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This study provides a descriptive characterization of the modern sedimentary processes in Lake Issyk Kul, Kyrgyzstan, important for the selection of a suitable coring or deep‐drilling site, interpretation of future core data and applicability of proxies. The quasi‐equidistant sampling grid of 66 sediment surface samples covers the entirety of the lake basin and is complemented by 10 samples from the major inflows. The methodological approach includes geochemical, granulometric, lipid biomarker, diatom, and statistical analyses. The quantitative and qualitative changes in sediment composition yield information on its generic origin and prevailing transport and depositional environments. The composition of the surface sediments in Issyk Kul is highly heterogenous. Nearshore deposition is mainly controlled by wave action and by fluvial sediment supply with highest quantities of detrital input coming from the high‐energetic, eastern tributaries. Sediments in the deep central basin are mainly produced in situ and dominated by authigenic calcite. Biogenic accumulation is overall low, except for the western extremity of the lake, where the nearshore, shallow‐water, and low‐energetic environment favors aquatic productivity and subsequent preservation of organic material and diatoms. Redeposition of sediments is a dominant process along the slopes across the southern and western basin floor, where run‐out distances of mass movement deposits are up to 5 km. Directional sediment transport by lake currents appears to be less important, except for the transport of very fine‐grained organic matter. Biomarker‐inferred temperature reconstructions suggest lake surface temperatures of ∼15°C in the western littoral zone and in Tyup Bay and a decrease to ∼13°C basinward. Plain Language Summary: Intensive research on the natural component of climate variability on geological time scales is needed to better understand and validate current and future climate change. Lakes can provide continuous sediment successions that allow us to reconstruct regional trends in climate and environment dynamics far beyond the industrial age. In continental Eurasia, Lake Issyk Kul, one of the deepest and largest mountain lakes in the world, has long been targeted for a deep‐drilling campaign, because its sediment succession potentially holds information of the past ∼10 million years. Prerequisite for future drilling is a better understanding of prevailing transport and (re)deposition mechanisms in Lake Issyk Kul. The overarching aim of this study is to test the applicability of different proxies, vital for the interpretation of future sediment core data. Therefore, a quasi‐equidistant sampling grid of up to 66 sediment surface (and 10 river) samples spanning the entire lake basin of Lake Issyk Kul was examined by means of sedimentological, geochemical, biological, and statistical analyses. The interpretation provides insights into spatial differences in, for example, clastic input from major rivers, biogenic sedimentation, and endogenic precipitation of calcium carbonates. Key Points: The study provides information on the prevailing transport and (re)deposition mechanisms in Lake Issyk Kul todayGeochemical, granulometric, lipid biomarker, diatom, and statistical analyses were performed on surface sediment and inlet stream samplesThe results are prerequisite to interpret longer sediment successions from the lake [ABSTRACT FROM AUTHOR]

Outstanding garnet beads were found recently in an elite tumulus dated to the fourth century AD and located at the cemetery of Hagar el‐Beida in the Upper Nubian Nile Valley region. Whereas contacts of Northeast Africa with South Asia have just been proven through analysis of glass beads found in Nubia and dating to the time of intensive Indian Ocean trade, scientific evidence for Nubia's link with the regions to the west was lacking. Laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) was used to determine the elemental composition of three garnet beads to gain information about their type and origin. Additionally, we analyzed twelve garnets from two nearby alluvial placer deposits. While the garnet beads are inclusion‐free Cr‐poor and Ti‐rich pyropes related to alkaline mafic volcanic rocks, the local garnet deposits are shown to be inclusion‐rich almandines and thus unrelated to the investigated Nubian beads. Detailed comparison of data from Merovingian cloisonné jewellery and all known sources of the Cr‐poor and Ti‐rich pyropes shows identical ranges of elemental contents. The source of raw materials for the beads found in Nubia has been not identified with certainty yet, but sources in Portugal and Nigeria are suggested and a connection is shown to similar garnets from Merovingian contexts. [ABSTRACT FROM AUTHOR]

Functionalized octamers of polyaniline neutral forms (leucoemeraldine, emeraldine, pernigraniline) were studied in order to optimize the first hyperpolarizabilities (β). Remarkable static β values were found for the pernigraniline and emeraldine derivatives by using the coupled perturbed Kohn‐Sham (CPKS) approach at the PBE1PBE/6‐31G** level. The enhanced nonlinear response was achieved through the introduction of donor (D) and/or acceptor (A) groups into the oligoanilines structures. The nonlinear optical (NLO) properties of the octamers missing the substituent groups were also investigated. The largest β values were obtained for the pernigraniline and emeraldine derivatives having the tert‐butyl (D) and dicyanoethenyl (A) substituents at opposite ends, as well as the ones with only the acceptor group. These oligomers show charge transfer transitions with large oscillator strengths according to the time dependent density functional theory (TD‐DFT). Predicted β values for the majority of functionalized oligoanilines strongly indicate them as potential building blocks for molecular‐based nonlinear materials with second‐order response. [ABSTRACT FROM AUTHOR]

Keywords: estimated fetal weight; gestational diabetes; large-for-gestational age; LGA; ultrasound EN estimated fetal weight gestational diabetes large-for-gestational age LGA ultrasound 901 905 5 12/03/20 20201201 NES 201201 CONTRIBUTION B What are the novel findings of this work? Discussion In patients with LGA diagnosed during a second-trimester ultrasound examination at our institution, the incidence of GDM was 6.0% and the incidence of LGA at birth was 14.9%. In patients diagnosed with LGA at the time of the second-trimester ultrasound examination, those who developed GDM gained less weight compared with those who did not develop GDM, while those who delivered a LGA infant gained more weight compared with those who did not deliver a LGA infant. Our study substantiates and expands this existing body of literature by highlighting the important role of ultrasound alone in predicting neonatal LGA, as well as the development of GDM at an even earlier gestational age, by assessing the diagnosis of LGA during the second trimester. [Extracted from the article]

The study analyses the chemical composition of 57 glass samples from 40 beads discovered at 20 archaeological sites in Poland. The beads are dated to Hallstatt C–Early La Tène periods (c.800/750–260/250 bce). Analyses were carried out using laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). Two groups were distinguished among the glasses based on the MgO/K2O ratio: high‐magnesium glass (HMG), five samples; and low‐magnesium glass (LMG), 52 samples. The former were melted with halophyte plant ash, the second with mineral soda. These glasses were produced in the Eastern Mediterranean (more likely in Mesopotamia or Syro‐Palestine than in Egypt) and transported in the form of semi‐products to secondary glass workshops in Europe. Some of the white opaque glass was coloured and opacified in Europe. [ABSTRACT FROM AUTHOR]

Objectives: Development of novel antiretrovirals aims at reducing long‐term toxicities. Tenofovir disoproxil fumarate (TDF) has been associated with potential nephrotoxicity. The aim of our study was to assess the impact of switching from TDF to tenofovir alafenamide (TAF) on functional nephropathy and lipid parameters in a real‐life setting. Methods: We retrospectively analysed data from 347 HIV‐infected patients switching from a TDF‐ to a TAF‐containing regimen between April and December 2016. Sociodemographic, clinical and laboratory data were collected at TDF‐to‐TAF switch, and at 3 and 6 months thereafter. Proteinuria and albuminuria were classified according to Kidney Diseases Improving Global Outcomes (KDIGO) guidelines. Results: At time of switch, moderately and severely increased proteinuria was detected in 32% and 8% of patients, respectively; however, urine dipstick analysis was negative in 84% and 42%, respectively. Moderately and severely increased albuminuria was found in 17% and 3% of patients, respectively. In patients with a urinary protein‐to‐creatinine ratio (UPCR) ≥ 150 mg/g, the mean value declined from 416 mg/g at baseline to 272 mg/g (P < 0.001) and 242 mg/g (P < 0.001) after 3 and 6 months, respectively. Patients with an albumin‐to‐creatinine ratio (UACR) ≥ 30 mg/g showed no significant decrease of albuminuria. Mean total cholesterol increased from 187 mg/dL at baseline to 202 (P < 0.001) and 208 mg/dL (P < 0.001) at 3 and 6 months, respectively, and mean low‐density lipoprotein (LDL) cholesterol increased from 114 mg/dL at baseline to 124 (P < 0.001) and 128 mg/dL (P < 0.001), respectively. As mean high‐density lipoprotein (HDL) cholesterol increased from 50 mg/dL at baseline to 54 (P < 0.001) and 57 mg/dL (P < 0.001) at 3 and 6 months, respectively, the LDL:HDL ratio remained stable. Conclusions: In an aging HIV‐infected cohort, proteinuria and albuminuria were common findings and were underdiagnosed via urine dipstick. Our real‐life data suggest that laboratory markers of moderately/severely increased proteinuria improved after TDF‐to‐TAF‐switch. Lipid profiles were not aggravated. Long‐term follow‐up is needed to determine the clinical benefit of the TDF‐to‐TAF switch. [ABSTRACT FROM AUTHOR]

