Effects of oral health-related quality of life on total mortality: a prospective cohort study.

BACKGROUND: The effects of oral health on mortality have been reported; however, the association between mortality and Oral Health-Related Quality of Life (OHQOL) is unknown. We investigated the effect of OHQOL on total mortality in a cohort consisting of dentists. METHODS: In this cohort study, we analyzed data from the Longitudinal Evaluation of Multi-phasic, Odonatological and Nutritional Associations in Dentists study. We conducted a baseline survey of general and oral health factors. We called for 31,178 participants and collected responses from 10,256 participants. We followed up with 10,114 participants (mean age ± standard deviation, 52.4 ± 12.1 years; females, 8.9%) for 7.7 years, until March 2014, to determine the average total mortality. OHQOL was assessed using the General Oral Health Assessment Index (GOHAI). The total score was divided into quartiles (Q1 ≤ 51.6, Q2 = 51.7-56.7, Q3 = 56.8-59.9, and Q4 = 60.0), with higher GOHAI scores indicating better OHQOL (score range, 12-60). The association between OHQOL and total mortality was analyzed using the Cox proportional hazards model. RESULTS: We documented 460 deaths. Males with low GOHAI scores possessed a remarkably high risk of total mortality. The multivariate adjusted-hazard ratios (aHRs), were 1.93 (95% confidence interval [CI], 1.07 - 3.48) for Q1, 1.69 (95% CI, 0.90 - 3.17) for Q2, and 0.65 (95% CI, 0.29 - 1.46) for Q3, relative to Q4 (trend p = 0.001). The aHRs in the multivariate model with all background variables were 1.69 (95% CI, 1.15-2.46) for Q1, 1.53 (95% CI, 1.04-2.27) for Q2, and 1.09 (95% CI, 0.71-1.70) for Q3, relative to Q4 (trend p = 0.001). In females, there was no significant association between the quartiles, in both the multivariate-adjusted model (trend p = 0.52) and multivariate-adjusted model with all background variables (trend p = 0.79). CONCLUSIONS: A lower OHQOL indicated an increased risk of total mortality in dentists. OHQOL may be used as an indicator for selecting treatment plans and personalized care interventions, thus contributing to increased healthy life expectancy. TRIAL REGISTRATION: Aichi Cancer Center, Nagoya University Graduate School of Medicine, and Hiroshima University (Approval numbers: 33, 632-3, 8-21, and E2019-1603).

Tooth brushing, tooth loss, and risk of upper aerodigestive tract cancer: a cohort study of Japanese dentisits.

Previous studies have focused on the association between poor oral health and upper aerodigestive tract (UADT) cancer. However, whether toothbrushing and tooth loss are associated with UADT cancer risk is still unclear. Therefore, we investigated the association between toothbrushing or tooth loss and UADT cancer in the Longitudinal Evaluation of Multi-phasic, Odontological, and Nutritional Associations in Dentists (LEMONADE) cohort study. From 2001 to 2006, we recruited 20,445 dentists (mean age ± standard deviation, 51.8 ± 12.0 years; 1,607 women [7.9%]) and followed for incidence or mortality of UADT cancer through March 2014. Information on lifestyle and oral health was collected by the baseline questionnaire. The Cox proportional hazards model was used to estimate hazard ratios (HRs) for UADT cancer and corresponding 95% confidence intervals (CI) for brushing frequency and tooth loss with adjustment for covariates. During the mean follow-up of 9.5 years, we confirmed 62 incident or fatal cases of UADT cancer. Infrequent toothbrushing (< 2 times/day) was significantly associated with increased risk of UADT cancer (multivariate HR = 2.13, 95% CI: 1.04-4.37). On the contrary, tooth loss was not significantly correlated with UADT cancer risk; multivariate HR was 1.03 (95% CI: 0.41-2.61) for loss of 15-27 teeth and 1.37 (0.50-3.75) for that of 28 teeth compared to tooth loss of 0-14 teeth. In conclusion, Infrequent toothbrushing was significantly associated with the risk of UADT cancer.

Tooth loss and pneumonia mortality: A cohort study of Japanese dentists.

