Neural correlates of affective empathy and reinforcement learning in boys with conduct problems: fMRI evidence from a gambling task.

PubMed

Schwenck, Christina; Ciaramidaro, Angela; Selivanova, Marina; Tournay, Jennifer; Freitag, Christine M; Siniatchkin, Michael

2017-03-01

Conduct problems (CP) comprise abnormal behaviors associated with aberrant aspects of affective empathy as well as learning. However, behavioral measures for affective empathy are challenging, and previous results concerning learning in patients with CP are inconsistent. Nineteen boys with CP and 24 typically developing (TD) boys aged 11-17 years (M=14.34, SD=1.93) participated in the study. An ultimatum-game was applied in order to elicit the feeling of like or dislike towards the opponent for a subsequent gambling task, which was played by the opponents (OTHER-condition) and by the participants themselves (SELF-condition). Functional MRI data were recorded throughout the experiment. In accordance with the model of insensitivity to punishment, hypo-activation of the left amygdala, left anterior insula, ventral medial prefrontal cortex (MPFC), and bilateral temporo-parietal junction (TPJ) was observed as a response to losing in participants with CP during the SELF-condition. Callous-unemotional (CU)-traits correlated negatively with activation of amygdala and right TPJ. During the OTHER-condition, TD participants showed activation in brain areas associated with theory of mind (right TPJ, left IFG), and affect regulation (right DLPFC) rather than areas associated with affective empathy. This pattern was not found in adolescents with CP. Moreover, and independently of individual characteristics of their opponents, adolescents with CP demonstrated reward-associated activation (ventral striatum) observing others win, which was positively correlated with CU-traits. This may be interpreted in line with the theory of reward dominance. The current study provides support for the theory of abnormal learning processing in adolescents with CP which yields implications for further research as well as clinical practice. The gambling task did not activate affective empathy networks, but was specific for cognitive empathy, inhibition, and affect regulation. Copyright © 2016 Elsevier B.V. All rights reserved.

Perceptions of Barriers and Facilitators During Implementation of a Complex Model of Group Prenatal Care in Six Urban Sites

PubMed Central

Novick, Gina; Womack, Julie A.; Lewis, Jessica; Stasko, Emily C.; Rising, Sharon S.; Sadler, Lois S.; Cunningham, Shayna C.; Tobin, Jonathan N.; Ickovics, Jeannette R.

2016-01-01

Group prenatal care improves perinatal outcomes, but implementing this complex model places substantial demands on settings designed for individual care. To describe perceived barriers and facilitators to implementing and sustaining Centering Pregnancy Plus (CP+) group prenatal care, 24 in-depth interviews were conducted with 22 clinicians, staff, administrators, and study personnel in six of the 14 sites of a randomized trial of the model. All sites served low-income, minority women. Sites for the present evaluation were selected for variation in location, study arm, and initial implementation response. Implementing CP+ was challenging in all sites, requiring substantial adaptations of clinical systems. All sites had barriers to meeting the model’s demands, but how sites responded to these barriers affected whether implementation thrived or struggled. Thriving sites had organizational cultures that supported innovation, champions who advocated for CP+, and staff who viewed logistical demands as manageable hurdles. Struggling sites had bureaucratic organizational structures and lacked buy-in and financial resources, and staff were overwhelmed by the model’s challenges. Findings suggested that implementing and sustaining health care innovation requires new practices and different ways of thinking, and health systems may not fully recognize the magnitude of change required. Consequently, evidence-based practices are modified or discontinued, and outcomes may differ from those in the original controlled studies. Before implementing new models of care, clinical settings should anticipate model demands and assess capacity for adapting to the disruptions of innovation. PMID:26340483

The impact of a simplified documentation method for the Edmonton classification system for cancer pain (ECS-CP) on clinician utilization.

PubMed

Tanco, Kimberson; Arthur, Joseph; Haider, Ali; Stephen, Saneese; Yennu, Sriram; Liu, Diane; Bruera, Eduardo

2017-02-01

The use of standardized pain classification systems such as the ECS-CP can assist in the assessment and management of cancer pain. However, its completion has been limited due to its perceived complexity of decoding each feature. The objectives of this study were to determine the rate of clinician documentation and completion of the ECS-CP features after revision and simplification of the response for each feature. Electronic records of consecutive patient visits at the outpatient supportive care center seen by 12 palliative medicine specialists were collected at 6 months before (pre-interventional period), 6 and 24 months after (post-interventional period) the implementation of the simplified ECS-CP tool. Rate of ECS-CP documentation, completion, and analysis of patient and physician predictors were completed. One thousand and twelve patients' documentation was analyzed: 343 patients, before; 341 patients, 6 months after, and 328 patients, 24 months after the intervention. ≥2/5 items were completed before the intervention, 6 months after the intervention and 24 months after intervention in 0/343 (0 %), 136/341 (40 %), and 238/328 (73 %), respectively (p < 0.001). 5/5 items were completed before the intervention, 6 months after the intervention and 24 months after intervention in 0/343 (0 %), 131/341 (38 %), and 222/328 (68 %), respectively, (p < 0.001). There were no patient or physician predictors found significant for successful documentation of ECS-CP. Our findings suggest that significant simplification and intensive education is necessary for successful adoption of a scoring system. More research is needed in order to identify how to adopt tools for daily clinical practice in palliative care.

RAP2.4a Is Transported through the Phloem to Regulate Cold and Heat Tolerance in Papaya Tree (Carica papaya cv. Maradol): Implications for Protection Against Abiotic Stress.

PubMed

Figueroa-Yañez, Luis; Pereira-Santana, Alejandro; Arroyo-Herrera, Ana; Rodriguez-Corona, Ulises; Sanchez-Teyer, Felipe; Espadas-Alcocer, Jorge; Espadas-Gil, Francisco; Barredo-Pool, Felipe; Castaño, Enrique; Rodriguez-Zapata, Luis Carlos

2016-01-01

Plants respond to stress through metabolic and morphological changes that increase their ability to survive and grow. To this end, several transcription factor families are responsible for transmitting the signals that are required for these changes. Here, we studied the transcription factor superfamily AP2/ERF, particularly, RAP2.4 from Carica papaya cv. Maradol. We isolated four genes (CpRap2.4a, CpRAap2.4b, CpRap2.1 and CpRap2.10), and an in silico analysis showed that the four genes encode proteins that contain a conserved APETALA2 (AP2) domain located within group I and II transcription factors of the AP2/ERF superfamily. Semiquantitative PCR experiments indicated that each CpRap2 gene is differentially expressed under stress conditions, such as extreme temperatures. Moreover, genetic transformants of tobacco plants overexpressing CpRap2.4a and CpRap2.4b genes show a high level of tolerance to cold and heat stress compared to non-transformed plants. Confocal microscopy analysis of tobacco transgenic plants showed that CpRAP2.4a and CpRAP2.4b proteins were mainly localized to the nuclei of cells from the leaves and roots and also in the sieve elements. Moreover, the movement of CpRap2.4a RNA in tobacco grafting was analyzed. Our results indicate that CpRap2.4a and CpRap2.4b RNA in the papaya tree have a functional role in the response to stress conditions such as exposure to extreme temperatures via direct translation outside the parental RNA cell.

RAP2.4a Is Transported through the Phloem to Regulate Cold and Heat Tolerance in Papaya Tree (Carica papaya cv. Maradol): Implications for Protection Against Abiotic Stress

PubMed Central

Arroyo-Herrera, Ana; Rodriguez-Corona, Ulises; Sanchez-Teyer, Felipe; Espadas-Alcocer, Jorge; Espadas-Gil, Francisco; Barredo-Pool, Felipe; Castaño, Enrique; Rodriguez-Zapata, Luis Carlos

2016-01-01

Plants respond to stress through metabolic and morphological changes that increase their ability to survive and grow. To this end, several transcription factor families are responsible for transmitting the signals that are required for these changes. Here, we studied the transcription factor superfamily AP2/ERF, particularly, RAP2.4 from Carica papaya cv. Maradol. We isolated four genes (CpRap2.4a, CpRAap2.4b, CpRap2.1 and CpRap2.10), and an in silico analysis showed that the four genes encode proteins that contain a conserved APETALA2 (AP2) domain located within group I and II transcription factors of the AP2/ERF superfamily. Semiquantitative PCR experiments indicated that each CpRap2 gene is differentially expressed under stress conditions, such as extreme temperatures. Moreover, genetic transformants of tobacco plants overexpressing CpRap2.4a and CpRap2.4b genes show a high level of tolerance to cold and heat stress compared to non-transformed plants. Confocal microscopy analysis of tobacco transgenic plants showed that CpRAP2.4a and CpRAP2.4b proteins were mainly localized to the nuclei of cells from the leaves and roots and also in the sieve elements. Moreover, the movement of CpRap2.4a RNA in tobacco grafting was analyzed. Our results indicate that CpRap2.4a and CpRap2.4b RNA in the papaya tree have a functional role in the response to stress conditions such as exposure to extreme temperatures via direct translation outside the parental RNA cell. PMID:27764197

Influence of Cofermentation by Amylolytic Lactobacillus plantarum and Lactococcus lactis Strains on the Fermentation Process and Rheology of Sorghum Porridge

PubMed Central

Byaruhanga, Yusuf B.; Muyanja, Charles M. B. K.; Aijuka, Matthew; Schüller, Reidar B.; Sahlstrøm, Stefan; Langsrud, Thor; Narvhus, Judith A.

2012-01-01

Amylolytic lactic acid bacteria (ALAB) can potentially replace malt in reducing the viscosity of starchy porridges. However, the drawback of using ALAB is their low and delayed amylolytic activity. This necessitates searching for efficient ALAB and strategies to improve their amylolytic activity. Two ALAB, Lactobacillus plantarum MNC 21 and Lactococcus lactis MNC 24, isolated from Obushera, were used to ferment starches in MRS broth: sorghum, millet, sweet potato, and commercial soluble starch. The amylolytic activity of MNC 21 was comparable to that of the ALAB collection strain Lb. plantarum A6, while that of MNC 24 was extremely low. MNC 21, MNC 24, and their coculture were compared to A6 and sorghum malt for ability to ferment and reduce the viscosity of sorghum porridge (11.6% dry matter). ALAB and the coculture lowered the pH from 6.2 to <4.5 within 12 h, while malt as a carrier of wild starter took about 20 h. Coculturing increased lactic acid yield by 46% and 76.8% compared to the yields of MNC 21 and MNC 24 monocultures, respectively. The coculture accumulated significantly larger (P < 0.05) amounts of maltose and diacetyl than the monocultures. Sorghum malt control and the coculture hydrolyzed more starch in sorghum porridge than the monocultures. The coculture initiated changes in the rheological parameters storage modulus (G′), loss modulus (G″), phase angle (δ), and complex viscosity (η*) earlier than its constituent monocultures. The shear viscosity of sorghum porridge was reduced significantly (P < 0.05) from 1950 cP to 110 cP (malt), 281 cP (coculture), 382 cP (MNC 21), 713 cP (MNC 24), and 722 cP (A6). Coculturing strong ALAB with weak ALAB or non-ALAB can be exploited for preparation of nutrient-dense weaning foods and increasing lactic acid yield from starchy materials. PMID:22610432

Influence of cofermentation by amylolytic Lactobacillus plantarum and Lactococcus lactis strains on the fermentation process and rheology of sorghum porridge.

PubMed

Mukisa, Ivan M; Byaruhanga, Yusuf B; Muyanja, Charles M B K; Aijuka, Matthew; Schüller, Reidar B; Sahlstrøm, Stefan; Langsrud, Thor; Narvhus, Judith A

2012-08-01

Amylolytic lactic acid bacteria (ALAB) can potentially replace malt in reducing the viscosity of starchy porridges. However, the drawback of using ALAB is their low and delayed amylolytic activity. This necessitates searching for efficient ALAB and strategies to improve their amylolytic activity. Two ALAB, Lactobacillus plantarum MNC 21 and Lactococcus lactis MNC 24, isolated from Obushera, were used to ferment starches in MRS broth: sorghum, millet, sweet potato, and commercial soluble starch. The amylolytic activity of MNC 21 was comparable to that of the ALAB collection strain Lb. plantarum A6, while that of MNC 24 was extremely low. MNC 21, MNC 24, and their coculture were compared to A6 and sorghum malt for ability to ferment and reduce the viscosity of sorghum porridge (11.6% dry matter). ALAB and the coculture lowered the pH from 6.2 to <4.5 within 12 h, while malt as a carrier of wild starter took about 20 h. Coculturing increased lactic acid yield by 46% and 76.8% compared to the yields of MNC 21 and MNC 24 monocultures, respectively. The coculture accumulated significantly larger (P < 0.05) amounts of maltose and diacetyl than the monocultures. Sorghum malt control and the coculture hydrolyzed more starch in sorghum porridge than the monocultures. The coculture initiated changes in the rheological parameters storage modulus (G'), loss modulus (G″), phase angle (δ), and complex viscosity (η*) earlier than its constituent monocultures. The shear viscosity of sorghum porridge was reduced significantly (P < 0.05) from 1950 cP to 110 cP (malt), 281 cP (coculture), 382 cP (MNC 21), 713 cP (MNC 24), and 722 cP (A6). Coculturing strong ALAB with weak ALAB or non-ALAB can be exploited for preparation of nutrient-dense weaning foods and increasing lactic acid yield from starchy materials.

A mutation-led search for novel functional domains in MeCP2.

PubMed

Guy, Jacky; Alexander-Howden, Beatrice; FitzPatrick, Laura; DeSousa, Dina; Koerner, Martha V; Selfridge, Jim; Bird, Adrian

2018-04-27

Most missense mutations causing Rett syndrome affect domains of MeCP2 that have been shown to either bind methylated DNA or interact with a transcriptional co-repressor complex. Several mutations, however, including the C-terminal truncations that account for ∼10% of cases, fall outside these characterised domains. We studied the molecular consequences of four of these "non-canonical" mutations in cultured neurons and mice to see if they reveal additional essential domains without affecting known properties of MeCP2. The results show that the mutations partially or strongly deplete the protein and also in some cases interfere with co-repressor recruitment. These mutations therefore impact the activity of known functional domains and do not invoke new molecular causes of Rett syndrome. The finding that a stable C-terminal truncation does not compromise MeCP2 function raises the possibility that small molecules which stabilise these mutant proteins may be of therapeutic value.

Assessment of neurotoxic effects of tri-cresyl phosphates (TCPs) and cresyl saligenin phosphate (CBDP) using a combination of in vitro techniques.

PubMed

Hausherr, Vanessa; Schöbel, Nicole; Liebing, Julia; van Thriel, Christoph

2017-03-01

Environmental exposures to tri-cresyl phosphates (TCPs) and the possible formation of toxic metabolites (e.g. cresyl saligenin phosphate; CBDP) may cause a variety of neurotoxic effects in humans. As reported for other organophosphorus compounds (OPs), the inhibition of acetylcholine esterase (AChE) has also been proposed as the underlying mechanism for TCP neurotoxicity. The ortho-isomer, ToCP and its metabolite CBDP are also known to affect neuropathy target esterase (NTE) leading to organophosphate-induced delayed neuropathy (OPIDN). Recently, in vitro testing has led to the identification of other molecular targets and alternative mechanisms of ToCP toxicity. The metabolite CBDP and other isomers, as well as commercial mixtures have not been tested for such additional modes of actions. Accordingly, the present study investigates alterations of neurobiological correlates of central nervous processes using different in vitro techniques. The three symmetric TCP isomers - ToCP, TpCP, and TmCP - that contain a methyl group at the ortho-, para-, or meta-position of the aromatic ring system, respectively, together with a commercial TCP mixture, and CBDP were all tested using concentrations not exceeding their cytotoxic concentrations. Isolated cortical neurons were kept in culture for 6days followed by 24h incubation with different concentrations of the test compounds. Thus, all endpoints were assessed after 7days in vitro (DIV 7), at which time cell viability, neurite microstructure, and the function of glutamate receptors and voltage-gated calcium cannels (VGCC) were measured. While the cytotoxic potential of the TCP isomers and their mixture were comparable (IC 50 ≥80μM), CBDP was more cytotoxic (IC 50 : 15μM) to primary cortical neurons. In contrast, CBDP (up to 10μM) did not compromise the microstructure of neurites. Ten μM of ToCP significantly reduced the size and complexity of neurite networks, but neither TmCP and TpCP nor the mixture affected this second endpoint of neurotoxicity assessment. TCPs and their mixture significantly reduced the Ca 2+ influx in response to glutamate and KCl stimulation in concentrations of 10μM. Only ToCP showed a specific effect on glutamate receptors with 100nM reducing the evoked Ca 2+ influx. The effects of CBDP on the provoked Ca 2+ influx were much weaker than those observed for TCPs. These results confirmed that ToCP has a unique mode of action on glutamate receptors that are not observed with the metabolite CBDP and the other symmetric TCP isomers. In addition, the TmCP isomer seems to have the lowest potency with respect to inducing neurotoxic effects. CBDP did not affect the neurospecific endpoints investigated in this study. Therefore, the specific affinity of CBDP for NTE and the reported general cytotoxicity might be the most relevant modes of action of this toxic metabolite in the context of ToCP-induced neurotoxicity, including OPIDN. Copyright © 2016 Elsevier B.V. All rights reserved.

The protective effect of Moringa oleifera leaves against cyclophosphamide-induced urinary bladder toxicity in rats.

PubMed

Taha, Nevine R; Amin, Hanan Ali; Sultan, Asrar A

2015-02-01

Cyclophosphamide (CP), an alkylating antineoplastic agent is widely used in the treatment of solid tumors and B-cell malignant disease. It is known to cause urinary bladder damage due to inducing oxidative stress. Moringa oleifera (Mof) is commonly known as drumstick tree. Moringa leaves have been reported to be a rich source of β-carotene, protein, vitamin C, calcium, and potassium. It acts as a good source of natural antioxidants; due to the presence of various types of antioxidant compounds such as ascorbic acid, flavonoids, phenolics and carotenoids. The aim of this work was to test the possible antioxidant protective effects of M. oleifera leaves against CP induced urinary bladder toxicity in rats. Female Wister albino rats were divided into 4 groups. Group I served as control, received orally normal saline, group II received a single dose CP 100mg/kg intraperitoneally, group III and VI both received orally hydroethanolic extract of Mof; 500 mg/kg and 1000 mg/kg respectively daily for a week, 1h before and 4h after CP administration. Rats were sacrificed 24h after CP injection. The bladder was removed, sectioned, and subjected to light, transition electron microscopic studies, and biochemical studies (measuring the parameter of lipid peroxidation; malondialdehyde along with the activities of the antioxidant enzyme reduced glutathione). The bladders of CP treated rats showed ulcered mucosa, edematous, hemorrhagic, and fibrotic submucosa by light microscopy. Ultrastructure observation showed; losing large areas of uroepithelium, extended intercellular gaps, junction complexes were affected as well as damage of mitochondria in the form of swelling and destruction of cristae. Biochemical analysis showed significant elevation of malondialdhyde, while reduced glutathione activity was significantly lowered. From the results obtained in this work, we can say that Moringa leaves play an important role in ameliorating and protecting the bladder from CP toxicity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Profiles of vocal development in Korean children with and without cleft palate.

PubMed

Ha, Seunghee

2018-01-01

This study longitudinally investigated vocal development in Korean children from 9 to 18 months of age with and without cleft palate (CP). Utterance samples were collected from 24 children with and without CP at 9, 12, 15 and 18 months of age. Each utterance was categorised into levels of vocalisation using the Korean-translated version of the Stark Assessment of Early Vocal Development-Revised (SAEVD-R). The results showed children with CP produced a significantly higher rate of precanonical vocalisations (the combination of Levels 1, 2, and 3) and a lower rate of Level 4 and 5 vocalisations than children without CP. Both groups showed decreases in Levels 1 and 2 and increases in Level 5 from 9 to 18 months of age. A significant increase in the proportion of Level 4 vocalisations across age was observed only in children without CP. Young Korean children with CP showed lower proportions of advanced vocalisation levels characterised by canonical and complex syllable structures across 9 and 18 months of age compared to children without CP.

Biological role and structural mechanism of twinfilin–capping protein interaction

PubMed Central

Falck, Sandra; Paavilainen, Ville O; Wear, Martin A; Grossmann, J Günter; Cooper, John A; Lappalainen, Pekka

2004-01-01

Twinfilin and capping protein (CP) are highly conserved actin-binding proteins that regulate cytoskeletal dynamics in organisms from yeast to mammals. Twinfilin binds actin monomer, while CP binds the barbed end of the actin filament. Remarkably, twinfilin and CP also bind directly to each other, but the mechanism and role of this interaction in actin dynamics are not defined. Here, we found that the binding of twinfilin to CP does not affect the binding of either protein to actin. Furthermore, site-directed mutagenesis studies revealed that the CP-binding site resides in the conserved C-terminal tail region of twinfilin. The solution structure of the twinfilin–CP complex supports these conclusions. In vivo, twinfilin's binding to both CP and actin monomer was found to be necessary for twinfilin's role in actin assembly dynamics, based on genetic studies with mutants that have defined biochemical functions. Our results support a novel model for how sequential interactions between actin monomers, twinfilin, CP, and actin filaments promote cytoskeletal dynamics. PMID:15282541

Open-Shell Lanthanide(II+) or -(III+) Complexes Bearing σ-Silyl and Silylene Ligands: Synthesis, Structure, and Bonding Analysis

PubMed Central

2015-01-01

Complexes featuring lanthanide (Ln)–Si bonds represent a highly neglected research area. Herein, we report a series of open-shell LnII+ and LnIII+ complexes bearing σ-bonded silyl and base-stabilized N-heterocyclic silylene (NHSi) ligands. The reactions of the LnIII+ complexes Cp3Ln (Ln = Tm, Ho, Tb, Gd; Cp = cyclopentadienide) with the 18-crown-6 (18-cr-6)-stabilized 1,4-oligosilanyl dianion [(18-cr-6)KSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2K(18-cr-6)] (1) selectively afford the corresponding metallacyclopentasilane salts [Cp2Ln({Si(SiMe3)2SiMe2}2)]−[K2(18-cr-6)2Cp]+ [Ln = Tm (2a), Ho (2b), Tb (2c), Gd (2d)]. Complexes 2a–2d represent the first examples of structurally characterized Tm, Ho, Tb, and Gd complexes featuring Ln–Si bonds. Strikingly, the analogous reaction of 1 with the lighter element analogue Cp3Ce affords the acyclic product [Cp3CeSi(SiMe3)2SiMe2SiMe2Si(SiMe3)2-Cp3Ce]2–2[K(18-cr-6)]+ (3) as the first example of a complex featuring a Ce–Si bond. In an alternative synthetic approach, the aryloxy-functionalized benzamidinato NHSi ligand Si(OC6H4-2-tBu){(NtBu)2CPh} (4a) and the alkoxy analogue Si(OtBu){(NtBu)2CPh} (4b) were reacted with Cp*2Sm(OEt2), affording, by OEt2 elimination, the corresponding silylene complexes, both featuring SmII+ centers: Cp*2Sm ← :Si(O–C6H4-2-tBu){(NtBu)2CPh} (6) and Cp*2Sm ← :Si(OtBu){(NtBu)2CPh} (5). Complexes 5 and 6 are the first four-coordinate silylene complexes of any f-block element to date. All complexes were fully characterized by spectroscopic means and by single-crystal X-ray diffraction analysis. In the series 2a–2d, a linear correlation was observed between the Ln–Si bond lengths and the covalent radii of the corresponding Ln metals. Moreover, in complexes 5 and 6, notably long Sm–Si bonds are observed, in accordance with a donor–acceptor interaction between Si and Sm [5, 3.4396(15) Å; 6, 3.3142(18) Å]. Density functional theory calculations were carried out for complexes 2a–2d, 5, and 6 to elucidate the bonding situation between the LnII+ or LnIII+ centers and Si. In particular, a decrease in the Mayer bond order (MBO) of the Ln–Si bond is observed in the series 2a–2d in moving from the lighter to the heavier lanthanides (Tm = 0.53, Ho = 0.62, Tb = 0.65, and Gd = 0.75), which might indicate decreasing covalency in the Ln–Si bond. In accordance with the long bond lengths observed experimentally in complexes 5 and 6, comparatively low MBOs were determined for both silylene complexes (5, 0.24; 6, 0.25) . PMID:25756230

Oxidative Degradation of Chlorophenolic Compounds with Modified-Fenton Process Using Pyrite as the Catalyst

NASA Astrophysics Data System (ADS)

Kantar, Cetin; Urken, Ozge; Oral, Ozlem; Kaplan, Iremsu; Ayman Oz, Nilgun

2017-04-01

Oxidative dehalogenation has been shown to be a viable and cost effective process for dealing with a particularly persistent class of contaminants (e.g., chlorophenolic compounds (CP)) often found in contaminated soil and ground water. Here, the degradation of various chlorophenolic compounds (e.g., 2-CP, 4-CP, 2,3-di CP, 2,4-di CP, 2,4,6-tri CP, 2,3,4,6-Tetra CP) was investigated by modified Fenton process using pyrite as source of Fe2+ (catalyst) . The effects of different parameters such as chlorophenol type, pH and chlorophenol, pyrite and H2O2 concentrations on the degradation kinetics of chlorophenols were studied in batch reactors. Our results show that while the rate of chloropehenol degradation increased with decreasing solution pH, no direct correlation was observed between H2O2 concentration and chlorophenol degradation, indicating a complex mechanism involved in CP degradation by modified Fenton process. The batch results also show that the CP degradation was highly dependent on CP type, the number and location of chloride ions in the structure. Overall, the results of this study suggest that pyrite can be effectively used in reactive treatment barriers for in-situ treatment of subsurface systems contaminated with chlorophenols.

Structural and Electrochemical Consequences of [Cp*] Ligand Protonation.