State‐of‐the‐art paleoclimate research strongly depends on the availability of time‐equivalent markers as chronological control to disentangle interrelationships in the climate system from regional to global scale. Geomagnetic reversals are regarded as excellent age constraints because they are global events and independent from climatic conditions. However, spatial variations of timing and internal dynamics of reversals may limit their precision. Our 1.2 Ma high‐resolution (~25 cm/kyr) sediment record from Lake Ohrid is promising to precisely depict the Matuyama‐Brunhes (MB) reversal and the Jaramillo subchron. Two generations of diagenetic ferrimagnetic minerals are present in glacial intervals of the Lake Ohrid record. Early diagenetic greigite acquired a quasi synsedimentary chemical magnetization, while a late diagenetic greigite formation, triggered by the upward diffusion of H2S‐rich waters, obscures the polarity record at the top of the Jaramillo. Interglacial intervals are unaffected by greigite formation, likely due to low iron concentrations. Based on an orbitally tuned age model with tephrostratigraphic markers, the base of Jaramillo can be precisely dated to 1072.4 ka, and the MB reversal to 778.5 ka. Both polarity reversals occurred very rapidly in our record, lasting 2.3 and 1 kyr, respectively. Our results reveal that the dipole component of the Earth's magnetic field fell below the nondipole components only for a short duration in the Mediterranean region. The comparison of the timing of the MB boundary across different archives implies that the onset of the reversal provides a more synchronous age marker compared to often used midpoint ages. Key Points: Two generations of diagenetic greigite occur in Lake Ohrid sediments but are constrained to glacial intervalsPaleomagnetic reversal processes took less than 1 kyr for the Matuyama‐Brunhes reversal and 2.3 kyr for the base of the Jaramillo subchronThe onset of the Matuyama‐Brunhes reversal is spatially more synchronous than its midpoint and should be used for stratigraphic correlation [ABSTRACT FROM AUTHOR]

Aims: Amyotrophic lateral sclerosis/motor neurone disease (ALS/MND) is characterized by the presence of inclusions containing TDP‐43 within motor neurones. In rare cases, ALS/MND may be associated with inclusions containing other proteins, such as fused in sarcoma (FUS), while motor system pathology may rarely be a feature of other neurodegenerative disorders. We here have investigated the association of FUS and tau pathology. Methods: We report a case with an ALS/MND‐plus clinical syndrome which pathologically demonstrated both FUS pathology and an atypical tauopathy. Results: Clinical motor involvement was predominantly present in the upper motor neurone, and was accompanied by extrapyramidal features and sensory involvement, but with only minimal cognitive impairment. The presentation was sporadic and gene mutation screening was negative. Post mortem study demonstrated inclusions positive for FUS, including basophilic inclusion bodies. This was associated with 4R‐tauopathy, largely as non‐fibrillary diffuse phospho‐tau in neurones, with granulovacuolar degeneration in a more restricted distribution. Double‐staining revealed that neurones contained both types of protein pathology. Conclusion: FUS‐positive basophilic inclusion body disease is a rare cause of ALS/MND, but in this case was associated with an unusual atypical tauopathy. The coexistence of two such rare neuropathologies raises the question of a pathogenic interaction. [ABSTRACT FROM AUTHOR]

This paper presents a detailed elemental analysis of 64 glass beads and pendants dated to the Meroitic period (first–third centuries ad) and the Nobadian period (fourth–sixth centuries) from burial sites in the Lower Nubian Nile Valley region. Laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) was used to determine the chemical composition of the glass and to gain knowledge about its origin. Four main glass types were identified: low‐alumina soda‐lime glass, high‐alumina glass, plant‐ash soda‐lime glass, and mixed‐alkali glass. Mineral soda‐lime glass (m‐Na‐Ca) of East Mediterranean/Egyptian provenance is dominant within the low‐alumina glass group from Meroitic and Nobadian periods. Mineral soda high‐alumina glass (m‐Na‐Al) appeared in the Nobadian bead assemblages, and the m‐Na‐Al 1 subtype was produced in Sri Lanka/South India. An initial insight into the origin of the glass beads in Nubia from the first to sixth centuries is described, indicating the first evidence for the presence of Asian objects in Nubia. The data obtained for the bead trade in North‐east Africa in this study has allowed a new light to be shed on the westward flow of Asian glass during a time of intensive maritime trade contacts with the wider Indian Ocean world. [ABSTRACT FROM AUTHOR]

As the knowledge of the predominant molecular structure of antioxidant and anticancer flavonoid rutin in solution is very important for understanding the mechanism of action, a quantum chemical investigation of plausible rutin structures including solvent effects is of relevance. In this work, DFT calculations were performed to find possible minimum energy structures for the rutin molecule. 1H NMR chemical shift DFT calculations were carried out in DMSO solution using the polarizable continuum model (PCM) to simulate the solvent effect. Analysis of the experimental and theoretical 1H NMR chemical shift profiles offers a powerful fingerprint criterion to determine the predominant molecular structure in solution. Therefore, our aim is to find the best match between experimental (in DMSO‐d) and theoretical (PCM–DMSO) 1H NMR spectrum profiles. Among 34 optimized structures located on the potential energy surface, we found that structure 32, with a B‐ring deviated 30° from a planar configuration (geometry usually assumed for polyphenols), showed an almost perfect agreement with experimental the 1H NMR pattern when compared to the corresponding fully optimized planar geometry. This structure is also predicted as the global minimum based on room‐temperature Gibbs free energy calculations in solution and, therefore, should be experimentally observed. This is new and valuable structural information regarding structure–activity relationship studies, and such information is hard to obtain by experimentalists without the aid of the X‐ray diffraction technique. Proving a point: A definitive proof, based on 1H NMR analysis, that the B and A–C rings of flavonoid rutin are not planar (as predicted by gas‐phase calculations) in DMSO solution. According to our structural analysis, the structure 32 (shown picture) should be predominantly observed in solution. [ABSTRACT FROM AUTHOR]

Epithelial to mesenchymal transition (EMT) is a developmental program reactivated by tumor cells that leads to the switch from epithelial to mesenchymal phenotype. During EMT, cells are transcriptionally regulated to decrease E‐cadherin expression while expressing mesenchymal markers such as vimentin, fibronectin, and N‐cadherin. Growing body of evidences suggest that cells engaged in EMT undergo a metabolic reprograming process, redirecting glucose flux toward hexosamine biosynthesis pathway (HBP), which fuels aberrant glycosylation patterns that are extensively observed in cancer cells. HBP depends on nutrient availability to produce its end product UDP‐GlcNAc, and for this reason is considered a metabolic sensor pathway. UDP‐GlcNAc is the substrate used for the synthesis of major types of glycosylation, including O‐GlcNAc and cell surface glycans. In general, the rate limiting enzyme of HBP, GFAT, is overexpressed in many cancer types that present EMT features as well as aberrant glycosylation. Moreover, altered levels of O‐GlcNAcylation can modulate cell morphology and favor EMT. In this review, we summarize some of the current knowledge that correlates glucose metabolism, aberrant glycosylation and hyper O‐GlcNAcylation supported by HBP that leads to EMT activation. Developmental Dynamics 247:481–491, 2018. © 2017 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