Although associations between oral health and pneumonia have been reported in previous studies, particularly in the institutionalized elderly, few prospective studies have investigated the association between oral condition and pneumonia among community-dwelling people and whether the findings among inpatients or patients in nursing homes are applicable to the general population is still unclear. The oral bacteria propagated in the periodontal regions may drop into the lung and increase the risk of pneumonia. We, therefore, investigated the association of tooth loss with mortality from pneumonia in a cohort study of Japanese dentists. Members of the Japan Dental Association (JDA) participated in the LEMONADE (Longitudinal Evaluation of Multi-phasic, Odontological and Nutritional Associations in Dentists) Study. From 2001 to 2006, they completed a baseline questionnaire on lifestyle and health factors including the number of teeth lost (excluding third molars). We followed 19,775 participants (mean age ± standard deviation, 51.4 ± 11.7 years; 1,573 women [8.0%] and 18,202 men [92.0%]) for mortality from pneumonia (ICD-10, J12-J18). Mortality data were collected via the fraternal insurance program of the JDA. The hazard ratios (HRs) were estimated with adjustment for sex, age, body mass index, smoking status, physical activity and diabetes history. During the median follow-up period of 9.5 years, we documented 68 deaths from pneumonia. Participants who were edentulous at baseline were at significantly increased risk of mortality from pneumonia. The multivariable-adjusted HRs were 2.07 (95% confidence interval [CI], 1.09-3.95) for the edentulous and 1.60 (95% CI, 0.83-3.10) for loss of 15-27 teeth relative to loss of 0-14 teeth (trend p = 0.026). The HR per one tooth loss was also significant; 1.031 (95% CI, 1.004-1.060). In conclusion, a large number of teeth lost may indicate an increased risk of mortality from pneumonia in community-dwelling populations.

Palladium(ii) mononuclear and palladium(ii)/ruthenium(ii) heterodinuclear complexes containing 2-quinolyl-substituted (pyridine-2-carbonyl)hydrazone.

A reaction of [PdCl2(cod)] (cod = 1,5-cyclooctadiene) and an E/Z mixture of quinoline-2-carbaldehyde (pyridine-2-carbonyl)hydrazone (HL) gave two kinds of Pd(II) mononuclear complexes, [PdCl(Z-L-κ(3)N,N',N'')] (1) and [PdCl2(E-HL'-κ(2)N,N')] (2), where L(-) is the deprotonated hydrazonate anion and HL' is the quinolinium-hydrazonate zwitterionic form of HL. Complex 2 is gradually converted to 1 in solution, and complex 1 is a good precursor to prepare a Pd(II)/Ru(II) heterodinuclear complex bridged by hydrazonate, trans(Cl,Cl)-[RuCl2(PPh3)2(µ-L)PdCl] (3).

Scan Rate Dependent Spin Crossover Iron(II) Complex with Two Different Relaxations and Thermal Hysteresis fac-[Fe(II)(HL(n-Pr))3]Cl·PF6 (HL(n-Pr) = 2-Methylimidazol-4-yl-methylideneamino-n-propyl).

Solvent-free spin crossover Fe(II) complex fac-[Fe(II)(HL(n-Pr))3]Cl·PF6 was prepared, where HL(n-Pr) denotes 2-methylimidazol-4-yl-methylideneamino-n-propyl. The magnetic susceptibility measurements at scan rate of 0.5 K min(-1) showed two successive spin transition processes consisting of the first spin transition T1 centered at 122 K (T1↑ = 127.1 K, T1↓ = 115.8 K) and the second spin transition T2 centered at ca. 105 K (T2↑ = 115.8 K, T2↓ = 97.2 K). The magnetic susceptibility measurements at the scan rate of 2.0, 1.0, 0.5, 0.25, and 0.1 K min(-1) showed two scan speed dependent spin transitions, while the Mössbauer spectra detected only the first spin transition T1. The crystal structures were determined at 160, 143, 120, 110, 95 K in the cooling mode, and 110, 120, and 130 K in the warming mode so as to follow the spin transition process of high-spin HS → HS(T1) → HS(T2) → low-spin LS → LS(T2) → LS(T1) → HS. The crystal structures at all temperatures have a triclinic space group P1̅ with Z = 2. The complex-cation has an octahedral N6 coordination geometry with three bidentate ligands and assume a facial-isomer with Δ- and Λ-enantimorphs. Three imidazole groups of fac-[Fe(II)(HL(n-Pr))3](2+) are hydrogen-bonded to three Cl(-) ions. The 3:3 NH(imidazole)···Cl(-) hydrogen-bonds form a stepwise ladder assembly structure, which is maintained during the spin transition process. The spin transition process is related to the structural changes of the FeN6 coordination environment, the order-disorder of PF6(-) anion, and the conformation change of n-propyl groups. The Fe-N bond distance in the HS state is longer by 0.2 Å than that in the LS state. Disorder of PF6(-) anion is not observed in the LS state but in the HS state. The conformational changes of n-propyl groups are found in the spin transition processes except for HS → HS(T1) → HS(T2).

