bluuebunny/crossref_metadata_2025_split huggingface dataset:
Zinc Complexes of a Bioinspired Binucleating Ligand Platform – Equilibria in Solution and Structures in the Solid State
Authors: Wöckel Simone , Gałęzowska Joanna , Dechert Sebastian , Meyer‐Klaucke Wolfram , Nordlander Ebbe , Meyer Franc 
Published: July 2012

AbstractThe zinc(II) coordination chemistry of the bioinspired bis(tetradentate) ligand 3,5‐bis{bis[2‐(1‐methylimidazolyl)methyl]aminomethyl}pyrazole (L) was studied in detail both in solution and in the solid state. Six different species were determined in aqueous solution by means of potentiometry within the pH range 2–11, namely mononuclear [ZnH2L]4+, dinuclear [Zn2L]4+, [Zn2H–1L]3+ and [Zn2H–2L]2+, as well as tetranuclear [Zn4H–5L2]3+ and [Zn4H–6L2]2+. Complexes representing the protonation state of four of these species could be isolated and structurally characterized by X‐ray diffraction, namely [ZnH2L(MeCN)](ClO4)4 (1), [Zn2H–1L](SO3CF3)3 (4), [Zn2H–1L(MeOHOMe)](ClO4)2 (5a), [Zn2H–1L(OMe)](ClO4)2 (5b), and [(Zn2H–1L)2(μ‐O)(μ‐OH)](ClO4)3 (6). In addition, a bis(pyrazolato)‐bridged complex, [(ZnH–1L)2](ClO4)2 (2), was obtained and structurally characterized, and it was found to exhibit ligand dynamics in solution. Both 5a and 5b are likely present in solution, which requires significant plasticity of the Zn···Zn distance (4.21 Å in 5a vs. 3.38 Å in 5b). Interconversion of 5a and 5b is proposed to be a facile process, supporting the idea that the Zn–O2H3–Zn moiety is a functionally relevant hydrolytic zinc–aqua structure in oligozinc metalloenzymes. The tetranuclear complex 6 that features two {Zn2H–1L} subunits connected by a central μ‐oxido‐μ‐hydroxido moiety is unprecedented in zinc(II) chemistry. Combining X‐ray crystallography with potentiometry, ESI mass spectrometry, as well as NMR and EXAFS spectroscopy has provided a comprehensive picture of the multitude of species present in this rather complex system.
Occurrence of polyfunctional thiols in sorghum beer ‘ikigage’ made with Vernonia amygdalina ‘umubirizi’
Authors: Lyumugabe Francois , Gros Jacques , Thonart Philippe , Collin Sonia 
Published: July 2012

ABSTRACTSeveral polyfunctional thiols have been previously identified in beers made from barley and hops. These compounds have not been investigated in beers brewed with ‘non‐Western’ raw materials. Here we have performed a thiol‐specific extraction with p‐hydroxymercuribenzoic acid on a traditional ikigage sorghum beer from Rwandese peasants (use of Vernonia amygdalina just for yeast propagation), and on two pilot beers with addition (or not) of V. amygdalina in the boiling kettle, instead of hops. Gas chromatography–olfactometry, gas chromatography–mass spectrometry and gas chromatography with pulsed flame photometric detection analyses of the extracts enabled us to identify 14 polyfunctional thiols. The well‐known hop constituent 3‐methyl‐2‐buten‐1‐thiol emerged as a key flavour in the unhopped beers containing V. amygdalina (flavour dilution > 262 144). The addition of V. amygdalina during boiling also resulted in the presence of 1‐butanethiol, but the production of 2‐sulfanylethanol and 2‐sulfanylethyl acetate was inhibited. Complementary data are required to understand how V. amygdalina leaves are able to impact upon the Ehrlich pathway leading to cysteine and homocysteine‐derived thiols. Copyright © 2012 John Wiley & Sons, Ltd.
Preparation and characteristic odour of optically active 3‐hydroxy‐2‐octanone
Authors: Liu Yong‐guo , Chen Kai , Li Chen , Zhang Shuo , Chen Haitao , Tian Hong‐yu , Sun Bao‐guo 
Published: July 2012

