Japanese Wolves are Genetically Divided into Two Groups Based on an 8-Nucleotide Insertion/Deletion within the mtDNA Control Region.

The mitochondrial DNA (mtDNA) control region (198- to 598-bp) of four ancient Canis specimens (two Canis mandibles, a cranium, and a first phalanx) was examined, and each specimen was genetically identified as Japanese wolf. Two unique nucleotide substitutions, the 78-C insertion and the 482-G deletion, both of which are specific for Japanese wolf, were observed in each sample. Based on the mtDNA sequences analyzed, these four specimens and 10 additional Japanese wolf samples could be classified into two groups- Group A (10 samples) and Group B (4 samples)-which contain or lack an 8-bp insertion/deletion (indel), respectively. Interestingly, three dogs (Akita-b, Kishu 25, and S-husky 102) that each contained Japanese wolf-specific features were also classified into Group A or B based on the 8-bp indel. To determine the origin or ancestor of the Japanese wolf, mtDNA control regions of ancient continental Canis specimens were examined; 84 specimens were from Russia, and 29 were from China. However, none of these 113 specimens contained Japanese wolf-specific sequences. Moreover, none of 426 Japanese modern hunting dogs examined contained these Japanese wolf-specific mtDNA sequences. The mtDNA control region sequences of Groups A and B appeared to be unique to grey wolf and dog populations.

Selective synthesis of Co8S15 cluster in bowl-shaped template of the pentaaryl[60]fullerene ligand.

A cobalt-sulfur cluster Co8S15 with molecular formula of (C60Ar5)-Co8S15(n)Bu2-(C60Ar5) (Ar = 4-(t)BuC6H4) was selectively synthesized from a pentaaryl[60]fullerene cobalt trisulfide complex, (η(5)-C60Ar5)CoS3. The bowl-shaped steric templating fullerene ligand, as well as the metastable cobalt trisulfide moiety, played important roles in the exclusive cluster formation. X-ray crystallography, as well as electrochemical, time-resolved photophysical, and magnetic, measurements revealed a mixed-valence cluster with six cobalt(III) and two high-spin cobalt(II) centers showing reversible redox behavior and photoinduced charge separation.

Construction of long-wavelength-light photocurrent generation system based on self-assembled monolayer of cobaltadithiolene [60]fullerene complex.

[60]Fullerene pentaester and pentaacid derivatives bearing cobaltadithiolene dyes were successfully synthesized under mild reaction conditions. Self-assembled monolayers (SAMs) of the pentaacid derivative were prepared by an immersion method and the photocurrent generation properties of the SAMs were measured. Due to the introduction of the light-absorbing cobaltadithiolene moiety, the range of available wavelengths for photoelectric conversion was extended to lambda = 700 nm, which is longer than that of conventional penta(organo)[60]fullerene carboxylic acids.

Isolation of planar four-membered aromatic systems by using confined spaces of cobalt pentaaryl[60]fullerene complexes.

As a new class of neutral closed-shell aromatic four-membered ring systems, CoE(3) (E = S, Se) was constructed inside the bowl-shaped space of pentaaryl[60]fullerene. X-ray crystallographic analysis of CoS(3)(η(5)-C(60)Ar(5)) revealed that the CoS(3) unit is planar, and DFT calculations suggested an aromatic 6π-electron system. Steric protection by the pentaaryl[60]fullerene ligand is critical for isolation and characterization of the aromatic hetero cobaltacyclobutane. Unique reactivity of the CoS(3) unit was demonstrated by disruption of 6π-conjugation with abstraction of the sulfur atom, affording a dimer, [CoS(2)(η(5)-C(60)Ar(5))](2). This work provides new insight into the aromaticity of four-membered ring systems and advances the understanding of aromatic organometallic compounds.

High density culture of pancreatic islet-like 3D tissue organized in oxygen-permeable porous scaffolds with external oxygen supply.

Transplantation of macroencapsulated pancreatic islets within semipermeable membranes is a promising approach for the treatment of type 1 diabetes. Encapsulation beneficially isolates the implants from the host immune system. Deleteriously however, it also limits oxygen supply to the cells. This creates challenges in loading islets at the amount and density required to meet the practical demands of clinical usage. To overcome this challenge, we investigated the feasibility of using macroporous scaffolds made of an oxygen-permeable polymer, poly(dimethylsiloxane) (PDMS) by culturing pancreatic islet-like three-dimensional tissue made of a rat pancreatic beta cell line on the scaffolds. With external oxygenation, the density and function of cells on the PDMS scaffold were more than three times and almost two times higher than those without oxygenation, respectively. This suggests that the oxygenation afforded by the PDMS scaffolds allows for high-density loading of islet tissue into the devices.

pi-Conjugated multidonor/acceptor arrays of fullerene-cobaltadithiolene-tetrathiafulvalene: from synthesis and structure to electronic interactions.