PubMed

Peng, Yun; Ramos-Garcés, Mario V; Lionetti, Davide; Blakemore, James D

2017-09-05

There are few examples of the isolation of analogous metal complexes bearing [η 5 -Cp*] and [η 4 -Cp*H] (Cp* = pentamethylcyclopentadienyl) complexes within the same metal/ligand framework, despite the relevance of such structures to catalytic applications. Recently, protonation of Cp*Rh(bpy) (bpy = 2,2'-bipyridyl) has been shown to yield a complex bearing the uncommon [η 4 -Cp*H] ligand, rather than generating a [Rh III -H] complex. We now report the purification and isolation of this protonated species, as well as characterization of analogous complexes of 1,10-phenanthroline (phen). Specifically, reaction of Cp*Rh(bpy) or Cp*Rh(phen) with 1 equiv of Et 3 NH + Br - affords rhodium compounds bearing endo-η 4 -pentamethylcyclopentadiene (η 4 -Cp*H) as a ligand. NMR spectroscopy and single-crystal X-ray diffraction studies confirm protonation of the Cp* ligand, rather than formation of metal hydride complexes. Analysis of new structural data and electronic spectra suggests that phen is significantly reduced in Cp*Rh(phen), similar to the case of Cp*Rh(bpy). Backbonding interactions with olefinic motifs are activated by formation of [η 4 -Cp*H]; protonation of [Cp*] stabilizes the low-valent metal center and results in loss of reduced character on the diimine ligands. In accord with these changes in electronic structure, electrochemical studies reveal a distinct manifold of redox processes that are accessible in the [Cp*H] complexes in comparison with their [Cp*] analogues; these processes suggest new applications in catalysis for the complexes bearing endo-η 4 -Cp*H.

Detection of Specific Solvent Rearrangement Regions of an Enzyme: NMR and ITC Studies with Aminoglycoside Phosphotransferase(3??)-IIIa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ozen, C.; Norris, Adrianne; Land, Miriam L

2008-01-01

This work describes differential effects of solvent in complexes of the aminoglycoside phosphotransferase(3¢)-IIIa (APH) with different aminoglycosides and the detection of change in solvent structure at specific sites away from substrates. Binding of kanamycins to APH occurs with a larger negative ¢H in H2O relative to D2O (¢¢H(H2O-D2O) < 0), while the reverse is true for neomycins. Unusually large negative ¢Cp values were observed for binding of aminoglycosides to APH. ¢Cp for the APHneomycin complex was -1.6 kcalâmol-1âdeg-1. A break at 30 C was observed in the APH-kanamycin complex yielding ¢Cp values of -0.7 kcalâmol-1âdeg-1 and -3.8 kcalâmol-1âdeg-1 below andmore » above 30 C, respectively. Neither the change in accessible surface area (¢ASA) nor contributions from heats of ionization were sufficient to explain the large negative ¢Cp values. Most significantly, 15N-1H HSQC experiments showed that temperature-dependent shifts of the backbone amide protons of Leu 88, Ser 91, Cys 98, and Leu143 revealed a break at 30 C only in the APH-kanamycin complex in spectra collected between 21 C and 38 C. These amino acids represent solVent reorganization sites that experience a change in solvent structure in their immediate environment as structurally different ligands bind to the enzyme. These residues were away from the substrate binding site and distributed in three hydrophobic patches in APH. Overall, our results show that a large number of factors affect ¢Cp and binding of structurally different ligand groups cause different solvent structure in the active site as well as differentially affecting specific sites away from the ligand binding site.« less

Analysis of the parental origin of de novo MECP2 mutations and X chromosome inactivation in 24 sporadic patients with Rett syndrome in China.

PubMed

Zhu, Xingwang; Li, Meirong; Pan, Hong; Bao, Xinhua; Zhang, Jingjing; Wu, Xiru

2010-07-01

Rett syndrome is an X-linked neurodevelopmental disorder that predominantly affects females. It is caused by mutations in methyl-CpG-binding protein 2 gene. Due to the sex-limited expression, it has been suggested that de novo X-linked mutations may exclusively occur in male germ cells and thus only females are affected. In this study, the authors have analyzed the parental origin of mutations and the X-chromosome inactivation status in 24 sporadic patients with identified methyl-CpG-binding protein 2 gene mutations. The results showed that 22 of 24 patients have a paternal origin. Only 2 patients have a maternal origin. Except for 2 cases which were homozygotic at the androgen receptor gene locus, of the remaining 22 cases, 16 cases have a random X-chromosome inactivation pattern; the other 6 cases have a skewed X-chromosome inactivation and they favor expression of the wild allele. The relationship between X-chromosome inactivation and phenotype may need more cases to explore.

Synthesis of ruthenium(II) complexes containing hydroxymethylphosphines and their catalytic activities for hydrogenation of supercritical carbon dioxide.

PubMed

Kayaki, Yoshihito; Shimokawatoko, Yoshiki; Ikariya, Takao

2007-07-09

Ligand substitution of RuCl2[P(C6H5)3]3 and Cp*RuCl(isoprene) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) complexes with hydroxymethylphosphines was investigated to develop new catalyst systems for CO2 hydrogenation. A reaction of P(C6H5)2CH2OH with RuCl2[P(C6H5)3]3 in CH2Cl2 gave Ru(H)Cl(CO)[P(C6H5)2CH2OH]3 (1), which was characterized by NMR spectroscopy and X-ray crystallographic analysis. An isotope labeling experiment using P(C6H5)213CH2OH indicated that the carbonyl moiety in complex 1 originated from formaldehyde formed by degradation of the hydroxymethylphosphine. Elimination of formaldehyde from PCy2CH2OH (Cy=cyclohexyl) was also promoted by treatment of RuCl2[P(C6H5)3]3 in ethanol to give RuCl2(PHCy2)4 under mild conditions. On the other hand, the substitution reaction using Cp*RuCl(isoprene) with the hydroxymethylphosphine ligands proceeded smoothly with formation of Cp*RuCl(L)2 [2a-2c; L=P(C6H5)2CH2OH, PCy(CH2OH)2, and P(CH2OH)3] in good yields. The isolable hydroxymethylphosphine complexes 1 and 2 efficiently catalyzed the hydrogenative amidation of supercritical carbon dioxide (scCO2) to N,N-dimethylformamide (DMF).

Ceruloplasmin: Macromolecular Assemblies with Iron-Containing Acute Phase Proteins

PubMed Central

Samygina, Valeriya R.; Sokolov, Alexey V.; Bourenkov, Gleb; Petoukhov, Maxim V.; Pulina, Maria O.; Zakharova, Elena T.; Vasilyev, Vadim B.; Bartunik, Hans; Svergun, Dmitri I.

2013-01-01

Copper-containing ferroxidase ceruloplasmin (Cp) forms binary and ternary complexes with cationic proteins lactoferrin (Lf) and myeloperoxidase (Mpo) during inflammation. We present an X-ray crystal structure of a 2Cp-Mpo complex at 4.7 Å resolution. This structure allows one to identify major protein–protein interaction areas and provides an explanation for a competitive inhibition of Mpo by Cp and for the activation of p-phenylenediamine oxidation by Mpo. Small angle X-ray scattering was employed to construct low-resolution models of the Cp-Lf complex and, for the first time, of the ternary 2Cp-2Lf-Mpo complex in solution. The SAXS-based model of Cp-Lf supports the predicted 1∶1 stoichiometry of the complex and demonstrates that both lobes of Lf contact domains 1 and 6 of Cp. The 2Cp-2Lf-Mpo SAXS model reveals the absence of interaction between Mpo and Lf in the ternary complex, so Cp can serve as a mediator of protein interactions in complex architecture. Mpo protects antioxidant properties of Cp by isolating its sensitive loop from proteases. The latter is important for incorporation of Fe3+ into Lf, which activates ferroxidase activity of Cp and precludes oxidation of Cp substrates. Our models provide the structural basis for possible regulatory role of these complexes in preventing iron-induced oxidative damage. PMID:23843990

Solar photocatalytic degradation of chlorophenols mixture (4-CP and 2,4-DCP): Mechanism and kinetic modelling.

PubMed

Abeish, Abdulbasit M; Ang, Ha Ming; Znad, Hussein

2015-01-01

The solar-photocatalytic degradation mechanisms and kinetics of 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) using TiO2 have been investigated both individually and combined. The individual solar-photocatalytic degradation of both phenolic compounds showed that the reaction rates follow pseudo-first-order reaction. During the individual photocatalytic degradation of both 4-CP and 2,4-DCP under the same condition of TiO2 (0.5 g L(-1)) and light intensities (1000 mW cm(-2)) different intermediates were detected, three compounds associated with 4-CP (hydroquinone (HQ), phenol (Ph) and 4-chlorocatechol (4-cCat)) and two compounds associated with 2,4-DCP (4-CP and Ph). The photocatalytic degradation of the combined mixture (4-CP and 2,4-DCP) was also investigated at the same conditions and different 2,4-DCP initial concentrations. The results showed that the degradation rate of 4-CP decreases when the 2,4-DCP concentration increases. Furthermore, the intermediates detected were similar to that found in the individual degradation but with high Ph concentration. Therefore, a possible reaction mechanism for degradation of this combined mixture was proposed. Moreover, a modified Langmuir-Hinshelwood (L-H) kinetic model considering all detected intermediates was developed. A good agreement between experimental and estimated results was achieved. This model can be useful for scaling-up purposes more accurately as its considering the intermediates formed, which has a significant effect on degrading the main pollutants (4-CP and 2,4-DCP).

Inhibition of emesis by tachykinin NK1 receptor antagonists in Suncus murinus (house musk shrew).

PubMed

Rudd, J A; Ngan, M P; Wai, M K

1999-02-05

The anti-emetic potential of CP-122,721 ((+)-2S,3S)-3-(2-methoxy-5-trifluoromethoxybenzyl)amino-2-phenylpi peridine), CP-99,994 ((+)-(2S,3S)-3-(2-methoxybenzylamino)-2-phenylpiperidine), CP-100,263 ((-)-(2R,3R)-3-(2-methoxybenzylamino)-2-phenylpiperidine), RP 67580 ((3R, 7aR)-7,7-diphenyl-2-[1-imino-2-(2-methoxyphenyl)ethyl] po-hydroisoindol-4-one), FK 888 (N2-[(4R)-4-hydroxy-1-(1-methyl-1H-in-dole-3-yl)carbonyl-L-propyl] -N-methyl-N-phenylmethyl-1-3-(2-naphthyl)-alaninamide) and GR 82334 ([D-Pro9[spiro-g-lactam]Leu10]-physalaemin-(1-11)) was investigated to inhibit nicotine (5 mg/kg, s.c.)-, copper sulphate pentahydrate (120 mg/kg, intragastric)- and motion (4 cm horizontal displacement at 1 Hz for 5 min)-induced emesis in Suncus murinus. A 30 min intraperitoneal pre-treatment with CP-122,721, CP-99,994, RP 67580 and FK 888 significantly (P < 0.05) antagonized nicotine-induced emesis with ID50 values of 2.1, 2.3, 13.5 and 19.2 mg/kg, respectively CP-100,263, the less active enantiomer of CP-99,994, was inactive at doses up to 10 mg/kg. Infusion of GR 82334, CP-122,721, CP-99,994 and FK 888 into the dorsal vagal complex of the hindbrain also antagonized nicotine-induced emesis yielding ID50 values of 1.1, 3.0, 3.3 and 58.0 microg/dorsal vagal complex, respectively RP 67580 and CP-100,263 were inactive. RP 67580 and FK 888 failed to antagonize copper sulphate-induced emesis but CP-122,721 and CP-99,994 were active yielding ID50 values of 2.2 and 3.0 mg/kg, i.p., respectively. CP-99,994 also completely prevented motion-induced emesis at 10 mg/kg, i.p. (P < 0.05) and RP 67580 produced a significant reduction of motion-induced emesis at 10 mg/kg, i.p. (P < 0.05). These studies provide evidence of a central site of action of tachykinin NK1 receptor antagonists to inhibit nicotine-induced emesis in S. murinus and confirm the broad profile of inhibitory action. The rank order of potency of the antagonists following the intra-dorsal vagal complex administration suggests that the S. murinus tachykinin NK1 receptor has a unique pharmacological profile.

(Pentamethylcyclopentadienato)rhodium complexes for delivery of the curcumin anticancer drug [Rhodium pentamethylcyclopentadienato complexes for delivery of the curcumin anti-cancer drug

DOE Office of Scientific and Technical Information (OSTI.GOV)

Markham, Jack; Liang, Jun; Levina, Aviva

[RhIII(*Cp)Cl(X,Y)] n+ complexes {X, Y = Cl, PTA, n = 0 (2); X, Y = en, n = 1 (3, Cl– salt; 4, PF 6– salt); X, Y = acac, n = 0 (5); X, Y = cur, n = 0 (6), where *Cp = pentamethylcyclopentadienato, curH = curcumin; PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane; en = 1,2-ethanediamine; acac = acetylacetonato = 2,4-pentanedionato(1–)} were synthesized from [Rh(*Cp)(µ-Cl)Cl] 2 (1). While 2–5 were inactive against human epithelial A549 lung-cancer cells in assays of cytotoxicity, and antimetastatic and proapoptotic behaviors, 6 had a cytotoxic activity similar to that of curH over 72 h, but atmore » 24 h in real-time cell migration assays, it was less active, showing slow release of curH. All complexes underwent ligand-exchange reactions with biomolecules and cells within the timeframes of the assays (X-ray absorption spectroscopy). Intracellular elemental distributions (X-ray fluorescence microscopy) showed that 6 effectively delivered curH to cells, where it was released. Other elemental distributions and caspase activities were consistent with preapoptotic activities. As such, 6 is a promising delivery agent for bioactive ligands, such as curH. However, pure curcumin itself showed a previously unrecognized ability to promote migration of A549 cells at subtoxic concentrations in the presence of endothelial growth factor, which may be a concern for its widespread use as a nutritional supplement and as a potential drug. As a result, this aspect warrants further research.« less

(Pentamethylcyclopentadienato)rhodium complexes for delivery of the curcumin anticancer drug [Rhodium pentamethylcyclopentadienato complexes for delivery of the curcumin anti-cancer drug

DOE PAGES

Markham, Jack; Liang, Jun; Levina, Aviva; ...

2017-01-23

[RhIII(*Cp)Cl(X,Y)] n+ complexes {X, Y = Cl, PTA, n = 0 (2); X, Y = en, n = 1 (3, Cl– salt; 4, PF 6– salt); X, Y = acac, n = 0 (5); X, Y = cur, n = 0 (6), where *Cp = pentamethylcyclopentadienato, curH = curcumin; PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane; en = 1,2-ethanediamine; acac = acetylacetonato = 2,4-pentanedionato(1–)} were synthesized from [Rh(*Cp)(µ-Cl)Cl] 2 (1). While 2–5 were inactive against human epithelial A549 lung-cancer cells in assays of cytotoxicity, and antimetastatic and proapoptotic behaviors, 6 had a cytotoxic activity similar to that of curH over 72 h, but atmore » 24 h in real-time cell migration assays, it was less active, showing slow release of curH. All complexes underwent ligand-exchange reactions with biomolecules and cells within the timeframes of the assays (X-ray absorption spectroscopy). Intracellular elemental distributions (X-ray fluorescence microscopy) showed that 6 effectively delivered curH to cells, where it was released. Other elemental distributions and caspase activities were consistent with preapoptotic activities. As such, 6 is a promising delivery agent for bioactive ligands, such as curH. However, pure curcumin itself showed a previously unrecognized ability to promote migration of A549 cells at subtoxic concentrations in the presence of endothelial growth factor, which may be a concern for its widespread use as a nutritional supplement and as a potential drug. As a result, this aspect warrants further research.« less

The MeCP1 complex represses transcription through preferential binding, remodeling, and deacetylating methylated nucleosomes

PubMed Central

Feng, Qin; Zhang, Yi

2001-01-01

Histone deacetylation plays an important role in methylated DNA silencing. Recent studies indicated that the methyl-CpG-binding protein, MBD2, is a component of the MeCP1 histone deacetylase complex. Interestingly, MBD2 is able to recruit the nucleosome remodeling and histone deacetylase, NuRD, to methylated DNA in vitro. To understand the relationship between the MeCP1 complex and the NuRD complex, we purified the MeCP1 complex to homogeneity and found that it contains 10 major polypeptides including MBD2 and all of the known NuRD components. Functional analysis of the purified MeCP1 complex revealed that it preferentially binds, remodels, and deacetylates methylated nucleosomes. Thus, our study defines the MeCP1 complex, and provides biochemical evidence linking nucleosome remodeling and histone deacetylation to methylated gene silencing. PMID:11297506

Synthesis and oxidation of CpIrIII compounds: functionalization of a Cp methyl group.

PubMed

Park-Gehrke, Lisa S; Freudenthal, John; Kaminsky, Werner; Dipasquale, Antonio G; Mayer, James M

2009-03-21

[CpIrCl(2)](2) () and new CpIr(III)(L-L)X complexes (L-L = N-O or C-N chelating ligands; X = Cl, I, Me) have been prepared and their reactivity with two-electron chemical oxidants explored. Reaction of with PhI(OAc)(2) in wet solvents yields a new chloro-bridged dimer in which each of the Cp ligands has been singly acetoxylated to form [Cp(OAc)Ir(III)Cl(2)](2) () (Cp(OAc) = eta(5)-C(5)Me(4)CH(2)OAc). Complex and related carboxy- and alkoxy-functionalized Cp(OR) complexes can also be prepared from plus (PhIO)(n) and ROH. [Cp(OAc)Ir(III)Cl(2)](2) () and the methoxy analogue [Cp(OMe)Ir(III)Cl(2)](2) () have been structurally characterized. Treatment of [CpIrCl(2)](2) () with 2-phenylpyridine yields CpIr(III)(ppy)Cl () (ppy = cyclometallated 2-phenylpyridyl) which is readily converted to its iodide and methyl analogues CpIr(III)(ppy)I and CpIr(III)(ppy)Me (). CpIr(III) complexes were also prepared with N-O chelating ligands derived from anthranilic acid (2-aminobenzoic acid) and alpha-aminoisobutyric acid (H(2)NCMe(2)COOH), ligands chosen to be relatively oxidation resistant. These complexes and were reacted with potential two-electron oxidants including PhI(OAc)(2), hexachlorocyclohexadienone (C(6)Cl(6)O), N-fluoro-2,4,6-trimethylpyridinium (Me(3)pyF(+)), [Me(3)O]BF(4) and MeOTf (OTf = triflate, CF(3)SO(3)). Iridium(V) complexes were not observed or implicated in these reactions, despite the similarity of the potential products to known CpIr(V) species. The carbon electrophiles [Me(3)O]BF(4) and MeOTf appear to react preferentially at the N-O ligands, to give methyl esters in some cases. Overall, the results indicate that Cp is not inert under oxidizing conditions and is therefore not a good supporting ligand for oxidizing organometallic complexes.

Peripapillary and Macular Vessel Density in Glaucoma Patients with Single-Hemifield Visual Field Defect

PubMed Central

Yarmohammadi, Adeleh; Zangwill, Linda M.; Diniz-Filho, Alberto; Saunders, Luke J.; Suh, Min Hee; Wu, Zhichao; Manalastas, Patricia Isabel C.; Akagi, Tadamichi; Medeiros, Felipe A.; Weinreb, Robert N.

2017-01-01

Purpose To compare hemifield differences in the vessel density of the optic nerve head and macula in open-angle glaucoma (OAG) eyes with visual field (VF) defect confined to one hemifield using optical coherence tomography angiography (OCT-A). Design Cross-sectional study. Participants Fifty-eight eyes of 58 glaucoma patients with VF loss confined to a single hemifield, and 28 healthy eyes. Methods Retinal vasculature information was summarized as circumpapillary vessel density (cpVD) and perifoveal vessel density (pfVD). Circumpapillary retinal nerve fiber layer (cpRNFL) and macular ganglion cell complex (mGCC) thickness were also calculated using spectral domain OCT. Paired and unpaired t-tests were utilized to evaluate differences between the perimetrically affected and intact hemiretinae and healthy hemiretinae. Linear regression analyses were performed to evaluate the associations between VF measures with vascular and structural measurements. Main Outcome Measures Total and hemispheric cpVD, pfVD, cpRNFL, mGCC and mean sensitivity (MS). Results Mean cpVD and pfVD in the intact hemiretinae of OAG eyes (59.0% and 51.1%) were higher than the affected hemiretinae (54.7% and 48.3%; p<0.001) but lower than healthy eyes (62.4% and 53.8%; p<0.001). Similar results were noted with cpRNFL and mGCC thickness measurements (p<0.05 for both). The strongest associations between MS in the affected hemifields were found for cpVD (r = 0.707), followed by pfVD (r = 0.615), cpRNFL (r = 0.496) and mGCC (r = 0.482) in the corresponding hemiretinae (p<0.001 for all). Moreover the correlations in the intact hemifields between MS with cpVD and pfVD were found to be higher (r = 0.450 and 0.403) than the correlations between MS and cpRNFL and mGCC thickness measurements (r = 0.340 and 0.290; all p-values <0.05 for all). Conclusions Reduced peripapillary and macular vessel density was detectable in the perimetrically intact hemiretinae of glaucoma eyes with a single-hemifield defect. Moreover vessel density attenuation in both affected and intact hemiretinae was associated with the extent of VF damage in the corresponding hemifields. OCT-A potentially shows promise for identifying glaucomatous damage before focal VF defects are detectable. PMID:28196732

Effects of the [OC6F5] moiety upon structural geometry: crystal structures of half-sandwich tantalum(V) aryloxide complexes from reaction of Cp*Ta(N(t)Bu)(CH2R)2 with pentafluorophenol.

PubMed

Cole, Jacqueline M; Chan, Michael C W; Gibson, Vernon C; Howard, Judith A K

2011-10-01

The synthesis, chemical and structural characterization of a series of pentamethylcyclopentadienyl (Cp*) tantalum imido complexes and aryloxide derivatives are presented. Specifically, the imido complexes Cp*Ta(N(t)Bu)(CH(2)R)(2), where R = Ph [dibenzyl(tert-butylamido) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (1)], Me(2)Ph [tert-butylamido)bis(2-methyl-2-phenylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (2)], CMe(3) [(tert-butylamido)bis(2,2-dimethylpropyl) (η(5)-pentamethylcyclopentadienyl)tantalum(IV) (3)], are reported. The crystal structure of (3) reveals α-agostic interactions with the Ta atom. The resulting increase in the tantalum core coordination improves electronic stability. As such it does not react with pentafluorophenol, in contrast to the other two reported imido complexes [(1) and (2)]. Addition of C(6)F(5)OH to (1) yields a dimeric aryl-oxide derivative, [Cp*Ta(CH(2)Ph)(OC(6)H(5))(μ-O)](2) [di-μ-oxido-bis[benzyl(pentafluorophenolato) (η(5)-pentamethylcyclopentadienyl)tantalum(V)] (4)]. Its crystal structure reveals long Ta-O(C(6)H(5)) bonds but short oxo-bridging Ta-O bonds. This is explained by accounting for the fierce electronic competition for the vacant d(π) orbitals of the electrophilic Ta(V) centre. Steric congestion around each metal is alleviated by a large twist angle (77.1°) between the benzyl and pentafluorophenyl ligands and the ordering of each of these groups into stacked pairs. The imido complex (2) reacts with C(6)F(5)OH to produce a mixture of Cp*Ta(OC(6)F(5))(4) [tetrakis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V) (5)] and [Cp*Ta(OC(6)F(5))(2)(μ-O)](2) [di-μ-oxido-bis[bis(pentafluorophenolato)(η(5)-pentamethylcyclopentadienyl)tantalum(V)] (6)]. Steric congestion is offset in both cases by the twisting of its pentafluorophenyl ligands. Particularly strong electronic competition for the empty d(π) metal orbitals in (6) is reflected in its bond geometry, and owes itself to the more numerous electron-withdrawing pentafluorophenyl ligands. The balance of steric and electronic factors affecting the reactivity of Cp* tantalum imido based complexes with pentafluorophenol is therefore addressed.

Synthesis, structural characterization and conversion of dinuclear iron-sulfur clusters containing the disulfide ligand: [Cp*Fe(μ-η2:η2-bdt)(cis-μ-η1:η1-S2)FeCp*], [Cp*Fe(μ-S(C6H4S2))(cis-μ-η1:η1-S2)FeCp*], and [{Cp*Fe(bdt)}2(trans-μ-η1:η1-S2)].

PubMed

Ji, Xiaoxiao; Tong, Peng; Yang, Dawei; Wang, Baomin; Zhao, Jinfeng; Li, Yang; Qu, Jingping

2017-03-21

The treatment of [Cp*Fe(μ-η 2 :η 4 -bdt)FeCp*] (1, Cp* = η 5 -C 5 Me 5 , bdt = benzene-1,2-dithiolate) with 1/4 equiv. of elemental sulfur (S 8 ) gave a dinuclear iron-sulfur cluster [Cp*Fe(μ-η 2 :η 2 -bdt)(cis-μ-η 1 :η 1 -S 2 )FeCp*] (2), which contains a cis-1,2-disulfide ligand. When complex 2 further interacted with 1/8 equiv. of S 8 , another sulfur atom inserted into an Fe-S bond to give a rare product [Cp*Fe(μ-S(C 6 H 4 S 2 ))(cis-μ-η 1 :η 1 -S 2 )FeCp*] (3). Unexpectedly, a trans-1,2 disulfide-bridged diiron complex [{Cp*Fe(bdt)} 2 (trans-μ-η 1 :η 1 -S 2 )] (4) was isolated from the reaction of complex 1 with 1/2 equiv. of S 8 , which represents a structural isomer of [2Fe-2S] ferredoxin-type clusters. In addition, cis-1,2-disulfide-bridged complex 3 can slowly convert into trans-1,2-disulfide-bridged complex 4 and the complex [Cp*Fe(μ-η 2 :η 2 -S 2 )(cis-μ-η 1 :η 1 -S 2 )FeCp*] (5) by self-assembly reaction at ambient temperature, which is evidenced by time-dependent 1 H NMR spectroscopy.

Pentaarylcyclopentadienyl Iron, Cobalt, and Nickel Halides.

PubMed

Chakraborty, Uttam; Modl, Moritz; Mühldorf, Bernd; Bodensteiner, Michael; Demeshko, Serhiy; van Velzen, Niels J C; Scheer, Manfred; Harder, Sjoerd; Wolf, Robert

2016-03-21

The preparation of new stable half-sandwich transition metal complexes, having a bulky cyclopentadienyl ligand C5(C6H4-4-Et)5 (Cp(Ar1)) or C5(C6H4-4-nBu)5 (Cp(Ar2)), is reported. The tetrahydrofuran (THF) adduct [Cp(Ar1)Fe(μ-Br)(THF)]2 (1a) was synthesized by reacting K[Cp(Ar1)] with [FeBr2(THF)2] in THF, and its molecular structure was determined by X-ray crystallography. Complex 1a easily loses its coordinated THF molecules under vacuum to form the solvent-free complex [Cp(Ar1)Fe(μ-Br)]2 (1b). The analogous complexes [Cp(Ar1)Co(μ-Br)]2 (2), [Cp(Ar1)Ni(μ-Br)]2 (3), and [Cp(Ar2)Ni(μ-Br)]2 (4) were synthesized from CoBr2 and [NiBr2(1,2-dimethoxyethane)]. The mononuclear, low-spin cobalt(III) and nickel(III) complexes [Cp(Ar2)MI2] (5, M = Co; 6, M = Ni) were prepared by reacting the radical Cp(Ar2) with NiI2 and CoI2. The complexes were characterized by NMR and UV-vis spectroscopies and by elemental analyses. Single-crystal X-ray structure analyses revealed that the dimeric complexes 1a, 1b, and 3 have a planar M2Br2 core, whereas 2 and 4 feature a puckered M2Br2 ring.