The objective of this study was to assess the safety and humoral response of outer surface protein A (OspA) Borrelia burgdorferi vaccine in equids via the transdermal or subcutaneous route over 355 days. Prior to vaccination, serological testing confirmed the vaccination and exposure status to B. burgdorferi. Vaccine was administered on Days 0, 22 and 226. Equids were examined for vaccine reactions at 24 h post-vaccination. Antibodies to outer surface proteins were quantified over 355 days. A total of 42 healthy adult equids of various ages and breeds were used. These equids were selected based on unlikely exposure to B. burgdorferi. The equids were grouped according to full size, miniature, age and sex to create two relatively heterogeneous mirrored groups of 20 equids. Group TD (20 equids) was administered 1 mL (1/2 mL/site) vaccine transdermally over the pectoral region. Group SQ (19 equids) was administered 2 mL in a single injection subcutaneously at the left cervical region. Group C (3 equids) was unvaccinated. Vaccine was administered on Days 0, 22 and 226. Antibodies to outer surface proteins were quantified over 355 days. Both vaccinated groups responded with a significant increase in OspA antibodies as compared with the control group (P<0.0001) and to themselves prevaccination. The mean response was greater in vaccinated equids (Group SQ, P<0.0080; Group TD, P<0.0016) as compared prevaccine and control. Equids responded to the OspA vaccine via either route. This data may aid in strategic vaccination protocols and the development of a USDA approved vaccine for equids in the prevention of Lyme disease using the OspA vaccine. [ABSTRACT FROM AUTHOR]

Reasons for performing study Clinically useful biomarkers are needed for early identification of endotoxaemic horses. Soluble CD14 (sCD14) is amplified early in response to inflammatory signals, including bacterial lipopolysaccharide (LPS), and may prove a useful biomarker for clinical endotoxaemia. Objectives The aim of this study was to determine if sCD14 could serve as a more reliable biomarker of the clinical signs of endotoxaemia, compared to measuring LPS alone. Study design Prospective observational study in horses at a veterinary teaching hospital. Methods Plasma samples were collected from 20 healthy horses and 35 horses presenting for emergency evaluation. Horses were classified as clinically endotoxaemic, using previously established criteria, if they had a heart rate >70 beats/min, packed cell volume >45% and/or a lesion likely to result in endotoxaemia. Soluble CD14 was measured using a cytometric bead-based assay and LPS was measured using a Limulus amoebocyte lysate (LAL) assay. Results Soluble CD14 was higher in horses classified as clinically endotoxaemic (median 1102 ng/ml, interquartile range 439 ng/ml), compared to clinically nonendotoxaemic (median 692 ng/ml, interquartile range 455 ng/ml, P = 0.03. There was no difference in LPS concentrations between clinically nonendotoxaemic (median 5.4 endotoxin units [EU]/ml, interquartile range 5 EU/ml) and endotoxaemic horses (median 7.2 EU/ml, interquartile range 17 EU/ml, P = 0.2). There was no correlation between sCD14 and LPS values in paired serum samples. LPS and sCD14 values were used to generate a receiver operating characteristic curve. The area under the curve for LPS and sCD14 was <0.7, suggesting that sCD14 and LPS were poor predictors of clinical endotoxaemia for the horses in this study. Conclusions Further investigation is warranted to assess the utility of sCD14 measurement as a clinically useful biomarker to identify endotoxaemia in horses. [ABSTRACT FROM AUTHOR]

The HLA-G molecule belongs to the family of nonclassical human leukocyte antigen ( HLA) class I. At variance to classical HLA class I, HLA-G displays (i) a low number of nucleotide variations within the coding region, (ii) a high structural diversity, (iii) a restricted peptide repertoire, (iv) a limited tissue distribution and (v) strong immune-suppressive properties. The physiological HLA-G surface expression is restricted to the maternal-fetal interface and to immune-privileged adult tissues. Soluble forms of HLA-G ( sHLA-G) are detectable in various body fluids. Cellular activation and pathological processes are associated with an aberrant or a neo-expression of HLA-G/ sHLA-G. Functionally, HLA-G and its secreted forms are considered to be key players in the induction of short- and long-term tolerance. Thus, its unique expression profile and tolerance-inducing functions render HLA-G/ sHLA-G an attractive biomarker to monitor the systemic health/disease status and disease activity/progression for clinical approaches in disease management and treatments. Here, we place emphasis on (i) the current status of the tolerance-inducing functions by HLA-G/ sHLA-G, (ii) the current complexity to implement this molecule as a meaningful clinical biomarker regarding the three dimensions of structural diversity (monomers, dimers and HLA-G-expressing extracellular vesicles) with its functional implications, and (iii) novel and future approaches to detect and quantify sHLA-G structures and functions. [ABSTRACT FROM AUTHOR]

Objectives While idiopathic pulmonary arterial hypertension ( PAH) is a rare disease, it is seen more frequently in patients with HIV infection. The aim of this study was to evaluate the prevalence of pulmonary hypertension ( PH) in patients with HIV infection by echocardiographic screening. Methods Echocardiography and N-terminal of the prohormone brain natriuretic peptide measurement were used to examine the prevalence of PH prospectively in HIV-positive patients ( n = 374) during routine follow-up visits for HIV disease. Results In echocardiographic screening, PH was detected in a total of 23 of 374 HIV-infected patients (6.1%). Of these, three patients (13%) presented with symptoms of dyspnoea and fatigue, and diagnosis of PAH was confirmed by right heart catheterization. Patients with systolic pulmonary artery pressure ( sPAP) > 30 mmHg were more likely to be female, to have a history of injecting drug use and to originate from high-prevalence countries ( HPCs). Conclusions Echocardiographic screening detected PH in a substantial proportion of HIV-positive patients. Female gender, a history of injecting drug use and HPC origin were associated with a higher prevalence of HIV-associated PH. The relevance and long-term outcome of these findings need to be validated in follow-up studies, which are ongoing. [ABSTRACT FROM AUTHOR]

The development of equine immunity from the fetus to adulthood is complex. The foal's immune response and the immune mechanisms that they are equipped with, along with changes over the first months of life until the immune system becomes adult-like, are only partially understood. While several innate immune responses seem to be fully functional from birth, the onset of adaptive immune response is delayed. For some adaptive immune parameters, such as immunoglobin (Ig)G1, IgG3, IgG5 and IgA antibodies, the immune response starts before or at birth and matures within 3 months of life. Other antibody responses, such as IgG4, IgG7 and IgE production, slowly develop within the first year of life until they reach adult levels. Similar differences have been observed for adaptive T cell responses. Interferon-gamma (IFN-γ) production by T helper 1 (Th1)-cells and cytotoxicT cells starts shortly after birth with low level production that gradually increases during the first year of life. In contrast, interleukin-4 (IL-4) produced by Th2-cells is almost undetectable in the first 3 months of life. These findings offer some explanation for the increased susceptibility of foals to certain pathogens such as Rhodococcus equi. The delay in Th-cell development and in particular Th2 immunity during the first months of life also provides an explanation for the reduced responsiveness of young horses to most traditional vaccines. In summary, all immune components of adult horses seem to exist in foals but the orchestrating and regulation of the immune response in immature horses is strikingly different. Young foals are fully competent and can perform certain immune responses but many mechanisms have yet to mature. Additional work is needed to improve our understanding of immunity and immune regulation in young horses, to identify the preferred immune pathways that they are using and ultimately provide new preventive strategies to protect against infectious disease. [ABSTRACT FROM AUTHOR]