Natural anti-insulin autoantibodies in cats: enzyme-linked immunosorbent assay for the determination of plasma anti-insulin IgG and its concentrations in domestic cats.

Anti-insulin immunoglobulin G (IgG) has been found in the sera of healthy cats. To determine the concentrations of these antibodies, an enzyme-linked immunosorbent assay (ELISA) for anti-insulin IgG was developed. ELISA maintained the linearity of a standard concentration line between 67.5 and 2160 ng/ml. The coefficients of variances (CVs) of intra-assays in two different plasma samples were 4.0% and 3.7%, respectively. The inter-assay CVs in two different plasma samples were 5.1% and 6.9%, respectively. The dilution curves of two samples were rectilinear. Anti-insulin IgG was detected in all 84 of the healthy cats that were tested. Plasma anti-insulin IgG concentrations ranged from 80 to 1578 µg/ml, with a median concentration of 221 µg/ml, and this value correlated positively with total plasma IgG concentrations (r=0.383, p<0.01). In an intravenous glucose tolerance test, plasma anti-insulin IgG concentrations did not alter, even with changes in plasma glucose and insulin concentrations. The ELISA that was developed was able to determine plasma anti-insulin IgG in domestic cats, and confirmed that all healthy cats had plasma anti-insulin IgG. Determining the plasma concentrations of anti-insulin IgG in cats with various pathological conditions might clarify the role of anti-insulin IgG.

Comparison of ancillary ligand effects between 2,2'-bipyridine and 2-(2'-pyridyl)phenyl in the linkage and bridging isomerism of 5-methyltetrazolato iridium(III) and/or rhodium(III) complexes.

Several new iridium(III) and rhodium(III) complexes bearing 5-methyltetrazolate (MeCN4(-)) have been prepared, and their structures in the crystals and in solution have been determined by X-ray analysis and by NMR spectroscopy, respectively. In the crystals of the mononuclear complexes, κN(2)-coordination of MeCN4(-) was observed when the ancillary ligand was 2,2'-bipyridine (bpy): [Cp*M(bpy)(MeCN4-κN(2))]PF6 (Cp* = η(5)-C5Me5; M = Ir: 1 and Rh: 2), while the corresponding complexes with 2-(2'-pyridyl)phenyl (ppy(-)) were confirmed to have the κN(1)-coordination of MeCN4(-): [Cp*M(ppy)(MeCN4-κN(1))] (M = Ir: 3 and Rh: 4). In solution, the Ir(III) complexes (1 and 3) were robust enough to maintain their molecular structures, but the Rh(III) complexes (2 and 4) existed as an equilibrium mixture of the κN(1)- and κN(2)-isomers. In addition to the Ir(III)-Ir(III) and Rh(III)-Rh(III) homodinuclear complexes bridged by MeCN4(-) (5-8), the corresponding heterodinuclear Ir(III)-Rh(III) complexes (9-12) were prepared using the mononuclear Ir(III) complexes (1 and 3) as precursors. The molecular structures of these dinuclear complexes were also characterised. Interestingly, both of the heterodinuclear complexes comprised of Cp*M(bpy)(2+) and Cp*M'(ppy)(+) fragments, [Cp*M(bpy)(µ-MeCN4)M'(ppy)Cp*](PF6)2 (M = Ir, M' = Rh: 10 and M = Rh, M' = Ir: 11), exhibited selective crystallisation of a specific µ-κN(1)(M'-ppy):κN(3)(M-bpy) isomer. In solution, the dinuclear complexes with a Rh-N(MeCN4) bond and more than one positive charge (6 and 9-11) showed a dissociation equilibrium, while monocationic MeCN4-bridged complexes (7, 8 and 12) were inactive for dissociation. Furthermore, the heterodinuclear complexes of 9-12, as well as the Rh(III)-Rh(III) complex of 8, exhibited a bridging isomerisation, which would proceed via a η(2):η(2)-intermediate without dissociation of Cp*M(bpy or ppy) fragments.