Unravelling the shape and structural assembly of the photosynthetic GAPDH-CP12-PRK complex from Arabidopsis thaliana by small-angle X-ray scattering analysis.

PubMed

Del Giudice, Alessandra; Pavel, Nicolae Viorel; Galantini, Luciano; Falini, Giuseppe; Trost, Paolo; Fermani, Simona; Sparla, Francesca

2015-12-01

Oxygenic photosynthetic organisms produce sugars through the Calvin-Benson cycle, a metabolism that is tightly linked to the light reactions of photosynthesis and is regulated by different mechanisms, including the formation of protein complexes. Two enzymes of the cycle, glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK), form a supramolecular complex with the regulatory protein CP12 with the formula (GAPDH-CP122-PRK)2, in which both enzyme activities are transiently inhibited during the night. Small-angle X-ray scattering analysis performed on both the GAPDH-CP12-PRK complex and its components, GAPDH-CP12 and PRK, from Arabidopsis thaliana showed that (i) PRK has an elongated, bent and screwed shape, (ii) the oxidized N-terminal region of CP12 that is not embedded in the GAPDH-CP12 complex prefers a compact conformation and (iii) the interaction of PRK with the N-terminal region of CP12 favours the approach of two GAPDH tetramers. The interaction between the GAPDH tetramers may contribute to the overall stabilization of the GAPDH-CP12-PRK complex, the structure of which is presented here for the first time.

Capping protein regulatory cycle driven by CARMIL and V-1 may promote actin network assembly at protruding edges

PubMed Central

Fujiwara, Ikuko; Remmert, Kirsten; Piszczek, Grzegorz; Hammer, John A.

2014-01-01

Although capping protein (CP) terminates actin filament elongation, it promotes Arp2/3-dependent actin network assembly and accelerates actin-based motility both in vitro and in vivo. In vitro, capping protein Arp2/3 myosin I linker (CARMIL) antagonizes CP by reducing its affinity for the barbed end and by uncapping CP-capped filaments, whereas the protein V-1/myotrophin sequesters CP in an inactive complex. Previous work showed that CARMIL can readily retrieve CP from the CP:V-1 complex, thereby converting inactive CP into a version with moderate affinity for the barbed end. Here we further clarify the mechanism of this exchange reaction, and we demonstrate that the CP:CARMIL complex created by complex exchange slows the rate of barbed-end elongation by rapidly associating with, and dissociating from, the barbed end. Importantly, the cellular concentrations of V-1 and CP determined here argue that most CP is sequestered by V-1 at steady state in vivo. Finally, we show that CARMIL is recruited to the plasma membrane and only at cell edges undergoing active protrusion. Assuming that CARMIL is active only at this location, our data argue that a large pool of freely diffusing, inactive CP (CP:V-1) feeds, via CARMIL-driven complex exchange, the formation of weak-capping complexes (CP:CARMIL) at the plasma membrane of protruding edges. In vivo, therefore, CARMIL should promote Arp2/3-dependent actin network assembly at the leading edge by promoting barbed-end capping there. PMID:24778263

Some transition metal complexes derived from mono- and di-ethynyl perfluorobenzenes.

PubMed

Armitt, David J; Bruce, Michael I; Gaudio, Maryka; Zaitseva, Natasha N; Skelton, Brian W; White, Allan H; Le Guennic, Boris; Halet, Jean-François; Fox, Mark A; Roberts, Rachel L; Hartl, Frantisek; Low, Paul J

2008-12-21

Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) and RuCl(dppe)Cp' [Cp' = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(C[triple bond, length as m-dash]CC(6)F(5))(dppe)Cp' [Cp' = Cp (); Cp* ()], which are related to the known compound Ru(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3))(2)Cp (). Treatment of Me(3)SiC[triple bond, length as m-dash]CC(6)F(5) with Pt(2)(mu-dppm)(2)Cl(2) in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt(2)(mu-dppm)(2)(C[triple bond, length as m-dash]CC(6)F(5))(2) (). The Pd(0)/Cu(i)-catalysed reactions between Au(C[triple bond, length as m-dash]CC(6)F(5))(PPh(3)) and Mo( identical withCBr)(CO)(2)Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co(3)(mu(3)-CBr)(mu-dppm)(CO)(7) or IC[triple bond, length as m-dash]CFc [Fc = (eta(5)-C(5)H(4))FeCp] afford Mo( identical withCC[triple bond, length as m-dash]CC(6)F(5))(CO)(2)Tp* (), Co(3)(mu(3)-CC[triple bond, length as m-dash]CC(6)F(5))(mu-dppm)(CO)(7) () and FcC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CC(6)F(5) (), respectively. The diruthenium complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)F(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()] are prepared from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)F(4) in a manner similar to that described for the monoruthenium complexes -. The non-fluorinated complexes 1,4-{Cp'(PP)RuC[triple bond, length as m-dash]C}(2)C(6)H(4) [(PP)Cp' = (PPh(3))(2)Cp (); (dppe)Cp (); (dppe)Cp* ()], prepared for comparison, are obtained from 1,4-(Me(3)SiC[triple bond, length as m-dash]C)(2)C(6)H(4). Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes - and -, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes , , , and .

Practice on improving fattening local cattle production in Vietnam by increasing crude protein level in concentrate and concentrate level.

PubMed

Van Dung, Dinh; Ba, Nguyen Xuan; Van, Nguyen Huu; Phung, Le Dinh; Ngoan, Le Duc; Cuong, Vu Chi; Yao, Wen

2013-10-01

Two experiments were conducted to determine the effects of crude protein (CP) level in concentrate (experiment 1) and concentrate level (experiment 2) on feed intake, nutrient digestibility, nitrogen (N) retention, ruminal pH and NH3-N concentration and average daily gain (ADG) of Vietnamese local fattening cattle. Animals (24 cattle, initial live weight (LW) 150.3 ± 11.8 kg in experiment 1 and 145.1 ± 9.8 kg in experiment 2) were allotted based on LW to one of four treatments in a randomised complete block design. In experiment 1, concentrate with four levels of CP (10, 13, 16 and 19 %) was fed at 1.5 % of LW. In experiment 2, concentrate was fed at 1.0, 1.4, 1.8 and 2.2 % of LW. In both experiments, roughage was 5 kg/day native grass and ad libitum rice straw (fresh basis). Results showed that the CP level in concentrate significantly affected dry matter (DM) intake (P < 0.05), N retention, ADG and ruminal NH3-N concentration (P < 0.01), but it had no significant effect on DM, organic matter (OM) and neutral detergent fibre (NDF) digestibility (P > 0.05), whereas CP digestibility increased (P < 0.001) along with the CP level. DM intake, N retention and ADG increased (P < 0.001) linearly with concentrate intake. DM and CP digestibility were not significantly affected by concentrate intake (P > 0.05). OM digestibility and NH3-N concentration increased linearly (P < 0.05), whereas NDF digestibility and ruminal pH declined linearly with increased concentrate consumption (P < 0.01). These results indicate that 16 % CP in concentrate and feeding concentrate at the rate of 2.2 % of LW are recommendable for fattening local cattle in Vietnam.

Molybdenum Hydride and Dihydride Complexes Bearing Diphosphine Ligands with a Pendant Amine: Formation of Complexes With Bound Amines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Shaoguang; Bullock, R. Morris

2015-07-06

CpMo(CO)(PNP)H complexes (PNP = (R2PCH2)2NMe, R = Et or Ph) were synthesized by displacement of two CO ligands of CpMo(CO)3H by the PNP ligand; these complexes were characterized by IR and variable temperature 1H and 31P NMR spectroscopy. CpMo(CO)(PNP)H complexes are formed as mixture of cis and trans-isomers. Both cis-CpMo(CO)(PEtNMePEt)H and trans-CpMo(CO)(PPhNMePPh)H were analyzed by single crystal X-ray diffraction. Electrochemical oxidation of CpMo(CO)(PEtNMePEt)H and CpMo(CO)(PPhNMePPh)H in CH3CN are both irreversible at slow scan rates and quasi-reversible at higher scan rates, with E1/2 = -0.36 V (vs. Cp2Fe+/0) for CpMo(CO)(PEtNMePEt)H and E1/2 = -0.18 V for CpMo(CO)(PPhNMePPh)H. Hydride abstraction from CpMo(CO)(PNP)Hmore » with [Ph3C]+[A]- (A = B(C6F5)4 or BArF4; [ArF = 3,5-bis(trifluoromethyl)phenyl]) afforded “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes that feature the amine bound to the metal. Displacement of the κ3 Mo-N bond by CD3CN gives [CpMo(CO)(PNP)(CD3CN)]+. The kinetics of this reaction were studied by NMR spectroscopy, providing the activation parameters ΔH‡ = 22.1 kcal/mol, ΔS‡ = 1.89 cal/(mol·K), Ea = 22.7 kcal/mol. Protonation of CpMo(CO)(PEtNMePEt)H affords [CpMo(CO)(κ2-PEtNMePEt)(H)2]+ as a Mo dihydride complex, which loses H2 to generate [CpMo(CO)(κ3-PEtNMePEt)]+ at room temperature. CpMo(CO)(dppp)H (dppp = 1,2-bis(diphenylphosphino)propane) was studied as a Mo diphosphine analogue without a pendant amine, and the product of protonation of this complex gives [CpMo(CO)(dppp)(H)2]+. Our results show that the pendant amine has a strong driving force to form stable “tuck-in” [CpMo(CO)(κ3-PNP)]+ complexes, and also promotes hydrogen elimination from [CpMo(CO)(PNP)(H)2]+ complexes by formation of Mo-N dative bond. We thank the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences for support. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy. We thank Monte Helm, Elliott Hulley and Deanna Miller for help on the crystallography, and Ming Fang for assistance on the electrochemical experiments.« less

Hypo-electronic triple-decker sandwich complexes: synthesis and structural characterization of [(Cp*Mo)2{μ-η(6):η(6)-B4H4E-Ru(CO)3}] (E = S, Se, Te or Ru(CO)3 and Cp* = η(5)-C5Me5).

PubMed

Mondal, Bijan; Bhattacharyya, Moulika; Varghese, Babu; Ghosh, Sundargopal

2016-07-05

The syntheses and structural characterization of hypo-electronic di-molybdenum triple-decker sandwich clusters are reported. Thermolysis of [Ru3(CO)12] with an in situ generated intermediate obtained from the reaction of [Cp*MoCl4] with [LiBH4·THF] yielded an electron deficient triple-decker sandwich complex, [(Cp*Mo)2{μ-η(6):η(6)-B4H4Ru2(CO)6}], . In an effort to generate analogous triple-deckers containing group-16 elements, we isolated [(Cp*Mo)2{μ-η(6):η(6)-B4H4ERu(CO)3}] (: E = Te; : E = S; : E = Se). These clusters show a high metal coordination number and cross cluster Mo-Mo bond. The formal cluster electron count of these compounds is four or three skeletal electron pairs less than required for a canonical closo-structure of the same nuclearity. Therefore, these compounds represent a novel class of triple-decker sandwich complex with 22 or 24 valence-electrons (VE), wherein the "chair" like hexagonal middle ring is composed of B, Ru and chalcogen. One of the key differences among the synthesized triple-decker molecules is the puckering nature of the middle ring [B4RuE], which increases in the order S < Se < Ru(CO)3 < Te. In addition, Fenske-Hall and quantum-chemical calculations with DFT methods at the BP86 level of theory have been used to analyze the bonding of these novel complexes. The studies not only explain the electron unsaturation of the molecules, but also reveal the reason for the significant puckering of the middle deck. All the compounds have been characterized by IR, (1)H, (11)B, and (13)C NMR spectroscopy in solution and the solid state structures were established by crystallographic analysis.

Molecular characterization of the NADPH oxidase complex in the ergot fungus Claviceps purpurea: CpNox2 and CpPls1 are important for a balanced host-pathogen interaction.

PubMed

Schürmann, Janine; Buttermann, Dagmar; Herrmann, Andrea; Giesbert, Sabine; Tudzynski, Paul

2013-10-01

Reactive oxygen species producing NADPH oxidase (Nox) complexes are involved in defense reactions in animals and plants while they trigger infection-related processes in pathogenic fungi. Knowledge about the composition and localization of these complexes in fungi is limited; potential components identified thus far include two to three catalytical subunits, a regulatory subunit (NoxR), the GTPase Rac, the scaffold protein Bem1, and a tetraspanin-like membrane protein (Pls1). We showed that, in the biotrophic grass-pathogen Claviceps purpurea, the catalytical subunit CpNox1 is important for infection. Here, we present identification of major Nox complex partners and a functional analysis of CpNox2 and the tetraspanin CpPls1. We show that, as in other fungi, Nox complexes are important for formation of sclerotia; CpRac is, indeed, a complex partner because it interacts with CpNoxR, and CpNox1/2 and CpPls1 are associated with the endoplasmatic reticulum. However, unlike in all other fungi, Δcppls1 is more similar to Δcpnox1 than to Δcpnox2, and CpNox2 is not essential for infection. In contrast, Δcpnox2 shows even more pronounced disease symptoms, indicating that Cpnox2 controls the infection process and moderates damage to the host. These data confirm that fungal Nox complexes have acquired specific functions dependent of the lifestyle of the pathogen.

Reduction chemistry of neptunium cyclopentadienide complexes: from structure to understanding† †Electronic supplementary information (ESI) available: General procedures, synthetic details, spectroscopic data, X-ray crystallographic data. CCDC 1524162–1524166. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00034k Click here for additional data file. Click here for additional data file.

PubMed Central

Dutkiewicz, Michał S.; Apostolidis, Christos

2017-01-01

Neptunium complexes in the formal oxidation states II, III, and IV supported by cyclopentadienyl ligands are explored, and significant differences between Np and U highlighted as a result. A series of neptunium(iii) cyclopentadienyl (Cp) complexes [Np(Cp)3], its bis-acetonitrile adduct [Np(Cp)3(NCMe)2], and its KCp adduct K[Np(Cp)4] and [Np(Cp′)3] (Cp′ = C5H4SiMe3) have been made and characterised providing the first single crystal X-ray analyses of NpIII Cp complexes. In all NpCp3 derivatives there are three Cp rings in η5-coordination around the NpIII centre; additionally in [Np(Cp)3] and K[Np(Cp)4] one Cp ring establishes a μ-η1-interaction to one C atom of a neighbouring Np(Cp)3 unit. The solid state structure of K[Np(Cp)4] is unique in containing two different types of metal–Cp coordination geometries in the same crystal. NpIII(Cp)4 units are found exhibiting four units of η5-coordinated Cp rings like in the known complex [NpIV(Cp)4], the structure of which is now reported. A detailed comparison of the structures gives evidence for the change of ionic radii of ca. –8 pm associated with change in oxidation state between NpIII and NpIV. The rich redox chemistry associated with the syntheses is augmented by the reduction of [Np(Cp′)3] by KC8 in the presence of 2.2.2-cryptand to afford a neptunium(ii) complex that is thermally unstable above –10 °C like the UII and ThII complexes K(2.2.2-cryptand)[Th/U(Cp′)3]. Together, these spontaneous and controlled redox reactions of organo-neptunium complexes, along with information from structural characterisation, show the relevance of organometallic Np chemistry to understanding fundamental structure and bonding in the minor actinides. PMID:28553487

The kinetics and mechanism of the organo-iridium catalysed racemisation of amines.

PubMed

Stirling, Matthew J; Mwansa, Joseph M; Sweeney, Gemma; Blacker, A John; Page, Michael I

2016-08-07

The dimeric iodo-iridium complex [IrCp*I2]2 (Cp* = pentamethylcyclopentadiene) is an efficient catalyst for the racemisation of secondary and tertiary amines at ambient and higher temperatures with a low catalyst loading. The racemisation occurs with pseudo-first-order kinetics and the corresponding four rate constants were obtained by monitoring the time dependence of the concentrations of the (R) and (S) enantiomers starting with either pure (R) or (S) and show a first-order dependence on catalyst concentration. Low temperature (1)H NMR data is consistent with the formation of a 1 : 1 complex with the amine coordinated to the iridium and with both iodide anions still bound to the metal-ion, but at the higher temperatures used for kinetic studies binding is weak and so no saturation zero-order kinetics are observed. A cross-over experiment with isotopically labelled amines demonstrates the intermediate formation of an imine which can dissociate from the iridium complex. Replacing the iodides in the catalyst by other ligands or having an amide substituent in Cp* results in a much less effective catalysts for the racemisation of amines. The rate constants for a deuterated amine yield a significant primary kinetic isotope effect kH/kD = 3.24 indicating that hydride transfer is involved in the rate-limiting step.

Naturally occurring deletions/insertions in HBV core promoter tend to decrease in hepatitis B e antigen-positive chronic hepatitis B patients during antiviral therapy.

PubMed

Peng, Yaqin; Liu, Baoming; Hou, Jinlin; Sun, Jian; Hao, Ran; Xiang, Kuanhui; Yan, Ling; Zhang, Jiangbo; Zhuang, Hui; Li, Tong

2015-01-01

Mutations in HBV core promoter (CP) are suggested to affect viral replication and disease progression. We investigated CP deletion/insertion mutations (Del/Ins) in hepatitis B e antigen (HBeAg)-positive chronic hepatitis B (CHB) patients before and during antiviral treatment. Direct and clone sequencings were used for detection of CP Del/Ins in 12 patients. The dynamic changes of CP Del/Ins were tracked in these cases until week 48 of treatment. The effects of Del/Ins on CP activities and hepatitis B X protein (HBx) were analysed using luciferase assay and sequence comparison, respectively. Furthermore, 292 untreated HBeAg-positive CHB cases were also analysed. Twelve cases with multi-peak PCR direct sequencing electropherograms at baseline were confirmed to have CP Del/Ins by clone sequencing, with detection rates varying from 14.8% to 93.3% of clones analysed. Follow-up studies showed the detection rates of CP Del/Ins in patients decreased from 100% (12/12) at baseline to 16.7% (2/12) at week 48 of treatment (P<0.001), in parallel with a decline in HBV DNA, hepatitis B surface antigen (HBsAg), alanine aminotransferase (ALT) and aspartate transaminase (AST) levels along with an increase in HBeAg loss. Luciferase assay results showed distinct promoter activities among Del/Ins-harbouring CP sequences. Importantly, 71.8% (148/206) of Del/Ins sequences potentially resulted in HBx carboxy-terminal truncations. CP Del/Ins mutations were also found in 27.4% (80/292) of untreated cases. Naturally occurring complex of CP Del/Ins mutants existed in untreated HBeAg-positive CHB patients. These mutations would affect HBV transcription activities and integrity of HBx, which might correlate with disease progression. Their prevalence decreases on antiviral therapy in parallel with the decline in HBV DNA, HBsAg and ALT and AST levels.

Design and Characterization of Phosphine Iron Hydrides: Toward Hydrogen-Producing Catalysts.

PubMed

Weber, Katharina; Weyhermüller, Thomas; Bill, Eckhard; Erdem, Özlen F; Lubitz, Wolfgang

2015-07-20

Diamagnetic iron chloro compounds [(P(Ph)2N(Ph)2)FeCp*Cl] [1Cl] and [(P(Cy)2N(Ph)2)FeCp*Cl] [2Cl] and the corresponding hydrido complexes [(P(Ph)2N(Ph)2)FeCp*H] [1H] and [(P(Cy)2N(Ph)2)FeCp*H] [2H] have been synthesized and characterized by NMR spectroscopy, electrochemical studies, electronic absorption, and (57)Fe Mössbauer spectroscopy (P(Ph)2N(Ph)2 = 1,3,5,7-tetraphenyl-1,5-diphospha-3,7-diazacyclooctane, P(Cy)2N(Ph)2 = 1,5-dicyclohexyl-3,7-diphenyl-1,5-diphospha-3,7-diazacyclooctane, Cp* = pentamethylcyclopentadienyl). Molecular structures of [2Cl], [1H], and [2H], derived from single-crystal X-ray diffraction, revealed that these compounds have a typical piano-stool geometry. The results show that the electronic properties of the hydrido complexes are strongly influenced by the substituents at the phosphorus donor atoms of the P(R)2N(Ph)2 ligand, whereas those of the chloro complexes are less affected. These results illustrate that the hydride is a strong-field ligand, as compared to chloride, and thus leads to a significant degree of covalent character of the iron hydride bonds. This is important in the context of possible catalytic intermediates of iron hydrido species, as proposed for the catalytic cycle of [FeFe] hydrogenases and other synthetic catalysts. Both hydrido compounds [1H] and [2H] show enhanced catalytic currents in cyclic voltammetry upon addition of the strong acid trifluoromethanesulfonimide [NHTf2] (pKa(MeCN) = 1.0). In contrast to the related complex [(P(tBu)N(Bn))2FeCp(C6F5)H], which was reported by Liu et al. (Nat. Chem. 2013, 5, 228-233) to be an electrocatalyst for hydrogen splitting, the here presented hydride complexes [1H] and [2H] show the tendency for electrocatalytic hydrogen production. Hence, the catalytic direction of this class of monoiron compounds can be reversed by specific ligand modifications.

Comparison of inter-trial recovery times for the determination of critical power and W' in cycling.

PubMed

Karsten, Bettina; Hopker, James; Jobson, Simon A; Baker, Jonathan; Petrigna, Luca; Klose, Andreas; Beedie, Christopher

2017-07-01

Critical Power (CP) and W' are often determined using multi-day testing protocols. To investigate this cumbersome testing method, the purpose of this study was to compare the differences between the conventional use of a 24-h inter-trial recovery time with those of 3 h and 30 min for the determination of CP and W'. 9 moderately trained cyclists performed an incremental test to exhaustion to establish the power output associated with the maximum oxygen uptake (p[Formula: see text] max ), and 3 protocols requiring time-to-exhaustion trials at a constant work-rate performed at 80%, 100% and 105% of p[Formula: see text] max. Design: Protocol A utilised 24-h inter-trial recovery (CP 24 /W' 24 ), protocol B utilised 3-h inter-trial recovery (CP 3 /W' 3 ), and protocol C used 30-min inter-trial recovery period (CP 0.5 /W' 0.5 ). CP and W' were calculated using the inverse time (1/t) versus power (P) relation (P = W'(1/t) + CP). 95% Limits of Agreement between protocol A and B were -9 to 15 W; -7.4 to 7.8 kJ (CP/W') and between protocol A and protocol C they were -27 to 22 W; -7.2 to 15.1 kJ (CP/W'). Compared to criterion protocol A, the average prediction error of protocol B was 2.5% (CP) and 25.6% (W'), whilst for protocol C it was 3.7% (CP) and 32.9% (W'). 3-h and 30-min inter-trial recovery time protocols provide valid methods of determining CP but not W' in cycling.

The Ruthenostannylene Complex [Cp*(IXy)H2 Ru-Sn-Trip]: Providing Access to Unusual Ru-Sn Bonded Stanna-imine, Stannene, and Ketenylstannyl Complexes.

PubMed

Liu, Hsueh-Ju; Ziegler, Micah S; Tilley, T Don

2015-05-26

Reactivity studies of the thermally stable ruthenostannylene complex [Cp*(IXy)(H)2 Ru-Sn-Trip] (1; IXy=1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; Cp*=η(5) -C5 Me5 ; Trip=2,4,6-iPr3 C6 H2 ) with a variety of organic substrates are described. Complex 1 reacts with benzoin and an α,β-unsaturated ketone to undergo [1+4] cycloaddition reactions and afford [Cp*(IXy)(H)2 RuSn(κ(2) -O,O-OCPhCPhO)Trip] (2) and [Cp*(IXy)(H)2 RuSn(κ(2) -O,C-OCPhCHCHPh)Trip] (3), respectively. The reaction of 1 with ethyl diazoacetate resulted in a tin-substituted ketene complex [Cp*(IXy)(H)2 RuSn(OC2 H5 )(CHCO)Trip] (4), which is most likely a decomposition product from the putative ruthenium-substituted stannene complex. The isolation of a ruthenium-substituted stannene [Cp*(IXy)(H)2 RuSn(=Flu)Trip] (5) and stanna-imine [Cp*(IXy)(H)2 RuSn(κ(2) -N,O-NSO2 C6 H4 Me)Trip] (6) complexes was achieved by treatment of 1 with 9-diazofluorene and tosyl azide, respectively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Arsenic-Rich Polyarsenides Stabilized by Cp*Fe Fragments.

PubMed

Schmidt, Monika; Konieczny, David; Peresypkina, Eugenia V; Virovets, Alexander V; Balázs, Gabor; Bodensteiner, Michael; Riedlberger, Felix; Krauss, Hannes; Scheer, Manfred

2017-06-12

The redox chemistry of [Cp*Fe(η 5 -As 5 )] (1, Cp*=η 5 -C 5 Me 5 ) has been investigated by cyclic voltammetry, revealing a redox behavior similar to that of its lighter congener [Cp*Fe(η 5 -P 5 )]. However, the subsequent chemical reduction of 1 by KH led to the formation of a mixture of novel As n scaffolds with n up to 18 that are stabilized only by [Cp*Fe] fragments. These include the arsenic-poor triple-decker complex [K(dme) 2 ][{Cp*Fe(μ,η 2:2 -As 2 )} 2 ] (2) and the arsenic-rich complexes [K(dme) 3 ] 2 [(Cp*Fe) 2 (μ,η 4:4 -As 10 )] (3), [K(dme) 2 ] 2 [(Cp*Fe) 2 (μ,η 2:2:2:2 -As 14 )] (4), and [K(dme) 3 ] 2 [(Cp*Fe) 4 (μ 4 ,η 4:3:3:2:2:1:1 -As 18 )] (5). Compound 4 and the polyarsenide complex 5 are the largest anionic As n ligand complexes reported thus far. Complexes 2-5 were characterized by single-crystal X-ray diffraction, 1 H NMR spectroscopy, EPR spectroscopy (2), and mass spectrometry. Furthermore, DFT calculations showed that the intermediate [Cp*Fe(η 5 -As 5 )] - , which is presumably formed first, undergoes fast dimerization to the dianion [(Cp*Fe) 2 (μ,η 4:4 -As 10 )] 2- . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

NHC carbene supported half-sandwich hydridosilyl complexes of ruthenium: the impact of supporting ligands on Si∙∙∙H interligand interactions.