Lake Ohrid, located on the Balkan Peninsula within the Dinaride- Albanide- Hellenide mountain belt, is a tectonically active graben within the South Balkan Extensional Regime ( SBER). Interpretation of multichannel seismic cross sections and bathymetric data reveals that Lake Ohrid formed during two main phases of deformation: (1) a transtensional phase which opened a pull-apart basin, and (2) an extensional phase which led to the present geometry of Lake Ohrid. After the initial opening, a symmetrical graben formed during the Late Miocene, bounded by major normal faults on each side in a pull-apart type basin. The early-stage geometry of the basin has a typical rhomboidal shape restricted by two sets of major normal faults. Thick undisturbed sediments are present today at the site where the acoustic basement is deepest, illustrating that Lake Ohrid is a potential target for drilling a long and continuous sediment core for studying environmental changes within the Mediterranean region. Neotectonic activity since the Pliocene takes place along the roughly N-S-striking Eastern and Western Major Boundary Normal Faults that are partly exposed at the present lake floor. The tectono-sedimentary structure of the basin is divided into three main seismic units overlying the acoustic basement associated with fluvial deposits and lacustrine sediments. A seismic facies analysis reveals a prominent cyclic pattern of high- and low-amplitude reflectors. We correlate this facies cyclicity with vegetation changes within the surrounding area that are associated with glacial/interglacial cycles. A clear correlation is possible back to ca. 450 kyrs. Extrapolation of average sedimentation rates for the above mentioned period results in age estimate of ca. 2 Myrs for the oldest sediments in Lake Ohrid. [ABSTRACT FROM AUTHOR]

We performed an experiment to study the role of anisotropy in interfacial energy during the coarsening of a complex oxide CaCu3Ti4O12 (CCTO) material system. When we altered the interface anisotropy, we observed that evolution and sizes of spherical grains completely altered to facetted cubes. When interface became anisotropic, crystal growth appears to occur by the surface attachment/detachment, the motion of ledges, and the nucleation of new layers. Our observations showed that new layers grew by screw dislocation mechanism. This suggests that nucleation limited coarsening is occurring by the development of a transient bimodal grain size distribution consisting of large growing grains with step. In presence of PbO we always observed the development of shaped nucleus which grew larger. Sometimes very complex shaped crystals grew as a metastable shape. These shapes became uniform as the growth progressed and size of grains became larger. This process produces smaller grains that act as a source of material for the growing less defective larger grains. [ABSTRACT FROM AUTHOR]

With the worldwide increase in diabetes prevalence there is a pressing unmet need for novel antidiabetic therapies. Insufficient insulin production due to impaired β-cell function and apoptotic reduction of β-cell mass is a common denominator in the pathogenesis of diabetes. Current treatments are directed at improving insulin sensitivity, and stimulating insulin secretion or replacing the hormone, but do not target progressive apoptotic β-cell loss. Here we review the current development of small-molecule inhibitors designed to rescue β-cells from apoptosis. Several distinct classes of small molecules have been identified that protect β-cells from inflammatory, oxidative and/or metabolically induced apoptosis. Although none of these have yet reached the clinic, β-cell protective small molecules alone or in combination with current therapies provide exciting opportunities for the development of novel treatments for diabetes. [ABSTRACT FROM AUTHOR]

Reasons for performing study Lyme disease is caused by Borrelia burgdorferi, which is transmitted by infected ticks ( Ixodes spp.). Reports on Lyme disease in horses have increased in recent years. Nevertheless, the diagnosis of Lyme disease in horses is still challenging owing to its vague clinical presentation and the limitations of diagnostic tests. Objectives This study used a new serological Lyme multiplex assay to examine antibody responses to 3 antigens of B. burgdorferi, outer surface protein ( Osp) C, OspF and C6, and to verify their use as markers for early and late infection stages in horses. Methods Multiplex analysis of antibodies to OspC, OspF and C6 in equine patient sera (n = 191) was performed. A subset of the sera (n = 90) was also tested using a commercial C6-based Lyme test. Results Antibodies to OspF and C6 highly correlate as reliable markers of infection with B. burgdorferi in horses. Antibodies to OspC, which have been confirmed as early infection markers in man and dogs, were only detected in some patient sera, suggesting that OspC antibodies are indicators of early infection in horses. Commercial C6 testing identified most infected horses but also resulted in false positive and false negative interpretations. Conclusions Serological multiplex testing is a rapid and quantitative diagnostic method to confirm infection with B. burgdorferi and to identify the stage of infection. In horses with risk of exposure and clinical signs, multiplex testing supports the diagnosis of Lyme disease. Potential relevance Antimicrobial treatment of B. burgdorferi is time sensitive. Treatment success decreases with time of persistent infection, while the risk of developing chronic disease increases. The ability to identify early infection with B. burgdorferi provides practitioners and clinicians with a tool to improve the diagnosis of equine Lyme disease and make treatment decisions. [ABSTRACT FROM AUTHOR]

Background Insect bite hypersensitivity ( IBH) is a recurrent allergic dermatitis of horses with similarities to human atopic eczema, caused by bites of insects of the genus Culicoides. Previous studies suggested a dysregulated T cell tolerance to Culicoides allergen in IBH-affected horses. Objective We have investigated whether the suppressive function of CD4+ CD25high cells is impaired in IBH-affected horses and possible ways to restore it. Methods CD4+ CD25− cells sorted from peripheral blood mononuclear cells (PBMC) were stimulated with irradiated autologous PBMC pulsed with Culicoides or tetanus toxoid as control antigen, in the presence of CD4+ CD25high cells. Furthermore, Culicoides-specific CD4+ CD25high regulatory cells were expanded or induced from CD4+ CD25− cells in vitro in the presence of a combination of rIL-2 and rTGF-β1 ( rIL-2/ rTGF-β1) or of retinoic acid and rapamycin (RetA/Rapa). Proliferation was determined by [3H] thymidine incorporation and cytokine production measured by flow cytometry. Results The ability of Culicoides- but not tetanus-stimulated CD4+ CD25high cells to suppress proliferation of CD4+ CD25− cells was significantly lower in IBH-affected horses (28%) than in healthy controls (86%). The decreased suppression in IBH-affected horses was associated with a significantly higher proportion of IL-4+ cells and a lower percentage of FoxP3+ IL-10+ compared to controls. Addition of rIL-2/ rTGF-β1 or of RetA/Rapa to Culicoides-stimulated CD4+ CD25high cells from IBH-affected horses significantly increased the proportion of FoxP3+ IL-10+ cells. We also found that RetA/Rapa induced a more significant decrease in the frequency of IL-4+ cells than rIL-2/ rTGF-β1. Moreover, the suppressive activity of Culicoides-stimulated CD4+ CD25high cells was significantly restored by both rIL-2/ rTGF-β1and RetA/Rapa, albeit in an antigen-unspecific manner. In contrast, in vitro induced Culicoides-specific CD4+ CD25high cells suppressed proliferation of CD4+ CD25− cells in an antigen-specific manner. Conclusion and Clinical Relevance The in vitro induction of functional allergen-specific Treg cells in IBH-affected horses suggests a potential therapeutic use of these cells in allergy. [ABSTRACT FROM AUTHOR]