ABSTRACTThe preparation of optically active 3‐hydroxy‐2‐octanone was examined by Sharpless asymmetric dihydroxylation of a silyl enol ether derived from 2‐octanone. (R)‐3‐Hydroxy‐2‐octanone was obtained in 68% yield and 87.8% ee when AD‐mix‐β was used as an oxidant, while the (S)‐enantiomer was produced in 69% yield and 77.3% ee from AD‐mix‐α. The characteristic odour of the optically active products was evaluated by chiral gas chromatography–olfactometry. (R)‐3‐Hydroxy‐2‐octanone has a mushroom‐like, fresh grass odour, while the (S)‐enantiomer presents a mushroom‐like, earthy note. Aroma extract dilution analysis was applied to determine the flavour dilution factors of the two enantiomers. The flavour dilution factor of the (R)‐enantiomer was 1024, which is much higher than that of (S)‐enantiomer (256). They obviously differ in odour intensity. Copyright © 2012 John Wiley & Sons, Ltd.
Application of the VORTFIND algorithm for the identification of vortical flow features around complex three‐dimensional geometries
Authors: Phillips Alexander Brian , Turnock Stephen Richard 
Published: July 2012

SUMMARYAccurate prediction of the hydrodynamic forces and moments acting on a manoeuvring marine vehicle using Reynolds averaged Navier–Stokes simulations requires sufficient mesh resolution to capture off‐body vortical structures. Because the path of these structures is not known a priori, a vortex identification and capture strategy is required alongside an iterative mesh adaption process. An improved version of the VORTFIND algorithm, which can identify multiple vortices of variable strength and rotational direction using a K‐means algorithm is described. The algorithm is applied to velocity fields generated from Reynolds averaged Navier–Stokes simulations to increase the mesh resolution in the vortex core region, ensuring sufficient mesh density to capture the downstream propagation of the vortex for a submarine hull at drift and ship propeller–rudder interaction.Copyright © 2012 John Wiley & Sons, Ltd.
Development of a framework for recovery in older people with mental disorder
Authors: Daley Stephanie , Newton David , Slade Mike , Murray Joanna , Banerjee Sube 
Published: July 2012

ObjectiveTo evaluate whether a conceptual framework of recovery developed for working age adults holds value for users of older people's mental health services, including those with dementia.MethodThirty‐eight qualitative interviews were undertaken with service users and carers from an older people's mental health service in South London and were analysed using grounded theory methods.ResultsComponents of recovery, which appear to be meaningful to older people with mental disorder include the following: (i) the impact of illness, (ii) the significance of personal responsibility, and (iii) specific coping strategies. Unlike their younger peers, older people did not aspire to a new and revised sense of identity, nor did they seek peer support from others with lived experience of mental illness. Three components of recovery were identified as being distinct to older people: the significance of an established and enduring sense of identity; coping strategies, which provide continuity and reinforce identity; and the associated impact of physical illness. Finally, two additional components of recovery were identified for people with dementia: (i) the changing experience over time and (ii) support from others.ConclusionMental health policy is increasingly framed in terms of ‘recovery’. This paper provides empirical evidence of how it applies to users of older people's mental health services. Practice implications include the need to focus on the maintenance of identity, and embed the values of empowerment, agency and self‐management within service delivery. Copyright © 2012 John Wiley & Sons, Ltd.
An Abbreviated Screening Instrument for Autism Spectrum Disorders
Authors: Smith Nicola J. , Sheldrick R. Christopher , Perrin Ellen C. 
Published: July 2012