Syntheses, structures, and magnetic properties of acetato- and diphenolato-bridged 3d-4f binuclear complexes [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (M = Zn(II), Cu(II), Ni(II), Co(II); Ln = La(III), Gd(III), Tb(III), Dy(III); 3-MeOsaltn = N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato; ac = acetato; hfac = hexafluoroacetylacetonato; x = 0 or 1).

A series of 3d-4f binuclear complexes, [M(3-MeOsaltn)(MeOH)x(ac)Ln(hfac)2] (x = 0 for M = Cu(II), Zn(II); x = 1 for M = Co(II), Ni(II); Ln = Gd(III), Tb(III), Dy(III), La(III)), have been synthesized and characterized, where 3-MeOsaltn, ac, and hfac denote N,N'-bis(3-methoxy-2-oxybenzylidene)-1,3-propanediaminato, acetato, and hexafluoroacetylacetonato, respectively. The X-ray analyses demonstrated that all the complexes have an acetato- and diphenolato-bridged M(II)-Ln(III) binuclear structure. The Cu(II)-Ln(III) and Zn(II)-Ln(III) complexes are crystallized in an isomorphous triclinic space group P1, where the Cu(II) or Zn(II) ion has square pyramidal coordination geometry with N2O2 donor atoms of 3-MeOsaltn at the equatorial coordination sites and one oxygen atom of the bridging acetato ion at the axial site. The Co(II)-Ln(III) and Ni(II)-Ln(III) complexes are crystallized in an isomorphous monoclinic space group P2(1)/c, where the Co(II) or Ni(II) ion at the high-spin state has an octahedral coordination environment with N2O2 donor atoms of 3-MeOsaltn at the equatorial sites, and one oxygen atom of the bridged acetato and a methanol oxygen atom at the two axial sites. Each Ln(III) ion for all the complexes is coordinated by four oxygen atoms of two phenolato and two methoxy oxygen atoms of "ligand-complex" M(3-MeOsaltn), four oxygen atoms of two hfac(-), and one oxygen atom of the bridging acetato ion; thus, the coordination number is nine. The temperature dependent magnetic susceptibilities from 1.9 to 300 K and the field-dependent magnetization up to 5 T at 1.9 K were measured. Due to the important orbital contributions of the Ln(III) (Tb(III), Dy(III)) and to a lesser extent the M(II) (Ni(II), Co(II)) components, the magnetic interaction between M(II) and Ln(III) ions were investigated by an empirical approach based on a comparison of the magnetic properties of the M(II)-Ln(III), Zn(II)-Ln(III), and M(II)-La(III) complexes. The differences of χ(M)T and M(H) values for the M(II)-Ln(III), Zn(II)-Ln(III) and those for the M(II)-La(III) complexes, that is, Δ(T) = (χ(M)T)(MLn) - (χ(M)T)(ZnLn) - (χ(M)T)(MLa) = J(MLn)(T) and Δ(H) = M(MLn)(H) - M(ZnLn)(H) - M(MLa)(H) = J(MLn)(H), give the information of 3d-4f magnetic interaction. The magnetic interactions are ferromagnetic if M(II) = (Cu(II), Ni(II), and Co(II)) and Ln = (Gd(III), Tb(III), and Dy(III)). The magnitudes of the ferromagnetic interaction, J(MLn)(T) and J(MLn)(H), are in the order Cu(II)-Gd(III) > Cu(II)-Dy(III) > Cu(II)-Tb(III), while those are in the order of M(II)-Gd(III) ≈ M(II)-Tb(III) > M(II)-Dy(III) for M(II) = Ni(II) and Co(II). Alternating current (ac) susceptibility measurements demonstrated that the Ni(II)-Tb(III) and Co(II)-Tb(III) complexes showed out-of-phase signal with frequency-dependence and the Ni(II)-Dy(III) and Co(II)-Dy(III) complexes showed small frequency-dependence. The energy barrier for the spin flipping was estimated from the Arrhenius plot to be 14.9(6) and 17.0(4) K for the Ni(II)-Tb(III) and Co(II)-Tb(III) complexes, respectively, under a dc bias field of 1000 Oe.