Bariatric surgery is one of the most effective treatments for morbid obesity, and a large body of research indicates significant long-term weight loss. While overall mortality decreases in patients who received bariatric surgery, a number of studies have shown that suicide rates are higher in bariatric patients than in control groups. The objective of this study was to present a systematic review of suicide mortality after bariatric surgery and calculate an estimate for the suicide rate. Literature researches of the databases Pub Med, Web of Knowledge, Psych Info, Science Direct and Google Scholar were conducted. Thirty studies concerning bariatric surgery and completed suicides met the inclusion criteria. We included 28 studies in the estimation of a suicide rate for the bariatric population. Only one study ( Tindle et al.) put a main focus on suicide after bariatric surgery; this was therefore chosen as an adequate reference figure for comparison. The other 27 chosen studies were compared with World Health Organization data and the suicide rate reported by Tindle et al. Twenty-three thousand eight hundred eighty-five people were included in the analysis. In the literature, we found a total of 95 suicides when examining 190,000 person-years of post-bariatric surgery data. Little information was provided describing the reasons for suicide and the time-point of these events after surgery. We estimated a suicide rate of 4.1/10,000 person-years (95% confidence interval [3.2, 5.1]/10,000 person-years). A comparison with Tindle et al. demonstrates that their rate is significantly higher than our estimate ( P = 0.03). Bariatric surgery patients show higher suicide rates than the general population. Therefore, there is a great need to identify persons at risk and post-operative psychological monitoring is recommended. [ABSTRACT FROM AUTHOR]

This work describes the synthesis of inositol derivatives condensed with 2-mercaptobenzothiazole or 2-mercaptobenzimidazole, potential antimicrobial agents. These compounds were prepared by ring opening of epoxide intermediate (2 S,3 R-epoxy-1- O-methyl- l- chiro-inositol and 2 R,3 S-epoxy-1- O-methyl- l- chiro-inositol), which were obtained from l-quebrachitol (1- O-methyl- chiro-inositol). Microwave irradiation was used to promote the condensation reaction. [ABSTRACT FROM AUTHOR]

In this article, we conducted an extensive ab initio study on the importance of the level of theory and the basis set for theoretical predictions of the structure and reactivity of cisplatin [ cis-diamminedichloroplatinum(II) (cDDP)]. Initially, the role of the basis set for the Pt atom was assessed using 24 different basis sets, including three all-electron basis sets (ABS). In addition, a modified all-electron double zeta polarized basis set (mDZP) was proposed by adding a set of diffuse d functions onto the existing DZP basis set. The energy barrier and the rate constant for the first chloride/water exchange ligand process, namely, the aquation reaction, were taken as benchmarks for which reliable experimental data are available. At the B3LYP/mDZP/6-31+G(d) level (the first basis set is for Pt and the last set is for all of the light atoms), the energy barrier was 22.8 kcal mol−1, which is in agreement with the average experimental value, 22.9 ± 0.4 kcal mol−1. For the other accessible ABS (DZP and ADZP), the corresponding values were 15.4 and 24.5 kcal mol−1, respectively. The ADZP and mDZP are notably similar, raising the importance of diffuse d functions for the prediction of the kinetic properties of cDDP. In this article, we also analyze the ligand basis set and the level of theory effects by considering 36 basis sets at distinct levels of theory, namely, Hartree-Fock, MP2, and several DFT functionals. From a survey of the data, we recommend the mPW1PW91/mDZP/6-31+G(d) or B3PW91/mDZP/6-31+G(d) levels to describe the structure and reactivity of cDDP and its small derivatives. Conversely, for large molecules containing a cisplatin motif (for example, the cDDP-DNA complex), the lower levels B3LYP/LANL2DZ/6-31+G(d) and B3LYP/SBKJC-VDZ/6-31+G(d) are suggested. At these levels of theory, the predicted energy barrier was 26.0 and 25.9 kcal mol−1, respectively, which is only 13% higher than the actual value. © 2012 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Background Systemic inflammation in horses with heaves is poorly characterized. Objectives To assess acute phase proteins ( APP) and inflammatory cytokine profiles in serum of healthy horses and horses with heaves. Animals Six healthy horses and 6 heaves-affected horses belonging to the University of Montreal. Methods Prospective, observational study. Healthy and heaves-affected control horses were exposed to a 30-day natural challenge with hay and straw to induce clinical exacerbation of heaves. Serum samples were obtained by venipuncture before ( T0) as well as after 7 ( T7) and 30 days ( T30) of stabling. Serum APP (haptoglobin, serum amyloid A protein [ SAA] and C-reactive protein [ CRP]) and cytokines ( IL-2, IL-4, IFN-α, IL-10, IFN-γ, and CCL-2) were measured using singleplex or multiplex ELISA. Results Serum haptoglobin concentrations were significantly higher in heaves-affected horses at all time points with no overlap with those of healthy controls. They were also significantly increased by antigen challenge in both controls ( T7) and horses with heaves ( T7 and T30). Serum SAA was detected more frequently in heaves-affected horses compared with healthy controls at T7. There was no difference in serum concentrations of CRP, IL-10, IFN-γ, and CCL-2 between groups, whereas IL-2, IL-4, and IFN-α remained undetectable in all samples. Conclusions and Clinical Importance In heaves, haptoglobin is a marker of both acute and chronic systemic inflammation, whereas high concentrations of SAA indicate acute inflammation. [ABSTRACT FROM AUTHOR]

We report MP4(SDTQ) and CCSD(T) ab initio temperature-dependent conformational populations for a series of cycloalkanes with increasing ring size, cycloundecane (11-C), cyclododecane (12-C), and cyclotridecane (13-C), using extended basis sets. Our aim is to analyze the commonly used quantum chemical procedure for evaluating the thermal energy contribution to Gibbs free energy particularly the adequacy of standard harmonic oscillator vibrational partition function for large molecular systems. Experimental population data for cycloundecane, obtained from low temperature (90.1 K) 13C NMR, and cyclododecane, from gas phase electron diffraction experiment at 393.15 K, are available, and we found a good agreement with MP4(SDTQ) and CCSD(T) ab initio calculated conformational population. Our results indicate that the procedure of considering all 3N-6 vibrational modes as harmonic oscillators seems adequate for the prediction of the preferred conformer of cycloundecane, cyclododecane, and cyclotridecane, in the absence of a more appropriate approach to treat the low frequency modes that is applicable for large molecules. Therefore, it can be expected to work satisfactorily in room temperature conformational analysis studies on large molecules containing a great number of vibrational frequencies below 625 cm−1, such as in supramolecular chemistry, biological, and material science applications. © 2012 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]

Bariatric surgery is becoming more and more influential as efficient weight loss therapy for the morbidly obese. As many studies propose a relationship between sexual abuse and obesity in general, but especially with regard to weight regain after successful weight loss, sexual abuse might also have a crucial impact on the outcome of the surgical procedures. This review examines the literature comparing weight loss after bariatric surgery in sexually abused and non-abused individuals. We conducted a systematic electronic literature search covering PubMed/Medline, ScienceDirect, PsychInfo and Web of Science. While 13 studies examined prevalence rates of sexual abuse among bariatric patients, eight studies explicitly investigated the effect of sexual abuse on surgery outcome. We hypothesized that individuals with a history of sexual abuse lose less weight compared to individuals with no such abuse history. At first glance, only three out of eight studies demonstrated significantly reduced weight loss in the sexually abused patients. However, a closer investigation of all studies revealed that patients with abuse experiences may indeed tend to lose less weight initially. Still, this sub-population apparently benefits from the surgical procedure, as revealed by increased weight loss over time. Reasons for these mixed results are discussed, as well as the clinical implications that can be drawn from these studies. [ABSTRACT FROM AUTHOR]