The synthesis, structure, photoelectrochemical behavior, and nonlinear optical (NLO) properties of a symmetric acceptor-acceptor-donor-acceptor-acceptor array, C(60)-Co-TTF-Co-C(60), have been described. The precursors, namely, cobalt dicarbonyl complexes Co(C(60)Ar(5))(CO)(2) were synthesized from the penta(organo)[60]fullerenes, C(60)Ar(5)H, as starting materials. In the next step, two cobalt-fullerene complexes were connected to a tetrathiafulvalene (TTF) tetrathiolate bridge to obtain the C(60)-Co-TTF-Co-C(60) array. In addition, the monomeric compounds, Co(C(60)Ar(5))(S(2)C(2)R(2)) (R = CO(2)Me and CN) and Co(C(60)Ar(5))(S(2)C(2)S(2) C = CS(2)C(2)R(2)) were synthesized as references. The C(60)-Co-TTF-Co-C(60) array exhibits very strong transitions in the near-infrared region (lambda(max) = 1,100 nm, epsilon = 30 000 M(-1) x cm(-1)) due to a ligand-to-metal-charge-transfer (LMCT) transition and six reversible electron transfer processes. In the crystal, a fullerene/TTF-layered packing structure is evident. Femtosecond flash photolysis revealed that photoexcitation of the array results in a charge separated state involving the strongly interacting cobaltadithiolene and TTF constituents which electronically relax via a resonance effect that extends all throughout the acceptor parts of the C(60)-Co-TTF-Co-C(60) array. The third-order NLO measurement of the array gave the magnitude of the third-order nonlinear susceptibility, |chi((3))|, values to be 9.28 x 10(-12) esu, suggesting the pi-conjugation of donors and acceptors in the array.

ε-Polylysine-based thermo-responsive adsorbents for immunoglobulin adsorption-desorption under mild conditions.

Thermo-responsive adsorbents for immunoglobulin G (IgG) employing ε-polylysine (EPL) as a polymer backbone were developed. The introduction of mercaptoethylpyridine (MEP) as an IgG-binding ligand and hydrophobization of side chains afforded thermo-responsive IgG adsorbents, whose thermo-responsive IgG desorption ratio was up to 88% (EPL/MEP derivative 3m). The changes in surface densities of active MEP groups, which are caused by thermal conformational changes of the adsorbents, play key roles for IgG desorption. Although a trade-off of IgG adsorption capacity and IgG desorption ratio was observed, the present study offers a novel molecular design for thermo-responsive adsorbents with high synthetic accessibility and potentially low toxicity.

Regioselective [2 + 2] cycloaddition of a fullerene dimer with an alkyne triggered by thermolysis of an interfullerene C-C bond.

Heating of a singly bonded fullerene dimer in the presence of an alkyne forms a cyclobutene structure on only one of the two fullerene moieties, through a stereo- and regioselective [2 + 2] cycloaddition. Experimental and theoretical data suggest that the reaction is triggered by cleavage of the interfullerene C-C bond and formation of a monomeric fullerene radical.

The chemistry of four-membered aromatics.

This article provides an overview on the aromatic systems of four-membered rings. These aromatic four-membered ring systems are rather exotic because of a poor correspondence between the Hückel rule and the structure of four-membered rings. Consequently, such aromatics are generally dications or dianions, to form 2π or 6π electron systems respectively. Alternatively, the use of open-shell structures or empty d-orbitals of transition metal atoms could give neutral aromatic four-membered ring systems. This paper summarizes the four-membered aromatic compounds reported to date and describes the various methods for evaluating their aromaticity.

Covalently chemical modification of lithium ion-encapsulated fullerene: synthesis and characterization of [Li+@PCBM]PF6(-).

Covalently organic derivatization of [Li(+)@C60]PF6(-) to obtain Li(+)-encapsulated PCBM, [Li(+)@PCBM]PF6(-), is described. Synthetic procedures, electrochemical properties, light absorption properties, details of isomerization from [5,6]- to [6,6]-isomer, and X-ray crystal structure of [Li(+)@PCBM]PF6(-) are discussed.

FeCl3-mediated synthesis of fullerenyl esters as low-LUMO acceptors for organic photovoltaic devices.

C(60) reacted with aromatic and aliphatic carboxylic acids in the presence of inexpensive FeCl(3) at room temperature to produce hydroxyfullerenyl esters C(60)(OCOR)(OH) in up to 68% isolated yield. The hydroxyl group was utilized in functional group transformations to obtain a diester derivative C(60)(OCOAr)(OCOPh) (Ar = 2,6-xylyl) and a siloxyl derivative C(60)(OCOAr)(OSiMe(3)). The diester and siloxyl derivatives were found to possess low-lying LUMO levels were utilized in organic photovoltaic devices showing 1.3% power conversion efficiency.

Radical and superoxide scavenging activities of matairesinol and oxidized matairesinol.

The radical and superoxide scavenging activities of oxidized matairesinols were examined. It could be assumed that the free benzylic position was important for higher radical scavenging activity. The different level of activity was observed between 7'-oxomatairesinol (Mat 2) and 7-oxomatairesinol (Mat 3). The activity of 8-hydroxymatairesinol was lower than that of matairesinol (Mat 1). The superoxide scavenging activity of the oxidized matairesinols was also demonstrated for the first time. It is assumed that the pKa value of phenol in the oxidized matairesinols affected this activity.