Synthesis, structures, and magnetic properties of face-sharing heterodinuclear Ni(II)-Ln(III) (Ln = Eu, Gd, Tb, Dy) complexes

Heterodinuclear [(Ni (II)L)Ln (III)(hfac) 2(EtOH)] (H 3L = 1,1,1-tris[(salicylideneamino)methyl]ethane; Ln = Eu, Gd, Tb, and Dy; hfac = hexafluoroacetylacetonate) complexes ( 1.Ln) were prepared by treating [Ni(H 1.5L)]Cl 0.5 ( 1) with [Ln(hfac) 3(H 2O) 2] and triethylamine in ethanol (1:1:1). All 1.Ln complexes ( 1.Eu, 1.Gd, 1.Tb, and 1.Dy) crystallized in the triclinic space group P1 (No. 2) with Z = 2 with very similar structures. Each complex is a face-sharing dinuclear molecule. The Ni (II) ion is coordinated by the L (3-) ligand in a N 3O 3 coordination sphere, and the three phenolate oxygen atoms coordinate to an Ln (III) ion as bridging atoms. The Ln (III) ion is eight-coordinate, with four oxygen atoms of two hfac (-)'s, three phenolate oxygen atoms of L (3-), and one ethanol oxygen atom coordinated. Temperature-dependent magnetic susceptibility and field-dependent magnetization measurements showed a ferromagnetic interaction between Ni (II) and Gd (III) in 1.Gd. The Ni (II)-Ln (III) magnetic interactions in 1.Eu, 1.Tb, and 1.Dy were evaluated by comparing their magnetic susceptibilities with those of the isostructural Zn (II)-Ln (III) complexes, [(ZnL)Ln(hfac) 2(EtOH)] ( 2.Ln) containing a diamagnetic Zn (II) ion. A ferromagnetic interaction was indicated in 1.Tb and 1.Dy, while the interaction between Ni (II) and Eu (III) was negligible in 1.Eu. The magnetic behaviors of 1.Dy and 2.Dy were analyzed theoretically to give insight into the sublevel structures of the Dy (III) ion and its coupling with Ni (II). Frequency dependence in the ac susceptibility signals was observed in 1.Dy.     

Important mathematical structures of the topological index Z for tree graphs

Mathematical importance of the topological index, ZG, or the so-called Hosoya index is stressed by presenting and giving supporting evidence for the proposed conjecture. That is, for a given pair of positive integers (n1or=3), with Z(G1) = n1 and Z(G2) = n2.     

Biosynthesis and biodegradability of copolythioesters from 3,3'-thiodipropionic acid and plant oils by Cupriviadus necator

To prepare sulfur-containing natural polymers effectively, several plant oils and 3,3'-thiodipropionic acid (TDP) have been used as carbon sources for the biosynthesis of copolymer poly[(3-hydroxybutyrate)-co-(3-mercaptopropionate)] [poly(3HB-co-3MP)] by a wild-type bacterium Cupriviadus necator H16. By using the plant oils, copolymer accumulation and incorporation of 3MP units are greater than those of cases using sugars. The 3MP fraction is controllable over a range of 1-39 mol-% by adjusting the cultivation conditions. Microbial degradability of the copolymers has been examined in an activated sludge supernatant. The biodegradation proceeded by two mechanisms: surface erosion and auto-catalytic hydrolysis, depending on the 3MP unit fraction, and show preferential degradation of 3HB unit sequences.     

