Highly degenerate canted spin structure in bilayer manganite La1.1Sr1.9Mn2O7

We have observed magnetic diffuse signals of the bilayer manganite La1.1Sr1.9Mn2O7 by neutron scattering. Even at the low temperature, 20 K, there is a diffuse signal, which is much stronger than that observed in the high temperatures, 144 and 288 K. This signal cannot be characterized by a bilayer structure as observed at 144 K nor by a monolayer structure as at 288 K, but by a high degeneracy of a canted spin structure. Thus, an observation of this diffuse signal is the direct evidence for the establishment of the canted spin structure in La1.1Sr1.9Mn2O7.     

Observation of rotational population transfer effect for an HF chemical laser

When a CO₂ gas absorption cell was placed within the optical cavity of a low pressure pulsed HF laser, the specific vibration- rotation line of the HF laser disappeared, which influenced both the intensity and pulse duration of the neighbouring lines. This behavior strongly depends upon the rotational population transfer in HF. By measuring the time response of this behavior, it was found that the rate constant for the rotational population transfer was in the range of 10⁷ s^-1 torr^-1 for the SF₆/H₂ lasing mixture.     

Synthetic hologram made by variable magnification imaging system

For the purpose of improving the utilization efficiency of the gain bandwidth of active media and generating stable ultrashort light pulses, a passive-active mode locking technique has been applied to a cw Rhodamine 6G dye laser. A sufficient ability of this technique for the elimination of the multiple-pulse operation of the mode locking at a higher pumping level and a longer resonator length has been proved. Observed pulse-width by the SHG autocorrelation technique is 1.4 ps with assuming a sech² pulse profile.     

Fermi surface nesting and structural transition on a metal surface: In /Cu(001)

Peierls-type instability and structural phase transition are shown to occur on the surface of a normal metal. An In overlayer on Cu(001) undergoes a reversible transition at approximately 350 K. Scanning tunneling microscopy of the low-temperature, reduced-symmetry phase indicates a strong periodic lattice distortion (PLD). Angle-resolved photoemission of the high-temperature phase reveals that the In-derived surface resonance constitutes a square-shaped, quasi-two-dimensional Fermi surface within the projected bulk Cu bands. The Fermi surface exhibits one-dimensional nesting upon the transition, which is in agreement with the PLD periodicity.     

Absolute configurational assignments of secondary amines by CD-sensitive dimeric zinc porphyrin host

A general chiroptical protocol for determination of absolute configuration of secondary amines including acyclic and cyclic aliphatic amines, aromatic amines, amino acids, and amino alcohols is described. The chiral substrate is linked to the achiral carrier moiety (3-N-Boc-amino-propyl-N-Boc-amino)acetic acid 1 (BocHNCH(2)CH(2)CH(2)BocNCH(2)COOH), which after deprotection, yields a bidentate conjugate, capable of forming a 1:1 host/guest complex with dimeric zinc porphyrin host 2. As in the cases of primary amines and secondary alcohols reported earlier, the complexation of secondary amine conjugates to porphyrin tweezer host 2 represents a stereodifferentiating process, where the large (L) group at the stereogenic center (assigned on the basis of conformational energies A value) protrudes from the porphyrin binding pocket. This leads to formation of host/guest complexes with a preferred porphyrin helicity that exhibit intense exciton split CD spectra. It was found that the chiral sense of porphyrin twist is clearly controlled by the stereogenic center despite the Z/E conformational complexity around the tertiary amide bond of secondary amine conjugates that has greatly hampered previous configurational assignments. Thus, in cases where there is no ambiguity regarding the relative steric size of substituents, the observed CD couplet can be applied for straightforward assignment of absolute configurations. In addition, to extend the application to more difficult cases a molecular mechanics calculation approach using the Merck Molecular Force Field (MMFFs) was developed; this provides conformational information of host/guest complexes and leads to prediction of preferred porphyrin helicity independent of conformational A values. This chiroptical protocol in combination with molecular modeling represents a general method for configurational assignments of secondary amines.     

A novel organic intercalation system with layered polymer crystals as the host compounds derived from 1,3-diene carboxylic acids

A new type of organic intercalation system using poly(muconic acid) and poly(sorbic acid) crystals as the host compounds is described. The layered polymer crystals as the host are derived from benzyl-, dodecyl-, or naphthylmethylammonium salts of (Z,Z)-muconic or (E,E)-sorbic acids by topochemical polymerization. The subsequent solid-state hydrolysis of the resulting ammonium polymer crystals provides the corresponding carboxylic acid polymer crystals. When alkylamines are reacted with poly(muconic acid) or poly(sorbic acid) crystals dispersed in methanol at room temperature for a few hours, the intercalation proceeds to give layered ammonium polymer crystals via solid-state reactions, in which the polymers maintain a layered structure throughout. The interplanar spacing value of the polymer crystals changes according to the size of the guest molecules; that is, it exactly depends on the carbon number of the alkylamines used for each reaction of poly(muconic acid) or poly(sorbic acid) crystals. The stacking structure of alkyl chains with a tilt in the intercalated alkylammonium layers exists irrespective of the chemical and crystal structures of the host polymers. The intercalation of higher alkylamines into poly(muconic acid) crystals proceeds fast and quantitatively, while the conversion is dependent on the reaction conditions such as the structure and amount of the amine and the reaction time during the intercalation with poly(sorbic acid) crystals, due to the difference in the repeating layered structures of these polymer crystals. Some functional amines are also used as the guest molecules for this organic intercalation system.     

Enantioselective total synthesis of a potent antitumor antibiotic, fredericamycin A.

The asymmetric total synthesis of both enantiomers of the potent antitumor antibiotic fredericamycin A (1) is detailed based on the protocol for the construction of its peri-hydroxy polyaromatic skeleton bearing the chirality at the spiro carbon via a strong base-induced cycloaddition of suitably substituted homophthalic anhydrides (AB-ring unit) with an optically active CDEF-ring unit. Particular attention has been given to the novel synthesis of the optically active spiro carbon center by a stereospecific rearrangement of optically active benzofuzed-trans-epoxy acylates leading to spirocyclopentane-1,1'-indane systems. This method is quite useful for the construction of an optically active spiro compound and was applied to the synthesis of the optically pure CDEF-ring unit of 1. Cycloaddition of the optically pure CDEF-ring unit to AB-ring units prepared via benzyne afforded two natural and unnatural-type hexacyclic compounds, which were converted to natural and unnatural enantiomers of synthetic 1, and the absolute configuration of natural 1 was determined as S.     

Noncritical maps on geodesically complete spaces with curvature bounded above

Annals of Global Analysis and Geometry - We define and study the regularity of distance maps on geodesically complete spaces with curvature bounded above. We prove that such a regular map is...