvanting vaccine development.     

Library‐directed Solution‐ and Solid‐phase Synthesis of 2,4‐Disubstituted Pyridines: One‐pot Approach through 6 π‐Azaelectrocyclization

An efficient one‐pot synthetic procedure for the synthesis of 2,4‐disubstituted pyridines has been successfully established. The method proceeds through a 6π‐azaelectrocyclization‐aromatization sequence. Using this method, a wide variety of pyridine structures substituted at the 2‐position have been rapidly constructed from vinyl stannanes, vinyl iodide, sulfonamide, and a palladium catalyst. The method was further applied to the solid‐phase synthesis wherein the use of a “traceless” sulfonamide linker enabled the rapid preparation of a small library of pyridines with high purity, without any chromatographic separation.     

Tetraaryldiborane(4) Can Emit Dual Fluorescence Responding to the Structural Change around the B–B Bond

We report the successful synthesis of tetramesityldiborane(4) (Mes₄B₂) through the reductive coupling of a dimesitylborinium ion. Owing to the steric protection conferred by the mesityl groups, Mes₄B₂ shows exceptional chemical stability and remains intact in water. Single-crystal X-ray analysis revealed that Mes₄B₂ has an orthogonal geometry, where the B–B center is completely hidden by the mesityl groups. Remarkably, Mes₄B₂ emits dual fluorescence at 460 and 620 nm, both in solution and in the solid state. Theoretical calculations showed that Mes₄B₂ in the excited S₁ state adopts a twisted or planar geometry, which is responsible for the shorter- or longer-wavelength fluorescence, respectively. The intensity ratio of the dual fluorescence is sensitive to the viscosity of the medium, which suggests that Mes₄B₂ has potential as a ratiometric viscosity sensor.     

Synthesis of heteroarylazulenes: transition metal free coupling strategy of azulene with heterocycles

Azulene reacts with highly electrophilic trifluoromethanesulfonates of N-containing heterocycles to give 1-dihydroheteroaryl and 1,3-bis(dihydroheteroaryl)azulene derivatives in a good yield. Treatment of the dihydroheteroarylazulene derivatives with KOH or tert-BuOK afforded 1-heteroaryl and 1,3-bis(heteroaryl)azulenes in a good yield.     

Phase transition in Pd_(40)Ni_(10)Cu_(30)P_(20) bulk metallic glass under HP & HT

Bulk metallic glass (BMG) can be regarded as a metallic solid with a frozen-in melt structure which lacks atomic periodicity. Generally, BMG is not in an internal equilib- rium state (IES) but may change to the IES when it obtains an appropriate energy to overcome the energy barrier. High pressure and temperature can be a driving force to cause various transitions in amorphous materials, such as a transition from the amor- phous to the crystalline[1―8] or from the crystalline to the amorp…     

Remarks on duality of 1 dimensional quantum spin models

We present some results on duality maps and ground states of 1 dimensional quantum spin models. We also give some applications to Kramers Wannier duality and the nonlocal transformation that Kennedy and Tasaki discovered in their study of Haldane phase of quantum antiferromagnetic spin models.     

Spin transition in magnesiowüstite in earth's lower mantle

Iron in the major lower mantle (LM) minerals undergoes a high spin (HS) to low spin (LS) transition at relevant pressures (23-135 GPa). Previous failures of standard first principles approaches to describe this phenomenon have hindered its investigation and the clarification of important consequences. Using a rotationally invariant formulation of LDA + U we report a successful study of this transition in low solute concentration magnesiowüstite, (Mg(1-x)Fe(x)(O), (x < 0.2) the second most abundant LM phase. We show that the HS-LS transition goes through an insulating (semiconducting) intermediate mixed spins (MS) state without discontinuous changes in properties, as seen experimentally. We show that the HS state crosses over smoothly to the LS state passing through an insulating MS state where properties change continuously, as seen experimentally.