Density functional theory (DFT) calculations of 1H NMR chemical shifts for l-quebrachitol isomers were performed using the B3LYP functional employing the 6-31G(d,p) and 6-311 + G(2d,p) basis sets. The effect of the solvent on the B3LYP-calculated NMR spectrum was accounted for using the polarizable continuum model. Comparison is made with experimental 1H NMR spectroscopic data, which shed light on the average uncertainty present in DFT calculations of chemical shifts and showed that the best match between experimental and theoretical B3LYP 1H NMR profiles is a good strategy to assign the molecular structure present in the sample handled in the experimental measurements. Among four plausible O-methyl-inositol isomers, the l-quebrachitol 2a structure was unambiguously assigned based only on the comparative analysis of experimental and theoretical 1H NMR chemical shift data. The B3LYP infrared (IR) spectrum was also calculated for the four isomers and compared with the experimental data, with analysis of the theoretical IR profiles corroborating assignment of the 2a structure. Therefore, it is confirmed in this study that a combined experimental/DFT spectroscopic investigation is a powerful tool in structural/conformational analysis studies. Copyright © 2012 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Eighty-one samples taken from 68 glass beads found in southwestern Poland on sites of the Lusatian culture from the Hallstatt C and Hallstatt D subphases were analysed by EPMA. A subsample of 18 of these were additionally subjected to analysis by means of LA-ICP-MS in order to validate the results obtained by EPMA. Some glass was made using mineral soda and some using plant ash rich in sodium. Both high-magnesium soda-lime glass (HMG) and low-magnesium soda-lime glass (LMG) were identified. A large number of samples are characterized by low MgO content and medium K2O content (LMMK glass), combined with low concentrations of CaO and high Fe2O3 and Al2O3. All the LMMK glass contains numerous silica crystals and inclusions composed of a number of elements (most frequently Cu, Co, Sb, As, Ag, Ni and Fe). The LMMK glass was presumably made in Europe during the Hallstatt C. [ABSTRACT FROM AUTHOR]

The interest in the study of oligomers has been motivated mainly because of their solubility in common solvents and also their capacity to be crystallized, which allowed for chemical processing leading to important applications in the area of material sciences. In this work, we carried out an investigation of polydiethynylsilane (PDES) decamers substituted with electron donor ( D) and acceptor ( A) groups, which is certainly of relevance, once PDES itself is known to display large third-order optical susceptibility. Therefore, density functional theory calculations of static first hyperpolarizability (β) were performed using various functionals with the 6-31G(d) basis set along with correlated MP2 calculation used as reference for comparison. The influence of A and D substituents on the magnitude of β was investigated by matching the acceptor (dicyanovinyl, nitrobenzene) and donor (propyl, propoxy, and phenylamine) groups attached at both ends of the oligomer. The largest β value was predicted for the derivative having the phenylamine and dicyanovinyl groups, which is around 30 times the relative value for the nonsubstituted decamer, what is a very impressive enhancement reported for the first time in the literature, strongly suggesting that disubstituted diethynylsilane decamers are potential building blocks for molecular-based materials with second-order nonlinear responses. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1410-1419, 2011 [ABSTRACT FROM AUTHOR]

Vanmierlo T, Popp J, Kölsch H, Friedrichs S, Jessen F, Stoffel-Wagner B, Bertsch T, Hartmann T, Maier W, von Bergmann K, Steinbusch H, Mulder M, Lütjohann D. The plant sterol brassicasterol as additional CSF biomarker in Alzheimer's disease. Objective: Plant sterols (sitosterol, campesterol, stigmasterol and brassicasterol) are solely dietary-derivable sterols that are structurally very similar to cholesterol. In contrast to peripheral cholesterol, plant sterols can cross the blood-brain barrier and accumulate within mammalian brain. As an impaired function of the cerebrospinal fluid (CSF)-blood barrier is linked to neurodegenerative disorders, i.e. Alzheimer's disease (AD), we investigated whether this results in altered plant sterol concentrations in CSF. Method: Applying gas chromatography/mass spectrometry analysis, plant sterol concentrations were measured in plasma and CSF of patients with AD ( n = 67) and controls ( n = 29). Age, gender, plasma-to-CSF albumin ratio, CSF Aβ42, CSF pTau, APOE4 genotype, and serum creatinine were applied as covariates in the statistical analysis for individual plant sterols in order to compare plasma and CSF plant sterol concentrations between patients with AD and controls. Results: Albumin quotient was a consistent predictor in CSF for cholesterol and methyl plant sterols campesterol and brassicasterol. Comparison of lipid parameters per diagnosis based on relevant predictors revealed significantly lower concentrations of brassicasterol ( P < 0.001) in CSF of patients with AD. Binary logistic regression analysis revealed that brassicasterol improved the predictive value when added to pTau and Aβ42 in a biomarker model. Conclusion: Brassicasterol might be a relevant additional biomarker in AD. [ABSTRACT FROM AUTHOR]

The inclusion compound formed between cross-linked α-cyclodextrin dimer and substituted oligothiophene, was investigated using density functional theory (DFT). Energy gap, spectroscopy (IR, UV-vis, 13C NMR, and 1H NMR) and first hyperpolarizability data were analyzed for the free species and inclusion compound, pp-PT@(αCD-αCD). The semiconducting property of the included pp-PT was not substantially affected on inclusion, with the energy gap increasing by only 10% after interaction with αCD-αCD. On the other hand, the nonlinear optical (NLO) response was significantly decreased, with the first hyperpolarizability, β, predicted to be just more than 60% lower for the [2]rotaxane than for free pp-PT, but still having considerable magnitude. This was explained by the two-state model based on the charge-transfer contribution to the electronic transitions. The sensitivity of electronic spectra might also be useful for the inclusion complex characterization. The IR spectrum was slightly sensitive to the host-guest interaction and the calculated 13C NMR and 1H NMR chemical shifts for the pp-PT guest showed appreciable variations of 5-10 and 1-1.5 ppm, respectively, and so can be used for the characterization of inclusion compounds. We concluded that the formation of inclusion complexes with CDs, seems indeed very promising and the use of encapsulating conducting material should be experimentally pursued. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 [ABSTRACT FROM AUTHOR]

In this work, we have applied Density Functional Theory calculations to investigate the electronic and spacial effects of different phosphorus ligands on the selectivity of the olefin (propene and styrene) insertion reaction into the RhH bond of the complexes HRh(P)(CO)(olefin), where the modified ligand P, is a phosphine ( = H, F, Et, Ph) or phosphite ( = OEt, OPh). M06/SBKJC/cc-pVDZ calculations revealed that the olefin coordination and insertion reaction are dominated by the electronic effects of the phosphorus ligands. A very good correlation between the Tolman electronic factor, χ, with the backdonated charges from the metallic center to the olefin and also with the interaction energy of the olefin with the four-coordinated HRh(CO)(P) catalyst was found. Using the propene as the substrate and for all the phosphorus ligands investigated, the insertion always proceeds through the reaction path leading to the linear metal-alkyl intermediate. However, when styrene is used, the branched metal-alkyl intermediate is always favored. The structural results obtained for the transition states do not support the existence of a π-allilic intermediates. The regioselectivity obtained for the insertion reaction of styrene results from thermodynamic aspects of the reaction in which the branched metal-alkyl intermediate is always favored by ∼5 kcal/mol. The M06/SBKJC/cc-pVDZ results are in good agreement with the experimental findings. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [ABSTRACT FROM AUTHOR]

The objective of this study was to evaluate herd characteristics and management practices associated with presence of Salmonella in the farm environment and in bulk tank milk (BTM) in US dairy herds. Herd management data, environmental culture, BTM and in-line milk filter polymerase chain reaction results for Salmonella from 260 US dairy herds surveyed during the National Animal Health Monitoring System Dairy 2007 study were analysed. Herd characteristics and management practices were screened by univariate analysis, and selected variables were used to construct a logistic regression model to identify factors associated with the presence of Salmonella in environmental samples. To identify factors associated with the occurrence of Salmonella in BTM and milk filters, a priori selected variables that were related to milking procedures were analysed univariately and a logistic regression model was constructed. The presence of Salmonella in the farm environment was associated with location of the operation in the East (OR = 4.8; CI: 1.9-11.6), not using a broadcast manure spreader (OR = 3.2; CI: 1.4-7.5), use of bovine somatotropin (BST) (OR = 2.7; CI: 1.5-5.0) and use of anionic salts (OR = 2.2; CI: 1.2-3.9). In the final multivariable model, herds with fewer than 100 cows were at decreased odds (OR = 0.3; CI: 0.1-0.7) of being culture positive for Salmonella as were herds with between 100 and 499 cows (OR = 0.4; CI: 0.2-0.8) compared with herds having 500 or more cows. The presence of culture-positive environmental samples and herd size were significantly associated with Salmonella BTM contamination. The herd-level factors identified in this study were in agreement with prior studies but also identified other potential factors that can be targeted in Salmonella control programmes. [ABSTRACT FROM AUTHOR]