AbstractThe reliability and validity of the Parent's Observations of Social Interactions (POSI), a new, seven‐item screening instrument for autism spectrum disorders (ASD), is examined in two substudies. In Study 1, parents of 217 children (18–48 months) evaluated at a developmental clinic completed intake questionnaires that included the POSI and the Modified Checklist for Autism in Toddlers (M‐CHAT) checklist. POSI and M‐CHAT scores were compared to clinical evaluation results to assess reliability and validity. In Study 2, parents of 232 children (16–36 months) from both primary care and subspecialty settings completed the POSI, the M‐CHAT, and a report of their child's diagnoses. POSI and M‐CHAT scores were compared to reported diagnoses to assess reliability and validity. In both studies, the POSI demonstrated adequate internal reliability (Cronbach α = 0.83 and 0.86, respectively). In Study 1, POSI sensitivity (89%) was higher than that for the M‐CHAT (71%; p < .05); specificities were not significantly different (POSI: 54%, M‐CHAT: 62%). In Study 2, sensitivity (83%) compared favorably to that for the M‐CHAT (50%), although specificity was lower (75 vs. 84%). Despite its brevity, the POSI demonstrated good internal reliability and comparable sensitivity/specificity to the M‐CHAT checklist in two independent populations. If results are reproduced in larger, more diverse samples, the POSI may provide an efficient method for ASD screening in young children.
Osteopetrosis rescue upon RANKL administration to Rankl−/− mice: A new therapy for human RANKL-dependent ARO
Authors: Lo Iacono Nadia , Blair Harry C , Poliani Pietro L , Marrella Veronica , Ficara Francesca , Cassani Barbara , Facchetti Fabio , Fontana Elena , Guerrini Matteo M , Traggiai Elisabetta , Schena Francesca , Paulis Marianna , Mantero Stefano , Inforzato Antonio , Valaperta Serenella , Pangrazio Alessandra , Crisafulli Laura , Maina Virginia , Kostenuik Paul , Vezzoni Paolo , Villa Anna , Sobacchi Cristina 
Published: July 2012

Abstract
In the last decades the molecular basis of monogenic diseases has been largely unraveled, although their treatment has often remained unsatisfactory. Autosomal recessive osteopetrosis (ARO) belongs to the small group of genetic diseases that are usually treated with hematopoietic stem cell transplantation (HSCT). However, this approach is not effective in the recently identified form carrying mutations in the receptor activator of NF-κB ligand (RANKL) gene. In this subset, therapy replacement approach based on RANKL delivery has a strong rationale. Here we demonstrate that the systematic administration of RANKL for 1 month to Rankl−/− mice, which closely resemble the human disease, significantly improves the bone phenotype and has beneficial effects on bone marrow, spleen and thymus; major adverse effects arise only when mice are clearly overtreated. Overall, we provide evidence that the pharmacological administration of RANKL represents the appropriate treatment option for RANKL-deficient ARO patients, to be validated in a pilot clinical trial. © 2012 American Society for Bone and Mineral Research.
Androgen receptor (AR) in osteocytes is important for the maintenance of male skeletal integrity: Evidence from targeted AR disruption in mouse osteocytes
Authors: Sinnesael Mieke , Claessens Frank , Laurent Michaël , Dubois Vanessa , Boonen Steven , Deboel Ludo , Vanderschueren Dirk 
Published: July 2012