PubMed

Mai, Van Hung; Kuzmina, Lyudmila G; Churakov, Andrei V; Korobkov, Ilia; Howard, Judith A K; Nikonov, Georgii I

2016-01-07

Reaction of complex [CpRu(pyr)3][PF6] (3) with the NHC carbene IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) results in the NHC complex [Cp(IPr)Ru(pyr)2][PF6] (4), which was studied by NMR specroscopy and X-ray diffraction analysis. Reaction of [Cp(IPr)Ru(pyr)2][PF6] (4) with LiAlH4 leads to the trihydride Cp(IPr)RuH3 (5) characterised by spectroscopic methods. Heating compound 5 with hydrosilanes gives the dihydrido silyl derivatives Cp(IPr)RuH2(SiR3) (6). Systematic X-ray diffraction studies suggest that complexes 6 have stronger interligand Si∙∙∙H interactions than the isolobal phosphine complexes Cp(Pr3P)RuH2(SiR3).

Dynamic multi-segmental postural control in patients with chronic non-specific low back pain compared to pain-free controls: A cross-sectional study.

PubMed

McCaskey, Michael A; Wirth, Brigitte; Schuster-Amft, Corina; de Bruin, Eling D

2018-01-01

Reduced postural control is thought to contribute to the development and persistence of chronic non-specific low back pain (CNLBP). It is therefore frequently assessed in affected patients and commonly reported as the average amount of postural sway while standing upright under a variety of sensory conditions. These averaged linear outcomes, such as mean centre of pressure (CP) displacement or mean CP surface areas, may not reflect the true postural status. Adding nonlinear outcomes and multi-segmental kinematic analysis has been reported to better reflect the complexity of postural control and may detect subtler postural differences. In this cross-sectional study, a combination of linear and nonlinear postural parameters were assessed in patients with CNLBP (n = 24, 24-75 years, 9 females) and compared to symptom-free controls (CG, n = 34, 22-67 years, 11 females). Primary outcome was postural control measured by variance of joint configurations (uncontrolled manifold index, UI), confidence ellipse surface areas (CEA) and approximate entropy (ApEn) of CP dispersion during the response phase of a perturbed postural control task on a swaying platform. Secondary outcomes were segment excursions and clinical outcome correlates for pain and function. Non-parametric tests for group comparison with P-adjustment for multiple comparisons were conducted. Principal component analysis was applied to identify patterns of segmental contribution in both groups. CNLBP and CG performed similarly with respect to the primary outcomes. Comparison of joint kinematics revealed significant differences of hip (P < .001) and neck (P < .025) angular excursion, representing medium to large group effects (r's = .36 - .51). Significant (P's < .05), but moderate correlations of ApEn (r = -.42) and UI (r = -.46) with the health-related outcomes were observed. These findings lend further support to the notion that averaged linear outcomes do not suffice to describe subtle postural differences in CNLBP patients with low to moderate pain status.

Physical properties of superbulky lanthanide metallocenes: synthesis and extraordinary luminescence of [Eu(II)(Cp(BIG))2] (Cp(BIG) = (4-nBu-C6H4)5-cyclopentadienyl).

PubMed

Harder, Sjoerd; Naglav, Dominik; Ruspic, Christian; Wickleder, Claudia; Adlung, Matthias; Hermes, Wilfried; Eul, Matthias; Pöttgen, Rainer; Rego, Daniel B; Poineau, Frederic; Czerwinski, Kenneth R; Herber, Rolfe H; Nowik, Israel

2013-09-09

The superbulky deca-aryleuropocene [Eu(Cp(BIG))2], Cp(BIG) = (4-nBu-C6H4)5-cyclopentadienyl, was prepared by reaction of [Eu(dmat)2(thf)2], DMAT = 2-Me2N-α-Me3Si-benzyl, with two equivalents of Cp(BIG)H. Recrystallizyation from cold hexane gave the product with a surprisingly bright and efficient orange emission (45% quantum yield). The crystal structure is isomorphic to those of [M(Cp(BIG))2] (M = Sm, Yb, Ca, Ba) and shows the typical distortions that arise from Cp(BIG)⋅⋅⋅Cp(BIG) attraction as well as excessively large displacement parameter for the heavy Eu atom (U(eq) = 0.075). In order to gain information on the true oxidation state of the central metal in superbulky metallocenes [M(Cp(BIG))2] (M = Sm, Eu, Yb), several physical analyses have been applied. Temperature-dependent magnetic susceptibility data of [Yb(Cp(BIG))2] show diamagnetism, indicating stable divalent ytterbium. Temperature-dependent (151)Eu Mössbauer effect spectroscopic examination of [Eu(Cp(BIG))2] was examined over the temperature range 93-215 K and the hyperfine and dynamical properties of the Eu(II) species are discussed in detail. The mean square amplitude of vibration of the Eu atom as a function of temperature was determined and compared to the value extracted from the single-crystal X-ray data at 203 K. The large difference in these two values was ascribed to the presence of static disorder and/or the presence of low-frequency torsional and librational modes in [Eu(Cp(BIG))2]. X-ray absorbance near edge spectroscopy (XANES) showed that all three [Ln(Cp(BIG))2] (Ln = Sm, Eu, Yb) compounds are divalent. The XANES white-line spectra are at 8.3, 7.3, and 7.8 eV, for Sm, Eu, and Yb, respectively, lower than the Ln2O3 standards. No XANES temperature dependence was found from room temperature to 100 K. XANES also showed that the [Ln(Cp(BIG))2] complexes had less trivalent impurity than a [EuI2(thf)x] standard. The complex [Eu(Cp(BIG))2] shows already at room temperature strong orange photoluminescence (quantum yield: 45 %): excitation at 412 nm (24,270 cm(-1)) gives a symmetrical single band in the emission spectrum at 606 nm (νmax =16495 cm(-1), FWHM: 2090 cm(-1), Stokes-shift: 2140 cm(-1)), which is assigned to a 4f(6)5d(1) → 4f(7) transition of Eu(II). These remarkable values compare well to those for Eu(II)-doped ionic host lattices and are likely caused by the rigidity of the [Eu(Cp(BIG))2] complex. Sharp emission signals, typical for Eu(III), are not visible. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Daily Rhythmic Behaviors and Thermoregulatory Patterns Are Disrupted in Adult Female MeCP2-Deficient Mice

PubMed Central

Wu, Chiping; Bardakjian, Berj L.; Zhang, Liang; Eubanks, James H.

2012-01-01

Mutations in the X-linked gene encoding Methyl-CpG-binding protein 2 (MECP2) have been associated with neurodevelopmental and neuropsychiatric disorders including Rett Syndrome, X-linked mental retardation syndrome, severe neonatal encephalopathy, and Angelman syndrome. Although alterations in the performance of MeCP2-deficient mice in specific behavioral tasks have been documented, it remains unclear whether or not MeCP2 dysfunction affects patterns of periodic behavioral and electroencephalographic (EEG) activity. The aim of the current study was therefore to determine whether a deficiency in MeCP2 is sufficient to alter the normal daily rhythmic patterns of core body temperature, gross motor activity and cortical delta power. To address this, we monitored individual wild-type and MeCP2-deficient mice in their home cage environment via telemetric recording over 24 hour cycles. Our results show that the normal daily rhythmic behavioral patterning of cortical delta wave activity, core body temperature and mobility are disrupted in one-year old female MeCP2-deficient mice. Moreover, female MeCP2-deficient mice display diminished overall motor activity, lower average core body temperature, and significantly greater body temperature fluctuation than wild-type mice in their home-cage environment. Finally, we show that the epileptiform discharge activity in female MeCP2-deficient mice is more predominant during times of behavioral activity compared to inactivity. Collectively, these results indicate that MeCP2 deficiency is sufficient to disrupt the normal patterning of daily biological rhythmic activities. PMID:22523589

Effects of nutritional level of concentrate-based diets on meat quality and expression levels of genes related to meat quality in Hainan black goats.

PubMed

Wang, Dingfa; Zhou, Luli; Zhou, Hanlin; Hou, Guanyu; Shi, Liguang; Li, Mao; Huang, Xianzhou; Guan, Song

2015-02-01

The present study investigated the effects of the nutritional levels of diets on meat quality and related gene expression in Hainan black goat. Twenty-four goats were divided into six dietary treatments and were fed a concentrate-based diet with two levels of crude protein (CP) (15% or 17%) and three levels of digestive energy (DE) (11.72, 12.55 or 13.39 MJ/kg DM) for 90 days. Goats fed the concentrate-based diet with 17% CP had significantly (P < 0.05) higher average daily gains (ADG) and better feed conversion rates (FCR). The pH 24h value tended to decrease (P < 0.05) with increasing DE levels. The tenderness of Longissimus dorsi muscle (LD) and Semimembranosus muscle (SM) reduced with increasing CP levels (P < 0.05). With increasing DE levels, tenderness was increased (P < 0.05). The heart fatty acid-binding protein (H-FABP) mRNA expression levels in LD and SM increased with increasing DE levels (P < 0.05), but decreased with increasing CP levels (P < 0.05). The calpastatin (CAST) and μ-calpain mRNA expressions levels in LD and SM were affected significantly (P < 0.05) by CP and DE levels in the diet. Therefore, the nutritional levels of diets affect meat quality and expression levels of genes associated with meat quality in Hainan black goats. © 2014 Japanese Society of Animal Science.

CpG oligodeoxynucleotide nanomedicines for the prophylaxis or treatment of cancers, infectious diseases, and allergies.

PubMed

Hanagata, Nobutaka

2017-01-01

Unmethylated cytosine-guanine dinucleotide-containing oligodeoxynucleotides (CpG ODNs), which are synthetic agonists of Toll-like receptor 9 (TLR9), activate humoral and cellular immunity and are being developed as vaccine adjuvants to prevent or treat cancers, infectious diseases, and allergies. Free CpG ODNs have been used in many clinical trials implemented to verify their effects. However, recent research has reported that self-assembled CpG ODNs, protein/peptide-CpG ODN conjugates, and nanomaterial-CpG ODN complexes demonstrate higher adjuvant effects than free CpG ODNs, owing to their improved uptake efficiency into cells expressing TLR9. Moreover, protein/peptide-CpG ODN conjugates and nanomaterial-CpG ODN complexes are able to deliver CpG ODNs and antigens (or allergens) to the same types of cells, which enables a higher degree of prophylaxis or therapeutic effect. In this review, the author describes recent trends in the research and development of CpG ODN nanomedicines containing self-assembled CpG ODNs, protein/peptide-CpG ODN conjugates, and nanomaterial-CpG ODN complexes, focusing mainly on the results of preclinical and clinical studies.

Zirconocene-iridium hydrido complexes: arene carbon-hydrogen bond activation and formation of a planar square Zr2Ir2 complex.

PubMed

Oishi, Masataka; Suzuki, Hiroharu

2009-03-16

New early-late heterobimetallic hydrides (L(2)ZrCl)(Cp*Ir)(mu-H)(3) (1; L = Cp derivative, Cp* = eta(5)-C(5)Me(5)) were synthesized from zirconocene derivatives (L(2)ZrCl(2)) and LiCp*IrH(3) via a salt elimination reaction and structurally characterized by NMR and X-ray analyses. Upon treatment of 1 with an alkyllithium reagent, hydride abstraction complex 4 underwent thermolytic ligand elimination at the Zr-Ir system to yield a novel planar square complex (L(2)Zr)(2)(Cp*Ir)(2)(mu(3)-H)(4) (2). When a labeling study of the reaction was conducted, it was found that the conversion of 1 to 2 involves rapid aromatic and benzylic C-H activation by a coordinatively unsaturated dinuclear complex (L(2)Zr)(Cp*Ir)(H)(2) (3).

Two Discrete RuCp* (Cp*=Pentamethylcyclopentadienyl) Binding Modes of N-Confused Porphyrins: Peripheral π Complex and Sitting Atop Ruthenocenophane Complex by Skeletal Transformation.

PubMed

Yamamoto, Takaaki; Mitsuno, Koki; Mori, Shigeki; Itoyama, Shuhei; Shiota, Yoshihito; Yoshizawa, Kazunari; Ishida, Masatoshi; Furuta, Hiroyuki

2018-05-07

Complexation of a RuCp* cation with N-confused tetraarylporphyrins (NCPs) forms directly bound ruthenium(II) pentamethylcyclopentadienyl (Cp*) π-complex on a specific meso-aryl group (e.g., phenyl) neighboring peripheral imino nitrogen of NCPs in high yields. In contrast, in the case of NCPs bearing bulky meso-substituents (e.g., 3,5-di-tert-butylphenyl), new ruthenocenophane-like complex embedded on an N-confused calix[4]phyrin was formed through multiple C-H bond activation of methyl groups of Cp* ligand. The mechanistic insight into the formation of the ruthenocenophane was derived from DFT calculations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Base free N-alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp*Ir(iii) with chalcogenated Schiff bases of anthracene-9-carbaldehyde.

PubMed

Dubey, Pooja; Gupta, Sonu; Singh, Ajai K

2018-03-12

The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ](L1) and [PhSe(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ] (L2). On their reaction with [(η 5 -Cp*)IrCl(μ-Cl)] 2 and CH 3 COONa at 50 °C followed by treatment with NH 4 PF 6 , iridacycles, [(η 5 -Cp*)Ir(L-H)][PF 6 ] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH 3 COONa gives complexes [(η 5 -Cp*)Ir(L)Cl][PF 6 ] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [ 1 H, 13 C{ 1 H} and 77 Se{ 1 H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η 5 -Cp* and on the remaining three, donor atoms present are: N, S/Se and C - /Cl - , resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp* ring.

Synthesis and antibacterial studies of rhodium and iridium complexes comprising of dipyridyl hydrazones

NASA Astrophysics Data System (ADS)

Aradhyula, Basava Punna Rao; Joshi, Nidhi; Poluri, Krishna Mohan; Kollipara, Mohan Rao

2018-07-01

Reactions of Cp*Rh and Cp*Ir dimers with the dipyridyl hydrazones such as picolinic (L1), nicotinic (L2) and isonicotinic (L3) have been reported here with the formulations [Cp*MClL3](PF6) {where M = Rh (5) and Ir (6)}, [(Cp*MCl)2L1](PF6) {where M = Rh (7) and Ir (8)}, [(Cp*MCl)2L2Cl](PF6) {where M = Rh(9) and Ir(10)}, and [(Cp*MCl)2L3Cl](PF6) {where M = Rh (11) and Ir (12)} which resulted in a series of mono- and di-nuclear cationic complexes. The complexes have been characterized by various spectroscopic techniques. The solid-state structures of three complexes (5, 6 and 8) have been determined by single-crystal X-ray diffraction studies. These cationic complexes have been evaluated for the preliminary antibacterial activity towards four bacterial strains viz., Staphylococcus aureus; Bacillus thuringiensis; Escherichia coli and Pseudomonas aeruginosa by agar well diffusion method. Complexes have exhibited zone of inhibition over Bacillus thuringiensis; Escherichia coli and Pseudomonas aeruginosa strains while Staphylococcus aureus strain is resistant to the complexes 9-12. Surprisingly, these complexes are di-nuclear and trichloride complexes.

Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η(3)-allyl) Complexes.

PubMed

Baillie, Rhett A; Holmes, Aaron S; Lefèvre, Guillaume P; Patrick, Brian O; Shree, Monica V; Wakeham, Russell J; Legzdins, Peter; Rosenfeld, Devon C

2015-06-15

Sequential treatment at low temperatures of Cp*W(NO)Cl2 in THF with 1 equiv of a binary magnesium allyl reagent, followed by an excess of LiBH4, affords three new Cp*W(NO)(H)(η(3)-allyl) complexes, namely, Cp*W(NO)(H)(η(3)-CH2CHCMe2) (1), Cp*W(NO)(H)(η(3)-CH2CHCHPh) (2), and Cp*W(NO)(H)(η(3)-CH2CHCHMe) (3). Complexes 1-3 are isolable as air-stable, analytically pure yellow solids in good to moderate yields by chromatography or fractional crystallization. In solutions, complex 1 exists as two coordination isomers in an 83:17 ratio differing with respect to the endo/exo orientation of the allyl ligand. In contrast, complexes 2 and 3 each exist as four coordination isomers, all differing by the orientation of their allyl ligands which can have either an endo or an exo orientation with the phenyl or methyl groups being either proximal or distal to the nitrosyl ligand. A DFT computational analysis using the major isomer of Cp*W(NO)(H)(η(3)-CH2CHCHMe) (3a) as the model complex has revealed that its lowest-energy thermal-decomposition pathway involves the intramolecular isomerization of 3a to the 16e η(2)-alkene complex, Cp*W(NO)(η(2)-CH2═CHCH2Me). Such η(2)-alkene complexes are isolable as their 18e PMe3 adducts when compounds 1-3 are thermolyzed in neat PMe3, the other organometallic products formed during these thermolyses being Cp*W(NO)(PMe3)2 (5) and, occasionally, Cp*W(NO)(H)(η(1)-allyl)(PMe3). All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

Children with motor impairment related to cerebral palsy: Prevalence, severity and concurrent impairments in China.

PubMed

He, Ping; Chen, Gong; Wang, Zhenjie; Guo, Chao; Zheng, Xiaoying

2017-05-01

Cerebral palsy (CP) is the most common cause of motor impairment in childhood. This study aimed to examine the prevalence, severity and concurrent impairments of CP-related motor impairment among Chinese children. Children with CP-related motor impairment aged 0-17 years were identified through a national population-based survey based on World Health Organization International Classification of Functioning, Disability and Health. Logistic regression models allowing for weights were used to examine individual and family factors in relation to CP-related motor impairment. The weighted prevalence of CP-related motor impairment was 1.25 per 1000 children (95% confidence interval (CI): 1.16, 1.35) in China. Male children, children in multiples and in families where adults suffered from CP, were more likely to be affected by CP-related motor impairment. For mild, moderate, severe and extremely severe groups of motor impairment, weighted proportions of CP were 14.12% (95%CI: 11.70, 16.95), 20.35% (95%CI: 17.48, 23.56), 27.44% (95%CI: 24.25, 30.87) and 38.09% (95%CI: 34.55, 41.76), respectively; and weighted proportions of concurrent visual, hearing and cognitive impairment were 5.00% (95%CI: 3.59, 6.91), 6.98% (95%CI: 5.34, 9.08) and 71.06% (95%CI: 67.57, 74.31), respectively. Gender, multiple births and family adults with CP were significantly associated with CP-related motor impairment in Chinese children. Proportions of CP and concurrent impairments that increased with severity of motor impairment were observed. © 2017 Paediatrics and Child Health Division (The Royal Australasian College of Physicians).

Two key arginine residues in the coat protein of Bamboo mosaic virus differentially affect the accumulation of viral genomic and subgenomic RNAs.

PubMed

Hung, Chien-Jen; Hu, Chung-Chi; Lin, Na-Sheng; Lee, Ya-Chien; Meng, Menghsiao; Tsai, Ching-Hsiu; Hsu, Yau-Heiu

2014-02-01

The interactions between viral RNAs and coat proteins (CPs) are critical for the efficient completion of infection cycles of RNA viruses. However, the specificity of the interactions between CPs and genomic or subgenomic RNAs remains poorly understood. In this study, Bamboo mosaic virus (BaMV) was used to analyse such interactions. Using reversible formaldehyde cross-linking and mass spectrometry, two regions in CP, each containing a basic amino acid (R99 and R227, respectively), were identified to bind directly to the 5' untranslated region of BaMV genomic RNA. Analyses of the alanine mutations of R99 and R227 revealed that the secondary structures of CP were not affected significantly, whereas the accumulation of BaMV genomic, but not subgenomic, RNA was severely decreased at 24 h post-inoculation in the inoculated protoplasts. In the absence of CP, the accumulation levels of genomic and subgenomic RNAs were decreased to 1.1%-1.5% and 33%-40% of that of the wild-type (wt), respectively, in inoculated leaves at 5 days post-inoculation (dpi). In contrast, in the presence of mutant CPs, the genomic RNAs remained about 1% of that of wt, whereas the subgenomic RNAs accumulated to at least 87%, suggesting that CP might increase the accumulation of subgenomic RNAs. The mutations also restricted viral movement and virion formation in Nicotiana benthamiana leaves at 5 dpi. These results demonstrate that R99 and R227 of CP play crucial roles in the accumulation, movement and virion formation of BaMV RNAs, and indicate that genomic and subgenomic RNAs interact differently with BaMV CP. © 2013 BSPP AND JOHN WILEY & SONS LTD.

Unexpected Reactivity of [(η(5) -1,2,4-tBu3 C5 H2 )Ni(η(3) -P3 )] towards Main Group Nucleophiles and by Reduction.

PubMed

Mädl, Eric; Balázs, Gábor; Peresypkina, Eugenia V; Scheer, Manfred

2016-06-27

The reduction of [Cp'''Ni(η(3) -P3 )] (1; Cp'''=η(5) -1,2,4-tBu3 C5 H2 ) with potassium produces the complex anion [(Cp'''Ni)2 (μ,η(2:2) -P8 )](2-) (2), which contains a realgar-like P8 unit. The anionic triple-decker sandwich complex [(Cp'''Ni)2 (μ,η(3:3) -P3 )](-) (3) with a cyclo-P3 middle deck is obtained when 1 is treated with NaNH2 as a nucleophile. Na[3] can subsequently be oxidized with AgOTf to the neutral triple-decker complex [(Cp'''Ni)2 (μ,η(3:3) -P3 )] (4). In contrast, 1 reacts with LiPPh2 to give the anionic compound [(Cp'''Ni)2 (μ,η(2:2) -P6 PPh2 )](-) (5), a complex containing a bicyclic P7 fragment capped by two Cp'''Ni units. Protonation of Li[5] with HBF4 leads to the neutral complex [(Cp'''Ni)2 (μ,η(2:2) -(HP6 PPh2 )] (6). Adding LiNMe2 to 1 results in [Cp'''Ni(η(2) -P3 NMe2 )](-) (7) becoming accessible, a complex which forms as a result of nucleophilic attack at the cyclo-P3 ring of 1. The complexes K2 [2], Na[3], 4, 6, and Li[7] were fully characterized and their structures determined by single-crystal X-ray diffraction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of calculated and experimentally determined SID of CP and AA in complex diets differing in AA contents for grower finisher pigs.

PubMed

Büsing, K; Berk, A; Müller, S; Kieckhäven, S; Krüger, K; Zeyner, A

2017-10-01

In practice, the content of standardized ileal digestible AA in complex feeds for pigs is calculated on the basis of tabulated values for individual feedstuffs. It comes into question, however, whether this truly reflects an accurate content based upon the estimate made for the individual feedstuffs. The objective of this study was to compare standardized ileal digestibility (SID) of crude protein (CP) and selected AA in complex feeds for grower and finisher pigs either calculated or experimentally determined. Six diets with increasing AA levels were prepared for grower (BW from 30 to 70 kg) and finisher (BW from 70 to 120 kg) feed. Crystalline L-lys, DL-met and L-thr were added to both diets, L-trp and L-val only to the grower feed. SID of both CP and AA was calculated from feed tables and experimentally determined in six adult minipigs (MINILEWE) with ileorectal anastomosis. With increasing AA levels, experimentally determined SID of supplemented AA increased (p < 0.05), but SID of CP (p ≥ 0.05) was not affected. In both grower and finisher feed, calculated and experimentally determined SID of CP, Met, Cys, Trp, Ile and Tyr differed by more than 2% units, but those of Lys and His only in the finisher feed. Yet this effect was not directly consistent. The margin of error following estimation of SID of AA via tabulated values for individual feedstuffs, however, seems to be acceptable for practical use. Journal of Animal Physiology and Animal Nutrition © 2017 Blackwell Verlag GmbH.

The chloroplast signal recognition particle (CpSRP) pathway as a tool to minimize chlorophyll antenna size and maximize photosynthetic productivity.

PubMed

Kirst, Henning; Melis, Anastasios

2014-01-01

The concept of the Truncated Light-harvesting chlorophyll Antenna (TLA) size, as a tool by which to maximize sunlight utilization and photosynthetic productivity in microalgal mass cultures or high-density plant canopies, is discussed. TLA technology is known to improve sunlight-to-product energy conversion efficiencies and is hereby exemplified by photosynthetic productivity estimates of wild type and a TLA strain under simulated mass culture conditions. Recent advances in the generation of TLA-type mutants by targeting genes of the chloroplast signal-recognition particle (CpSRP) pathway, affecting the thylakoid membrane assembly of light-harvesting proteins, are also summarized. Two distinct CpSRP assembly pathways are recognized, one entailing post-translational, the other a co-translational mechanism. Differences between the post-translational and co-translational integration mechanisms are outlined, as these pertain to the CpSRP-mediated assembly of thylakoid membrane protein complexes in higher plants and green microalgae. The applicability of the CpSRP pathway genes in efforts to generate TLA-type strains with enhanced solar energy conversion efficiency in photosynthesis is evaluated. © 2013.

Design and Development of a 5,000 Barrel Collapsible Fabric Petroleum Fuel Tank Assembly.

DTIC Science & Technology

1981-08-01

Compounds 4 Characteristics of Coated Fabric 24 5 Caracteristics of Bonded Fittings 26 6 Characteristics of Seams 27 v LIST OF APPENDICES PAGE APPENDIX "A...Foot Hose, 6 Feet CP24-0061 Elastofab Ground Cloth, Polyethlene CP92-0037 Read Plastics 1/2-Inch Rising Stem Gate Valve CP24-0018 Speakman 6-Inch...Distributing Company Easton Steel 83 North Main Street P. 0. Box 599 Yardley PA 19067 Easton MD 21601 SAS Gasket and Supply Co. Bronze & Plastic Specialties

Comparative solution equilibrium studies on pentamethylcyclopentadienyl rhodium complexes of 2,2'-bipyridine and ethylenediamine and their interaction with human serum albumin.

