Search

Understanding the requisite geometry of molecules and peripheral components is an essential step in endowing molecules with logical functions in quantum-dot cellular automata. To respond to the rea...

Realization of molecular quantum cellular automata (QCA), a promising architecture for molecular computing through current-free processes, requires improved understanding and application of mixed-valence (MV) molecules. In this report, we present an electrostatic approach to creating MV subspecies through internalizing opposite charges in close proximity to MV ionic moieties. This approach is demonstrated by unsymmetrically attaching a charge-responsive boron substituent to a well-known organometallic MV complex, biferrocenium. Guest anions (CN- and F- ) bind to the Lewis acidic boron center, leading to unusual blue-shifts of the intervalence charge-transfer (IVCT) bands. To the best of our knowledge, this is the first reported example of a zwitterionic MV series in which the degree of positive charge delocalization can be varied by changing the bound anions, and serves to clarify the interplay between IVCT parameters. The key underlying factor is the variable zero-level energy difference in the MV states. This work provides new insight into imbuing MV molecules with external charge-responsiveness, a prerequisite of molecular QCA techniques.

1,2,3,4-Tetrahydroquinolines should be applicable to the development of new pharmaceutical agents. A facile synthesis of 1,2,3,4-tetrahydroquinolines that is achieved by a photoinduced formal [4+2] cycloaddition reaction of acyclic α,β-unsaturated amides and imides with N,N-dialkylanilines under visible-light irradiation, in which a new IrIII complex photosensitizer, a thiourea, and an oxidant act cooperatively in promoting the reaction, is reported. The photoreaction enables the synthesis of a wide variety of 1,2,3,4-tetrahydroquinolines, while controlling the trans/cis diastereoselectivity (>99:1) and constructing contiguous stereogenic centers. A chemoselective cleavage of an acyclic imide auxiliary is demonstrated.

Background/aim Bovine mastitis is caused by the invasion and propagation of pathogenic microorganisms into the udder and mammary gland tissues of cattle. In this study, the therapeutic effect of a low-molecular-weight whey protein (LMW-WP) on bovine mastitis was evaluated. Materials and methods LMW-WP was orally, intraperitoneally, and vaginally administered to bovine with mastitis. The number of somatic cells in milk was measured 24 h before the administration of LMW-WP. The effect of LMW-WP on cytokine production was measured with a microarray that evaluates the expression of cytokines. Results In the group that received 1,000 mg intraperitoneally, the somatic cell count was reduced to less than 400,000 at the shipment standard value in three of the four udders, indicating 75% efficacy. The group that received 1,000 mg by vaginal administration showed 67% efficacy. It was confirmed that LMW-WP increased the production of cytokines such as IL-5, IL-6, IL-9, IL-12, MCP-1, and VEGF in mouse macrophage cells, but it did not show any antibacterial activity. Conclusion LMW-WP may be an effective therapeutic agent for bovine mastitis.

Background/aim Whey protein is a mixture of globulins isolated from whey and mainly composed of β-lactoglobulin, α-lactoalbumin, and lactoferrin. In this study, whey protein was hydrolyzed using various proteases, and the macrophage activation was evaluated. Materials and methods Hydrolyzed whey protein was prepared using various proteases to evaluate phagocytic activity and cytokine productivity. Results The results of SDS-PAGE and gel permeation chromatography (GPC) analysis indicated that the molecular weight of whey protein was reduced using various proteases. The hydrolyzed whey protein showed a concentration-dependent induction of macrophage phagocytic activity. In addition, the hydrolyzed whey protein significantly enhanced the production of the inflammatory cytokine, TNF-α. Production of the anti-inflammatory cytokine, IL-10, was not observed at concentrations up to 1 μg, but significant production was confirmed at 100 μg. Conclusion Hydrolyzed whey protein can induce the phagocytic activity of macrophages and activation of the inflammatory/anti-inflammatory functions of the macrophages depends on the concentration of the hydrolyzed whey protein.