Abstract
Androgens play a key role in the maintenance of male skeletal integrity. The regulation of this integrity by androgen receptor (AR) signaling has been mainly attributed to osteoblasts. Although osteocytes have emerged as key regulators of bone remodeling, the influence of sex steroids on these cells has been poorly studied. We aimed to investigate the role of AR signaling, specifically in osteocytes using the Cre/LoxP system in male mice (driven by dentin matrix protein 1 [ocy-ARKOs]). Osteocyte fractions of control (AR(ex2)/Y) and ocy-ARKO (ARflox(ex2)/Y; DMP1-cre) mice isolated through sequential collagenase digestion showed increasing AR expression toward the mature osteocyte fraction of control males compared with the more immature fractions, whereas this was reduced by &gt;80% in ocy-ARKO osteocytes. The skeletal phenotype of mutant mice was further assessed by histomorphometry and quantitative micro-computed tomography at 12 and 32 weeks of age. Ocy-ARKOs had significantly lower trabecular bone volume and number in femora and tibias at 32 weeks as well as decreased trabecular number in the L5 vertebra at 12 weeks. Biomechanical testing showed that ocy-ARKO femora were also stiffer and required a lower ultimate force to induce failure at 32 weeks. However, femoral cortical structure was not significantly different at any time point. The absence of AR in osteocyte also did not appear to affect trabecular bone formation nor its response to mechanical loading. In conclusion, selective inactivation of the AR in osteocytes of male mice accelerates age-related deterioration of skeletal integrity. These findings provide evidence for a direct role of androgens in the maintenance of trabecular bone through actions of the AR in osteocytes. © 2012 American Society for Bone and Mineral Research.
Antiresorptives overlapping ongoing teriparatide treatment result in additional increases in bone mineral density
Authors: Muschitz Christian , Kocijan Roland , Fahrleitner-Pammer Astrid , Lung Solveig , Resch Heinrich 
Published: July 2012

Abstract
During teriparatide (TPTD) treatment, high levels of bone formation are accompanied by an increase in bone resorption. The aim of this work was to test if coadministration of raloxifene (RAL) or alendronate (ALN) following 9 months of ongoing TPTD therapy would reopen the anabolic window, thereby exerting additional benefit on bone mineral density (BMD). Postmenopausal women (n = 125) with severe osteoporosis on TPTD treatment for 9 months were randomized into three open-label groups for a further 9 months: ALN (70 mg/week) in addition to TPTD; RAL (60 mg/d) in addition to TPTD; or no medication in addition to TPTD. Amino-terminal propeptide of type I procollagen (P1NP) and cross-linked C-telopeptide (CTX), and areal and volumetric BMD at the lumbar spine and hip were assessed. During the combination period, P1NP concentrations did not change on TPTD monotherapy (693% ± 371%, p &lt; 0.0001) and decreased in the ALN (360% ± 153%, p &lt; 0.0001) and RAL (482% ± 243%, p &lt; 0.0001) combination groups; whereas CTX did not change on TPTD monotherapy (283% ± 215%, p &lt; 0.0001), decreased to the starting level in the ALN combination group (17% ± 72%, p = 0.39), and remained elevated in the RAL combination group (179% ± 341%, p &lt; 0.0001). The increase in lumbar spine BMD was 5% ± 6.3% in the ALN and 6% ± 5.2% in the RAL combination groups compared with 2.8% ± 9.3% in the TPTD monotherapy group (p = 0.085 and p = 0.033, respectively). The increase of trabecular lumbar spine BMD for both the ALN and RAL combination groups was superior to TPTD monotherapy. Total hip BMD changes were 4% ± 5.3% for the ALN combination group and 1.4% ± 5.1% for the TPTD monotherapy (p = 0.032), and 1.4% ± 3.4% (p = 0.02) for the RAL combination group. With the exception of no differences in the trabecular compartment of femoral neck, volumetric BMD changes in the ALN combination group for all other comparisons were significantly superior to the two other groups. Our data suggest that ALN when added to TPTD 9 months after initiation of TPTD monotherapy results in a more robust increase in BMD, probably due to a reopening of the anabolic window. The clinical relevance of the BMD increase is unknown. © 2013 American Society for Bone and Mineral Research
Sclerostin antibody improves skeletal parameters in a Brtl/+ mouse model of osteogenesis imperfecta
Authors: Sinder Benjamin P , Eddy Mary M , Ominsky Michael S , Caird Michelle S , Marini Joan C , Kozloff Kenneth M 
Published: July 2012