PubMed

Enyedy, Éva A; Mészáros, János P; Dömötör, Orsolya; Hackl, Carmen M; Roller, Alexander; Keppler, Bernhard K; Kandioller, Wolfgang

2015-11-01

Complex formation equilibrium processes of the (N,N) donor containing 2,2'-bipyridine (bpy) and ethylenediamine (en) with (η(5)-pentamethylcyclopentadienyl)rhodium(III) were investigated in aqueous solution via pH-potentiometry, (1)H NMR spectroscopy, and UV-vis spectrophotometry in the absence and presence of chloride ions. The structure of [RhCp*(en)Cl]ClO4 (Cp*, pentamethylcyclopentadienyl) was also studied by single-crystal X-ray diffraction. pKa values of 8.56 and 9.58 were determined for [RhCp*(bpy)(H2O)](2+) and [RhCp*(en)(H2O)](2+), respectively resulting in the formation of negligible amount of mixed hydroxido complexes at pH 7.4. Stability and the H2O/Cl(-) co-ligand exchange constants of bpy and en complexes considerably exceed those of the bidentate O-donor deferiprone. The strong affinity of the bpy and en complexes to chloride ions most probably contributes to their low antiproliferative effect. Interactions between human serum albumin (HSA) and [RhCp*(H2O)3](2+), its complexes formed with deferiprone, bpy and en were also monitored by (1)H NMR spectroscopy, ultrafiltration/UV-vis and spectrofluorometry. Numerous binding sites (≥ 8) are available for [RhCp*(H2O)3](2+); and the interaction takes place most probably via covalent bonds through the imidazole nitrogen of His. According to the various fluorescence studies [RhCp*(H2O)3](2+) binds on sites I and II, and coordination of surface side chain donor atoms of the protein is also feasible. The binding of the bpy and en complex is weaker and slower compared to that of [RhCp*(H2O)3](2+), and formation of ternary HSA-RhCp*-ligand adducts was proved. In the case of the deferiprone complex, the RhCp* fragment is cleaved off when HSA is loaded with low equivalents of the compound.

Reactivity of cyclopentadienyl transition metal(ii) complexes with borate ligands: structural characterization of the toluene-activated molybdenum complex [Cp*Mo(CO)2(η3-CH2C6H5)].

PubMed

Ramalakshmi, Rongala; Maheswari, K; Sharmila, Dudekula; Paul, Anamika; Roisnel, Thierry; Halet, Jean-François; Ghosh, Sundargopal

2016-10-18

Reactions of cyclopentadienyl transition-metal halide complexes [Cp*Mo(CO) 3 Cl], 1, and [CpFe(CO) 2 I], 2, (Cp = C 5 H 5 ; Cp* = η 5 -C 5 Me 5 ) with borate ligands are reported. Treatment of 1 with [NaBt 2 ] (Bt 2 = dihydrobis(2-mercapto-benzothiazolyl)borate) in toluene yielded [Cp*Mo(CO) 2 (C 7 H 4 S 2 N)], 3, and [Cp*Mo(CO) 2 (η 3 -CH 2 C 6 H 5 )], 4, with a selective binding of toluene through C-H activation followed by orthometallation. Note that compound 4 is a structurally characterized toluene-activated molecule in which the metal is in η 3 -coordination mode. Under similar reaction conditions, [NaPy 2 ] (Py 2 = dihydrobis(2-mercaptopyridyl)borate) produced only the mercaptopyridyl molybdenum complex [Cp*Mo(CO) 2 (C 5 H 4 SN)], 5, in good yield. On the other hand, when compound 2 was treated individually with [NaBt] (Bt = trihydro(2-mercapto-benzothiazolyl)borate) and [NaPy 2 ] in THF, formation of the η 1 -coordinated complexes [CpFe(CO) 2 (C 7 H 4 S 2 N)], 6, and [CpFe(CO) 2 (C 5 H 4 SN)], 7, was observed. The solid-state molecular structures of compounds 3, 4, 6, and 7 have been established by single-crystal X-ray crystallographic analyses.

DNA methylation levels at chromosome 8q24 in peripheral blood are associated with 8q24 cancer susceptibility loci.

PubMed

Barry, Kathryn Hughes; Moore, Lee E; Sampson, Joshua; Yan, Liying; Meyer, Ann; Oler, Andrew J; Chung, Charles C; Wang, Zhaoming; Yeager, Meredith; Amundadottir, Laufey; Berndt, Sonja I

2014-12-01

Chromosome 8q24 has emerged as an important region for genetic susceptibility to various cancers, but little is known about the contribution of DNA methylation at 8q24. To evaluate variability in DNA methylation levels at 8q24 and the relationship with cancer susceptibility single nucleotide polymorphisms (SNPs) in this region, we quantified DNA methylation levels in peripheral blood at 145 CpG sites nearby 8q24 cancer susceptibility SNPs or MYC using pyrosequencing among 80 Caucasian men in the Prostate, Lung, Colorectal, and Ovarian Cancer Screening Trial. For the 60 CpG sites meeting quality control, which also demonstrated temporal stability over a 5-year period, we calculated pairwise Spearman correlations for DNA methylation levels at each CpG site with 42 8q24 cancer susceptibility SNPs. To account for multiple testing, we adjusted P values into q values reflecting the false discovery rate (FDR). In contrast to the MYC CpG sites, most sites nearby the SNPs demonstrated good reproducibility, high methylation levels, and moderate-high between-individual variation. We observed 10 statistically significant (FDR < 0.05) CpG site-SNP correlations. These included correlations between an intergenic CpG site at Chr8:128393157 and the prostate cancer SNP rs16902094 (ρ = -0.54; P = 9.7 × 10(-7); q = 0.002), a PRNCR1 CpG site at Chr8:128167809 and the prostate cancer SNP rs1456315 (ρ = 0.52; P = 1.4 × 10(-6); q = 0.002), and two POU5F1B CpG sites and several prostate/colorectal cancer SNPs (for Chr8:128498051 and rs6983267, ρ = 0.46; P = 2.0 × 10(-5); q = 0.01). This is the first report of correlations between blood DNA methylation levels and cancer susceptibility SNPs at 8q24, suggesting that DNA methylation at this important susceptibility locus may contribute to cancer risk. ©2014 American Association for Cancer Research.

Organometallic rhodium(III) and iridium(III) cyclopentadienyl complexes with curcumin and bisdemethoxycurcumin co-ligands.

PubMed

Pettinari, Riccardo; Marchetti, Fabio; Pettinari, Claudio; Condello, Francesca; Petrini, Agnese; Scopelliti, Rosario; Riedel, Tina; Dyson, Paul J

2015-12-21

A series of half-sandwich cyclopentadienyl rhodium(III) and iridium(III) complexes of the type [Cp*M(curc/bdcurc)Cl] and [Cp*M(curc/bdcurc)(PTA)][SO3CF3], in which Cp* = pentamethylcyclopentadienyl, curcH = curcumin and bdcurcH = bisdemethoxycurcumin as O^O-chelating ligands, and PTA = 1,3,5-triaza-7-phosphaadamantane, is described. The X-ray crystal structures of three of the complexes, i.e. [Cp*Rh(curc)(PTA)][SO3CF3] (5), [Cp*Rh(bdcurc)(PTA)][SO3CF3] (6) and [Cp*Ir(bdcurc)(PTA)][SO3CF3] (8), confirm the expected "piano-stool" geometry. With the exception of 5, the complexes are stable under pseudo-physiological conditions and are moderately cytotoxic to human ovarian carcinoma (A2780 and A2780cisR) cells and also to non-tumorigenic human embryonic kidney (HEK293) cells, but lack the cancer cell selectivity observed for related arene ruthenium(II) complexes.

Kinetic and mechanistic aspects of propene oligomerization with ionic organozirconium and -hafnium compounds: Crystal structures of [Cp* {sub 2}MMe(THT)]{sup +}[BPh{sub 4}]{sup {minus}} (M=Zr, Hf)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eshuis, J.J.W.; Tan, Y.Y.; Meetsma, A.

1992-01-01

In N,N-dimethylaniline the ionic complexes [Cp{sup *}{sub 2}MMe(THT)]{sup +}[BPh{sub 4}]{sup {minus}}(M=Zr,Hf) oligomerize propene to low molecular weight oligomers. At room temperature for M = Zr a rather broad molecular weight distribution is obtained (C{sub 6} to C{sub 24}), whereas for M = Hf only one dimer (4-methyl-1-pentene) and one trimer (4,6-dimethyl-1-heptene) are formed. With an increase in temperature the product composition shifts to lower molecular weights, but the specific formation of head-to-tail oligomers is retained. The oligomers are formed by {beta}-Me transfer from the growing oligopropene alkyl chain to the metal center. The molecular weight distributions of the oligomers producedmore » at temperature between 5 and 45 {degrees}C are satisfactorily described by the Flory-Schulz theory. This allows the calculation of ratios of rate coefficients for propagation (k{sub p}) and termination (k{sub t}). Inactivation of the catalysts is caused by two different mechanisms. At room temperature allylic C-H activation of monomer and isobutene (formed by a minor {beta}-H transfer termination) gives inactive (meth) allyl compounds, [Cp{sup *} {sub 2}M({eta}{sup 3}-C{sub 3}H{sub 5})]{sup +} and [Cp{sup *}{sub 2}M({eta}{sup 3}-C{sub 4}H{sub 7})]{sup +} (M = Zr, Hf). At elevated temperatures (>45 {degrees}C) catalytically inactive zwitterionic complexes Cp{sup *}{sub M}{sup +}-m-C{sub 6}H{sub 4}-BPh{sub 3}{sup {minus}}(M = Zr, Hf) are formed through aromatic C-H activation. Reactivation of the inactive (meth)allyl complexes can be achieved by addition of hydrogen to the oligomerization mixtures. 38 refs., 4 figs., 7 tabs.« less

"Complex" Posttraumatic Stress Disorder/Disorders of Extreme Stress (CP/DES) in Sexually Abused Children: An Exloratory Study.

ERIC Educational Resources Information Center

Hall, Darlene Kordich

1999-01-01

Compares three groups of young sexually abused children on seven "Complex" Posttraumatic Stress Disorder/Disorders of Extreme Stress (CP/DES) indices. As cumulative number of types of trauma increased, the number of CP/DES symptoms rose. Results suggest that CP/DES also characterizes sexually abused children, especially those who have…

Effects of complex life cycles on genetic diversity: cyclical parthenogenesis.

PubMed

Rouger, R; Reichel, K; Malrieu, F; Masson, J P; Stoeckel, S

2016-11-01

Neutral patterns of population genetic diversity in species with complex life cycles are difficult to anticipate. Cyclical parthenogenesis (CP), in which organisms undergo several rounds of clonal reproduction followed by a sexual event, is one such life cycle. Many species, including crop pests (aphids), human parasites (trematodes) or models used in evolutionary science (Daphnia), are cyclical parthenogens. It is therefore crucial to understand the impact of such a life cycle on neutral genetic diversity. In this paper, we describe distributions of genetic diversity under conditions of CP with various clonal phase lengths. Using a Markov chain model of CP for a single locus and individual-based simulations for two loci, our analysis first demonstrates that strong departures from full sexuality are observed after only a few generations of clonality. The convergence towards predictions made under conditions of full clonality during the clonal phase depends on the balance between mutations and genetic drift. Second, the sexual event of CP usually resets the genetic diversity at a single locus towards predictions made under full sexuality. However, this single recombination event is insufficient to reshuffle gametic phases towards full-sexuality predictions. Finally, for similar levels of clonality, CP and acyclic partial clonality (wherein a fixed proportion of individuals are clonally produced within each generation) differentially affect the distribution of genetic diversity. Overall, this work provides solid predictions of neutral genetic diversity that may serve as a null model in detecting the action of common evolutionary or demographic processes in cyclical parthenogens (for example, selection or bottlenecks).

Damage Evolution in Complex-Phase and Dual-Phase Steels during Edge Stretching.

PubMed

Pathak, Nikky; Butcher, Cliff; Worswick, Michael James; Bellhouse, Erika; Gao, Jeff

2017-03-27

The role of microstructural damage in controlling the edge stretchability of Complex-Phase (CP) and Dual-Phase (DP) steels was evaluated using hole tension experiments. The experiments considered a tensile specimen with a hole at the center of specimen that is either sheared (sheared edge condition) or drilled and then reamed (reamed edge condition). The damage mechanism and accumulation in the CP and DP steels were systematically characterized by interrupting the hole tension tests at different strain levels using scanning electron microscope (SEM) analysis and optical microscopy. Martensite cracking and decohesion of ferrite-martensite interfaces are the dominant nucleation mechanisms in the DP780. The primary source of void nucleation in the CP800 is nucleation at TiN particles, with secondary void formation at martensite/bainite interfaces near the failure strain. The rate of damage evolution is considerably higher for the sheared edge in contrast with the reamed edge since the shearing process alters the microstructure in the shear affected zone (SAZ) by introducing work-hardening and initial damage behind the sheared edge. The CP microstructures were shown to be less prone to shear-induced damage than the DP materials resulting in much higher sheared edge formability. Microstructural damage in the CP and DP steels was characterized to understand the interaction between microstructure, damage evolution and edge formability during edge stretching. An analytical model for void evolution and coalescence was developed and applied to predict the damage rate in these rather diverse microstructures.

Damage Evolution in Complex-Phase and Dual-Phase Steels during Edge Stretching

PubMed Central

Pathak, Nikky; Butcher, Cliff; Worswick, Michael James; Bellhouse, Erika; Gao, Jeff

2017-01-01

The role of microstructural damage in controlling the edge stretchability of Complex-Phase (CP) and Dual-Phase (DP) steels was evaluated using hole tension experiments. The experiments considered a tensile specimen with a hole at the center of specimen that is either sheared (sheared edge condition) or drilled and then reamed (reamed edge condition). The damage mechanism and accumulation in the CP and DP steels were systematically characterized by interrupting the hole tension tests at different strain levels using scanning electron microscope (SEM) analysis and optical microscopy. Martensite cracking and decohesion of ferrite-martensite interfaces are the dominant nucleation mechanisms in the DP780. The primary source of void nucleation in the CP800 is nucleation at TiN particles, with secondary void formation at martensite/bainite interfaces near the failure strain. The rate of damage evolution is considerably higher for the sheared edge in contrast with the reamed edge since the shearing process alters the microstructure in the shear affected zone (SAZ) by introducing work-hardening and initial damage behind the sheared edge. The CP microstructures were shown to be less prone to shear-induced damage than the DP materials resulting in much higher sheared edge formability. Microstructural damage in the CP and DP steels was characterized to understand the interaction between microstructure, damage evolution and edge formability during edge stretching. An analytical model for void evolution and coalescence was developed and applied to predict the damage rate in these rather diverse microstructures. PMID:28772707

Theoretical Prediction on [5]Radialene Sandwich Complexes (CpM)2(C10H10) (Cp = η5-C5H5; M = Fe, Co, Ni): Geometry, Spin States, and Bonding.

PubMed

Liu, Nan-Nan; Xue, Ying-Ying; Ding, Yi-Hong

2017-02-09

[5]Radialene, the missing link for synthesis of radialene family, has been finally obtained via the preparation and decomplexation of the [5]radialene-bis-Fe(CO) 3 complex. The stability of [5]radialene complex benefits from the coordination with Fe(CO) 3 by losing free 1,3-butadiene structures to avoid polymerization. In light of the similar coordination ability of half-sandwiches CpM(Cp = η 5 -C 5 H 5 ; M = Fe, Co, Ni), there is a great possibility that the sandwiched complexes of [5]radialene with CpM are available. Herein, we present the first theoretical prediction on the geometry, spin states and bonding of (CpM)(C 10 H 10 ) and (CpM) 2 (C 10 H 10 ). For M = Fe, Co, Ni, the ground states of (CpM)(C 10 H 10 ) and (CpM) 2 (C 10 H 10 ) are doublet and triplet, singlet and singlet, and doublet and triplet states, where each Fe, Co, and Ni adopts 17, 18, and 19 electron-configuration, respectively. In particular, (CpFe) 2 (C 10 H 10 ) and (CpNi) 2 (C 10 H 10 ) have considerable open-shell singlet features. Generally the trans isomers of (CpM) 2 (C 10 H 10 ) with two CpM fragments on the opposite sides of the [5]radialene plane are apparently more stable than the cis ones with CpM fragments on the same side. However, for the singlet and triplet isomers of (CpNi) 2 (C 10 H 10 ) (both cis and trans isomers), the energy differences are relatively small, indicating that these isomers all have the opportunity to exist. Besides, the easy Diels-Alder (DA) dimerization between the [3]dendralene-like fragments of (CpM)(C 10 H 10 ) suggests the great difficulty in isolating the (CpM)(C 10 H 10 ) monomer.

Measuring the sterile neutrino CP phase at DUNE and T2HK

NASA Astrophysics Data System (ADS)

Choubey, Sandhya; Dutta, Debajyoti; Pramanik, Dipyaman

2018-04-01

The CP phases associated with the sterile neutrino cannot be measured in the dedicated short-baseline experiments being built to test the sterile neutrino hypothesis. On the other hand, these phases can be measured in long-baseline experiments, even though the main goal of these experiments is not to test or measure sterile neutrino parameters. In particular, the sterile neutrino phase δ _{24} affects the charged-current electron appearance data in long-baseline experiment. In this paper we show how well the sterile neutrino phase δ _{24} can be measured by the next-generation long-baseline experiments DUNE, T2HK (and T2HKK). We also show the expected precision with which this sterile phase can be measured by combining the DUNE data with data from T2HK or T2HKK. The T2HK experiment is seen to be able to measure the sterile phase δ _{24} to a reasonable precision. We also present the sensitivity of these experiments to the sterile mixing angles, both by themselves, as well as when DUNE is combined with T2HK or T2HKK.

Regulation of chromatin organization and inducible gene expression by a Drosophila insulator

PubMed Central

Wood, Ashley M.; Van Bortle, Kevin; Ramos, Edward; Takenaka, Naomi; Rohrbaugh, Margaret; Jones, Brian C.; Jones, Keith C.; Corces, Victor G.

2011-01-01

SUMMARY Insulators are multi-protein-DNA complexes thought to affect gene expression by mediating inter- and intra-chromosomal interactions. Drosophila insulators contain specific DNA binding proteins plus common components, such as CP190, that facilitate these interactions. Here we examine changes in the distribution of Drosophila insulator proteins during the heat-shock and ecdysone responses. We find that CP190 recruitment to insulator sites is the main regulatable step in controlling insulator function during heat shock. In contrast, both CP190 and DNA binding protein recruitment are regulated during the ecdysone response. CP190 is necessary to stabilize specific chromatin loops and for proper activation of transcription of genes regulated by this hormone. These findings suggest that cells may regulate recruitment of insulator proteins to the DNA in order to activate insulator activity at specific sites and create distinct patterns of nuclear organization that are necessary to achieve proper gene expression in response to different stimuli. PMID:21981916

Regulation of chromatin organization and inducible gene expression by a Drosophila insulator.

PubMed

Wood, Ashley M; Van Bortle, Kevin; Ramos, Edward; Takenaka, Naomi; Rohrbaugh, Margaret; Jones, Brian C; Jones, Keith C; Corces, Victor G

2011-10-07

Insulators are multiprotein-DNA complexes thought to affect gene expression by mediating inter- and intrachromosomal interactions. Drosophila insulators contain specific DNA-binding proteins plus common components, such as CP190, that facilitate these interactions. Here, we examine changes in the distribution of Drosophila insulator proteins during the heat-shock and ecdysone responses. We find that CP190 recruitment to insulator sites is the main regulatable step in controlling insulator function during heat shock. In contrast, both CP190 and DNA-binding protein recruitment are regulated during the ecdysone response. CP190 is necessary to stabilize specific chromatin loops and for proper activation of transcription of genes regulated by this hormone. These findings suggest that cells may regulate recruitment of insulator proteins to DNA to activate insulator activity at specific sites and create distinct patterns of nuclear organization that are necessary to achieve proper gene expression in response to different stimuli. Copyright © 2011 Elsevier Inc. All rights reserved.

Reactivity of lanthanocene hydroxides toward ketene, isocyanate, lanthanocene alkyl, and triscyclopentadienyllanthanide complexes.

PubMed

Zhang, Chunmei; Liu, Ruiting; Zhang, Jie; Chen, Zhenxia; Zhou, Xigeng

2006-07-24

The reactivity of [Cp(2)Ln(mu-OH)(THF)]2 (Ln = Y (1), Er (2), Yb (3)) toward PhEtCCO, PhNCO, Cp3Ln, [Cp2Ln(mu-CH3)]2, and the LiCl adduct of Cp2Ln(n)Bu(THF)x was examined. In all cases, OH-centered reactivity is observed: complexes 1-3 react with PhEtCCO to form the O-H addition products [Cp2Ln(mu-eta1:eta2-O2CCHEtPh)]2 (Ln = Yb (5), Er (6), Y (7), respectively, for 1-3), whereas treatment of 1 with PhNCO affords the addition/CpH-elimination/rearrangement product [{Cp2Y(THF)}2(mu-eta2:eta2-O2CNPh)] (8), which contains an unusual PhNCO(2) dianionic ligand. Analogous compound [Cp2Ln(THF)]2(mu-eta2:eta2-O2CNPh) (Ln = Yb (9), Er (10)) and 8 can be obtained in a higher yield by treatment of [Cp2Ln(mu-OH)(THF)]2 with PhNCO followed by reaction with the corresponding Cp3Ln. However, attempts to prepare the corresponding heterobimetallic complex by reacting stoichiometric amounts of [Cp2Y(mu-OH)(THF)]2 with PhNCO followed by treating it with Cp3Yb are unsuccessful. Instead, only rearrangement products 8 and 9 are obtained. Furthermore, the reaction of 3 with [Cp2Yb(mu-CH3)]2 or Cp3Yb forms oxo-bridged compound [Cp2Yb(THF)]2(mu-O) (11), whereas the reaction of [Cp2ErCl]2 with Li(n)Bu followed by treatment with 2 affords unexpected mu-oxo lanthanocene cluster (Cp2Er)3(mu-OH)(mu3-O)(mu-Cl)Li(THF)4 (12). In contrast to 1 and 2, 3 shows a strong tendency to undergo the intermolecular elimination of CpH at room temperature, giving trinuclear species [Cp2Yb(mu-OH)]2[CpYb(THF)](mu3-O) (4). The single-crystal X-ray diffraction structures of 1, 2, and 4-12 are described. All the results offer an interesting contrast to transition- and main-metal hydroxide complexes.

Association between Promoter Methylation of Gene ERCC3 and Benzene Hematotoxicity.

PubMed

Zheng, Min; Lin, Feiliang; Hou, Fenxia; Li, Guilan; Zhu, Caiying; Xu, Peiyu; Xing, Caihong; Wang, Qianfei

2017-08-16

Benzene is a primary industrial chemical and a ubiquitous environmental pollutant. ERCC3 is a key player in nucleotide excision repair. Recent studies suggested that site-specific methylation is a possible mechanism of the transcriptional dysregulation by blocking transcription factors binding. We previously found that the average promoter methylation level of ERCC3 was increased in benzene-exposed workers. In order to test whether specific CpG sites of ERCC3 play an important role in benzene-induced epigenetic changes and whether the specific methylation patterns are associated with benzene hematotoxicity, we analyzed the promoter methylation levels of individual CpG sites, transcription factor binding motif and the correlation between aberrant CpG methylation and hematotoxicity in 76 benzene-exposed workers and 24 unexposed controls in China. Out of all the CpGs analyzed, two CpG units located 43 bp upstream and 99 bp downstream of the transcription start site of ERCC3 (CpG 2-4 and CpG 17-18, respectively), showed the most pronounced increase in methylation levels in benzene-exposed workers, compared with unexposed controls (Mean ± SD: 5.86 ± 2.77% vs. 4.92 ± 1.53%, p = 0.032; 8.45 ± 4.09% vs. 6.79 ± 2.50%, p = 0.024, respectively). Using the JASPAR CORE Database, we found that CpG 2-4 and CpG 17-18 were bound by three putative transcription factors (TFAP2A, E2F4 and MZF1). Furthermore, the methylation levels for CpG 2-4 were correlated negatively with the percentage of neutrophils ( β = -0.676, p = 0.005) in benzene-exposed workers. This study demonstrates that CpG-specific DNA methylation in the ERCC3 promoter region may be involved in benzene-induced epigenetic modification and it may contribute to benzene-induced hematotoxicity.

Oxidation Chemistry of Inorganic Benzene Complexes.

PubMed

Fleischmann, Martin; Dielmann, Fabian; Balázs, Gábor; Scheer, Manfred

2016-10-17

The oxidation of the 28 VE cyclo-E 6 triple-decker complexes [(Cp R Mo) 2 (μ,η 6 :η 6 -E 6 )] (E=P, Cp R =Cp(2 a), Cp*(2 b), Cp Bn (2 c)=C 5 (CH 2 Ph) 5 ; E=As, Cp R =Cp*(3)) by Cu + or Ag + leads to cationic 27 VE complexes that retain their general triple-decker geometry in the solid state. The obtained products have been characterized by cyclic voltammetry (CV), EPR, Evans NMR, multinuclear NMR spectroscopy, MS, and structural analysis by single-crystal X-ray diffraction. The cyclo-E 6 middle decks of the oxidized complexes are distorted to a quinoid (2 a) or bisallylic (2 b, 2 c, 3) geometry. DFT calculations of 2 a, 2 b, and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the σ-system of the cyclo-E 6 ligands in 2 a-3. Among the starting complexes, 2 c is reported for the first time including its preparation and full characterization. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effectiveness of adaptive pretend play on affective expression and imagination of children with cerebral palsy.

PubMed

Hsieh, Hsieh-Chun

2012-01-01

Children with cerebral palsy (CP) have difficulty participating in role-pretending activities. The concept of adaptive play makes play accessible by modifying play materials for different needs or treatment goals for children with CP. This study examines the affective expressions and imagination in children with CP as a function of ordinary versus adaptive pretend play. The Affect in Play Scale-Brief Rating measured the affective expression and imagination for 29 children with CP and 29 typically developing children (mean age=7.34 years). Two groups of children were observed while playing with a standard set of ordinary toys for ten times and with a standard procedure of adaptive pretend play for ten times. The results show significantly different affective expressions and imagination between the two groups. Typically developing children displayed much more affective expression and imagination. However, a more positive influence of affective expression and imagination occurred in children with CP than in typically developing children. In repeated measures analysis, the frequency of positive affective expression and imagination of children with CP was higher when pretending with adaptive toys. Adaptive pretend play can promote more role-pretending behaviors and a sense of environmental control during the manipulating process for children with CP. Copyright © 2012 Elsevier Ltd. All rights reserved.

Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bullock, R.M.; Ghosh, P.; Fagan, P.J.