Fermented soybean powder with rice mold in the absence of salt stimulates the cellular immune system and suppresses the humoral immune response in mice.

The immunomodulatory effect of fermented non-salty soybean powder (NSBP) was investigated in C3H/HeN mice. The number of splenic CD11b(+), CD49b(+), and interferon (IFN)-γ(+)CD4(+) cells increased significantly, while that of interleukin (IL)-4(+)CD4(+) and CD19(+) cells decreased significantly in cultures containing NSBP. Similarly, in the spleen and Peyer's patches of mice fed a diet containing NSBP, the number of IL-12(+)CD11b(+), CD49b(+), and IFN-γ(+)CD4(+) cells increased noticeably, whereas the number of splenic IL-4(+)CD4(+) and CD19b(+) cells was lower compared to mice fed an NSBP-free diet. Superoxide production by peritoneal macrophages was significantly higher in mice fed an NSBP-containing diet. Both intestinal total IgA and serum total IgG levels declined in mice fed the NSBP-containing diet. Microarray analysis of mRNAs extracted from Peyer's patch cells of mice fed the NSBP-containing diet indicated an increase in the expression of several genes related to cellular immune responses, while the expression of genes related to immunoglobulin production decreased. These results indicate that NSBP stimulates the cellular immune response, but suppresses the acquired humoral immune response in C3H/HeN mice.

Tooth loss and risk of hip fracture: a prospective study of male Japanese dentists.

OBJECTIVES: To determine whether the number of teeth lost can predict the risk of subsequent hip fracture. METHODS: We followed up 9992 male Japanese dentists aged 50 years or more (mean age ± standard deviation [SD], 61.1 ± 9.6 years) for incidence of hip fracture. From 2001 through 2006, they completed a baseline questionnaire on lifestyle and health factors including the number of teeth lost (excluding third molars). Incidence rate ratios (IRRs) were estimated by fitting proportional hazard models. RESULTS: During the mean follow-up period of 6.0 years, 20 new cases of hip fracture occurred. Participants who had lost 15 or more teeth at baseline were at a significantly increased risk of hip fracture: the multivariate-adjusted IRRs were 4.1 (95% confidence interval [CI], 1.2-14.2) for loss of 15-27 teeth and 4.5 (1.1-18.0) for edentulousness relative to loss of 0-14 teeth (trend P, 0.028). Overall, the risk of hip fracture was weakly associated with the number of teeth lost: the IRR per tooth was 1.06 (95% CI, 1.01-1.12). CONCLUSIONS: Tooth loss was slightly associated with a higher risk of subsequent hip fracture. The number of teeth lost might be informative in predicting this risk.

Bis(µ(2)-4,7-dimethyl-4,7-diazadecane-1,10-dithiolato)trinickel(II) bis(perchlorate).

In the title compound, [Ni(3)(C(10)H(22)N(2)S(2))(2)](ClO(4))(2), the complex cation consists of a nickel(II) ion and two [Ni(C(10)H(22)N(2)S(2))] units with an N(2)S(2) tetra-dentate ligand, 3,3'-[1,2-ethane-diylbis(methyl-imino)]bis-(1-propane-thiol-ate). The central Ni(II) ion is located on a crystallographic inversion centre and is bound to the four S atoms of the two [Ni(C(10)H(22)N(2)S(2))] units to form a linear sulfur-bridged trimetallic moiety. The dihedral angle between the central NiS(4) plane and the terminal NiN(2)S(2) plane is 145.71 (5)°. In the [Ni(C(10)H(22)N(2)S(2))] unit, the two methyl groups on the chelating N atoms are cis to each other, and the two six-membered N,S-chelate rings adopt a chair conformation. The Ni-S bond lengths and the S-Ni-S bite angles in the central NiS(4) group are similar to those in the [Ni(C(10)H(22)N(2)S(2))] unit.