Abstract
Osteogenesis imperfecta (OI) is a genetic bone dysplasia characterized by osteopenia and easy susceptibility to fracture. Symptoms are most prominent during childhood. Although antiresorptive bisphosphonates have been widely used to treat pediatric OI, controlled trials show improved vertebral parameters but equivocal effects on long-bone fracture rates. New treatments for OI are needed to increase bone mass throughout the skeleton. Sclerostin antibody (Scl-Ab) therapy is potently anabolic in the skeleton by stimulating osteoblasts via the canonical wnt signaling pathway, and may be beneficial for treating OI. In this study, Scl-Ab therapy was investigated in mice heterozygous for a typical OI-causing Gly→Cys substitution in col1a1. Two weeks of Scl-Ab successfully stimulated osteoblast bone formation in a knock-in model for moderately severe OI (Brtl/+) and in WT mice, leading to improved bone mass and reduced long-bone fragility. Image-guided nanoindentation revealed no alteration in local tissue mineralization dynamics with Scl-Ab. These results contrast with previous findings of antiresorptive efficacy in OI both in mechanism and potency of effects on fragility. In conclusion, short-term Scl-Ab was successfully anabolic in osteoblasts harboring a typical OI-causing collagen mutation and represents a potential new therapy to improve bone mass and reduce fractures in pediatric OI. © 2013 American Society for Bone and Mineral Research
High serum sclerostin predicts the occurrence of osteoporotic fractures in postmenopausal women: The center of excellence for osteoporosis research study
Authors: Ardawi Mohammed-Salleh M , Rouzi Abdulrahim A , Al-Sibiani Sharifa A , Al-Senani Nawal S , Qari Mohammed H , Mousa Shaker A 
Published: July 2012

Abstract
Sclerostin regulates bone formation by inhibiting Wnt pathway signaling. Low circulating sclerostin levels cause high bone mass. We hypothesized that postmenopausal women with increased sclerostin levels have a greater risk for osteoporosis-related fractures. We examined the association between circulating sclerostin together with bone turnover markers and osteoporosis-related fracture risk in 707 postmenopausal women, in a population-based study with a mean follow-up period of 5.2 ± 1.3 years. Multivariate Cox proportional hazards regression models were used to analyze fracture risk, adjusted for age, body mass index, and other confounding risk factors. High sclerostin levels were strongly associated with increased fracture risk. After adjustment for age and other confounders, the relative fracture risk was more than sevenfold among postmenopausal women for each 1-SD increment increase in sclerostin level. Women in the highest quartile of sclerostin levels had about a 15-fold increase in fracture risk. Results were similar when we compared sclerostin at the 1-year visit to an average of two to three annual measurements. Fracture risk attributable to sclerostin levels was 56.6% in the highest quartile. Only high levels of bone resorption markers (plasma cross-linked C-terminal telopeptide of type 1 collagen [p-CTx], urinary CTx [u-CTx], and urinary N-telopeptide of type 1 collagen [u-NTx]) were predictive of osteoporosis-related fractures but at much lower hazard ratio (HR) values than that of serum sclerostin. Associations between sclerostin levels and fracture risk were independent of bone mineral density and other confounding risk factors. High sclerostin levels are a strong and independent risk factor for osteoporosis-related fractures among postmenopausal women. © 2012 American Society for Bone and Mineral Research.
Hospitalized osteoporotic vertebral fracture increases the risk of stroke: A population-based cohort study
Authors: Chen Yu-Chun , Wu Jau-Ching , Liu Laura , Huang Wen-Cheng , Cheng Henrich , Chen Tzeng-Ji , Thien Peck-Foong , Lo Su-Shun 
Published: July 2012

