Photoreactive polyamides having m- or 1-type dimer moiety derived from 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid derivatives

Photoreactive polyamides having m- or 1 -type cyclobutane moiety were prepared via a topochemical photodimerization of 4-(3-oxo-3-phenyl-1-propenyl)benzoic derivatives,⁴ followed by polycondensation of cyclobutane dicarboxylate derivatives with diamines. From the spectral studies of resulted polyamides compared with the corresponding reference diamides, it was concluded that both types of polyamides were depolymerized photochemically to give the same type of amide derivative having chalcone moiety with a small amount of undefined side reaction. The cyclobutane ring of the m-dimer from 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid in crystal is severely twisted presumably because of the enhanced steric repulsions between two pairs of adjacent substituents. The higher quantum yield of the m-dimer for the photocleavege, compared with that of the 1 -dimer, has been interpreted in terms of such steric repulsions by the strained structure of the m-dimer.     

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).     

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.     

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.     

Diastereoselective imino-aldol condensation of chiral 3-(p-Tolylsulfinyl)-2-furaldimine and ester enolates

(Ss)-3-(p-Tolylsufinyl)-2-furaldimine was synthesized, and condensation of the chiral furaldimine with lithium ester enolates has been examined. The product distribution of the reaction is dependent upon reaction conditions and on the kind of the substituent placed on the esters. Disubstituted ester enolate resulted in the exclusive formation of (4R)-beta-lactam, while unsubstituted, tert-butyl ester enolate preferentially gave (3R)-beta-amino ester. With the monosubstituted ester enolates, the condensation afforded (4R)-beta-lactams and/or (3R)-beta-amino esters as major products. This method has been applied to an efficient route to chiral furyl beta-lactams.     

Concise synthesis of anti-HIV-1 active (+)-inophyllum B and (+)-calanolide A by application of (-)-quinine-catalyzed intramolecular oxo-Michael addition

(-)-Quinine-catalyzed intramolecular oxo-Michael addition (IMA) of 7-hydroxy-5-methoxy-8-tigloylcoumarins was developed for the enantioselective construction of 2,3-dimethyl-4-chromanone systems in the context of the asymmetric synthesis of anti-HIV-1 active Calophyllum coumarins. Combination of the IMA and MgI(2)-assisted demethylation of the 5-methoxy group along with isomerization of the formed chromanone systems as key steps successfully led to the concise synthesis of (+)-inophyllum B and (+)-calanolide A, possible candidates for AIDS drugs. Further examination of the asymmetric IMA with cinchona alkaloids lacking a methoxy group on the quinoline skeleton suggested the influence of the methoxy substituent on stereoselectivity at the stereogenic centers of the chromanone systems.     

Film structures of poly(amido amine) dendrimers with an azacrown core and long alkyl chain spacers on water or Ag nanoparticle suspension

Newly designed poly(amido amine) dendrimers, which have an azacrown core, hexyl spacers, and methyl ester terminals (aza-C6-PAMAM dendrimer), were spread at the air-water and air-silver nanoparticle suspension interfaces, and their film structures were examined by surface pressure-area (pi-A) and surface potential-area (DeltaV-A) isotherms and epifluorescence microscopy. It was revealed that generation (G) 1.5 aza-C6-PAMAM dendrimer on a water subphase formed homogeneous film with face-on configuration, and this configuration was maintained during compression. On the other hand, a G2.5 dendrimer film on the air-water interface took initially homogeneous and face-on configuration that was followed by the conformational change during compression. Using a silver nanoparticle suspension as subphase, G1.5 film was significantly reinforced, and the partial collapse (cracks) in the film appeared as network texture. For a G2.5 dendrimer film, the pi-A and DeltaV-A isotherm properties were similar to that on the water subphase except for the collapsed film; small spots instead of cracks were formed under the film after collapse. These effects of the silver nanoparticle may be due to the formation of a dendrimer/silver nanoparticle composite. The formation process of the nanocomposite film was verified by UV-vis spectroscopy. For the G1.5 dendrimer, silver clusters and nanoparticles adsorbed to the dendrimer film after spreading and formed a small amount of aggregates. During compression, the aggregation proceeded even at low surface pressure. For the G2.5 dendrimer, a dendrimer/nanoparticle composite was also formed after spreading. However, with the initial compression, the absorption bands of clusters, nanoparticles, and aggregate increased together. Upon further compression, while the bands of cluster and nanoparticles decreased, the bands of aggregate still increased. These results suggest that the G2.5 dendrimer covered the cluster and nanoparticles more efficiently than the G1.5 dendrimer did because of the larger molecular size.     

Chain-growth polycondensation for well-defined aramide. Synthesis of unprecedented block copolymer containing aramide with low polydispersity

Poly(p-benzamide) with a defined molecular weight and a low polydispersity and a block copolymer containing this well-defined aramide was synthesized. Phenyl 4-aminobenzoate, which would yield poly(p-benzamide), did not polymerize under the conditions of chain-growth polycondensation. However, phenyl 4-(4-octyloxybenzylamino)benzoate (1b) polymerized at room temperature in the presence of base and phenyl 4-nitrobenzoate (2) as an initiator in a chain-growth polycondensation manner to give well-defined aromatic polyamides having the 4-octyloxybenzyl groups as a protecting group on nitrogen in an amide. It was confirmed by a model reaction that deprotection of this protecting group proceeded completely with trifluoroacetic acid (TFA) without breaking the amide linkage. The utility of this approach to poly(p-benzamide) with a low polydispersity was demonstrated by the synthesis of block copolymers. Thus, phenyl 4-(octylamino)benzoate (1a) polymerized in the presence of 2 and base, followed by addition of 1b and base to the reaction mixture of the prepolymer to yield the block copolymer of 1a and 1b with a controlled molecular weight and a low polydispersity. The block copolymer was treated with TFA, resulting in a soluble block copolymer of poly(N-octyl-p-benzamide) and poly(p-benzamide). The SEM images of the supramolecular assemblies of the block copolymer showed mum-sized bundles and aggregates of flake structures.