1D and 2D assembly structures by imidazole···chloride hydrogen bonds of iron(II) complexes [Fe(II)(HL(n-Pr))3]Cl·Y (HL(n-Pr) = 2-methylimidazol-4-yl-methylideneamino-n-propyl; Y = AsF6, BF4) and their spin states.

Two Fe(II) complexes fac-[Fe(II)(HL(n-Pr))(3)]Cl·Y (Y = AsF(6) (1) and BF(4) (2)) were synthesized, where HL(n-Pr) is 2-methylimidazole-4-yl-methylideneamino-n-propyl. Each complex-cation has the same octahedral N(6) geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[Fe(II)(HL(n-Pr))(3)](2+) with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) are hydrogen-bonded to three Cl(-) ions or, from the viewpoint of the Cl(-) ion, one Cl(-) ion is hydrogen-bonded to three neighbouring fac-[Fe(II)(HL(n-Pr))(3)](2+) cations. The 3 : 3 NH···Cl(-) hydrogen bonds between Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) and Cl(-) generate two kinds of assembly structures. The directions of the 3 : 3 NH···Cl(-) hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) enantiomorphs are bridged by two NH···Cl(-) hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[Fe(II)(HL(n-Pr))(3)](2+)···Cl(-)}(3) giving a smaller cavity, in which Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) species with the same chirality are linked by NH···Cl(-) hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and Mössbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T(c↓) = 125.5 K and T(c↑) = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.

A hydrogen bond motif giving a variety of supramolecular assembly structures and spin-crossover behaviors.

A series of spin-crossover (SCO) iron(II) compounds, fac-[Fe(II)(HL(R))(3)]Cl·PF(6) [R = methyl (Me, 1), ethyl (Et, 2), n-propyl (n-Pr, 3), n-butyl (n-Bu, 4), and n-pentyl (n-Pen, 5)], were synthesized, where HL(R) denotes a series of [(2-methylimidazol-4-yl)methylidene]monoalkylamines. The cations fac-[Fe(II)(HL(R))(3)](2+) and chloride anions associate through 3:3 imidazole···chloride hydrogen bonding. This hydrogen-bonding motif gives rise to a variety of assembly structures consisting of a one-dimensional ladder for 3 and 4, two kinds of two-dimensional networks for 1 and 2, and a cubane-like structure for 5. The compounds exhibit various types of SCO transitions between high-spin (S = 2) and low-spin (S = 0) states as a result of their intermolecular interactions.

A single tripodal ligand stabilizing three different oxidation states (II, III, and IV) of manganese.

A series of mononuclear Mn(II), Mn(III), and Mn(IV) complexes was prepared using a single tripodal ligand (H(3)L). Addition of a cation (NH(4)(+), K(+), Na(+)) to [Mn(III)L] showed a pronounced effect on the redox potentials. Different variants of Jahn-Teller distortion, axial elongation and compression, were observed in the Mn(III) complexes.

Orange and yellow crystals of copper(I) complexes bearing 8-(diphenylphosphino)quinoline: a pair of distortion isomers of an intrinsic tetrahedral complex.

The tetrafluoroborate salt of bis{8-(diphenylphosphino)quinoline}copper(I), [Cu(Ph(2)Pqn)(2)]BF(4), afforded orange prismatic (2O) or yellow columnar (2Y) crystals, dependent on the solvent and concentration of the recrystallization solution used. X-ray analysis revealed that crystals of 2O and 2Y had the same composition and exhibited different crystal systems: 2O was triclinic, with space group P ̅1 and Z = 2, and 2Y was monoclinic with space group P2(1)/c and Z = 4. In these crystals, the tetrahedral copper(I) complex exhibited a strong "rocking distortion" toward a trigonal pyramidal coordination geometry (by a slide translation of one of the unsymmetrical bidentate chelating ligands along the tetrahedral edge). In addition, both the 2O and 2Y complexes showed a "flattening distortion", meaning that the dihedral angle between the two chelate planes were off-perpendicular and oriented toward opposite directions, which resulted in a pair of distortion isomers: syn clinal (sc: 2O) and anti clinal (ac: 2Y). (31)P CP-MAS NMR spectroscopy indicated that 2O and 2Y could be distinguished. Both isomers exhibited inequivalent P atoms, but a larger difference in chemical shift was observed in 2Y. TD-DFT calculations reproduced the difference in spectra between the orange- and yellow-colored complexes, which originated from metal-to-ligand charge-transfer transitions.