DFT calculations were carried out to study the full catalytic cycle for the hydroformylation of propene, catalyzed by the heterobimetallic model catalyst trans-Pt(H)(PH3)2(SnCl3). Before the study of the full catalytic cycle, the performance of six pure GGA, one GGA with inclusion of dispersion corrections, four hybrid-GGA, and three meta-GGA exchange correlation functional to describe a model reaction promoted by Pt-Sn catalyst were assessed. It is shown that the BP86 and GPW91 functionals, using extended basis set, provides reliable energetic results when compared with the CCSD(T) calculations. All intermediates and transition states along the elementary steps of the entire catalytic cycle were located and the energies involved in the catalytic cycle calculated using BP86 functional. The solvent effects along the entire catalytic cycle were evaluated using the polarizable continuum model. In contrast with the rhodium catalysts, the regioselectivity of the hydroformylation is set at the carbonylation step. The hydrogenolysis is the rate determining step of the entire cycle, with the activation energy of ∼21 kcal mol-1 in agreement with the experimental value of ∼25 kcal mol-1. The trans effect of the SnCl3- ligand seems to be pronounced only in the first step of the catalytic cycle, facilitating the insertion of the olefin into the Pt&bond;H bond trans to it. The analysis of the stationary points obtained along each elementary step of the catalytic cycle is carried out separately and discussed. The BP86/cc-pVTZ/SBKJC results shows that the pathway leading to the linear aldehyde is preferred, being in agreement with the experimental findings. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 [ABSTRACT FROM AUTHOR]

Catechol oxidases (COs) are plant enzymes that belong to the oxidoreductases class. They contain a dinuclear copper center in their active site. In this article, we have investigated the dicopper(II) model complex [Cu2(μ-OH)(C21H33ON6)]2+ (Complex-A) under a computational perspective, using the DFT method, since this approach has been very useful in the treatment of bimetallic copper systems. The structural and spectroscopic study of Complex-A as well as the structural analysis of the BDNPP/Complex-A (Complex-B) adduct have been carried out. The calculated parameters for Complex-A are in good accordance with the experimental X-ray data. Some remarkable points can be observed from the calculated UV–vis relative excitations. The Complex-B computed structure verifies its identity as a key intermediate species in the BDNPP hydrolysis mechanism. The CuII···CuII calculated distance in Complex-B (3.026 Å) is shorter than the calculated for Complex-A (3.080 Å); one copper atom is bonded to the oxygen of phosphate [Cu (2)···O64–P] at 2.511 Å. These arguments clearly suggest a monodentate interaction and lead to a new mechanism involving terminal substrate coordination and subsequent intramolecular nucleophilic attack by a bridging hydroxide. Such a hypothesis is completely new in terms of homobimetallic copper systems, and may have important implications regarding the chemistry of several biological dinuclear catalytic sites. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [ABSTRACT FROM AUTHOR]

Density functional theory (DFT) calculations with different exchange-correlation functionals were performed for a mixed valence Fe(II)/Fe(III) binuclear complex with μ-methoxo and two μ-carboxylate bridging ligands, (1) with geometry optimizations being performed for all possible spin multiplicities (MS = 2, 4, 6, 8, and 10). Within the exchange-correlation functionals studied, only the hybrid GGA functionals B3P and B3LYP and also the pure GGA functional RPBE, predicts the geometry with high spin (S = 9/2) to be more stable than the geometry with low spin state (S = 1/2) by 20 kcal/mol, in agreement with the experimental findings. These functionals also predict the same stability order for the different spin states, being MS = 10>8>6>2>4. The meta-GGA functionals TPSS and TPSSh and also the pure GGA functionals BLYP and BP86 predict different stability orders. The computed average EPR g-tensor, gav, of 2.03, at the B3LYP level, is in good agreement with the experimental findings. Heisenberg exchange coupling constants, J, were calculated within the broken-symmetry formalism, at the B3LYP level, showing that the two iron centers are antiferromagnetic coupling, with a very weak coupling constant of about -7 cm-1, in good agreement with the experimental value. Additionally, the effect of using different multiplicities of the reference geometries on the computed J value is discussed. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [ABSTRACT FROM AUTHOR]

The United States Department of Agriculture (USDA) initiated the National Animal Health Monitoring System (NAHMS) in 1983 to collect, analyse and disseminate data on animal health, management and productivity in US domestic livestock populations, including swine. The programme includes an on-farm serological sampling component which can be used to monitor seroprevalence of various pathogens, including Toxoplasma gondii. The purpose of this study was to determine the seroprevalence of T. gondii in grower/finisher pigs using sera collected during NAHMS Swine 2006 and to determine farm level factors associated with differences in seroprevalence on farms where sera was collected during the Swine 2006 survey. Sera and data on management practices for this study were collected from 185 grower/finisher swine production sites located in 16 states accounting for >90% of US swine production (Arkansas, Colorado, Iowa, Illinois, Indiana, Kansas, Michigan, Minnesota, Missouri, Nebraska, North Carolina, Ohio, Pennsylvania, South Dakota, Texas and Wisconsin). A total of 6238 sera were tested for T. gondii antibodies using a commercial ELISA assay ( Vet. Parasitol. 128, 2005, 177). Seroprevalence in this study, as determined by ELISA, was 2.6%, with a herd prevalence of 21.6% and a mean within-herd prevalence of 2.7%. Analysis of swine management practices indicated that rodent control methods and carcass disposal methods were associated with differences in the number of T. gondii positive samples on farm. These results are consistent with current epidemiological knowledge of the transmission of Toxoplasma on the farm (ingestion of organic matter containing oocysts, or ingestion of infected animal tissues). Production practices which eliminate these sources of exposure can reduce the risk of Toxoplasma infection in pigs, and reduce the likelihood of human infection from consumption of infected pork. [ABSTRACT FROM AUTHOR]

In this work we attempt to elucidate the chronological and geographical origin of deeply coloured and black glass dating between 100bc andad 300 on the basis of their major and trace element compositions. Samples from the western and eastern parts of the Roman Empire were analysed. Analytical data were obtained by means of a scanning electron microscope – energy-dispersive system (SEM–EDS, 63 samples analysed) and laser ablation – inductively coupled plasma – mass spectrometry (LA–ICP–MS, 41 samples analysed). Among the glass fragments analysed, dark brown, dark purple and dark green hues could be distinguished. Only among the dark green fragments could a clear compositional distinction be observed between fragments dated to the periods before and afterad 150. In the early samples (first centurybc to first centuryad), iron, responsible for the green hue, was introduced by using impure sand containing relatively high amounts of Ti. In contrast, a Ti-poor source of iron was employed, containing Sb, Co and Pb in trace quantities, in order to obtain the dark green colour in the later glass samples. The analytical results obtained by combining SEM–EDS and LA–ICP–MS are therefore consistent with a differentiation of glassmaking recipes, detectable in glass composition, occurring in the period aroundad 150. [ABSTRACT FROM AUTHOR]

The objective of the study was to screen a large number of herd management practices and herd characteristics from US dairies to identify herd-level risk factors associated with the presence of Listeria monocytogenes in bulk tank milk (BTM). A total of 71 variables was univariately evaluated for their association with the presence of L. monocytogenes in BTM. Results from the univariate analysis indicated that using automatic take offs and having an open herd management increased the risk of BTM contamination with L. monocytogenes, while storing manure in outside pens not accessible to cattle decreased the risk. These variables, however, were not sustained in the multivariable model, which indicated that the presence of L. monocytogenes in BTM was significantly associated with region of the country (farms in the southeast and northeast were six and four times more likely respectively, to have BTM contamination than farms in the west) and number of milking cows (herds with >500 milking cows were five times more likely to have BTM contamination than herds with <100 milking cows). In conclusion, our results suggest that risk factors associated with BTM contamination are different depending on the geographical region and herd size of the operation. [ABSTRACT FROM AUTHOR]