Ethyl 2-cyano-3-alkoxypent-2-enoates were synthesized in moderate yields via the coupling reaction between α,β-unsaturated acetals and cyanoacetate, catalyzed by [RuHCl(CO)(PPh3)3]. The E- and Z-isomers were separated and determined by X-ray crystallography for the first time. Structural distortion associated with steric hindrance around the tetrasubstituted alkene moiety was revealed: e.g., the C(carbonyl)–C(α)–C(β) angle expands to about 125°. Density functional theory calculation was performed, and the restricted B3LYP hybrid functional with the 6-31G(d,p) basis set was found to successfully elucidate the solid-state structure and conformation, as well as spectroscopic properties. A plausible formation mechanism was proposed, in which the Ru complex catalyzed the C=C bond migration of the α,β-unsaturated acetal to give the corresponding ketene acetal and assisted the subsequent condensation reaction with cyanoacetate to some extent.

The motions of a solvation motor in a Lennard-Jones solvent were calculated by using molecular dynamics simulation. The results were analyzed considering the large spatial scale effects caused by the motion of the solvation motor. A reaction site was located on the surface of the solvation motor and the attraction between the reaction site and the solvent molecules was varied for 100 fs. The motion of the motor was driven by solvation changes near the reaction site on the motor. Two finite-size effects were observed in the motion. One was the hydrodynamic effect and the other was the increase in solvent viscosity caused by heat generation. The latter affected not only the displacement of the motor caused by the reaction but also the wave propagation phenomena. Both effects reduced the motor displacement. Heat generation affects the displacement, in particular for small systems. By contrast, the hydrodynamic effect remained even for large systems. An extrapolation method was proposed for the displacement.

In this study, we report the generation of new mixed-valence (MV) subspecies with charge-separated (CS) characters from an unsymmetrical acceptor–donor–donor (A–D–D) triad. The triad was synthesized by attaching a dimesitylboryl group (A) to a D–D conjugate that consisted of triarylamine (NAr3) units. The MV radical cation, obtained by chemical oxidation of the triad, exhibited a strong intervalence charge transfer (IVCT) absorption derived from the bis(NAr3)•+ moiety in the near-IR region. The charge-separated MV (CSMV) state, obtained by photoexcitation of the triad, caused a blue shift in IVCT energy in the femtosecond transient absorption spectra, reflecting a bias of positive charge distributions to the D end site. This resulted from increased electron density at the A site and restructuring of the central D site from NAr3 to NAr2 sites. Interestingly, any shift in the IVCT energy that was caused by the polarity of the solvent was minimal, reflecting the unique characteristics of the CSMV state. Thes...

A novel asymmetric photodimerization reaction of coumarin derivatives bearing the (S)-4-benzyl-2-oxazolidinone auxiliary provides only the syn-head-to-tail (syn-HT) dimer with moderate diastereoselectivity (up to 75 : 25). The mechanism of complete syn-HT selectivity and moderate diastereoselectivity is proposed based on the result of density functional theory (DFT) calculation. The benzyl group of the (S)-4-benzyl-2-oxazolidinone auxiliary in combination with a Lewis acid exerts effective diastereofacial shielding of the reaction site.

The solid-state structures of 1′,1‴-biferrocenediboronic acid (1) were elucidated by X-ray crystallography, to obtain insight into controlling the structures of hydrogen-bonded (H-bonded) assemblies from a functional organobimetallic building block. Four solvated crystal forms of 1 were newly obtained by recrystallization under different solvent conditions. The dioxane-, pyridine-, and pyrimidine-solvated crystals (Forms III to V) involved chain-like 1D H-bonded networks of 1. The 1D chains of 1 were capped with solvent molecules with lateral H-bonds. The pyrazine-solvated crystals (Form VI) involved 1D chains of 1, which were connected by pyrazine molecules with lateral H-bonds to afford sheet-like 2D networks. The suitable bidentate H-bond acceptor was found to transform 1D chains into 2D networks. Two crystal forms of 1′,1‴-biferroceniumdiboronic acid (1+) were also prepared and investigated the geometry of the H-bonded assemblies and the valence states of 1+. The mixed-valence (MV) cation 1+ forms 1D chains (Form VII) and discrete dimers (Form VIII) with triiodide anions in the valence-detrapped and trapped states, respectively. This study demonstrates the usefulness of the boronic acid-based method to obtain MV supramolecular structures in the solid state.