Nanoscale self-hosting of molecular spin-states in the intermediate phase of a spin-crossover material.

A new spin-crossover (SC) complex [Fe(II)H(2)L(2-Me)][AsF(6)](2) has been synthesized, in which H(2)L(2-Me) denotes the chirogenic hexadentate N(6) Schiff-base ligand bis{[(2-methylimidazol-4-yl)methylidene]-3-aminopropyl}ethylenediamine. This complex has revealed a rich variety of phases during its two-step thermal crossover, as well as photoinduced spin-state switching. A high-symmetry high-spin (HS, S=2) phase, a low-symmetry low-spin (LS, S=0) phase, an intermediate phase characterized by an unprecedented lozenge pattern of 12 predominantly HS molecular crystallographic sites confining 18 predominantly LS molecular crystallographic sites, and a photoinduced low-symmetry HS phase have been accurately evidenced by temperature-dependent magnetic susceptibility, Mössbauer spectroscopy, and crystallographic studies. This variety of phases illustrates the multi-stability of this system, which results from coupling between the electronic states and structural instabilities.

Determination of immuno-reactive rabbit apolipoprotein B-48 in serum by ELISA.

Apolipoprotein B-48 (apoB-48) is produced by the small intestine, is associated with chylomicrons, and appears to be a suitable marker for clinical studies of postprandial dynamics of lipoproteins. It is also associated with cardiovascular risk factors. We have developed an assay system to quantify immuno-reactive apoB-48 in rabbit serum or plasma. A microtiter-plate was coated with monoclonal antibody raised against human apoB-48 C-terminal specific decapeptide that has high homology to the rabbit C-terminal sequence. Appropriate ELISA standard curves were obtained using apoB-48 extracted from rabbit serum by immuno-affinity chromatography. No cross-reactivity was found with apoB-100 in western blot analyses. Intra- and inter-assay CVs were less than 3%. Recovery of rabbit apoB-48 spiked in serum was within 93.4-105%. ApoB-48 levels in healthy controls rabbits fed a normal diet were within the range of 0.903-1.09 microg/ml (mean +/- SD: 1.03 +/- 0.084 microg/ml). In healthy animals, the blood apoB-48 level was markedly increased by a high fat diet and in the postprandial state in parallel with serum triglyceride. Ezetimibe, cholesterol absorption inhibitor, given orally to rabbits fed on a high fat diet blocked further increase of blood levels of apoB-48 and triglyceride. This method for measuring apoB-48 using the monoclonal antibody is simple, reliable, and suitable for routine analyses.

Fasting concentrations of nesfatin-1 are negatively correlated with body mass index in non-obese males.

BACKGROUND: We recently identified a novel anorexigenic protein, nesfatin-1, which is processed from nesfatin/nucleobindin-2 (NUCB2). However, the clinical importance of this protein has not been determined. OBJECTIVE: To investigate its clinical significance in humans, we have established a new specific enzyme-linked immunosorbent assay (ELISA) for human nesfatin-1 in peripheral blood and measured its circulating concentration in healthy subjects. DESIGN: The new sandwich-type ELISA method was validated and then used to measure nesfatin-1 levels in plasma samples, under overnight fasting conditions, followed by oral glucose tolerance and meal tests. PATIENTS AND MEASUREMENTS: A total of 43 nonobese males (age: 24.5 ± 0.6, body mass index (BMI); 21.1 ± 0.3 kg/m(2)) were recruited to the study for evaluating fasting concentrations of nesfatin-1. In those, fifteen subjects underwent a 75- g oral glucose tolerance test (OGTT) and another 15 underwent a meal test. In addition, fasting concentrations of nesfatin-1 were measured in nine males with high BMI (age: 32.4 ± 3.7, BMI; 37.3 ± 3.8 kg/m(2)). RESULTS: Peripheral concentrations of nesfatin-1 showed a significant negative correlation with BMI, percentage body fat, body fat weight and blood glucose (P < 0.05). Nesfatin-1 concentrations were not significantly changed during OGTT and meal tests. Fasting nesfatin-1 levels were significantly lower in subjects with high BMI compared to nonobese subjects (P < 0.05). CONCLUSIONS: A new specific and sensitive ELISA for nesfatin-1 was established. Further accumulation of clinical observations is necessary to clarify the role of circulating nesfatin-1 in various metabolic disorders.