Background: Equine protozoal myeloencephalitis (EPM) is a serious and often fatal neurologic disease of horses, but few studies have investigated risk factors. Objectives: To evaluate operation- and individual-level factors associated with likelihood of the occurrence of EPM. Animals: Data were collected as part of a study of the US equine industry from 1,178 operations representing 83.9% of horses and 51.6% of operations with ≥3 horses in 28 states. Methods: Probability-based sampling was used to enroll representative operations in a cross-sectional study. Interviews were conducted to collect information regarding health and management of horses. A nested case-control study was used to investigate risk factors among individual horses. Interview data were combined with climate data, human population density, and opossum regional ecology categories. Data were analyzed using logistic regression to identify risk factors for the occurrence of EPM. Results: Owners reported that 95% of EPM cases included in this study were diagnosed by veterinarians. Variables associated with EPM occurrence on premises included opossum regional ecology, reported exposure to small wildlife, climate, terrain, housing, choice of bedding material, method of storing feeds, equine stocking density, and primary use of horses. Among individual horses, age was most strongly associated with disease risk. Associations also were identified with sex, breed, primary use, and participation in competitions. Conclusions and Clinical Importance: Because the risk of EPM occurrence on operations is closely tied to factors that impact exposure to opossums, their feces, and their environment, controlling these exposures may be important in preventing the occurrence of EPM. [ABSTRACT FROM AUTHOR]

Recent evidence suggests that alloantibody may play an aetiological role in the pathogenesis of membranous glomerulopathy in native kidneys. There is an increased awareness of the significance of alloantibody on renal transplant outcome, particularly with the development of more sensitive assays. We describe a kidney transplant patient who developed de novo membranous glomerulopathy (DNMG) with heavy proteinuria in the context of a donor-specific alloantibody (DSA) directed against HLA DQ7. Proteinuria resolved and kidney function stabilized following treatment with mycophenolate mofetil and an angiotensin receptor blocker. The titre of the DSA fell in parallel with resolution of the proteinuria. This is the first reported case of DNMG after kidney transplantation clearly associated with a DSA. We hypothesize that de novo membranous glomerulopathy may be an atypical manifestation of acute antibody-mediated damage. Cases of DNMG should be screened for alloantibody and the presence of alloantibody may influence the choice of therapy. [ABSTRACT FROM AUTHOR]

Quantum chemical methods were used for the theoretical determination of the conformational population for the relevant conformers of cyclononane, i.e., TBC, TCB, TCC, and M4 (or C1), which have been previously investigated experimentally through detailed examination of the nuclear magnetic resonance (NMR) spectrum. Our best Gibbs free energy result, evaluated with MP4(SDTQ)/6-31G(d,p)//MP2/6-31G(d,p) energy differences and MP2/6-31G(d,p) thermal corrections, lead to a temperature-dependent population in excellent agreement with the experimental results based on the analysis of the low temperature 13C NMR spectrum. The nice agreement with experiment is achieved using MP2 harmonic frequencies for the evaluation of vibration partition functions within the standard statistic thermodynamics formalism. Theoretical temperature-dependent infrared (IR) and 13C NMR spectra were simulated and compared with experimental data, which confirmed the ab initio conformational population reported here. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [ABSTRACT FROM AUTHOR]

The distribution of infectious salmon anaemia (ISA) was examined among 80 cages from three Atlantic salmon grow-out farms in Maine, USA that were stocked with smolts from a single hatchery. Cage-level disease was broadly defined as one or more moribund fish testing positive for infectious salmon anaemia virus (ISAV) by RT-PCR and a second confirmatory test (IFAT, culture or genotype sequence). Spatio-temporal and cage-level risks were explored using logistic regression and survival analysis. Non-spatial risk factors associated with ISA, or shortened survival time to disease, included increased predation, trucking company choice for smolt transfers, a finely-sedimented benthic substrate, and smaller average size of smolts at stocking. Univariable analysis identified the time-dependent spatial factor ‘adjacency to newly infected cages’ to be predictive of new infection in neighbouring cages 11–12 weeks later. However, none of the spatial factors, or their lags retained relevance in multiple-variable models. The results suggest a diffuse distribution of virus exposure throughout infected sites, with host-susceptibility factors probably influencing disease manifestation in individual cages. The narrow focus of the current study may limit application of the findings to other sites and year-classes. However, these data support the relevance of husbandry efforts to optimize fish health in regions affected by ISAV. [ABSTRACT FROM AUTHOR]

A relationship between haemophilia and osteoporosis has been suggested, leading to the initiative for a larger study assessing this issue. Bone mineral density (BMD) was measured by osteodensitometry using dual energy X-ray absorptiometry (DEXA) in 62 male patients with severe haemophilia A; mean age 41 ± 13.1 years, mean body mass index (BMI) 23.5 ± 3.6 kg m−2. Using the clinical score suggested by the World Federation of Hemophilia, all patients were assessed to determine the severity of their arthropathy. A reduced BMD defined as osteopenia and osteoporosis by World Health Organization criteria was detected in 27/62 (43.5%) and 16/62 (25.8%) patients, respectively. Fifty-five of sixty-two (88.7%) patients suffered from haemophilic arthropathy. An increased number of affected joints and/or an increased severity were associated with lower BMD in the neck of femur. Pronounced muscle atrophy and loss of joint movement were also associated with low BMD. Furthermore, hepatitis C, low BMI and age were found to be additional risk factors for reduced BMD in the haemophiliac. Our data shows that in haemophilic patients osteoporosis represents a frequent concomitant observation. The main cause for reduced bone mass in the haemophiliac is most probably the haemophilic arthropathy being typically associated with chronic pain and loss of joint function subsequently leading to inactivity. Further studies including control groups are necessary to elucidate the impact of comorbidities such as hepatitis C or HIV on the development of osteoporosis in the haemophiliac. [ABSTRACT FROM AUTHOR]

The interaction of cisplatin with guanine DNA bases has been investigated using ab initio Hartree–Fock (HF) and density functional levels of theory in gas phase and aqueous solution. The overall process was divided into three steps: the reaction of the monoaqua [Pt(NH3)2Cl(H2O)]+ species with guanine (G) (reaction 1), the hydrolysis process yielding the adduct [Pt(NH3)2(G) (H2O)]2+ (reaction 2) and the reaction with a second guanine leading to the product [Pt(NH3)2(G)2]2+ (reaction 3). The functionals B3LYP, BHandH, and mPW1PW91 were used in the present study, to develop an understanding of the role of the distinct models. The geometries presented for the intermediate structures were obtained by IRC calculations from the transition state structure for each reaction. The structural analysis for the intermediates and transition states showed that hydrogen bonds with the guanine O6 atom play an important role in stabilizing these species. The geometries were not very sensitive to the level of theory applied with the HF level, giving a satisfactory overall performance. However, the energy barriers and the rate constants were found to be strongly dependent on the level of calculation and basis set, with the DFT calculations giving more accurate results. For reaction 1 the rate constant calculated in aqueous solution at PCM‐BHandH/6‐311G* (k1 = 7.55 × 10−1 M−1 s−1) was in good agreement with the experiment (5.4 × 10−1 M−1 s−1). The BHandH/6‐31G* calculated gas phase rate constants for reactions 2 and 3 were: k2 = 0.9 × 10−6 M−1 s−1 and k3 = 2.99 × 10−4 M−1 s−1 in fairly good accordance with the experimental findings for reaction 2 (1.0 × 10−6 M−1 s−1) and reaction 3 (3.0 × 10−4 M−1 s−1). © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [ABSTRACT FROM AUTHOR]