The target compound of this study is the macrocyclic tetraferrocenyl boronate complex CP2C, which has two types of metal connections (i.e., FeII–CpCp–FeII and FeII–CpBO2C5H8O2BCp–FeII (Cp = cyclopentadienyl)) in the finite structure (C = 1′,1‴-biferrocenediboronic acid, P = pentaerythritol). The electrochemical behavior of CP2C in dichloromethane was compared with that of the related boronate complexes APA and BP2B, having FeII–CpBO2C5H8O2BCp–FeII, and Cester, having FeII–CpCp–FeII. The effects of the counteranion of the supporting electrolyte on potential splitting revealed that CP2C exhibits an intrabiferrocenyl through-bond interaction through the CpCp ligand, as well as an interbiferrocenyl through-space interaction across the CpBO2C5H8O2BCp ligand. Chemical oxidation of CP2C with AgSbF6 produced the one- and two-electron-oxidized species CP2C+ and CP2C2+, which exhibit intervalence charge transfer transition bands through the CpCp ligand in the near-infrared region, giving one and two valence isomers...

BACKGROUND AND OBJECTIVE: Proprioceptive information from muscle receptors is important in force control and disturbed sensation due to fatigue may reduce the precision of force control. The aim of this study was to clarify the relationship between force sensation and force control ability in knee extensor muscles during fatigue. METHODS: Eighteen healthy young volunteers participated in this study. Force matching tasks with and without feedback were performed immediately before and after the fatigue protocol consisting of 20 s isometric contractions. The target force was 10% and 30% of the maximal voluntary contraction force in the pre-fatigue protocol. The accuracy of force control ability was estimated by the root mean square error (RMS error) and average difference (average error) between the target and output force. Surface electromyograms were recorded simultaneously from the quadriceps. RESULTS:In the 30% task, there was a significant interaction effect of fatigue and feedback condition in RMS error and average error. RMS error and average error were degenerated significantly by fatigue in the feedback removal condition, but not in the feedback condition. Though the activation of quadriceps was increased by fatigue, increase of muscle activation was lower in the feedback removal condition than that in the feedback conditions. CONCLUSION: Since participants controlled their force output depending on the force sensation in the feedback removal condition, these results indicate that the decline in force sensation may be a significant factor in the decreases of accuracy in force output during fatigue.

Through-space electron transfer between the benzene rings of [3 n ]cyclophanes, n = 2 – 5, was investigated using density functional theory calculations, CAM-B3LYP/6-311++G**. An external point charge, q , was placed on the axis perpendicular to a benzene ring of the cyclophane molecule. The dependence of the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap and bond overlap population (BOP) of cyclophanes on the values of q and n are discussed. The HOMO–LUMO gap generally decreases as q decreases and n increases. It is found from the BOP analysis that electron transfer occurs mainly through LUMO + 2 for n = 2, LUMO for n = 3 and n = 4, and LUMO + 4 for n = 5. The result that the values of the BOP for n = 2 and 5 increase as q decreases means that the through-space electron transfer is enhanced by the negative charge on the neighboring molecule in the solid.

Energy gap, Mulliken population, and bond-overlap population analyses were carried out to investigate the intermolecular interaction modulation in pentacene clusters by neighboring artificially charged pentacene molecules, which model a charge-carrier injection into a crystal. Two common pentacene clusters, type-1 and type-2, obtained from the crystal structure of pentacene, were examined. A larger decrease in the band gap was observed for the type-2 orientation, whereas a positive intermolecular interaction was observed for the type-1 cluster. Both closing of the energy gap and the positive intermolecular interaction (bonding nature) were found only in the extreme n-type state.

1',1'''-Biferrocenediboronic acid () was synthesized from 1',1'''-dibromobiferrocene by a typical procedure of converting Br to B(OH)2 groups in 76% yield and identified by (1)H-, (13)C- and (11)B-NMR and ESI-MS. X-ray diffraction (XRD) studies showed that, in non-solvated crystals (Form I), the new organobimetallic building block formed 1D hydrogen-bonded networks (i.e., chain) with octaatomic rings composed of the neighbouring two molecules. In solvated crystals with a composition of ()3(THF)2 (Form II), exists in two conformers (Conformers A and B) with respect to the rotation of the CpB(OH)2 moieties relative to the Cp rings of the fulvalenide moieties; Conformer A formed 1D hydrogen-bonded networks laterally hydrogen-bonding with THF molecules while Conformer B formed a new planar hydrogen-bonded motif involving four B(OH)2 groups and stepwise laminated networks of the planar motif. A macrocyclic tetraferrocenyl boronate ester was synthesized by cyclocondensation between and pentaerythritol in 33% yield and identified by (1)H-, (13)C- and (11)B-NMR, ESI-MS and XRD. In electrochemical measurements, the cyclocondensed compound exhibited four defined reversible waves with a total spread of 756 mV in CH2Cl2 containing n-Bu4NBArF4 (ArF = 3,5-bis(trifluoromethyl)phenyl), displaying both intra- and inter-biferrocenyl interactions.