Folding/unfolding kinetics of lattice proteins studied using a simple statistical mechanical model for protein folding, I: Dependence on native structures and amino acid sequences

The folding/unfolding kinetics of a three-dimensional lattice protein was studied using a simple statistical mechanical model for protein folding that we developed earlier. We calculated a characteristic relaxation rate for the free energy profile starting from a completely unfolded structure (or native structure) that is assumed to be associated with a folding rate (or an unfolding rate). The chevron plot of these rates as a function of the inverse temperature was obtained for four lattice proteins, namely, proteins a1, a2, b1, and b2, in order to investigate the dependency of the folding and unfolding rates on their native structures and amino acid sequences. Proteins a1 and a2 fold to the same native conformation, but their amino acid sequences differ. The same is the case for proteins b1 and b2, but their native conformation is different from that of proteins a1 and a2. However, the chevron plots of proteins a1 and a2 are very similar to each other, and those of proteins b1 and b2 differ considerably. Since the contact orders of proteins b1 and b2 are identical, the differences in their kinetics should be attributed to the amino acid sequences and consequently to the interactions between the amino acid residues. A detailed analysis revealed that long-range interactions play an important role in causing the difference in the folding rates. The chevron plots for the four proteins exhibit a chevron rollover under both strongly folding and strongly unfolding conditions. The slower relaxation time on the broad and flat free energy surfaces of the unfolding conformations is considered to be the main origin of the chevron rollover, although the free energy surfaces have features that are rather complicated to be described in detail here. Finally, in order to concretely examine the relationship between changes in the free energy profiles and the chevron plots, we illustrate some examples of single amino acid substitutions that increase the folding rate.     

Detection and grading for esophageal varices in patients with chronic liver damage: comparison of gadolinium-enhanced and unenhanced steady-state coherent MR images

The purpose of this study was to compare observer interpreted steady-state coherent coronal images and gadolinium-enhanced axial images in terms of the detection and grading of esophageal varices. Magnetic resonance imaging (MRI) and gastrointestinal endoscopy were performed within 2 weeks in 90 patients with chronic liver damage, including 55 with untreated esophageal varices, for periodic screening purposes. Two blinded readers retrospectively reviewed T1- and T2-weighted images with gadolinium-enhanced (gadolinium image set) and steady-state coherent (coherent image set) images. Sensitivity for the detection of esophageal varices was higher (P<.001) in the gadolinium image set (76%) than in the coherent image set (35%); on the other hand, specificity was higher (P<.001) in the coherent image set (91%) than in the gadolinium image set (66%). Furthermore, area under the ROC curve was higher for the gadolinium image set (Az=0.823) than the coherent image set (Az=0.761) (P=.48). Moderate and weak positive correlations with endoscopic grades were found for the gadolinium image (r=0.48, P<.01) and coherent image sets (r=0.34, P=.018). The addition of steady-state coherent imaging to the current routine liver imaging protocol did not improve the detection or grading of esophageal varices, whereas gadolinium-enhanced imaging was found to be potentially valuable. Nevertheless, endoscopy was confirmed to be mandatory in patients with esophageal varices suspected by MRI of the liver.     

On the necessary and sufficient condition for the extended Wedderburn–Guttman theorem

Let A be a u by v matrix, and let M and N be u by p and v by q matrices, where p may not be equal to q or rank(M^′AN)<min(p,q). Recently, Galantai [A. Galantai, A note on the generalized rank reduction, Acta Math. Hungarica 116 (2007) 239–246] presented what he claimed to be the necessary and sufficient condition for rank(A-AN(M^′AN)^-M^′A)=rank(A)-rank(AN(M^′AN)^-M^′A) to hold. This rank subtractivity formula along with the condition under which it holds is called the extended Wedderburn–Guttman theorem. In this paper, we show that some of Galantai’s assertions are incorrect.     

Light-harvesting energy transfer and subsequent electron transfer of cationic porphyrin complexes on clay surfaces

A novel energy-transfer system involving nonaggregated cationic porphyrins adsorbed on an anionic-type clay surface and the electron-transfer reaction that occurs after light harvesting are described. In the clay-porphyrin complexes, photochemical energy transfer from excited singlet zinc porphyrins to free-base porphyrins proceeds. The photochemical electron-transfer reaction from an electron donor in solution (hydroquinone) to the adsorbed porphyrin in the excited singlet state was also examined. Because the electron-transfer rate from the hydroquinone to the excited singlet free-base porphyrin is larger than that to the excited singlet zinc porphyrin, we conclude that the energy transfer accelerates the overall electron-transfer reaction.     