Abstract
The association between osteoporosis and cardiovascular diseases has been demonstrated. Higher cardiovascular risk has also been correlated with vertebral fractures. However, the association between osteoporotic vertebral fracture and the possibly higher risk of stroke remains uncertain. This study aimed to evaluate the incidence, risk, and type of stroke in patients with osteoporotic vertebral fracture. Patients with osteoporotic vertebral fracture were identified (n = 380) and 10 age- and sex-matched controls per case (comparison group, n = 3795) were chosen from a nationwide representative cohort of 999,997 people from 1998 to 2005. Both groups were followed-up for stroke events for 3 years, matched by propensity scores with adjustments for covariates such as comorbidities (ie, hypertension, diabetes, arrhythmia, or coronary heart diseases) and exposure to medications (ie, aspirin, lipid lowering drug, or nitrates), and assessed by Kaplan-Meier and Cox regression analyses. The incidence rate of stroke in the osteoporotic vertebral fracture group (37.5 per 1000 person-years; 95% confidence interval [CI], 27.5–51.2) was significantly higher than in the comparison group (14.0 per 1000 person-years; 95% CI, 12.0–16.4, p &lt; 0.001). Stroke was more likely to occur in the osteoporotic vertebral fracture patients than in the normal controls (crude hazard ratio [HR] 2.68, 95% CI 1.89–3.79, p &lt; 0.001; adjusted HR 2.71, 95% CI 1.90–3.86, p &lt; 0.001). In conclusion, patients with osteoporotic vertebral fracture have a higher risk of stroke (ie, both ischemic and hemorrhagic) and require stroke prevention strategies. © 2013 American Society for Bone and Mineral Research.
Natural bond critical point analysis: Quantitative relationships between natural bond orbital‐based and QTAIM‐based topological descriptors of chemical bonding
Authors: Weinhold Frank 
Published: July 2012

AbstractWe have developed a “Natural Bond Critical Point” (NBCP) module for the natural bond orbital (NBO) program that allows mutual analysis of NBO‐basedversusBader‐type quantum theory of atoms in molecules (QTAIM) topological descriptors of chemical bonding interactions. Conventional QTAIM bond path and bond critical point (BCP) descriptors deduced from total electron density ρ(r) can thereby be compared with analogous “natural” (NBCP) descriptors for idealized densities ρNAIM(r) composed solely from NBO‐based “natural atoms in molecules” (NAIM) at the terminal nuclei. Standard ρ(rBCP) and ∇2ρ(rBCP) descriptors can also be decomposed into unique contributions from individual NBOs or other localized, semilocalized, or delocalized orbital components. These results allow one to recognize many relationships between QTAIM and NBO analyses, showing why close correlations are often found between NBO‐basedversusρ(rBCP)‐based characterizations of chemical bonding interactions, despite strongly divergent conceptions of “the atom in the molecule.” © 2012 Wiley Periodicals, Inc.
Extraction of zinc(II) from ammoniacal solution into hydrophobic ionic liquids
Authors: Hu Jiugang , Chen Qiyuan , Hu Huiping , Ma Qian , Yin Zhoulan , Hu Fengchun 
Published: July 2012

AbstractBACKGROUND: Separation and recovery of zinc from ammoniacal solutions with solvent extraction is very important in the hydrometallurgical industry. Ionic liquids (ILs) have considerable potential for the separation of metal ions. The extraction behaviour of zinc from ammoniacal solution into three hydrophobic ILs was investigated using β‐diketone as the extractant.RESULTS: The extraction efficiency of zinc for three ILs reached a maximum at pH 7.5 and subsequently decreased with increase of pH and it also decreases with increase of the total ammonia concentration. The overall extraction process is exothermic. The extractability decreases in the IL order: [BMIM]NTf2 > [OMIM]PF6 > [OMIM]NTf2. The results of X‐ray absorption spectra indicate that the coordination number of the extracted zinc complexes decreases with increase in the hydrophobicity of the ILs. The results of five recycling experiments indicate that the three hydrophobic ILs are more stable than [BMIM]PF6 for the extraction of zinc in ammoniacal solutions.CONCLUSION: Hydrophobic ILs combined with β‐diketone can be used to extract zinc from ammoniacal solutions. The extraction of zinc is dependent on the zinc species in ammoniacal solutions and the hydrophobicity of ILs. Moreover, the latter affects both the extractability of extraction systems and the structure of the extracted complexes. © 2012 Society of Chemical Industry