Reorganization energies λ of isomers of hydrogenated fullerenes, C70H n (n = 4, 6, 8), are investigated by the density functional theory (B3LYP/6–311G**). The smallest value of λ (λ min) of C70H4 is 74 meV and is smaller than those of C70H2 (79 meV) and C60H4 (83 meV). λ min of C70H6 and C70H8 are 72 meV and 74 meV, respectively. Addition of H atoms to [6,6]-ring fusion generally gives smaller λ than that to [5,6]-ring fusion. Hydrogenation can reduce λ min of C70 materials and the result that C70H6 has the smallest λ min is same with the result of hydrogenation of C60.

This study evaluated the effect of foot progression angle on the reduction in knee adduction moment caused by a lateral wedged insole during walking. Twenty healthy, young volunteers walked 10 m at their comfortable velocity wearing a lateral wedged insole or control flat insole in 3 foot progression angle conditions: natural, toe-out, and toe-in. A 3-dimensional rigid link model was used to calculate the external knee adduction moment, the moment arm of ground reaction force to knee joint center, and the reduction ratio of knee adduction moment and moment arm. The result indicated that the toe-out condition and lateral wedged insole decreased the knee adduction moment in the whole stance phase. The reduction ratio of the knee adduction moment and the moment arm exhibited a close relationship. Lateral wedged insoles decreased the knee adduction moment in various foot progression angle conditions due to decrease of the moment arm of the ground reaction force. Moreover, the knee adduction moment during the toe-out gait with lateral wedged insole was the smallest due to the synergistic effect of the lateral wedged insole and foot progression angle. Lateral wedged insoles may be a valid intervention for patients with knee osteoarthritis regardless of the foot progression angle.

Hydrogen including a trace amount of tritium was loaded on the edge surface of an F82H rod. After the loading, the rod was held at 298 or 323 K to allow hydrogen diffuse in and release out. Tritium tracer techniques have been applied to determine hydrogen depth profiles and hydrogen release rates by using an tritium imaging plate technique and a liquid scintillation counting technique, respectively. The depth profiles were composed of a surface localized component within 200 μm of the surface and a diffused component extending over 1 mm in depth. The apparent hydrogen diffusion coefficients obtained from the depth profile of the diffused component are near the extrapolated value of the literature data determined at higher temperatures. The surface localized component, which is attributed to trapping at surface oxides and/or defects, was released very slowly to give apparent diffusion coefficients much smaller than those determined from the diffused component.

Isotope and charge effects on vibronic coupling constant (V) and energy gradient (g) of ethylenedioxy-tetrathiafulvalen (EDO-TTF) upon the electron injection into cation and electron removal from neutral molecule are investigated. It is found that normal modes which include C = C stretching motion generally have large V and g. For electron removal, three normal modes (v460, v470, and v480) have large Vi+ and gi+, and deuteration results in decrease of V46+ and increase of V47+. For electron injection, five normal modes (ν+42, ν+44, ν+45, ν+47, and ν+48) have large vi0 and gi0 deuteration results in increase of V045 and V048 and decrease of V047. From the analysis of vibronic coupling constants using vibronic coupling density (VCD), regional vibronic coupling constant (RVCC), and atomic vibronic coupling constant (AVCC), it is revealed that the change in normal mode vectors (d) due to the deuteration and electron removal (or injection) leads to the change in V.

