Synthesis of 12-deoxyroyleanone, cryptoquinone, 11,14-dihydroxy-8,11,13-abietatrien-7-one, and related derivatives from dehydroabietic acid

Naturally occurring abietane quinones and hydroquinone, namely, 12-deoxyroyleanone (1a), cryptoquinone (4a), and 11,14-dihydroxyabieta-8,11,13-trien-7-one (5a), together with the epimers of tryptoquinones D (2) and F (3), were first synthesized from dehydroabietic acid (6).     

New ferromagnets of Sr8ARe3Cu4O24 (A=Sr, Ca) with an ordered perovskite structure

New phases Sr₈ARe₃Cu₄O₂₄ (A=Sr,Ca) were discovered under high-pressure/high-temperature condition. X-ray powder diffraction and electron diffraction studies for these phases indicated that they have an ordered perovskite-type structure with cubic lattices of ∼8 Å. They showed ferromagnetism at room temperature when they were synthesized under high-oxygen-pressure condition. The Ca-containing phase has a very high T_c of 440 K with a spontaneous magnetization of ∼1 μ_B/f.u.     

LIGHT INDUCED FLUORESCENCE SPECTRAL CHANGES IN NATIVE PHYTOCHROME FROM Secale cereale L. AT LIQUID NITROGEN TEMPERATURE

Abstract— Fluorescence spectra of native rye phytochrome were determined under different light conditions at liquid nitrogen temperature. Fluorescence spectrum of the red-light-absorbing form (Pr) had a major peak at about 685 nm (14 600 cm⁻¹) and a broad sub-peak at about 515 nm (19 400 cm⁻¹). The peak height at 685 nm was reduced by irradiation with monochromatic light of 640 nm, and a new peak became obvious at about 702 nm (14250 cm⁻¹). This spectral change was almost completely reversed by subsequent irradiation with 700-nm light. Fluorescence spectrum of the photoequilibrium mixture of Pr and far-red-light absorbing form under continuous red light showed a sharp peak at about 685 nm having a peak height ca. 12% of Pr, and a broad sub-peak at about 508 nm (19 700 cm⁻¹). Light of 730 nm did not reduce the peak height at about 685 nm but induced a new shoulder at about 699 nm (14300 cm⁻¹). Monochromatic light of 640 and 700 nm given following the light of 730 nm could not reverse the spectral change at 699 nm induced by the irradiation with 730-nm light. Fluorescence spectrum of Pr in partially degraded phytochrome was similar to that in native phytochrome but the peak position in the red region was shifted by about 5 nm (100 cm⁻¹) to the blue.     

Magnetic properties of isostructural BaCoP2O7, BaNiP2O7, and BaCuP2O7 studied with dc and ac magnetization and specific heat

Magnetic properties of three isostructural compounds BaMP2O7 (M = Co, Ni, and Cu) were investigated by dc and ac magnetization and specific heat measurements. BaCuP2O7 was shown to be an excellent quasi-one-dimensional linear-chain Heisenberg antiferromagnet with an exchange constant (J/kB) of 103.8 K (Hamiltonian H = J Sigma SiS(i+1)) and a temperature for the long-range magnetic order (TN) of 0.81 K giving the ratio kBTN/J = 0.78%. BaCoP2O7 and BaNiP2O7 exhibited long-range antiferromagnetic order at TN = 10.4 and 10.1 K, respectively. BaCoP2O7 and BaNiP2O7 showed a large contribution of the short-range correlation above TN. BaNiP2O7 remained in the antiferromagnetic state up to 90 kOe at 2 K, whereas BaCoP2O7 demonstrated two metamagnetic phase transitions at about 52 and 71 kOe at 2 K if the magnetic field was parallel to the easy direction. BaMP2O7 melted incongruently at 1323 K (M = Co), 1344 K (M = Ni), and 1338 K (M = Cu).     

