To identify susceptibility loci for ankylosing spondylitis, we performed a two-stage genome-wide association study in Han Chinese. In the discovery stage, we analyzed 1,356,350 autosomal SNPs in 1,837 individuals with ankylosing spondylitis and 4,231 controls; in the validation stage, we analyzed 30 suggestive SNPs in an additional 2,100 affected individuals and 3,496 controls. We identified two new susceptibility loci between EDIL3 and HAPLN1 at 5q14.3 (rs4552569; P = 8.77 × 10(-10)) and within ANO6 at 12q12 (rs17095830; P = 1.63 × 10(-8)). We also confirmed previously reported associations in Europeans within the major histocompatibility complex (MHC) region (top SNP, rs13202464; P < 5 × 10(-324)) and at 2p15 (rs10865331; P = 1.98 × 10(-8)). We show that rs13202464 within the MHC region mainly represents the risk effect of HLA-B*27 variants (including HLA-B*2704, HLA-B*2705 and HLA-B*2715) in Chinese. The two newly discovered loci implicate genes related to bone formation and cartilage development, suggesting their potential involvement in the etiology of ankylosing spondylitis.
Sequential reactions of heptadentate phosphinoamine LH 3 with rare-earth metal tris-alkyl precursor (Me 3 SiCH 2 ) 3 Ln-(THF) 2 (Ln = Sc, Lu, Yb, Y, Gd) and a low-valent cobalt complex (Ph 3 P) 3 CoI afforded rare-earth metal-supported cobalt iodide complexes. Reduction of these iodide complexes under N 2 allowed the isolation of the first series of dinitrogen complexes of Co(−I) featuring dative Co(−I) → Ln (Ln = Sc, Lu, Yb, Y, Gd) bonding interactions. These compounds were characterized by multinuclear NMR spectroscopy, X-ray diffraction analysis, electrochemistry, and computational studies. The correlation of N−N vibrational frequencies with the pK a of [Ln(H 2 O) 6 ] 3+ showed that strongest activation of N 2 was achieved with the least Lewis acidic Gd(III) ion. Interestingly, these Ln−Co−N 2 complexes catalyzed silylation of N 2 in the presence of KC 8 and Me 3 SiCl with turnover numbers (TONs) up to 16, where the lutetium-supported Co(−I) complex showed the highest activity within the series. The role of the Lewis acidic Ln(III) was crucial to achieve catalytic turnovers and tunable reactivity toward N 2 functionalization.
The aim of the study was to investigate and compare the clinical manifestations between HLA-B27(+) and HLA-B27(-) ankylosing spondylitis (AS) patients in order to obtain knowledge of the impact of HLA-B27 status on AS, and to inform clinical treatment. A nationwide epidemiological investigation was performed from November 2008 to October 2010. The demographic data and clinical characteristics, and the status of HLA-B27 were collected using questionnaires and laboratory assay, respectively. A total of 2144 patients (78.5% males and 78.4% HLA-B27(+) AS patients) participated in this study. The percentages of males, patients with family history, and involvement of lumbar spine, thoracic spine and hip joints, were observed to be significantly higher in the HLA-B27(+) AS patients than in their HLA-B27(-) AS peers.
While research on lanthanide (Ln) complexes with silyl
ligands
is receiving growing attention, significantly unbalanced efforts have
been devoted to different Ln elements. In comparison with the intense
investigations on Ln elements such as Sm and Yb, the chemistry of
silyl lanthanum and cerium complexes is much slower to develop, and
no solid-state structure of a silyl lanthanum complex has been reported
so far. In this research, four types of ate complexes, including [(DME)3Li][Cp3LnSi(H)Mes2], [(18-crown-6)K][Cp3LnSi(CH3)Ph2], [(DME)3Li][Cp3LnSiPh3], and [(12-crown-4)2Na] [Cp3LnSi(Ph)2Si(H)Ph2] (Ln = La, Ce), were
synthesized by reacting [(DME)3Na][Cp3La(μ-Cl)LaCp3] or Cp3Ce(THF) with alkali metal silanides. All
of the synthesized silyl Ln ate complexes were structurally characterized.
La–Si bond lengths are in a range of 3.1733(4)–3.1897(10)
Å, and the calculated formal shortness ratios of the La–Si
bonds (1.071.08) are comparable to those in the reported silyl complexes
having other Ln metal centers. The Ce–Si bond lengths (3.1415(6)–3.1705(9)
Å) are within the typical range of reported silyl cerium ate
complexes. 29Si solid-state NMR measurements on the diamagnetic
silyl lanthanum complexes were conducted, and large one-bond hyperfine
splitting constants arising from = 7/2) were resolved. Computational
studies on these silyl lanthanum and cerium complexes suggested the
polarized covalent feature of the Ln–Si bonds, which is in
line with the measured large 1
J
139La–Si splitting constants.
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