Dynamic behavior of signal transmission through metal complexes[L 5 M-BL-ML 5 ] 5+ (M=Fe, Ru, Os, BL=pyrazine (py), 4,4’-bipyridine (bpy), L=NH 3 ),which are simplified models of the molecular quantum-dot cellular automata (molecularQCA), is discussed from the viewpoint of one-electron theory, density functional theory.It is found that for py complexes, the signal transmission time ( t st ) is Fe(0.6fs) < Os(0.7fs) < Ru(1.1fs) and the signal amplitude ( A ) is Fe(0.05e) < Os(0.06e) < Ru(0.10e). For bpycomplexes, t st and A are Fe(1.4fs) < Os(1.7fs) < Ru(2.5fs) and Os(0.11e) < Ru(0.12e) < Fe(0.13e), respectively. Bpy complexes generally have stronger signal amplitude, but wastelonger time for signal transmission than py complexes. Among all complexes, Fe complexwith bpy BL shows the best result. These results are discussed from overlap integral andenergy gap of molecular orbitals.Keywords: quantum dot; automaton; QCA; mixed-valence complexes; Creutz-Taubecomplexes; quantum dynamics; Fe; Ru; Os; density functional theory1. IntroductionQuantum-dot cellular automata (QCA) device [1], which utilizes two degenerate states of metal dots“0” and “1” (Figure 1(a)) for operation, is one of next-generation devices which have been activelystudied [2]. The QCA devices such as an AND logic gate (Figure 1(b)) and a signal transmission wire(Figure 1(c)) are expected to achieve a dramatic saving of energy and an increase in processing speed ofcomputing since these devices are free from a current flow.

Hybrid density functional theory (DFT) calculations have been carried out for oligomer species of a fused porphyrin, denoted by P(n), where n represents the number of porphyrin rings in the oligomer, to elucidate the electronic structures at ground and excited states. A polymer of fused porphyrin (p-Por) was also investigated using one-dimensional periodic boundary conditions (PBC) for comparison. It was found that the lowest energy band is located below 0.6 eV in the case of oligomers larger than n = 8, which corresponds to a band gap of p-Por. Carrier transport pathways in p-Por were discussed on the basis of theoretical results.

The usefulness of the difluoromethylene fullerenes C 60 (CF 2 ) n ( n = 1, 2) materials for the organic devices is theoretically discussed, comparing with C 60 , about the following three points: electron transport in the material, electron injection from the electrode into the material, and thin-film formation of the material. Concerning the thin-film formation, dipole moments are calculated. Frontier orbital energies and adiabatic electron affinities are discussed in connection with the electron injection from the electrode into the material. Additionally, the inter-molecular electron transport is discussed from the viewpoint of the reorganization energy based on the Marcus theory. These results indicate the usage of some C 60 (CF 2 ) n isomers as the useful electron-transport materials.

Electronic properties of fullerene C 60 and its derivatives C 60 X 2 , where X = H, C 4 H 9 , ( C H 2 ) n COOH ( n = 3 , 5 , 7 ) , and C 4 H 8 SH, are investigated by the density functional theory (B3LYP/6-31+G ∗ ) aiming at efficient design of new organic semiconductors. Concerning electron-injection and electron-transport properties of the materials, LUMO energy, adiabatic electron affinity, and reorganization energy are discussed. The electronic properties of C 60 X 2 are considerably different from those of C 60 . They are determined by the addition position of X and not by the chemical nature of X . Generally, C 60 X 2 is predicted to be superior to C 60 in the electron-injection property but to be inferior in the electron-transport property.

The novel and convenient method for improving the hole-transport property of fullerene C60 [K. Tokunaga et al.: Jpn. J. Appl. Phys. 47 (2008) 1089], that is the hydrogenation of C60, was extended to fullerene hydride C60H4. On the basis of Marcus theory, the reorganization energy (λ) and the hole-transfer rate constant (kht) of nine isomers were calculated by the density functional theory [B3LYP/6-311G(d)], assuming that the electronic coupling (HAB) was the same as that of C60. Almost all isomers of C60H4 have smaller λ and larger kht than C60. This originates from the fact that the hydrogenation results in the localization of a part of the injected carrier on the added H atoms. Remarkably, isomer 1, the major product of C60H4, has the smallest λ (83 meV) which is over 50% less than C60, and its kht is 3.28 times as large as that of C60. It was also found that isomers with the delocalized distribution of the highest occupied molecular orbital (HOMO) tend to have smaller λ, so that the hydrogenation which leaves the uniformity of the HOMO distribution of the original C60 is very effective for the improvement. It gives a clear guideline for the theoretical design of useful materials, and could open a way to the engineering of organic devices.

