Reactions of Neomycin B under Mitsunobu Conditions: A Correction of the Literature

Reaction of N‐Boc neomycin with triphenylphosphine and diissopropyl azodicarboxylate in either toluene or THF results in an epoxide in ring IV, not an aziridine or azetidine as previously reported.     

Effects of Ag–La codoping on structure and electrical properties of BaTiO3 powder

Ag–La codoped BaTiO₃ powders were prepared by sol–gel technology after the preparation of Ag-doped and La-doped BaTiO₃ powders. Variations in the structure, constitution, morphology, and electrical properties of the modified BaTiO₃ powders were characterized. It can be concluded that Ag–La codoping decreases the resistivity of the modified powders more significantly than Ag doping and La doping, respectively. The sample with the lowest resistivity was obtained by codoping with 0.1 at.% Ag and 0.3 at.% La, where the resistivity decreased to 7.13 × 10² Ω m from the value of 4.30 × 10⁹ Ω m of the undoped powder. X-ray diffractometry (XRD) and Fourier-transform infrared (FTIR) analyses indicate that the main phase of the codoped powders transitions from tetragonal to cubic with increasing La doping content. Scanning electron microscopy (SEM) observations illustrate that codoping makes the particles distribute more equably. The relationship between the resistivity and the structure of the doped BaTiO₃ powders is discussed based on defect chemistry.     

Three‐Dimensional Architectures Incorporating Stereoregular Donor–Acceptor Stacks

We report the synthesis of two [2]catenane‐containing struts that are composed of a tetracationic cyclophane (TC⁴⁺) encircling a 1,5‐dioxynaphthalene (DNP)‐based crown ether, which bears two terphenylene arms. The TC⁴⁺ rings comprise either 1) two bipyridinium (BIPY²⁺) units or 2) a BIPY²⁺ and a diazapyrenium (DAP²⁺) unit. These degenerate and nondegenerate catenanes were reacted in the presence of Cu(NO₃)₂?2.5 H₂O to yield Cu‐paddlewheel‐based MOF‐1050 and MOF‐1051. The solid‐state structures of these MOFs reveal that the metal clusters serve to join the heptaphenylene struts into grid‐like 2D networks. These 2D sheets are then held together by infinite donor–acceptor stacks involving the [2]catenanes to produce interpenetrated 3D architectures. As a consequence of the planar chirality associated with both the DNP and hydroquinone (HQ) units present in the crown ether, each catenane can exist as four stereoisomers. In the case of the nondegenerate (bistable) catenane, the situation is further complicated by the presence of translational isomers. Upon crystallization, however, only two of the four possible stereoisomers—namely, the enantiomeric RR and SS forms—are observed in the crystals. An additional element of co‐conformational selectivity is present in MOF‐1051 as a consequence of the substitution of one of the BIPY²⁺ units by a DAP²⁺ unit: only the translational isomer in which the DAP²⁺ unit is encircled by the crown ether is observed. The overall topologies of MOF‐1050 and MOF‐1051, and the selective formation of stereoisomers and translational isomers during the kinetically driven crystallization, provide evidence that weak noncovalent bonding interactions play a significant role in the assembly of these extended (super)structures.     

Tiara[5]arenes: Synthesis,Solid‐State Conformational Studies,Host–Guest Properties,and Application as Nonporous Adaptive Crystals

Tiara[5]arenes (T[5]s), a new class of five‐fold symmetric oligophenolic macrocycles that are not accessible from the addition of formaldehyde to phenol, were synthesized for the first time. These pillar[5]arene‐derived structures display both unique conformational freedom, differing from that of pillararenes, with a rich blend of solid‐state conformations and excellent host–guest interactions in solution. Finally we show how this novel macrocyclic scaffold can be functionalized in a variety of ways and used as functional crystalline materials to distinguish uniquely between benzene and cyclohexane.     

Amiloride-sensitive channels in type I fungiform taste cells in mouse

Background  

Taste buds are the sensory organs of taste perception. Three types of taste cells have been described. Type I cells have voltage-gated outward currents, but lack voltage-gated inward currents. These cells have been presumed to play only a support role in the taste bud. Type II cells have voltage-gated Na⁺ and K⁺ current, and the receptors and transduction machinery for bitter, sweet, and umami taste stimuli. Type III cells have voltage-gated Na⁺, K⁺, and Ca²⁺ currents, and make prominent synapses with afferent nerve fibers. Na⁺ salt transduction in part involves amiloride-sensitive epithelial sodium channels (ENaCs). In rodents, these channels are located in taste cells of fungiform papillae on the anterior part of the tongue innervated by the chorda tympani nerve. However, the taste cell type that expresses ENaCs is not known. This study used whole cell recordings of single fungiform taste cells of transgenic mice expressing GFP in Type II taste cells to identify the taste cells responding to amiloride. We also used immunocytochemistry to further define and compare cell types in fungiform and circumvallate taste buds of these mice.     

Determination of the orbital moment and crystal-field splitting in LaTiO3

Utilizing a sum rule in a spin-resolved photoelectron spectroscopic experiment with circularly polarized light, we show that the orbital moment in LaTiO3 is strongly reduced from its ionic value, both below and above the Ne el temperature. Using Ti L2,3 x-ray absorption spectroscopy as a local probe, we found that the crystal-field splitting in the t2g subshell is about 0.12-0.30 eV. This large splitting does not facilitate the formation of an orbital liquid.     

Bonding configurations and collective patterns of Ge atoms adsorbed on Si(111)-(7 x 7)

We report scanning tunneling microscopy observations of Ge deposited on the Si(111)-(7 x 7) surface for a sequence of submonolayer coverages. We demonstrate that Ge atoms replace so-called Si adatoms. Initially, the replacements are random, but distinct patterns emerge and evolve with increasing coverage, until small islands begin to form. Corner adatom sites in the faulted half unit cells are preferred. First-principles density functional calculations find that adatom substitution competes energetically with a high-coordination bridge site, but atoms occupying the latter sites are highly mobile. Thus, the observed structures are indeed more thermodynamically stable.     

Spectroscopy of stripe order in La1.8Sr0.2NiO4 using resonant soft x-ray diffraction

Strong resonant enhancements of the charge-order and spin-order superstructure-diffraction intensities in La1.8Sr0.2NiO4 are observed when x-ray energies in the vicinity of the Ni L2,3 absorption edges are used. The pronounced photon-energy and polarization dependences of these diffraction intensities allow for a critical determination of the local symmetry of the ordered spin and charge carriers. We found that not only the antiferromagnetic order but also the charge-order superstructure resides within the NiO2 layers; the holes are mainly located on in-plane oxygens surrounding a Ni2+ site with the spins coupled antiparallel in close analogy to Zhang-Rice singlets in the cuprates.     

Spin and orbital magnetic moments of Fe3O4

We present measurements of the spin and orbital magnetic moments of Fe3O4 by using SQUID and magnetic circular dichroism in soft x-ray absorption. The measurements show that Fe3O4 has a noninteger spin moment, in contrast to its predicted half-metallic feature. Fe3O4 also exhibits a large unquenched orbital moment. Calculations using the local density approximation including the Hubbard U method and the configuration interaction cluster-model suggest that strong correlations and spin-orbit interaction of the 3d electrons result in the noninteger spin and large orbital moments of Fe3O4.