Synthesis, structure and thermal stability of fully hydrophobic porphyrin-DNA conjugates

The DNAs modified with tetraphenyl porphyrin at the center of 13mer oligonucleotide were synthesized using phosphoramidite chemistry and automated DNA synthesis. When the porphyrin modified oligonucleotide was annealed with its complementary strand, they formed a standard B-form duplex. The porphyrin moiety intercalated in the duplex, and moderately lowered the thermal stability.     

Rational design and crystal structure determination of a 3-D metal-organic jungle-gym-like open framework

A new three-dimensional (3-D) jungle-gym-like open metal-organic framework has been synthesized from a two-dimensional (2-D) layer compound using a heterogeneous pillar insertion reaction. Both the starting 2-D layer and the resulting 3-D open compounds have been characterized using X-ray crystallography.     

Multiple fluorescence spectra and stable encapsulation of 7-hydroxy-4-methylcoumarin and rhodamine 6g in silicate glasses by the sol-gel method

7-Hydroxy-4-methylcoumarin(4-methylumbelliferone, HMC) and Rhodamine 6G(R6G) were encapsulated into silicate polymeric glass prepared by the sol-gel method under acidic, basic, and neutral conditions from tetraethyl orthosilicate. The fluorescence spectra of these molecules encapsulated into the xerogel state depend on the used catalysts. Three types of fluorescence emissions having peak wavelengths of ca. 390 nm, 470 nm, and 550 run, respectively, were observed simultaneously in the xerogel state composed of HMC and R6G which were prepared by acid catalysts. The encapsulated HMC remains stable for more than one year in the prepared xerogel. The results open the way to the development of simultaneous three-band laser emissions. The observation of the fluorescence spectrum of HMC is useful for a molecular level photophysical probe elucidating the structural changes oftetraethyl orthosilicate during sol to gel to xerogel transitions.     

Cover Picture

The cover picture shows a section of the electron charge density of the first metal carbide endohedral metallofullerene (Sc(2)C(2))@C(84) obtained from a synchrotron X-ray powder diffraction study by the maximum entropy method (MEM). The several density maxima, which correspond to scandium and carbon atoms, are clearly seen inside the C(84) carbon cage. The MEM charge density distribution also reveals that the C(84) cage has D(2d) symmetry (no. 23) and that the C(2) axis is parallel to the <100> face-centered cubic (fcc) direction of the unit cell. As a consequence of the site symmetry being 4mm, the C(2) axis of (Sc(2)C(2))@C(84) is oriented to six equivalent <100> directions and shows a merohedral disorder. The resultant Sc small middle dot small middle dot small middle dotSc distances and C-C bond lengths of the Sc(2)C(2) cluster are 0.429(2) and 0.142(6) nm, respectively. The observed C-C bond length is between that of a typical single and a double bond, and is very close to that of the C-C bond (0.143 nm) combining two pentagons in a C(60) molecule. More about this fascinating structure can be found in the contribution by Shinohara and co-workers on p. 397 ff.     

Manipulating the Through‐Space Spin–Spin Interaction of Organic Radicals in the Confined Cavity of a Self‐Assembled Cage

We show a new approach to manipulating the through‐space spin–spin interaction by utilizing the confined cavity of a self‐assembled M₆L₄ coordination cage. The coordination cage readily encapsulates stable organic radicals in solution, which brings the spin centers of the radicals closer to each other. In sharp contrast to the fact that the radical in solution in the absence of the cage is in a doublet state, in the presence of the cage through‐space spin–spin interaction is induced through cage‐encapsulation effects in solution as well as in the solid state, resulting in the triplet state of the complex. These results were confirmed by ESR spectroscopy and X‐ray crystallography. The quantity of triplet species generated by encapsulation in the cage increases with increasing affinity of the radicals to the cage. We estimated the affinity between several types of guests and the cage in solution by cyclic voltammetry. We also demonstrate that the through‐space interaction of organic radicals within the self‐assembled coordination cage can be controlled by external stimuli such as heat or pH.