As a novel and convenient method for modifying the hole-transport property of fullerene C60 materials, its hydrogenation, which gives C60H2, was considered. Firstly, for the analysis of the carrier-transfer mechanism between C60H2 molecules, the geometrical difference between C60H2 and C60H2+, the natural population analysis (NPA) charge, and the electron spin resonance (ESR) parameters of C60H2+ were calculated by density functional theory [B3LYP/6-311G(d)]. Secondly, the reorganization energies (λ) of eleven isomers of C60H2 with a small heat of formation ΔHf° were calculated and compared with that of C60. It was shown that the magnitude of λ of C60H2 isomers is closely related to the geometrical difference between C60H2 and C60H2+. On the basis of Marcus theory, a smaller λ results in larger hole mobility. It was found that six isomers of C60H2 have a smaller λ than C60 (169 meV). The smallest λ of C60H2 (102 meV), which is over 40% less than that of C60, belongs to isomer 2b. At 300 K, its hole-transfer rate constant (kht) is about 2.5 times as large as that of C60. It is remarkable that two synthesized isomers, 0a and 2a, also have 20% smaller λ than C60, and the kht of these isomers are about 1.5 times as large as that of C60. These results indicate that the hydrogenation of C60 is an effective method for modifying the hole-transport property, and some isomers of C60H2 have potential utility as hole-transport materials.

Hybrid density functional theory (DFT) calculations have been carried out for neutral and radical cation species of a fused thiophene oligomer, denoted by T(n), where n represents the number of thiophene rings in the oligomer, to elucidate the electronic structures at ground and low-lying excited states. A polymer of fused thiophene was also investigated using one-dimensional periodic boundary conditions (PBCs) for comparison. It was found that the reorganization energy of a radical cation of T(n) from a vertical hole trapping point to its relaxed structure is significantly small. Also, the reorganization energy decreased gradually with increasing n, indicating that T(n) has an effective hole transport property. It was found that the radical cation species of T(n) has a low energy band in the near-IR region, which is strongly correlated to hole conductivity. The relationship between the electronic states and hole conductivity was discussed on the basis of theoretical calculations.

Vibronic coupling, or electron-phonon coupling, of naphthalene is calculated. A method of vibronic coupling density analysis, which has been proposed for the vibronic coupling of the Jahn-Teller active modes in a Jahn-Teller molecule, is extended for totally symmetric vibrational modes of a molecule including a non-Jahn-Teller molecule. Contrary to non-totally-symmetric modes, orbital relaxation upon a charge transfer plays a crucial role in the vibronic coupling calculation for the totally symmetric modes. The method is applied for the ground state of the naphthalene anion to compare with that of the benzene anion. The relationship between the vibronic coupling density and a nuclear Fukui function is also discussed.

Motion of the encapsulated metal in M@C74 (M = Be, Mg, Ca, Sr, and Ba) is studied in terms of vibronic coupling using group theory approach. The selection rule for the symmetry of metal motion is presented. This agrees well with experimental findings for Ca@C74. The metal motion can be regarded as a pseudo-Jahn–Teller effect. The electronic structures and adiabatic potential surfaces of M@C74 are calculated using the tight-binding approximation.

Vibronic coupling, electron–phonon interaction, constants of Jahn–Teller molecules, C5H5 and C5D5, are computed as matrix elements of the electronic operator of the vibronic coupling operator using the electronic wave functions calculated by generalized restricted Hartree–Fock (GRHF) and state-averaged complete active space self-consistent-field (CASSCF) methods. The calculated values of vibronic coupling constants for C5H5 and C5D5 agree well with the experimental values. Vibronic coupling density analysis can explain the isotope effect on the vibronic coupling from view of the electronic and vibrational structures. Changes of the vibrational modes as well as the frequencies upon the deuteration can affect the vibronic coupling. Vibronic density analysis provides a local picture of the coupling in a molecule, and it enables us to control the coupling. This could open a way to engineering of the vibronic coupling, vibronics.