2009-07-20

A ruthenium hydride with a bulky tetra-substituted Cp ligand, (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H (Cp{sup iPr{sub 4}} = C{sub 5}(i-C{sub 3}H{sub 7}){sub 4}H) was prepared from the reaction of Ru{sub 3}(CO){sub 12} with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H was determined by X-ray crystallography. The ruthenium hydride complex (C{sub 5}Bz{sub 5})Ru(CO){sub 2}H (Bz = CH{sub 2}Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}, was produced from the reaction of 1,2,3-trimethylindene with Ru{sub 3}(CO){sub 12}, and protonation of this dimer with HOTf gives {l_brace}[(1,2,3-trimethylindenyl)Ru(CO){sub 2}]{sub 2}-({mu}-H){r_brace}{sup +}OTf{sup -}. A series of ruthenium hydride complexes CpRu(CO)(L)H [Lmore » = P(OPh){sub 3}, PCy{sub 3}, PMe{sub 3}, P(p-C{sub 6}H{sub 4}F){sub 3}] were prepared by reaction of Cp(CO){sub 2}RuH with added L. Protonation of (Cp{sup iPr{sub 4}})Ru(CO){sub 2}H, Cp*Ru(CO){sub 2}H, or CpRu(CO)[P-(OPh){sub 3}]H by HOTf at -80 C led to equilibria with the cationic dihydrogen complexes, but H{sub 2} was released at higher temperatures. Protonation of CpRu[P(OPh){sub 3}]{sub 2}H with HOTf gave an observable dihydrogen complex, {l_brace}CpRu[P-(OPh){sub 3}]{sub 2}({eta}{sup 2}-H{sub 2}){r_brace}+OTf{sup -} that was converted at -20 C to the dihydride complex {l_brace}CpRu[P(OPh){sub 3}]{sub 2}(H){sub 2}{r_brace}{sup +}OTf{sup -}. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H{sub 2} (750 psi) at 110 C.« less

Ferrocene/fullerene hybrids showing large second-order nonlinear optical activities: impact of the cage unit size.

PubMed

Wang, Wen-Yong; Wang, Li; Ma, Na-Na; Zhu, Chang-Li; Qiu, Yong-Qing

2015-06-07

The electron donor-acceptor complexes, which undergo intramolecular charge transfer under external stimulus, are an emerging class of materials showing important application in nonlinear optics. Synthesizing ferrocene/fullerene complexes through face-to-face fusion would enjoy the merits of both ferrocene and fullerene due to their strong donor-acceptor interactions. Four ferrocene/fullerene hybrid complexes with the gradual extension of fullerene cage size, including CpFe(C60H5), CpFe(C66H5), CpFe(C70H5), and CpFe(C80H5) (Cp is cyclopentadienyl), have been investigated by density functional theory. These hybrid molecules give eclipsed and staggered isomers. The main reason that the eclipsed isomer is stable is that the eclipsed structure possesses large CpFefullerene bonding energy. The CpFefullerene interaction is smaller than that of CpFefullerene, which must come from two different interfaces. The presence of covalent bond character between CpFe and fullerene is supported by the localized orbital locator, deformation of electron density distribution and energy decomposition analysis. Significantly, the absorption bands and first hyperpolarizabilities of these hybrid complexes are strongly sensitive to the fullerene cage size, which is ascribed to a change in the charge transfer pattern, especially for CpFe(C80H5), which displays reverse π → π* charge transfer from bottom to top cage, leading to notable hyperpolarizability. Investigation of the structure-property relationship at the molecular level can benefit the design and preparation of such hybrid complexes in chemistry and materials science.

Synthesis and electrochemistry of heterobimetallic ruthenium/platinum and molybdenum/platinum complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Orth, S.D.; Terry, M.R.; Abboud, K.A.

1996-02-14

As starting materials for heterobimetallic complexes, [RuCp(PPh{sub 3})CO(PPh{sub 2}H)]PF{sub 6} and [RuCp(PPh{sub 3})CO({eta}-dppm)]-PF{sub 6} were prepared from RuCp(PPh{sub 3})(CO)Cl. In the course of preparing [RuCp({eta}{sup 2}-dppm)({eta}-dppm)]Cl from RuCp(Ph{sub 3}P)({eta}-dppm)Cl, the monomer RuCpCl({eta}-dppm){sub 2} was isolated. The uncommon coordination mode of the two monodentatebis(phosphines) was confirmed by X-ray crystallography [a = 11.490(1) {angstrom}, b = 14.869(2) {angstrom}, c = 15.447(2) {angstrom}, {alpha} = 84.63(1){degrees}, {beta} = 70.55(1){degrees}, {gamma} = 72.92(1){degrees}, V = 2378.7(5) {angstrom}{sup 3}, d{sub calc} = 1.355 g cm{sup -3} (298 K), triclinic, P1, Z = 2]. The dppm-bridged bimetallic complexes RuCp(PPh{sub 3})Cl({mu}-dppm)PtCl{sub 2}, RuCpCl({mu}-dppm){sub 2}PtCl{sub 2}, and [RuCp(PPh{submore » 3})CO({mu}-dppm)PtCl{sub 2}]PF{sub 6} each exhibit electrochemistry consistent with varying degrees of metal-metal interaction. The cationic heterobimetallic complexes [Mo(CO){sub 3}({mu}-dppm){sub 2}Pt(H)]PF{sub 6} and [MoCp-(CO){sub 2}-({mu}-PPh{sub 2})({mu}-H)Pt(PPh{sub 3})(MeCN)]PF{sub 6} were prepared by chloride abstraction from the corresponding neutral bimetallic species and show electrochemical behavior similar to the analogous Ru/Pt complexes.« less

Syntheses, structures and redox properties of some complexes containing the Os(dppe)Cp* fragment, including [{Os(dppe)Cp*}2(mu-C triple bondCC triple bond C)].

PubMed

Bruce, Michael I; Costuas, Karine; Davin, Thomas; Halet, Jean-François; Kramarczuk, Kathy A; Low, Paul J; Nicholson, Brian K; Perkins, Gary J; Roberts, Rachel L; Skelton, Brian W; Smith, Mark E; White, Allan H

2007-12-14

The sequential conversion of [OsBr(cod)Cp*] (9) to [OsBr(dppe)Cp*] (10), [Os([=C=CH2)(dppe)Cp*]PF6 ([11]PF6), [Os(C triple bond CH)(dppe)Cp*] (12), [{Os(dppe)Cp*}2{mu-(=C=CH-CH=C=)}][PF6]2 ([13](PF6)2) and finally [{Os(dppe)Cp*}(2)(mu-C triple bond CC triple bond C)] (14) has been used to make the third member of the triad [{M(dppe)Cp*}2(mu-C triple bond CC triple bond C)] (M = Fe, Ru, Os). The molecular structures of []PF6, 12 and 14, together with those of the related osmium complexes [Os(NCMe)(dppe)Cp*]PF6 ([15]PF6) and [Os(C triple bond CPh)(dppe)Cp*] (16), have been determined by single-crystal X-ray diffraction studies. Comparison of the redox properties of 14 with those of its iron and ruthenium congeners shows that the first oxidation potential E1 varies as: Fe approximately Os < Ru. Whereas the Fe complex has been shown to undergo three sequential 1-electron oxidation processes within conventional electrochemical solvent windows, the Ru and Os compounds undergo no fewer than four sequential oxidation events giving rise to a five-membered series of redox related complexes [{M(dppe)Cp*}2(mu-C4)]n+ (n = 0, 1, 2, 3 and 4), the osmium derivatives being obtained at considerably lower potentials than the ruthenium analogues. These results are complimented by DFT and DT DFT calculations.

FRET analysis of CP12 structural interplay by GAPDH and PRK.

PubMed

Moparthi, Satish Babu; Thieulin-Pardo, Gabriel; de Torres, Juan; Ghenuche, Petru; Gontero, Brigitte; Wenger, Jérôme

2015-03-13

CP12 is an intrinsically disordered protein playing a key role in the regulation of the Benson-Calvin cycle. Due to the high intrinsic flexibility of CP12, it is essential to consider its structural modulation induced upon binding to the glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK) enzymes. Here, we report for the first time detailed structural modulation about the wild-type CP12 and its site-specific N-terminal and C-terminal disulfide bridge mutants upon interaction with GAPDH and PRK by Förster resonance energy transfer (FRET). Our results indicate an increase in CP12 compactness when the complex is formed with GAPDH or PRK. In addition, the distributions in FRET histograms show the elasticity and conformational flexibility of CP12 in all supra molecular complexes. Contrarily to previous beliefs, our FRET results importantly reveal that both N-terminal and C-terminal site-specific CP12 mutants are able to form the monomeric (GAPDH-CP12-PRK) complex. Copyright © 2015 Elsevier Inc. All rights reserved.

Anionic tantalum dihydride complexes: heterobimetallic coupling reactions and reactivity toward small-molecule activation.

PubMed

Ostapowicz, Thomas G; Fryzuk, Michael D

2015-03-02

The anionic dihydride complex [Cp2TaH2](-) was synthesized as a well-defined molecular species by deprotonation of Cp2TaH3 while different solubilizing agents, such as [2.2.2]cryptand and 18-crown-6, were applied to encapsulate the alkali-metal counterion. The ion pairs were characterized by multiple spectroscopic methods as well as X-ray crystallography, revealing varying degrees of interaction between the hydride ligands of the anion and the respective countercation in solution and in the solid state. The [Cp2TaH2](-) complex anion shows slow exchange of the hydride ligands when kept under a D2 atmosphere, but a very fast reaction is observed when [Cp2TaH2](-) is reacted with CO2, from which Cp2TaH(CO) is obtained as the tantalum-containing reaction product, along with inorganic salts. Furthermore, [Cp2TaH2](-) can act as a synthon in heterobimetallic coupling reactions with transition-metal halide complexes. Thus, the heterobimetallic complexes Cp2Ta(μ-H)2Rh(dippp) and Cp2Ta(μ-H)2Ru(H)(CO)(P(i)Pr3)2 were synthesized and characterized by various spectroscopies and via single-crystal X-ray diffraction. The new hydride bridged tantalum-rhodium heterobimetallic complex is cleaved under a CO atmosphere to yield mononuclear species and slowly exchanges protons and hydride ligands when exposed to D2 gas.

Pyrroloindolone synthesis via a Cp*Co(III)-catalyzed redox-neutral directed C-H alkenylation/annulation sequence.

PubMed

Ikemoto, Hideya; Yoshino, Tatsuhiko; Sakata, Ken; Matsunaga, Shigeki; Kanai, Motomu

2014-04-09

A unique synthetic utility of a Cp*Co(III) catalyst in comparison with related Cp*Rh(III) catalysts is described. A C2-selective indole alkenylation/annulation sequence proceeded smoothly with catalytic amount of a [Cp*Co(III)(C6H6)](PF6)2 complex and KOAc. Intramolecular addition of an alkenyl-Cp*Co species to a carbamoyl moiety gave pyrroloindolones in 58-89% yield in one pot. Clear difference was observed between the catalytic activity of the Cp*Co(III) complex and those of Cp*Rh(III) complexes, highlighting the unique nucleophilic activity of the organocobalt species. The Cp*Co(III) catalysis was also suitable for simple alkenylation process of N-carbamoyl indoles, and broad range of alkynes, including terminal alkynes, were applicable to give C2-alkenylated indoles in 50-99% yield. Mechanistic studies on C-H activation step under Cp*Co(III) catalysis with the aid of an acetate unit as well as evaluation of the difference between organo-Co(III) species and organo-Rh(III) species are also described.

The effect of thymoquinone treatment on the combined renal and pulmonary toxicity of cisplatin and diesel exhaust particles

PubMed Central

Ali, Badreldin H; Shalaby, Asem; Manoj, Priyadarsini; Waly, Mostafa I; Yasin, Javed; Fahim, Mohamed; Nemmar, Abderrahim

2015-01-01

Particulate air pollution (PAP) exposure is associated with increased morbidity and mortality, particularly in patients with renal disease. However, there are only a few studies on the interaction between PAP and renal injury, and none on agents that may ameliorate it. We studied the interaction between cisplatin (CP) nephrotoxicity and a single exposure to diesel exhaust particle (DEP) in rats 24 h before sacrifice, and assessed the effect of co-treatment with the active ingredient in Nigella Sativa seed oil, thymoquinone (TQ) thereon. Rats were injected intraperitoneally with CP (6 mg/kg) and four days later, they were exposed intratracheally to DEP (0.5 mg/kg), and were sacrificed 24 h later. Oral TQ (20 mg/kg) was given daily throughout the experimental period. CP alone caused several physiological, biochemical, and histopathological changes that included reduced growth and creatinine clearance, and raised plasma neutrophil gelatinase-associated lipocalin (NGAL), interleukin 6 (IL-6) and C-reactive protein (CRP), creatinine and urea concentrations, and urinary N-acetyl-b-D-glucosaminidase (NAG) activities. It adversely affected several indices of oxidative damage in the kidneys, and induced renal tubular necrosis. Most of these actions were significantly potentiated in rats given both CP and DEP. TQ significantly abrogated many of the effects of CP and DEP, given alone and in combination. These results provide experimental evidence that subjects with renal diseases can be at higher risk from PAP, and that TQ, pending further pharmacological and toxicological studies, can be considered a useful agent in patients with renal diseases and exposed to PAP. PMID:25925792

Inactive and sedentary lifestyles amongst ambulatory adolescents and young adults with cerebral palsy

PubMed Central

2014-01-01

Background To assess physical behaviour, including physical activity and sedentary behaviour, of ambulatory adolescents and young adults with cerebral palsy (CP). We compared participant physical behaviour to that of able-bodied persons and assessed differences related to Gross Motor Functioning Classification System (GMFCS) level and CP distribution (unilateral/bilateral). Methods In 48 ambulatory persons aged 16 to 24 years with spastic CP and in 32 able-bodied controls, physical behaviour was objectively determined with an accelerometer-based activity monitor. Total duration, intensity and type of physical activity were assessed and sedentary time was determined (lying and sitting). Furthermore, distribution of walking bouts and sitting bouts was specified. Results Adolescents and young adults with CP spent 8.6% of 24 hours physically active and 79.5% sedentary, corresponding with respectively 123 minutes and 1147 minutes per 24 hours. Compared to able-bodied controls, persons with CP participated 48 minutes less in physical activities (p < 0.01) and spent 80 minutes more sedentary per 24 hours (p < 0.01). Physical behaviour was not different between persons with GMFCS level I and II and only number of short sitting bouts were significantly more prevalent in persons with bilateral CP compared to unilateral CP (p < 0.05). Conclusions Ambulatory adolescents and young adults with CP are less physically active and spend more time sedentary compared to able-bodied persons, suggesting that this group may be at increased risk for health problems related to less favourable physical behaviour. Trial registration Nederlands trial register: NTR1785 PMID:24708559

Recognition of platinum-DNA adducts by HMGB1a.

PubMed

Ramachandran, Srinivas; Temple, Brenda; Alexandrova, Anastassia N; Chaney, Stephen G; Dokholyan, Nikolay V

2012-09-25

Cisplatin (CP) and oxaliplatin (OX), platinum-based drugs used widely in chemotherapy, form adducts on intrastrand guanines (5'GG) in genomic DNA. DNA damage recognition proteins, transcription factors, mismatch repair proteins, and DNA polymerases discriminate between CP- and OX-GG DNA adducts, which could partly account for differences in the efficacy, toxicity, and mutagenicity of CP and OX. In addition, differential recognition of CP- and OX-GG adducts is highly dependent on the sequence context of the Pt-GG adduct. In particular, DNA binding protein domain HMGB1a binds to CP-GG DNA adducts with up to 53-fold greater affinity than to OX-GG adducts in the TGGA sequence context but shows much smaller differences in binding in the AGGC or TGGT sequence contexts. Here, simulations of the HMGB1a-Pt-DNA complex in the three sequence contexts revealed a higher number of interface contacts for the CP-DNA complex in the TGGA sequence context than in the OX-DNA complex. However, the number of interface contacts was similar in the TGGT and AGGC sequence contexts. The higher number of interface contacts in the CP-TGGA sequence context corresponded to a larger roll of the Pt-GG base pair step. Furthermore, geometric analysis of stacking of phenylalanine 37 in HMGB1a (Phe37) with the platinated guanines revealed more favorable stacking modes correlated with a larger roll of the Pt-GG base pair step in the TGGA sequence context. These data are consistent with our previous molecular dynamics simulations showing that the CP-TGGA complex was able to sample larger roll angles than the OX-TGGA complex or either CP- or OX-DNA complexes in the AGGC or TGGT sequences. We infer that the high binding affinity of HMGB1a for CP-TGGA is due to the greater flexibility of CP-TGGA compared to OX-TGGA and other Pt-DNA adducts. This increased flexibility is reflected in the ability of CP-TGGA to sample larger roll angles, which allows for a higher number of interface contacts between the Pt-DNA adduct and HMGB1a.

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations.

PubMed

Huh, Daniel N; Darago, Lucy E; Ziller, Joseph W; Evans, William J

2018-02-19

The utility of lithium compared to other alkali metals in generating Ln 2+ rare-earth metal complexes via reduction of Ln 3+ precursors in reactions abbreviated as LnA 3 /M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp' 3 Ln (Cp' = C 5 H 4 SiMe 3 ; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln 2+ complexes of these metals, [Li(crypt)][Cp' 3 Ln]. In each complex, lithium is found in an N 2 O 4 donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f n 5d 1 electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ B , respectively. Lithium reduction of Cp' 3 Y under N 2 at -35 °C forms the Y 2+ complex (Cp' 3 Y) 1- , which reduces dinitrogen upon warming to room temperature to generate the (N 2 ) 2- complex [Cp' 2 Y(THF)] 2 (μ-η 2 :η 2 -N 2 ). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

Resolution and identification of the protein components of the photosystem II antenna system of higher plants by reversed-phase liquid chromatography with electrospray-mass spectrometric detection.

PubMed

Corradini, D; Huber, C G; Timperio, A M; Zolla, L

2000-07-21

Reversed-phase liquid chromatography (RPLC) was interfaced to mass spectrometry (MS) with an electrospray ion (ESI) source for the separation and accurate molecular mass determination of the individual intrinsic membrane proteins that comprise the photosystem II (PS II) major light-harvesting complex (LHC II) and minor (CP24, CP26 and CP29) antenna system, whose molecular masses range between 22,000 and 29,000. PS II is a supramolecular complex intrinsic of the thylacoid membrane, which plays the important role in photosynthesis of capturing solar energy, and transferring it to photochemical reaction centers where energy conversion occurs. The protein components of the PS II major and minor antenna systems were extracted from spinach thylacoid membranes and separated using a butyl-silica column eluted by an acetonitrile gradient in 0.05% (v/v) aqueous trifluoroacetic acid. On-line electrospray MS allowed accurate molecular mass determination and identification of the protein components of PS II major and minor antenna system. The proposed RPLC-ESI-MS method holds several advantages over sodium dodecyl sulfate-polyacrylamide gel electrophoresis, the conventional technique for studying membrane proteins, including a better protein separation, mass accuracy, speed and efficiency.

Coincidence studies of He ionized by C{sup 6+}, Au{sup 24+}, and Au{sup 53+}

DOE Office of Scientific and Technical Information (OSTI.GOV)

McGovern, M.; Walters, H. R. J.; Assafrao, D.

2010-04-15

A recently developed [Phys. Rev. A 79, 042707 (2009)] impact parameter coupled pseudostate approximation (CP) is applied to calculate triple differential cross sections for single ionization of He by C{sup 6+}, Au{sup 24+}, and Au{sup 53+} projectiles at impact energies of 100 and 2 MeV/amu for C{sup 6+} and 3.6 MeV/amu for Au{sup 24+} and Au{sup 53+}. For C{sup 6+}, satisfactory, but not perfect, agreement is found with experimental measurements in coplanar geometry, but there is substantial disagreement with data taken in a perpendicular plane geometry. The CP calculations firmly contradict a projectile-nucleus interaction model which has been used tomore » support the perpendicular plane measurements. For Au{sup 24+} and Au{sup 53+}, there is a complete lack of accord with the available experiments. However, for Au{sup 24+} the theoretical position appears to be quite firm with clear indications of convergence in the CP approximation and very good agreement between CP and the completely different three-distorted-waves eikonal-initial-state (3DW-EIS) approximation. The situation for Au{sup 53+} is different. At the momentum transfers at which the measurements were made, there are doubts about the convergence of the CP approximation and a factor of 2 difference between the CP and 3DW-EIS predictions. The discord between theory and experiment is even greater with the experiment giving cross sections a factor of 10 larger than the theory. A study of the convergence of the CP approximation shows that it improves rapidly with reducing momentum transfer. As a consequence, lower-order cross sections than the triple are quite well converged and present an opportunity for a more reliable test of the experiment.« less

24 CFR 115.304 - Agencies eligible for contributions funds.

Code of Federal Regulations, 2013 CFR

2013-04-01

.... Contributions funding consists of five categories: (1) Complaint processing (CP) funds; (2) Special enforcement...) funds; and (5) Partnership (P) funds. (b) CP funds. (1) Agencies receiving CP funds will receive such... percent of the agency's total FHAP payment amount for the preceding year, in addition to CP funds...

24 CFR 115.304 - Agencies eligible for contributions funds.

Code of Federal Regulations, 2014 CFR

2014-04-01

.... Contributions funding consists of five categories: (1) Complaint processing (CP) funds; (2) Special enforcement...) funds; and (5) Partnership (P) funds. (b) CP funds. (1) Agencies receiving CP funds will receive such... percent of the agency's total FHAP payment amount for the preceding year, in addition to CP funds...

24 CFR 115.304 - Agencies eligible for contributions funds.

Code of Federal Regulations, 2010 CFR

2010-04-01

.... Contributions funding consists of five categories: (1) Complaint processing (CP) funds; (2) Special enforcement...) funds; and (5) Partnership (P) funds. (b) CP funds. (1) Agencies receiving CP funds will receive such... percent of the agency's total FHAP payment amount for the preceding year, in addition to CP funds...

24 CFR 115.304 - Agencies eligible for contributions funds.

Code of Federal Regulations, 2011 CFR

2011-04-01

.... Contributions funding consists of five categories: (1) Complaint processing (CP) funds; (2) Special enforcement...) funds; and (5) Partnership (P) funds. (b) CP funds. (1) Agencies receiving CP funds will receive such... percent of the agency's total FHAP payment amount for the preceding year, in addition to CP funds...

24 CFR 115.304 - Agencies eligible for contributions funds.

Code of Federal Regulations, 2012 CFR

2012-04-01

.... Contributions funding consists of five categories: (1) Complaint processing (CP) funds; (2) Special enforcement...) funds; and (5) Partnership (P) funds. (b) CP funds. (1) Agencies receiving CP funds will receive such... percent of the agency's total FHAP payment amount for the preceding year, in addition to CP funds...

Half-sandwich rhodium(III) transfer hydrogenation catalysts: Reduction of NAD(+) and pyruvate, and antiproliferative activity.

PubMed

Soldevila-Barreda, Joan J; Habtemariam, Abraha; Romero-Canelón, Isolda; Sadler, Peter J

2015-12-01

Organometallic complexes have the potential to behave as catalytic drugs. We investigate here Rh(III) complexes of general formula [(Cp(x))Rh(N,N')(Cl)], where N,N' is ethylenediamine (en), 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen) or N-(2-aminoethyl)-4-(trifluoromethyl)benzenesulfonamide (TfEn), and Cp(x) is pentamethylcyclopentadienyl (Cp*), 1-phenyl-2,3,4,5-tetramethylcyclopentadienyl (Cp(xPh)) or 1-biphenyl-2,3,4,5-tetramethyl cyclopentadienyl (Cp(xPhPh)). These complexes can reduce NAD(+) to NADH using formate as a hydride source under biologically-relevant conditions. The catalytic activity decreased in the order of N,N-chelated ligand bpy > phen > en with Cp* as the η(5)-donor. The en complexes (1-3) became more active with extension to the Cp(X) ring, whereas the activity of the phen (7-9) and bpy (4-6) compounds decreased. [Cp*Rh(bpy)Cl](+) (4) showed the highest catalytic activity, with a TOF of 37.4±2h(-1). Fast hydrolysis of the chlorido complexes 1-10 was observed by (1)H NMR (<10min at 310K). The pKa* values for the aqua adducts were determined to be ca. 8-10. Complexes 1-9 also catalysed the reduction of pyruvate to lactate using formate as the hydride donor. The efficiency of the transfer hydrogenation reactions was highly dependent on the nature of the chelating ligand and the Cp(x) ring. Competition reactions between NAD(+) and pyruvate for reduction by formate catalysed by 4 showed a preference for reduction of NAD(+). The antiproliferative activity of complex 3 towards A2780 human ovarian cancer cells increased by up to 50% when administered in combination with non-toxic doses of formate, suggesting that transfer hydrogenation can induce reductive stress in cancer cells. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

An fMRI investigation of empathic processing in boys with conduct problems and varying levels of callous-unemotional traits.

PubMed

Sethi, Arjun; O'Nions, Elizabeth; McCrory, Eamon; Bird, Geoffrey; Viding, Essi

2018-01-01

The ability to empathise relies in part on using one's own affective experience to simulate the affective experience of others. This process is supported by a number of brain areas including the anterior insula (AI), anterior cingulate cortex (ACC), medial prefrontal cortex (mPFC), and the amygdala. Children with conduct problems (CP), and in particular those with high levels of callous-unemotional traits (CP/HCU) present with less empathy than their peers. They also show reduced neural response in areas supporting empathic processing when viewing other people in distress. The current study focused on identifying brain areas co-activated during affective introspection of: i) One's own emotions ('Own emotion'); ii) Others' emotions ('Other emotion'); and iii) One's feelings about others' emotions ('Feel for other') during fearful vs neutral scenarios in typically developing boys (TD; n  = 31), boys with CP/HCU ( n  = 31), and boys with CP and low levels of CU (CP/LCU; n  = 33). The conjunction analysis across conditions within the TD group revealed significant clusters of activation in the AI, ACC/mPFC, and occipital cortex. Conjunction analyses across conditions in the CP/HCU and CP/LCU groups did not identify these areas as significantly activated. However, follow-up analyses were not able to confirm statistically significant differences between groups across the whole network, and Bayes-factor analyses did not provide substantial support for either the null or alternate hypotheses. Post-hoc comparisons indicated that the lack of conjunction effects in the CP/HCU group may reflect reduced affective introspection in the 'Other emotion' and 'Feel for other' conditions, and by reduced affective introspection in the 'Own emotion' condition in the CP/LCU group. These findings provide limited and ultimately equivocal evidence for altered affective introspection regarding others in CP/HCU, and altered affective introspection for own emotions in CP/LCU, and highlight the need for further research to systematically investigate the precise nature of empathy deficits in children with CP.