Face-sharing heterotrinuclear M(II)-Ln(III)-M(II) (M = Mn, Fe, Co, Zn; Ln = La, Gd, Tb, Dy) complexes: synthesis, structures, and magnetic properties.

Trinuclear linear 3d-4f-3d complexes (3d = Mn(II), Fe(II), Co(II), Zn(II) and 4f = La(III), Gd(III), Tb(III), Dy(III)) were prepared by using a tripodal nonadentate Schiff base ligand, N,N',N''-tris(2-hydroxy-3-methoxybenzilidene)-2-(aminomethyl)-2-methyl-1,3-propanediamine. The structural determinations showed that in these complexes two distorted trigonal prismatic transition metal complexes of identical chirality are assembled through 4f cations. The Mn and Fe entities crystallize in the chiral space group P2(1)2(1)2(1) as pure enantiomers; the cobalt complexes exhibit a less straightforward behavior. All Mn, Fe, and Co complexes experience M(II)-Ln(III) ferromagnetic interactions. The Mn-Gd interaction is weak (0.08 cm(-1)) in comparison to the Fe-Gd (0.69 cm(-1)) and Co-Gd (0.52 cm(-1)) ones while the single ion zero field splitting (ZFS) term D is larger for the Fe complexes (5.7 cm(-1)) than for the cobalt ones. The cobalt complexes behave as single-molecules magnets (SMMs) with large magnetization hysteresis loops, as a consequence of the particularly slow magnetic relaxation characterizing these trinuclear molecules. Such large hysteresis loops, which are observed for the first time in Co-Ln complexes, confirm that quantum tunnelling of the magnetization does not operate in the Co-Gd-Co complex.

One-dimensional spin-crossover Iron(II) complexes bridged by intermolecular imidazole-pyridine NH...N hydrogen bonds, [Fe(HL(Me))(3)]X(2) (HL(Me) = (2-methylimidazol-4-yl-methylideneamino-2-ethylpyridine; X = PF(6), ClO(4), BF(4)).

2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine (abbreviated as HL(Me)) is the 1:1 condensation product of 2-methyl-4-formylimidazole and 2-aminoethylpyridine and functions as a bidentate ligand to the iron(II) ion to produce the 3:1 complexes together with anions, [Fe(HL(Me))(3)]X(2) (X = PF(6) (1), ClO(4) (2), BF(4) (3)). The magnetic susceptibilities, differential scanning calorimetric measurements, and Mossbauer spectral measurements demonstrated that complexes 1, 2, and 3 showed a steep one-step spin crossover (SCO) between the high-spin (HS, S = 2) and low-spin (LS, S = 0) states with small thermal hysteresis. Three complexes have an isomorphous structure and are crystallized in the same monoclinic space group, C2/c, both in the HS and LS states. The iron(II) ion has the octahedral coordination geometry of a facial isomer with N(6) donor atoms of three bidentate ligands, in which an imidazole and an imine nitrogen atom per ligand participate in the formation of the coordination bond, but the pyridine nitrogen is free from coordination. The complex cation fac-[Fe(HL(Me))(3)](2+) is a chiral species with a Delta or Lambda isomer, and the adjacent Delta and Lambda isomers are linked alternately by an intermolecular imidazole-pyridine NH...N hydrogen bond to produce an achiral 1D chain. The two remaining imidazole moieties per complex are hydrogen-bonded to the anions that occupy the space among the chains. The SCO profile becomes steeper with the decrease of the anion size (73.0 A(3) for PF(6)(-), 54.4 A(3) for ClO(4)(-), and 53.4 A(3) for BF(4)(-)). The SCO transition temperature T(1/2) of the PF(6) (1), ClO(4) (2), and BF(4) (3) salts estimated from the magnetic susceptibility measurements are (T( downward arrow) = 151.8 K, T( upward arrow) = 155.3 K), (T( downward arrow) = 184.5 K, T( upward arrow) = 186.0 K), and (T( downward arrow) = 146.4 K, T( upward arrow) = 148.2 K), respectively, indicating that the T(1/2) value is not in accord with the anion size.