The purpose of this study was to determine whether a lateral wedge insole reduces the external knee adduction moment during slope walking. Twenty young, healthy subjects participated in this study. Subjects walked up and down a slope using 2 different insoles: a control flat insole and a 7° lateral wedge insole. A three-dimensional motion analysis system and force plate were used to examine the knee adduction moment, the ankle valgus moment, and the moment arm of the ground reaction force to the knee joint center in the frontal plane. The lateral wedge insole significantly decreased the moment arm of the ground reaction force, resulting in a reduction of the knee adduction moment during slope walking, similar to level walking. The reduction ratio of knee adduction moment by the lateral wedge insole during the early stance of up-slope walking was larger than that of level walking. Conversely, the lateral wedge insole increased the ankle valgus moment during slope walking, especially during the early stance phase of up-slope walking. Clinicians should examine the utilization of a lateral wedge insole for knee osteoarthritis patients who perform inclined walking during daily activity, in consideration of the load on the ankle joint.

In this study, we report intramolecular charge transfer (ICT) properties and charge distributions in a series of FcC derivatives (FcC = 4-ferrocenylcatecholate where Fc = ferrocene and C = catecholate). This series consists of a previously reported complex FcV (4-ferrocenylveratrole) and newly synthesized complexes FcA (4-ferrocenylcatechol bis(acetate) and Pt((t)Bu2bpy)(FcC) ((t)Bu2bpy = 4,4'-di-tert-butyl-2,2'-dipyridyl). An electrochemical analysis of Pt((t)Bu2bpy)(FcC) using cyclic voltammetry revealed two well-defined, reversible waves which were assigned to the sequential oxidation of the Pt((t)Bu2bpy)(C) and Fc moieties. The potential splitting between the waves (524 mV) indicated that there was an electronic interaction between both moieties. ICT property and charge distribution of [Pt((t)Bu2bpy)(FcC)]˙(+) were rationalized by comparison with the [FcV]˙(+) and [FcA]˙(+) (4-ferrocenylcatechol bis(acetate)). DFT calculations and UV-vis-NIR spectroscopy revealed that [Pt((t)Bu2bpy)(FcC)]˙(+), [FcV]˙(+), and [FcA]˙(+) were ferrocenium (Fc(+))-centered rather than semiquinone ligand-centered and that these complexes exhibited ICT transition bands from the catechol-derivatized framework to the Fc(+) moiety in the near infrared (NIR) region. Both the electronic coupling parameter (HAB) and delocalization parameter (α) increased in value as the electron-donating strength of the substituent groups in the catechol-derivatized framework increased (OCOCH3 ([FcA]˙(+)) < OCH3 ([FcV]˙(+)) < O(-) ([Pt((t)Bu2bpy)(FcC)]˙(+))). The electronic interactions between the organometallic center and the non-innocent framework were tuned by changing the substituents. The potential energy surfaces of the Fc(+) derivatives, obtained using two-state Marcus-Hush theory, can be modulated by changing the energy level of the molecular orbitals of the appended catechol-derivatized moieties.

Colostrum contains antibodies, such as immunoglobulin G (IgG), immunoglobulin A (IgA) and immunoglobulin M (IgM), and, therefore, has potent immunomodulating activity. In particular, IgA has an O-linked sugar chain similar to that in the group-specific component (Gc) protein, a precursor of the Gc protein-derived macrophage-activating factor (GcMAF). In the present study, we investigated the macrophage-activating effects of degalactosylated/desialylated bovine colostrum.We detected the positive band in degalactosylated/ desialylated bovine colostrum by western blotting using Helix pomatia agglutinin lectin. We also found that degalactosylated/ desialylated bovine colostrum could significantly enhance the phagocytic activity of mouse peritoneal macrophages in vitro and of intestinal macrophages in vivo. Besides, degalactosylated/desialylated bovine colostrum did not mediate the production of inflammatory cytokines such as tumor necrosis factor-α (TNF-α) and interleukin-1β (IL-1β).Similar to the use of GcMAF, degalactosylated/desialylated bovine colostrum can be used as a potential macrophage activator for various immunotherapies.