Thermal Chemistry of Cp*W(NO)(CH2CMe3)(H)(L) Complexes (L = Lewis Base).

PubMed

Fabulyak, Diana; Handford, Rex C; Holmes, Aaron S; Levesque, Taleah M; Wakeham, Russell J; Patrick, Brian O; Legzdins, Peter; Rosenfeld, Devon C

2017-01-03

The complexes trans-Cp*W(NO)(CH 2 CMe 3 )(H)(L) (Cp* = η 5 -C 5 Me 5 ) result from the treatment of Cp*W(NO)(CH 2 CMe 3 ) 2 in n-pentane with H 2 (∼1 atm) in the presence of a Lewis base, L. The designation of a particular geometrical isomer as cis or trans indicates the relative positions of the alkyl and hydrido ligands in the base of a four-legged piano-stool molecular structure. The thermal behavior of these complexes is markedly dependent on the nature of L. Some of them can be isolated at ambient temperatures [e.g., L = P(OMe) 3 , P(OPh) 3 , or P(OCH 2 ) 3 CMe]. Others undergo reductive elimination of CMe 4 via trans to cis isomerization to generate the 16e reactive intermediates Cp*W(NO)(L). These intermediates can intramolecularly activate a C-H bond of L to form 18e cis complexes that may convert to the thermodynamically more stable trans isomers [e.g., Cp*W(NO)(PPh 3 ) initially forms cis-Cp*W(NO)(H)(κ 2 -PPh 2 C 6 H 4 ) that upon being warmed in n-pentane at 80 °C isomerizes to trans-Cp*W(NO)(H)(κ 2 -PPh 2 C 6 H 4 )]. Alternatively, the Cp*W(NO)(L) intermediates can effect the intermolecular activation of a substrate R-H to form trans-Cp*W(NO)(R)(H)(L) complexes [e.g., L = P(OMe) 3 or P(OCH 2 ) 3 CMe; R-H = C 6 H 6 or Me 4 Si] probably via their cis isomers. These latter activations are also accompanied by the formation of some Cp*W(NO)(L) 2 disproportionation products. An added complication in the L = P(OMe) 3 system is that thermolysis of trans-Cp*W(NO)(CH 2 CMe 3 )(H)(P(OMe) 3 ) results in it undergoing an Arbuzov-like rearrangement and being converted mainly into [Cp*W(NO)(Me)(PO(OMe) 2 )] 2 , which exists as a mixture of two isomers. All new complexes have been characterized by conventional and spectroscopic methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

Detection of porcine circovirus type 2 and viral replication by in situ hybridization in primary lymphoid organs from naturally and experimentally infected pigs.

PubMed

Hansen, M S; Segalés, J; Fernandes, L T; Grau-Roma, L; Bille-Hansen, V; Larsen, L E; Nielsen, O L

2013-11-01

Porcine circovirus type 2 (PCV2) infection is the cause of postweaning multisystemic wasting syndrome (PMWS). It has been speculated whether cell types permissive of replication are found in the primary lymphoid organs and whether infection of these tissues has an important role in the pathogenesis of PMWS. The aim of this study was to determine if primary lymphoid organ cells support viral replication during PCV2 infection. This was done by histopathological examination of thymus and bone marrow from pigs experimentally inoculated with PCV2 (n = 24), mock-infected pigs (n = 12), pigs naturally affected by PMWS (n = 33), and age-matched healthy control animals (n = 29). In situ hybridization (ISH) techniques were used to detect PCV2 nucleic acid irrespective of replicative status (complementary probe, CP) or to detect only the replicative form of the virus (replicative form probe, RFP). PCV2 was not detected in the experimentally PCV2-inoculated pigs or the control animals. Among the PMWS-affected pigs, 19 of 20 (95%) thymuses were positive for PCV2 by CP ISH, and 7 of 19 (37%) of these also supported viral replication. By CP ISH, PCV2 was detected in 16 of 33 (48%) bone marrow samples, and 5 of 16 (31%) of these also supported replication. The 2 ISH probes labeled the same cell types, which were histiocytes in both organs and lymphocytes in thymus. The RFP labeled fewer cells than the CP. Thus, PCV2 nucleic acids and replication were found in bone marrow and thymus of PMWS-affected pigs, but there was no evidence that primary lymphoid organ cells are major supporters of PCV2 replication.

Effects of complex life cycles on genetic diversity: cyclical parthenogenesis

PubMed Central

Rouger, R; Reichel, K; Malrieu, F; Masson, J P; Stoeckel, S

2016-01-01

Neutral patterns of population genetic diversity in species with complex life cycles are difficult to anticipate. Cyclical parthenogenesis (CP), in which organisms undergo several rounds of clonal reproduction followed by a sexual event, is one such life cycle. Many species, including crop pests (aphids), human parasites (trematodes) or models used in evolutionary science (Daphnia), are cyclical parthenogens. It is therefore crucial to understand the impact of such a life cycle on neutral genetic diversity. In this paper, we describe distributions of genetic diversity under conditions of CP with various clonal phase lengths. Using a Markov chain model of CP for a single locus and individual-based simulations for two loci, our analysis first demonstrates that strong departures from full sexuality are observed after only a few generations of clonality. The convergence towards predictions made under conditions of full clonality during the clonal phase depends on the balance between mutations and genetic drift. Second, the sexual event of CP usually resets the genetic diversity at a single locus towards predictions made under full sexuality. However, this single recombination event is insufficient to reshuffle gametic phases towards full-sexuality predictions. Finally, for similar levels of clonality, CP and acyclic partial clonality (wherein a fixed proportion of individuals are clonally produced within each generation) differentially affect the distribution of genetic diversity. Overall, this work provides solid predictions of neutral genetic diversity that may serve as a null model in detecting the action of common evolutionary or demographic processes in cyclical parthenogens (for example, selection or bottlenecks). PMID:27436524

MBD3L2 interacts with MBD3 and components of the NuRD complex and can oppose MBD2-MeCP1-mediated methylation silencing.

PubMed

Jin, Seung-Gi; Jiang, Chun-Ling; Rauch, Tibor; Li, Hongwei; Pfeifer, Gerd P

2005-04-01

MBD2 and MBD3 are two proteins that contain methyl-CpG binding domains and have a transcriptional repression function. Both proteins are components of a large CpG-methylated DNA binding complex named MeCP1, which consists of the nucleosome remodeling and histone deacetylase complex Mi2-NuRD and MBD2. MBD3L2 (methyl-CpG-binding protein 3-like 2) is a protein with substantial homology to MBD2 and MBD3, but it lacks the methyl-CpG-binding domain. Unlike MBD3L1, which is specifically expressed in haploid male germ cells, MBD3L2 expression is more widespread. MBD3L2 interacts with MBD3 in vitro and in vivo, co-localizes with MBD3 but not MBD2, and does not localize to methyl-CpG-rich regions in the nucleus. In glutathione S-transferase pull-down assays, MBD3L2 is found associated with several known components of the Mi2-NuRD complex, including HDAC1, HDAC2, MTA1, MBD3, p66, RbAp46, and RbAp48. Gel shift experiments with nuclear extracts and a CpG-methylated DNA probe indicate that recombinant MBD3L2 can displace a form of the MeCP1 complex from methylated DNA. MBD3L2 acts as a transcriptional repressor when tethered to a GAL4-DNA binding domain. Repression by GAL4-MBD3L2 is relieved by MBD2 and vice versa, and repression by MBD2 from a methylated promoter is relieved by MBD3L2. The data are consistent with a role of MBD3L2 as a transcriptional modulator that can interchange with MBD2 as an MBD3-interacting component of the NuRD complex. Thus, MBD3L2 has the potential to recruit the MeCP1 complex away from methylated DNA and reactivate transcription.

In vitro neurotoxic hazard characterization of different tricresyl phosphate (TCP) isomers and mixtures.

PubMed

Duarte, Daniel J; Rutten, Joost M M; van den Berg, Martin; Westerink, Remco H S

2017-03-01

Exposure to tricresyl phosphates (TCPs), via for example contaminated cabin air, has been associated with health effects including the so-called aerotoxic syndrome. While TCP neurotoxicity is mainly attributed to ortho-isomers like tri-ortho-cresyl phosphate (ToCP), recent exposure and risk assessments indicate that ToCP levels in cabin air are very low. However, the neurotoxic potential of non-ortho TCP isomers and TCP mixtures is largely unknown. We therefore measured effects of exposure (up to 48h) to different TCP isomers, mixtures and the metabolite of ToCP (CBDP: cresyl saligenin phosphate) on cell viability and mitochondrial activity, spontaneous neuronal electrical activity, and neurite outgrowth in primary rat cortical neurons. The results demonstrate that exposure to TCPs (24-48h, up to 10μM) increases mitochondrial activity, without affecting cell viability. Effects of acute TCP exposure (30min) on neuronal electrical activity are limited. However, electrical activity is markedly decreased for the majority of TCPs (10μM) following 48h exposure. Additional preliminary data indicate that exposure to TCPs (48h, 10μM) did not affect the number of neurites per cell or average neurite length, except for TmCP and the analytical TCP mixture (Sigma) that induced a reduction of average neurite length. The combined neurotoxicity data demonstrate that the different TCPs, including ToCP, are roughly equipotent and a clear structure-activity relation is not apparent for the studied endpoints. The no-observed-effect-concentrations (1μM) are well above current exposure levels indicating limited neurotoxic health risk, although exposures may have been higher in the past. Moreover, prolonged and/or repeated exposure to TCPs may exacerbate the observed neurotoxic effects, which argues for additional research. Copyright © 2016 Elsevier B.V. All rights reserved.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non-Polar Solvents by using Conductometry.

PubMed

Iseda, Kazuya; Kokado, Kenta; Sada, Kazuki

2018-03-01

In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride ( TBACl ) ion-pair salt to the free ions through complexation with meso -octamethylcalix[4]pyrrole ( CP ), which is a well-known receptor for chloride anions. In the presence of CP , the conductivity of TBACl increases in various non-polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non-polar solvents. In other words, CP recognizes chloride as an ion-paired salt as well as a free anion in non-polar solvents. Additionally, the TBA(CP - Cl ) complex exhibited a considerably lower ion-pairing constant ( K ip ) than TBACl in non-polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli-responsive soft materials in organic solvents using coulombic forces.

A comparative study of magnetization dynamics in dinuclear dysprosium complexes featuring bridging chloride or trifluoromethanesulfonate ligands.

PubMed

Burns, Corey P; Wilkins, Branford O; Dickie, Courtney M; Latendresse, Trevor P; Vernier, Larry; Vignesh, Kuduva R; Bhuvanesh, Nattamai S; Nippe, Michael

2017-07-25

We utilized a rigid ligand platform PyCp 2 2- (PyCp 2 2- = [2,6-(CH 2 C 5 H 3 ) 2 C 5 H 3 N] 2- ) to isolate dinuclear Dy 3+ complexes [(PyCp 2 )Dy-(μ-O 2 SOCF 3 )] 2 (1) and [(PyCp 2 )Dy-(μ-Cl)] 2 (3) as well as the mononuclear complex (PyCp 2 )Dy(OSO 2 CF 3 )(thf) (2). Compounds 1 and 2 are the first examples of organometallic Dy 3+ complexes featuring triflate binding. The isolation of compounds 1 and 3 allows us to comparatively evaluate the effects of the bridging anions on the magnetization dynamics of the dinuclear systems. Our investigations show that although the exchange coupling interactions differ for 1 and 3, the dynamic magnetic properties are dominated by relaxation via the first excited state Kramers doublet of the individual Dy sites. Compounds 1 and 3 exhibit barriers to magnetization reversal (U eff = 49 cm -1 ) that can be favorably compared to those of the previously reported examples of [Cp 2 Dy(μ-Cl)] 2 (U eff = 26 cm -1 ) and [Cp 2 Dy(thf)(μ-Cl)] 2 (U eff = 34 cm -1 ).

Complexes with Tunable Intramolecular Ferrocene to Ti(IV) Electronic Transitions: Models for Solid State Fe(II) to Ti(IV) Charge Transfer.

PubMed

Turlington, Michael D; Pienkos, Jared A; Carlton, Elizabeth S; Wroblewski, Karlee N; Myers, Alexis R; Trindle, Carl O; Altun, Zikri; Rack, Jeffrey J; Wagenknecht, Paul S

2016-03-07

Iron(II)-to-titanium(IV) metal-to-metal-charge transfer (MMCT) is important in the photosensitization of TiO2 by ferrocyanide, charge transfer in solid-state metal-oxide photocatalysts, and has been invoked to explain the blue color of sapphire, blue kyanite, and some lunar material. Herein, a series of complexes with alkynyl linkages between ferrocene (Fc) and Ti(IV) has been prepared and characterized by UV-vis spectroscopy and electrochemistry. Complexes with two ferrocene substituents include Cp2Ti(C2Fc)2, Cp*2Ti(C2Fc)2, and Cp2Ti(C4Fc)2. Complexes with a single ferrocene utilize a titanocene with a trimethylsilyl derivatized Cp ring, (TMS)Cp, and comprise the complexes (TMS)Cp2Ti(C2Fc)(C2R), where R = C6H5, p-C6H4CF3, and CF3. The complexes are compared to Cp2Ti(C2Ph)2, which lacks the second metal. Cyclic voltammetry for all complexes reveals a reversible Ti(IV/III) reduction wave and an Fe(II/III) oxidation that is irreversible for all complexes except (TMS)Cp2Ti(C2Fc)(C2CF3). All of the complexes with both Fc and Ti show an intense absorption (4000 M(-1)cm(-1) < ε < 8000 M(-1)cm(-1)) between 540 and 630 nm that is absent in complexes lacking a ferrocene donor. The energy of the absorption tracks with the difference between the Ti(IV/III) and Fe(III/II) reduction potentials, shifting to lower energy as the difference in potentials decreases. Reorganization energies, λ, have been determined using band shape analysis (2600 cm(-1) < λ < 5300 cm(-1)) and are in the range observed for other donor-acceptor complexes that have a ferrocene donor. Marcus-Hush-type analysis of the electrochemical and spectroscopic data are consistent with the assignment of the low-energy absorption as a MMCT band. TD-DFT analysis also supports this assignment. Solvatochromism is apparent for the MMCT band of all complexes, there being a bathochromic shift upon increasing polarizability of the solvent. The magnitude of the shift is dependent on both the electron density at Ti(IV) and the identity of the linker between the titanocene and the Fc. Complexes with a MMCT are photochemically stable, whereas Cp2Ti(C2Ph)2 rapidly decomposes upon photolysis.

Effect of amino groups of mesoporous silica nanoparticles on CpG oligodexynucleotide delivery

NASA Astrophysics Data System (ADS)

Xu, Yi; Claiden, Peter; Zhu, Yufang; Morita, Hiromi; Hanagata, Nobutaka

2015-08-01

In this study, we proposed to modify mesoporous silica nanoparticles (MSNs) with 3-aminopropyltriethoxysilane (NH2-TES), aminoethylaminopropyltriethoxysilane (2NH2-TES) and 3-[2-(2-aminoethylamino)ethylamino] propyl-trimethoxysilane (3NH2-TES) for binding of cytosine-phosphate-guanosine oligodexynucleotides (CpG ODN), and investigated the effect of different amino groups of MSNs on the CpG ODN delivery. Serum stability, in vitro cytotoxicity, and cytokine interleukin-6 (IL-6) induction by MSN-NH2/CpG, MSN-2NH2/CpG and MSN-3NH2/CpG complexes were investigated in detail. The results showed that three kinds of aminated-MSN-based CpG ODN delivery systems had no cytotoxicity to RAW264.7 cells, and binding of CpG ODN to MSN-NH2, MSN-2NH2 and MSN-3NH2 nanoparticles enhanced the serum stability of CpG ODN due to protection by the nanoparticles. However, three aminated MSN-based CpG ODN delivery systems exhibited different CpG ODN delivery efficiency, and MSN-NH2/CpG complexes had the highest ability to induce IL-6 secretion.

A Readily Accessible Class of Chiral Cp Ligands and their Application in RuII -Catalyzed Enantioselective Syntheses of Dihydrobenzoindoles.

PubMed

Wang, Shou-Guo; Park, Sung Hwan; Cramer, Nicolai

2018-05-04

Chiral cyclopentadienyl (Cp x ) ligands have a large application potential in enantioselective transition-metal catalysis. However, the development of concise and practical routes to such ligands remains in its infancy. We present a convenient and efficient two-step synthesis of a novel class of chiral Cp x ligands with tunable steric properties that can be readily used for complexation, giving Cp x Rh I , Cp x Ir I , and Cp x Ru II complexes. The potential of this ligand class is demonstrated with the latter in the enantioselective cyclization of azabenzonorbornadienes with alkynes, affording dihydrobenzoindoles in up to 98:2 e.r., significantly outperforming existing binaphthyl-derived Cp x ligands. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intramolecular mobility of η(5)-ligands in chiral zirconocene complexes and the enantioselectivity of alkene functionalization by organoaluminum compounds.

PubMed

Parfenova, Lyudmila V; Zakirova, Irina V; Kovyazin, Pavel V; Karchevsky, Stanislav G; Istomina, Galina P; Khalilov, Leonard M; Dzhemilev, Usein M

2016-08-09

The effect of solvent nature (CD2Cl2, d8-toluene, d8-THF) on the conformational behavior of neomenthyl-substituted zirconocenes CpInd*ZrCl2 (Cp = η(5)-C5H5, Ind* = η(5)-neomenthylindenyl), CpCp'ZrCl2 (Cp = η(5)-C5H5, Cp' = η(5)-neomenthyl-4,5,6,7-tetrahydroindenyl), and Ind*2ZrCl2 (Ind* = η(5)-neomenthylindenyl) was shown by means of dynamic NMR spectroscopy, and the constants and thermodynamic parameters of conformer exchange were determined. The experimental conformational composition of the complexes was compared with structures obtained by quantum chemical modeling using the DFT methods PBE/3ζ and M06-2X/cc-pVDZ(H, C, Cl)/cc-pVDZ-PP(Zr), which predicted three rotamers in the case of both CpInd*ZrCl2 and CpCp'ZrCl2, and seven rotational isomers for Ind*2ZrCl2, three of these being C2-symmetric and the others being asymmetric. The enantioselectivity of the conformationally mobile complex Ind*2ZrCl2 in the reactions of terminal alkenes with AlR3 (R = Me, Et) was compared with that of rigid ansa-complexes, rac-p-S, p-S-[Y(η(5)-C9H10)2]ZrX2 (Y = SiMe2, C2H4; X = S-binaphtholate). Faster exchange between the conformers of Ind*2ZrCl2 in a chlorinated solvent gives the structural isomer of catalytically active sites, which affords higher substrate conversion and reaction enantioselectivity. Binding of the ligands to ansa-zirconocenes prevents the rotational isomerism of the complexes, providing the same configuration of the β-stereogenic center in the methyl- and ethylalumination products (unlike the conformationally mobile complex Ind*2ZrCl2) with an enantiomeric purity of 50-65%.

Growth performance and certain body measurements of ostrich chicks as affected by dietary protein levels during 2-9 weeks of age.

PubMed

Mahrose, Kh M; Attia, A I; Ismail, I E; Abou-Kassem, D E; El-Hack, M E Abd

2015-01-01

The present work was conducted to examine the effects of dietary crude protein (CP) levels (18, 21 and 24%) on growth performance (Initial and final body weight, daily body weight gain, feed consumption, feed conversion and protein efficiency ratio) during 2-9 weeks of age and certain body measurements (body height, tibiotarsus length and tibiotarsus girth) at 9 weeks of age. A total of 30 African Black unsexed ostrich chicks were used in the present study in simple randomized design. The results of the present work indicated that initial and final live body weight, body weight gain, feed consumption, feed conversion of ostrich chicks were insignificantly affected by dietary protein level used. Protein efficiency ratio was high in the group of chicks fed diet contained 18% CP. Results obtained indicated that tibiotarsus girth was decreased (P≤0.01) with the increasing dietary protein level, where the highest value of tibiotarsus girth (18.38 cm) was observed in chicks fed 18% dietary protein level. Body height and tibiotarsus length were not significantly different. In conclusion, the results of the present study indicate that ostrich chicks (during 2-9 weeks of age) could grow on diets contain lower levels of CP (18%).

Growth performance and certain body measurements of ostrich chicks as affected by dietary protein levels during 2–9 weeks of age

PubMed Central

Mahrose, Kh.M.; Attia, A.I.; Ismail, I.E.; Abou-Kassem, D.E.; El-Hack, M.E. Abd

2015-01-01

The present work was conducted to examine the effects of dietary crude protein (CP) levels (18, 21 and 24%) on growth performance (Initial and final body weight, daily body weight gain, feed consumption, feed conversion and protein efficiency ratio) during 2-9 weeks of age and certain body measurements (body height, tibiotarsus length and tibiotarsus girth) at 9 weeks of age. A total of 30 African Black unsexed ostrich chicks were used in the present study in simple randomized design. The results of the present work indicated that initial and final live body weight, body weight gain, feed consumption, feed conversion of ostrich chicks were insignificantly affected by dietary protein level used. Protein efficiency ratio was high in the group of chicks fed diet contained 18% CP. Results obtained indicated that tibiotarsus girth was decreased (P≤0.01) with the increasing dietary protein level, where the highest value of tibiotarsus girth (18.38 cm) was observed in chicks fed 18% dietary protein level. Body height and tibiotarsus length were not significantly different. In conclusion, the results of the present study indicate that ostrich chicks (during 2-9 weeks of age) could grow on diets contain lower levels of CP (18%). PMID:26623373

Sperm abnormalities induced by pre-pubertal exposure to cyclophosphamide are effectively mitigated by Moringa oleifera leaf extract.

PubMed

Nayak, G; Vadinkar, A; Nair, S; Kalthur, S G; D'Souza, A S; Shetty, P K; Mutalik, S; Shetty, M M; Kalthur, G; Adiga, S K

2016-03-01

Moringa oleifera L. is a medicinal plant with potential antioxidant property. This study was aimed at investigating the chemoprotective effect of Moringa oleifera leaf extract (MOE) on cyclophosphamide (CP)-induced testicular toxicity. Two-week-old male Swiss albino mice were intraperitoneally injected with phosphate-buffered saline, 50 mg kg(-1) of CP and 25 mg kg(-1) of MOE. In combination treatment, mice were injected with 25 mg kg(-1) of MOE 24 h prior to CP injection, 24 h prior and post-CP injection and 24 h post-CP injection for 5 consecutive days (10 mg kg(-1) ). Six weeks later, mice were sacrificed to assess epididymal sperm parameters. MOE alone did not have any significant effect on sperm parameters. However, acute injection of CP resulted in significant decline in motility (P < 0.001), increase in head abnormality (P < 0.01) and DNA damage (P < 0.05). Combining MOE with CP increased the sperm density, motility and reduced head defect and DNA damage, irrespective of the schedule and dosage of MOE. Administration of MOE prior to CP significantly elevated the level of superoxide dismutase and catalase with concomitant decrease in lipid peroxidation in the testicular tissue. In conclusion, MOE may have potential benefit in reducing the loss of male gonadal function following chemotherapy. © 2015 Blackwell Verlag GmbH.

Heterodimerization of the Entamoeba histolytica EhCPADH virulence complex through molecular dynamics and protein-protein docking.

PubMed

Montaño, Sarita; Orozco, Esther; Correa-Basurto, José; Bello, Martiniano; Chávez-Munguía, Bibiana; Betanzos, Abigail

2017-02-01

EhCPADH is a protein complex involved in the virulence of Entamoeba histolytica, the protozoan responsible for human amebiasis. It is formed by the EhCP112 cysteine protease and the EhADH adhesin. To explore the molecular basis of the complex formation, three-dimensional models were built for both proteins and molecular dynamics simulations (MDS) and docking calculations were performed. Results predicted that the pEhCP112 proenzyme and the mEhCP112 mature enzyme were globular and peripheral membrane proteins. Interestingly, in pEhCP112, the propeptide appeared hiding the catalytic site (C167, H329, N348); while in mEhCP112, this site was exposed and its residues were found structurally closer than in pEhCP112. EhADH emerged as an extended peripheral membrane protein with high fluctuation in Bro1 and V shape domains. 500 ns-long MDS and protein-protein docking predictions evidenced different heterodimeric complexes with the lowest free energy. pEhCP112 interacted with EhADH by the propeptide and C-terminal regions and mEhCP112 by the C-terminal through hydrogen bonds. In contrast, EhADH bound to mEhCP112 by 442-479 residues, adjacent to the target cell-adherence region (480-600 residues), and by the Bro1 domain (9-349 residues). Calculations of the effective binding free energy and per residue free energy decomposition showed that EhADH binds to mEhCP112 with a higher binding energy than to pEhCP112, mainly through van der Waals interactions and the nonpolar part of solvation energy. The EhADH and EhCP112 structural relationship was validated in trophozoites by immunofluorescence, TEM, and immunoprecipitation assays. Experimental findings fair agreed with in silico results.

Ultrafine particles affect the balance of endogenous pro- and anti-inflammatory lipid mediators in the lung: in-vitro and in-vivo studies

PubMed Central

2012-01-01

Background Exposure to ultrafine particles exerts diverse harmful effects including aggravation of pulmonary diseases like asthma. Recently we demonstrated in a mouse model for allergic airway inflammation that particle-derived oxidative stress plays a crucial role during augmentation of allergen-induced lung inflammation by ultrafine carbon particle (UfCP) inhalation. The mechanisms how particle inhalation might change the inflammatory balance in the lungs, leading to accelerated inflammatory reactions, remain unclear. Lipid mediators, known to be immediately generated in response to tissue injury, might be strong candidates for priming this particle-triggered change of the inflammatory balance. Methods We hypothesize that inhalation of UfCP may disturb the balance of pro- and anti-inflammatory lipid mediators in: i) a model for acute allergic pulmonary inflammation, exposing mice for 24 h before allergen challenge to UfCP inhalation (51.7 nm, 507 μg/m3), and ii) an in-vitro model with primary rat alveolar macrophages (AM) incubated with UfCP (10 μg/1 x 106 cells/ml) for 1 h. Lungs and AM were analysed for pro- and anti-inflammatory lipid mediators, namely leukotriene B4 (LTB4), prostaglandin E2 (PGE2), 15(S)-hydroxy-eicosatetraenoic acid (15(S)-HETE), lipoxin A4 (LXA4) and oxidative stress marker 8-isoprostane by enzyme immunoassays and immunohistochemistry. Results In non-sensitized mice UfCP exposure induced a light non-significant increase of all lipid mediators. Similarly but significantly in rat AM all lipid mediators were induced already within 1 h of UfCP stimulation. Also sensitized and challenge mice exposed to filtered air showed a partially significant increase in all lipid mediators. In sensitized and challenged mice UfCP exposure induced highest significant levels of all lipid mediators in the lungs together with the peak of allergic airway inflammation on day 7 after UfCP inhalation. The levels of LTB4, 8-isoprostane and PGE2 were significantly increased also one day after UfCP exposure. Immunohistochemistry localized highest concentrations of PGE2 especially in AM one day after UfCP exposure. Conclusion Our results suggest that UfCP exposure affects the balance between pro- and anti-inflammatory lipid mediators. In allergic mice, where the endogenous balance of pro- and anti-inflammatory mediators is already altered, UfCP exposure aggravates the inflammation and the increase in anti-inflammatory, pro-resolving lipid mediators is insufficient to counterbalance the extensive inflammatory response. This may be a contributing mechanism that explains the increased susceptibility of asthmatic patients towards particle exposure. PMID:22809365

Concomitant loss of NDH complex-related genes within chloroplast and nuclear genomes in some orchids.