Tandem nucleophilic addition/fragmentation reactions and synthetic versatility of vinylogous acyl triflates

A thorough analysis of the chemistry of vinylogous acyl triflates provides insight into important chemical processes and opens new directions in synthetic technology. Tandem nucleophilic addition/C-C bond cleaving fragmentation reactions of cyclic vinylogous acyl triflates 1 yield a variety of acyclic acetylenic compounds. Full details are disclosed herein. A wide array of nucleophiles, such as organolithium and Grignard reagents, lithium enolates and their analogues, hydride reagents, and lithium amides, are applied. The respective reactions produce ketones 2, 1,3-diketones and their analogues 3, alcohols 4, and amides 5. The present reactions are proposed to proceed through a 1,2-addition of the nucleophile to the carbonyl group of starting triflates 1 to form tetrahedral alkoxide intermediates C, followed by Grob-type fragmentation, which effects C-C bond cleavage to yield acyclic acetylenic compounds 2-5 and 7. The potent nucleofugacity of the triflate moiety is channeled through the sigma-bond framework of 1, providing direct access to the fragmentation pathway without denying other typical reactions of cyclic vinylogous esters. The synthetic versatility of vinylogous acyl triflates, including functionalization reactions of the cyclic enone core (1 --> 6 or 8), is also illustrated.     

Syntheses and characterization of oxygen/sulfur-bridged incomplete cubane-type clusters, [Mo3S4Tp3]+ and [Mo3OS3Tp3]+, and a mixed-metal cubane-type cluster, [Mo3FeS4ClTp3]. X-ray structures of [Mo3S4Tp3]Cl, [Mo3OS3Tp3]PF6, and [Mo3FeS4ClTp3

The reaction of [Mo3S4(H2O)9]4+ (1) with hydrotris(pyrazolyl)borate (Tp) ligands produced [Mo3S4Tp3]Cl x 4 H2O ([3]Cl x 4 H2O) in an excellent yield. An X-ray structure analysis of [3]Cl x 4 H2O revealed that each molybdenum atom bonded to the Tp ligand. We report four salts of 3, [3]Cl x 4 H2O, [3]tof x 2 H2O, [3]PF6 x H2O, and [3]BF4 x 2 H2O in this paper. The solubility and stability of the chloride salt in organic solvents differ completely from those of the other salts. We have also prepared a new compound, [Mo3OS3Tp3]PF6 x H2O ([4]PF6 x H2O), via the reaction of [Mo3OS3(H2O)9]4+ (2) with KTp in the presence of NH4PF6. All the molybdenum atoms bonded to Tp ligand. 1H NMR signals corresponding to nine protons bonded to three pyrazole rings in one Tp were observed in a spectrum (at 253 K) of [3]BF4 x 2 H2O. It shows that cluster 3 has a 3-fold rotation axis in CD2Cl2 solution. Twenty-one 1H NMR signals corresponding to twenty-seven protons bonded to nine pyrazole rings in three Tp ligands were observed in a spectrum (at 233 K) of [4]PF6 x H2O; obviously, 4 has no 3-fold rotation axis, in contrast to 3. The short CH...mu3S distance caused large upfield chemical shifts in the 1H NMR spectra of 3 and 4. The reaction of 3 with metallic iron in CH2Cl2 produced [Mo3FeS4XTp3] (X = Cl (5), Br (6)). X-ray structure analysis of 5 has revealed the existence of a cubane-type core Mo3FeS4. Complex 3 functions as a metal-complex ligand for preparing a novel mixed-metal complex even in nonaqueous solvents. The cyclic voltammogram of 5 shows two reversible one-electron couples (E(1/2) = -1.40 and 0.52 V vs SCE) and two irreversible one-electron oxidation processes (E(pc) = 1.54 and 1.66 V vs SCE).