Tungsten coatings of 0.5 and 1 mm thickness were successfully deposited by the vacuum plasma spraying technique on carbon/carbon fiber composite (CFC), CX-2002U, and isotropic fine grained graphite, IG-430U. High heat flux experiments by irradiation of electron beam with uniform profile were performed on the coated samples in order to prove the suitability and load limit of such coating materials. Heat load properties, gases emission, surface modification and structure changes of cross-section of the samples were investigated. Cracks on the surface and exfoliation between the joint interface of the samples were not formed below the melting point. These results indicated that the thermal and adhesion properties between the substrate and coatings were good under high heat flux. Microstructure of the joint interface of the sample was changed in the case of a peak temperature at about 2800°C. Many cracks and traces of melted tungsten flow were observed on the surface after melting and solidification. Large cavities were also formed inside the resolidified tungsten layer.

Tungsten coatings of 0.5 and 1.0 mm thickness were successfully deposited by the vacuum plasma spraying technique (VPS) on carbon/carbon fiber composite, CX-2002U, and isotropic fine grained graphite, IG-430U. High heat flux experiments were performed on the coated and non-coated samples in order to prove the suitability and load limit of such coating materials. The electron beam irradiation experiments showed that there was little difference in temperature increases among CX-2002U and the coated materials below surface temperature of 2200°C. These results indicated that thermal and adhesion properties between the substrate and coatings were good under high heat flux. A few cracks with a width of 15 μm were formed from the surface to the bottom side of the all coated samples, but plastic deformation and microcracks due to grain growth by recrycrallzation were not observed below a surface temperature of about 2200°C. The cracks are expected to be formed due to local thermal stress produced by spot-like beams.

In order to understand the damage and impurity emission of plasma-facing materials by a long-pulse high-heat-flux loading, a high-heat-flux test simulator with electron beams, which is capable of detecting emission gases and particles, was constructed. High-heat-load experiments were carried out for molybdenum. The surface modification and impurity emission depended on the surface temperature. At a surface temperature of about 1500°C, the surface became uneven after repeated heat loads. This changed the thermal character of the surface layer and the surface became molten. Above the melting point, vapor stream and droplets were generated and intense evaporation occurred.

Recently, research and development of next-generation devices have been very active (1). Quantum-dot cellular automata (QCA) (2) which is constructed frommany quantum dot cells (QDC, Fig. 1) is one of such new-generation devices. The QCAdevices such as amajority logic gate and a signal transmissionwire (Fig. 2) are expected to achieve a dramatic saving of energy and an increase in processing speed of computing since these devices are free from a current flow. Successful operations of several QCA devices have been already demonstrated (3; 4). However, for improvement in operation temperature and size of the QCA devices, the idea of molecular quantum-dot cellular automata (molecular QCA) devices (5), in which a QDC constructed from small metallic dots is replaced by a single molecule, was proposed. Toward the experimental operation of molecular QCA devices, syntheses of tetranuclear complexes (6–10) and simplified dinuclear complexes (11; 12), and single-molecule observation of the dinuclear complexes (13–16) have been paid attention. However, the capacity of molecular QCA devices for molecular computing is still not clear.

Many systems in which the hydrolysis of ATP is finally converted into the mechanical work are known (e.g. actin‐myosin motor protein system). It seems that there are various types of the conversion mechanism. In this work, we examined a possibility of conversion from chemical reaction into mechanical work due to solvation change around the reaction site by using the molecular dynamics simulation (MD) with explicit solvent model. In our model, solvent molecules, S, and a motor (colloidal particle), M, are treated as Lennard‐Jones (LJ) particles. Effect of chemical reaction is taken in the system as the change of LJ potential parameter e between S and M, however the reaction site is restricted on the M. The parameter e is switched to e′ = 1000 e during the reaction (Δt), Fig. (a). Averaged displacement of the motor M is shown in Fig. (b). The motor M is driven by this reaction model, however the direction and efficiency are dependent on the reaction time Δt and the thermodynamic state of the solvent.

Pulse and steady-state heating effects on the microstructure of nickel implanted with helium or deuterium ions have been investigated, in order to examine the combined effects of particle bombardment and heat loading on the plasma-facing components of fusion reactors. Large dimensional changes of the plasma-facing surfaces due to bubble growth is expected when they are implanted with helium or hydrogen isotopes and then pulse heated. Grain boundary degradation may be small, however, for the case of pulsed heating because of the small accumulation of bubbles at the grain boundaries.