PubMed

Lin, Choun-Sea; Chen, Jeremy J W; Chiu, Chi-Chou; Hsiao, Han C W; Yang, Chen-Jui; Jin, Xiao-Hua; Leebens-Mack, James; de Pamphilis, Claude W; Huang, Yao-Ting; Yang, Ling-Hung; Chang, Wan-Jung; Kui, Ling; Wong, Gane Ka-Shu; Hu, Jer-Ming; Wang, Wen; Shih, Ming-Che

2017-06-01

The chloroplast NAD(P)H dehydrogenase-like (NDH) complex consists of about 30 subunits from both the nuclear and chloroplast genomes and is ubiquitous across most land plants. In some orchids, such as Phalaenopsis equestris, Dendrobium officinale and Dendrobium catenatum, most of the 11 chloroplast genome-encoded ndh genes (cp-ndh) have been lost. Here we investigated whether functional cp-ndh genes have been completely lost in these orchids or whether they have been transferred and retained in the nuclear genome. Further, we assessed whether both cp-ndh genes and nucleus-encoded NDH-related genes can be lost, resulting in the absence of the NDH complex. Comparative analyses of the genome of Apostasia odorata, an orchid species with a complete complement of cp-ndh genes which represents the sister lineage to all other orchids, and three published orchid genome sequences for P. equestris, D. officinale and D. catenatum, which are all missing cp-ndh genes, indicated that copies of cp-ndh genes are not present in any of these four nuclear genomes. This observation suggests that the NDH complex is not necessary for some plants. Comparative genomic/transcriptomic analyses of currently available plastid genome sequences and nuclear transcriptome data showed that 47 out of 660 photoautotrophic plants and all the heterotrophic plants are missing plastid-encoded cp-ndh genes and exhibit no evidence for maintenance of a functional NDH complex. Our data indicate that the NDH complex can be lost in photoautotrophic plant species. Further, the loss of the NDH complex may increase the probability of transition from a photoautotrophic to a heterotrophic life history. © 2017 The Authors The Plant Journal © 2017 John Wiley & Sons Ltd.

Hemilability of the 1,2-Bis(dimethylphosphino)ethane (dmpe) Ligand in Cp*Mo(NO)(κ2-dmpe).

PubMed

Holmes, Aaron S; Patrick, Brian O; Levesque, Taleah M; Legzdins, Peter

2017-09-18

Reaction of Cp*Mo(NO)Cl 2 with 1 equiv of 1,2-bis(dimethylphosphino)ethane (dmpe) in THF at ambient temperature forms [Cp*Mo(NO)(Cl)(κ 2 -dmpe)]Cl (1), which is isolable as an analytically pure yellow powder in 65% yield. Further addition of 2 equiv of Cp 2 Co to 1 in CH 2 Cl 2 affords dark red Cp*Mo(NO)(κ 2 -dmpe) (2), which was isolated in 36% yield by recrystallization from Et 2 O at -30 °C. Reaction of a benzene solution of 2 with an equimolar amount of elemental sulfur results in the immediate production of dark blue (μ-S)[Cp*Mo(NO)(κ 1 -dmpeS)] 2 (3), which is a rare example of a bimetallic transition-metal complex bridged by only a single sulfur atom and involving Mo═S═Mo bonding. In contrast, reaction of 2 with an excess of sulfur in benzene results in the formation of Cp*Mo(NO)(η 2 -S 2 )(κ 1 -dmpeS) (4). Complex 4 can also be formed by the addition of elemental sulfur to 3, thereby indicating that 3 is a precursor to 4. Cp*Mo(NO)(κ 2 -dmpe) (2) also undergoes interesting transformations when treated with organic bromides. For instance, reaction of 2 with 5 equiv benzyl bromide in THF produces the bimetallic complex (μ-dmpe)[Cp*Mo(NO)Br 2 ] 2 (5) and bibenzyl after 4 d at 70 °C probably via radical intermediates. In contrast to its reaction with benzyl bromide, complex 2 forms [Mo(NO)Br 2 (κ 2 -dmpe)] 2 (6), olefin, alkane, and Cp*H when treated with 5 equiv of 1-bromopropane or 1-bromooctane in THF at 70 °C for 72 h. Interestingly, complex 2 does not display any reactivity with bromobenzene or 1-bromoadamantane even after being heated for several days at 70 °C. All new complexes were characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them were established by single-crystal X-ray crystallographic analyses.

Effects of Coordinating a Hemilabile Ligand to 14e Cp*M(NO) Scaffolds (M = Mo, W).

PubMed

Handford, Rex C; Patrick, Brian O; Legzdins, Peter

2017-10-16

This article describes the differing chemical properties imparted by the two ligands, hemilabile 2-[(diisopropylphosphino)methyl]-3-methylpyridine ( i Pr 2 PN) and the related 1,2-bis(dimethylphosphino)ethane (dmpe), when attached to the 14e Cp*M(NO) scaffolds (Cp* = η 5 -C 5 Me 5 ; M = W, Mo). For instance, the treatment of [Cp*W(NO)Cl 2 ] 2 with 2 or 1 equiv of dmpe in C 6 H 6 affords excellent yields of [Cp*W(NO)(κ 2 -dmpe)Cl]Cl (1) or [Cp*W(NO)Cl 2 ] 2 [μ-dmpe] (2). In contrast, the treatment of [Cp*W(NO)Cl 2 ] 2 with 1 equiv of i Pr 2 PN in C 6 H 6 does not produce the complex analogous to 1 but rather affords orange [Cp*W(NO)(κ 2 -P-N- i Pr 2 PN)Cl][Cp*W(NO)Cl 3 ] (3) in 90% yield. Furthermore, subsequent reduction of 1 or 2 with 2 or 4 equiv of Cp 2 Co in tetrahydrofuran (THF), respectively, results in the production of orange Cp*W(NO)(κ 2 -dmpe) (4) in good yields. However, a similar treatment of 3 with 1 equiv of Cp 2 Co in THF does not result in the production of Cp*W(NO)(κ 2 -P,N- i Pr 2 PN), the analogue of 4, but rather generates a 1:1 mixture of the novel complexes Cp*W(NO)(H)(κ 1 -P- i Pr 2 PN)Cl (5) and Cp*W(NO)(κ 2 -P,N- i Pr 2 PCH-2-(3-Me-C 5 H 3 N))Cl (6), which are separable by crystallization from pentane and diethyl ether solutions, respectively. The divergent reactivity imparted by the dmpe and i Pr 2 PN proligands is a unique demonstration of the unusual properties of a mixed-donor ligand. In the case of molybdenum, the reaction of [Cp*Mo(NO)Cl 2 ] 2 with 2 equiv of i Pr 2 PN in C 6 H 6 first forms Cp*Mo(NO)(κ 1 -P- i Pr 2 PN)Cl 2 , which then converts to [Cp*Mo(NO)(κ 2 -P,N- i Pr 2 PN)Cl][Cp*Mo(NO)Cl 3 ], the analogue of 3. Reduction of the Cp*Mo(NO)(κ 1 -P- i Pr 2 PN)Cl 2 intermediate complex with 2 equiv of Cp 2 Co affords dark-green Cp*Mo(NO)(κ 2 -P,N- i Pr 2 PN) (7). All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

Synthesis of Ruthenium Carbonyl Complexes with Phosphine or Substituted Cp Ligands, and Their Activity in the Catalytic Deoxygenation of 1,2-Propanediol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Prasenjit; Fagan, Paul J.; Marshall, William J.

2009-07-20

A ruthenium hydride with a bulky substituted Cp ligand, (CpiPr4)Ru(CO)2H (CpiPr4 = C5(i-C3H7)4H) was prepared from the reaction of Ru3(CO)12 with 1,2,3,4-tetraisopropylcyclopentadiene. The molecular structure of (CpiPr4)Ru(CO)2H was determined by x-ray crystallography. The ruthenium hydride complex (C5Bz5)Ru(CO)2H (Bz = CH2Ph) was similarly prepared. The Ru-Ru bonded dimer, [(1,2,3-trimethylindenyl)Ru(CO)2]2, was produced from the reaction of 1,2,3-trimethylindene with Ru3(CO)12, and protonation of this dimer with HOTf gives {[(1,2,3-trimethylindenyl)Ru(CO)2]2(μ H)}+OTf –. A series of ruthenium hydride complexes CpRu(CO)(L)H [L = P(OPh)3, PCy3, PMe3, P(p C6H4F)3] were prepared by reaction of Cp(CO)2RuH with added L. Protonation of (CpiPr4)Ru(CO)2H, Cp*Ru(CO)2H or CpRu(CO)[P(OPh)3]H by HOTf 80more » °C led to equilibria with the cationic dihydrogen complexes, but H2 was released at higher temperatures. Protonation of CpRu[P(OPh)3]2H with HOTf gave an observable dihydrogen complex, {CpRu[P(OPh)3]2(η2 H2)}+OTf – that was converted at -20 °C to the dihydride complex {CpRu[P(OPh)3]2(H)2}+OTf –. These Ru complexes serve as catalyst precursors for the catalytic deoxygenation of 1,2-propanediol to give n-propanol. The catalytic reactions were carried out in sulfolane solvent with added HOTf under H2 (750 psi) at 110 °C. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. Pacific Northwest National Laboratory is operated by Battelle for DOE.« less

Dental Decay and Oral Findings in Children and Adolescents Affected by Different Types of Cerebral Palsy: A Comparative Study.

PubMed

Rodríguez, Juan Pablo Loyola; Ayala-Herrera, Jose Luis; Muñoz-Gomez, Noel; Martínez-Martínez, Rita E; Santos-Díaz, Miguel Angel; Olvera-Delgado, Jose Honorio; Loyola-Leyva, Alejandra

To compare dental caries and oral findings in patients affected by different types of Cerebral Palsy (CP). This cross-sectional study involved 120 children and adolescents with a diagnosis of CP. WHO diagnostic criteria were used to determine DMFT (caries diagnosis), the pocket depth and attachment level (periodontitis diagnosis). Additionally, the study evaluated dental erosion, traumatic dental injuries, treatment needs index (TNI), oral habits, malocclusions, gingival overgrowth, and dental fluorosis. The most frequent CP type was spastic (62.5%), followed by mixed (18.3%), ataxic (10%), and athetoid (9.1). Patients affected by mixed CP showed a higher prevalence in decayed, DMFT index and TNI compared with the other types of CP (p<0.05). The frequency of malocclusion in the clinical evaluation was 87.5% and in plaster models was 49.2%. Dental caries was an important issue in mixed and athetoid CP groups. Oral habits and malocclusions were the most significant oral health problems in individuals with CP.

Effect of crude protein concentration and dietary electrolyte balance on litter quality, foot pad dermatitis, growth performance and processing yields in two medium heavy turkey hybrids.

PubMed

Veldkamp, T; Hocking, P M; Vinco, L J

2017-10-01

1. An experiment was conducted to investigate the effect of crude protein (CP) concentration and dietary electrolyte balance (DEB) on growth performance, processing yields, litter quality and foot pad dermatitis (FPD) in male turkeys from two commercial hybrids. Soya bean meal was replaced by vegetable protein sources selected for lower K concentrations to lower DEB in order to improve litter quality and subsequent quality of foot pads. 2. Effects of CP on litter friability and wetness were not consistent during the production period. FPD in turkeys fed on diets with low CP was significantly lower than FPD in turkeys fed on diets with high CP until 84 d. Growth performance was adversely affected at low CP. Processing yields were not affected by CP. 3. Litter was significantly dryer in pens of turkeys fed on diets with low DEB than in pens of turkeys fed on diets with high DEB. FPD in turkeys fed on diets with low DEB was significantly lower than in turkeys fed on diets with high DEB. Growth performance and processing yields were adversely affected at low DEB. 4. FPD in turkey hybrid A was higher than in turkey hybrid B at 28 d of age. Thereafter, no differences in FPD between turkey hybrids were observed. Growth performance and processing yields were not affected by turkey hybrid. 5. Overall, a significant interaction effect of CP × DEB was observed for FCR: in turkeys fed on the high DEB treatment, FCR of turkeys fed on the high CP diets was lower than FCR of turkeys fed on the low CP (LCP) diets whereas on the low DEB treatment, FCR was not affected by CP treatment. 6. It was concluded that litter quality can be improved and FPD may be decreased in turkeys fed on diets containing lower CP and DEB levels.

Process for functionalizing alkanes

DOEpatents

Bergman, R.G.; Janowicz, A.H.; Periana-Pillai, R.A.

1984-06-12

Process for functionalizing saturated hydrocarbons selectively in the terminal position comprises: (a) reacting said saturated hydrocarbons with a metal complex CpRhPMe/sub 3/H/sub 2/ in the presence of ultraviolet radiation at -60/sup 0/ to -17/sup 0/C to form a hydridoalkyl complex CpRhPMe/sub 3/RH; (b) reacting said hydridoalkyl complex with a haloform CHX/sub 3/ at -60/sup 0/ to -17/sup 0/C to form the corresponding haloalkyl complex of step (a) CpRhPMe/sub 3/RX; and (c) reacting said haloalkyl complex with halogen -60 to 25/sup 0/C to form a functional haloalkyl compound.

CpG methylation increases the DNA binding of 9-aminoacridine carboxamide Pt analogues.

PubMed

Kava, Hieronimus W; Murray, Vincent

2016-10-01

This study investigated the effect of CpG methylation on the DNA binding of cisplatin analogues with an attached aminoacridine intercalator. DNA-targeted 9-aminoacridine carboxamide Pt complexes are known to bind at 5'-CpG sequences. Their binding to methylated and non-methylated 5'-CpG sequences was determined and compared with cisplatin. The damage profiles of each platinum compound were quantified via a polymerase stop assay with fluorescently labelled primers and capillary electrophoresis. Methylation at 5'-CpG was shown to significantly increase the binding intensity for the 9-aminoacridine carboxamide compounds, whereas no significant increase was found for cisplatin. 5'-CpG methylation had the largest effect on the 9-ethanolamine-acridine carboxamide Pt complex, followed by the 9-aminoacridine carboxamide Pt complex and the 7-fluoro complex. The methylation state of a cell's genome is important in maintaining normal gene expression, and is often aberrantly altered in cancer cells. An analogue of cisplatin which differentially targets methylated DNA may be able to improve its therapeutic activity, or alter its range of targets and evade the chemoresistance which hampers cisplatin efficacy in clinical use. Copyright © 2016 Elsevier Ltd. All rights reserved.

Interplay between Organic-Organometallic Electrophores within Bis(cyclopentadienyl)Molybdenum Dithiolene Tetrathiafulvalene Complexes.

PubMed

Bellec, Nathalie; Vacher, Antoine; Barrière, Frédéric; Xu, Zijun; Roisnel, Thierry; Lorcy, Dominique

2015-05-18

Tetrathiafulvalenes (TTF) and bis(cyclopentadienyl) molybdenum dithiolene complexes, Cp2Mo(dithiolene) complexes, are known separately to act as good electron donor molecules. For an investigation of the interaction between both electrophores, two types of complexes were synthesized and characterized. The first type has one Cp2Mo fragment coordinated to one TTF dithiolate ligand, and the second type has one TTF bis(dithiolate) bridging two Cp2Mo fragments. Comparisons of the electrochemical properties of these complexes with those of models of each separate electrophore provide evidence for their mutual influence. All of these complexes act as very good electron donors with a first oxidation potential 430 mV lower than the tetrakis(methylthio)TTF. DFT calculations suggest that the HOMO of the neutral complex and the SOMO of the cation are delocalized across the whole TTF dithiolate ligand. The X-ray crystal structure analyses of the neutral and the mono-oxidized Cp2Mo(dithiolene)(bismethylthio)TTF complexes are consistent with the delocalized assignment of the highest occupied frontier molecular orbitals. UV-vis-NIR spectroelectrochemical investigations confirm this electronic delocalization within the TTF dithiolate ligand.

Synthesis, structure and DFT conformation analysis of CpNiX(NHC) and NiX2(NHC)2 (X = SPh or Br) complexes

NASA Astrophysics Data System (ADS)

Malan, Frederick P.; Singleton, Eric; van Rooyen, Petrus H.; Conradie, Jeanet; Landman, Marilé

2017-11-01

The synthesis, density functional theory (DFT) conformational study and structure analysis of novel two-legged piano stool Ni N-heterocyclic carbene (NHC) complexes and square planar Ni bis-N-heterocyclic carbene complexes, all containing either bromido- or thiophenolato ligands, are described. [CpNi(SPh)(NHC)] complexes were obtained from the neutral 18-electron [CpNiBr(NHC)] complexes by substitution of a bromido ligand with SPh, using NEt3 as a base to abstract the proton of HSPh. The 16-electron biscarbene complexes [Ni(SPh)2{NHC}2] were isolated when an excess of HSPh was added to the reaction mixture. Biscarbene complexes of the type [NiBr2(NHC)2] were obtained in the reaction of NiCp2 with a slight excess of the specific imidazolium bromide salt. The molecular and electronic structures of the mono- and bis-N-heterocyclic carbene complexes have been analysed using single crystal diffraction and density functional theory (DFT) calculations, to give insight into their structural properties.

Reaction of BH4- with [Mo2Cp2(mu-SMe)n] species to give tetrahydroborato, hydrido or dimetallaborane compounds: control of product by ancillary ligands.

PubMed

Cabon, Nolwenn; Petillon, Francois Y; Schollhammer, Philippe; Talarmin, Jean; Muir, Kenneth W

2004-09-07

The reaction of mono- or dichloro-dimolybdenum(III) complexes [Mo2Cp2(mu-SMe)2(mu-Cl)(mu-Y)] (Cp=eta5-C5H5; 1, Y=SMe; 2, Y=PPh2; 3, Y=Cl) with NaBH4 at room temperature gave in high yields tetrahydroborato (8), hydrido (9) or metallaborane (12) complexes depending on the ancillary ligands. The correct formulation of derivatives and has been unambigously determined by X-ray diffraction methods. That of the hydrido compound 9 has been established in solution by NMR analysis and confirmed by an X-ray study of the mu-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-PPh2)(mu-N=CHMe)] (10) obtained from the insertion of acetonitrile into the Mo-H bond of 9. Reaction of NaBH4 with nitrile derivatives, [Mo2Cp2(mu-SMe)4-n(CH3CN)2n]n+(5, n=1; 6 n=2), afforded the tetrahydroborato compound 8, together with a mu-azavinylidene species [Mo2Cp2(mu-SMe)3(mu-N=CHMe)](14), when n=1, and the metallaborane complex 12, together with a mixed borohydrato-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-BH4)(mu-N=CHMe)] (13), when n=2. The molecular structures of these complexes have been confirmed by X-ray analysis. Preparations of some of the starting complexes (3 and 4) are also described, as are the molecular structures of the precursors [Mo2Cp2(mu-SMe)2(mu-X)(mu-Y)] (1, X/Y=Cl/SMe; 2, X/Y=Cl/PPh2; 4, X/Y=SMe/PPh2).

Optimizing donor heart outcome after prolonged storage with endothelial function analysis and continuous perfusion.

PubMed

Poston, Robert S; Gu, Junyan; Prastein, Deyanira; Gage, Fred; Hoffman, John W; Kwon, Michael; Azimzadeh, Agnes; Pierson, Richard N; Griffith, Bartley P

2004-10-01

By minimizing tissue ischemia, continuous perfusion (CP) during organ transport may increase the safety of "marginal donors." My colleagues and I investigated whether an analysis of donor heart viability predicts recovery of grafts challenged with a 24-hour preservation interval. Dog hearts underwent cold static storage (CS) for 8 hours (n = 8) or 24 hours (n = 2) or CP for 24 hours with cold asanguinous, oxygenated solution (n = 8). Myocardial systolic and diastolic function and oxygen and lactate consumption were assessed at base line, during CP, and after Langendorff blood reperfusion. Base line endothelial function was evaluated by the percentage transcoronary change ([coronary sinus - aorta]/aorta) in myeloperoxidase and by platelet function and coronary flow reserve after 20 seconds of coronary artery occlusion. During CP, the endothelium was assessed by transcoronary protein release and coronary resistance. Edema was assessed by weight gain and histology. Base line systolic and metabolic functions showed no relation to post-Langendorff function. Compared with CS, CP resulted in a greater recovery in systolic function (87% +/- 35% vs 65% +/- 15% of baseline; p = 0.05) and a shorter interval required for lactate consumption to exceed production (7.0 +/- 6.8 minutes vs 15.0 +/- 8.9 minutes; p = 0.06). Endothelial function was heterogeneous: coronary flow reserve, 2.7 +/- 0.7; percentage change in myeloperoxidase, -8.4% +/- 6.8%; and change in platelet function, 4.3% +/- 3.5%, as determined by thromboelastography angle at base line. Protein release during CP for 24 hours was 8.3 +/- 7.1 g. Two factors predicted more than 75% systolic pressure generation recovery: use of CP and normal endothelial function (p = 0.05; Fisher's exact test). However, CP led to edema according to histology, weight gain (72 +/- 29 g), and impaired diastolic function versus CS (end-diastolic pressure-volume relationship, 1.4 +/- 0.4 mm Hg/mL vs 0.8 +/- 0.3 mm Hg/mL; p = 0.08). Better systolic function despite 16 hours' more preservation than cold storage corroborates the idea that CP supports aerobic metabolism at physiologically important levels. Viability analysis focused on endothelial function and identified organs that were able to tolerate this 24-hour preservation interval.

Loss of myogenic potential and fusion capacity of muscle stem cells isolated from contractured muscle in children with cerebral palsy.

PubMed

Domenighetti, Andrea A; Mathewson, Margie A; Pichika, Rajeswari; Sibley, Lydia A; Zhao, Leyna; Chambers, Henry G; Lieber, Richard L

2018-04-25

Cerebral palsy (CP) is the most common cause of pediatric neurodevelopmental and physical disability in the United States. It is defined as a group of motor disorders caused by a non-progressive perinatal insult to the brain. While the brain lesion is non-progressive, there is a progressive, lifelong impact on skeletal muscles, which are shorter, spastic, and may develop debilitating contractures. Satellite cells are resident muscle stem cells that are indispensable for postnatal growth and regeneration of skeletal muscles. Here we measured the myogenic potential of satellite cells isolated from contractured muscles in children with CP. When compared to typically developing (TD) children, satellite cell-derived myoblasts from CP differentiated more slowly (Slope: 0.013{plus minus}0.013 CP vs. 0.091{plus minus}0.024 TD over 24 hours, P<0.001) and fused less (Fusion Index: 21.3{plus minus}8.6 CP vs. 81.3{plus minus}7.7 TD after 48 hours, P<0.001) after exposure to low-serum conditions that stimulated myotube formation. This impairment was associated with downregulation of several markers important for myoblast fusion and myotube formation, including DNA methylation-dependent inhibition of pro-myogenic Integrin Beta 1D (ITGB1D) protein expression levels (-50% at 42 hours), and ~25% loss of integrin-mediated FAK kinase phosphorylation. The cytidine analog 5-Azacytidine (5-AZA), a demethylating agent, restored ITGB1D levels and promoted myogenesis in CP cultures. Our data demonstrate that muscle contractures in CP are associated with loss of satellite cell myogenic potential that is dependent on DNA methylation patterns affecting expression of genetic programs associated with muscle stem cell differentiation and muscle fiber formation.

Registration of ‘CP 06-2425’, ‘CP 06-2495’, ‘CP 06-2964’, ‘CP 06-3103’, and ‘CP 07-1313’ Sugarcane for Sand Soils in Florida

USDA-ARS?s Scientific Manuscript database

‘CP 06-2425’ (Reg. No. CV-172; PI 678574), ‘CP 06-2495’ (Reg. No. CV-173; PI 678575), ‘CP 06-2964’ (Reg. No. CV-174; PI 678576), ‘CP 06-3103’ (Reg. No. CV-175; PI 678577), and ‘CP 07-1313’ (Reg. No. CV-176; PI 678578) sugarcane (a complex hybrid of Saccharum spp.) were released in June 2015 to be cu...

Heterometallic niobium complexes containing the {open_quotes}CpNb{close_quotes} unit. X-ray crystal structures of CpNbCl{sub 2}({mu}-SEt){sub 2}NiCp and CpNb(PhCCPh)({mu}-SPr{sup 1}){sub 2}Mo(CO){sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woodward, S.; Curtis, M.D.; Rheingold, A.L.

1992-06-01

Cp{sub 2}Nb{sub 2}Cl{sub 2}({mu}-Cl{sub 2})(CO){sub 4} reacts with Cp{sub 2}Ni{sub 2}({mu}-SEt){sub 2} to yield paramagnetic CpNbCl{sub 2}({mu}-SEt){sub 2}NiCp: (g) = 2.004, A = 129 G; space group = P2{sub 1}/c,a = 7.466 (1) {Angstrom}, b = 28.427 (5) {Angstrom}, c = 8.620 (2) {Angstrom}, {beta} = 104.81 (1){degree}. CpNb(PhCCPh)({mu}-SPr{sup i}){sub 2}Mo(CO){sub 4} is synthesized by the addition of LiSPr{sup i} to CpNbCl{sub 2}PhCCPh resulting in formation of CpNb(SPr{sup i}){sub 2}(PhCCPh) followed by the reaction of the thiolate complex with Mo(MeCN){sub 3}(CO){sub 3} and CO (1 equiv). The crystal structure for CpNb(PhCCPh)({mu}-SPr{sup i}){sub 2}Mo(CO){sub 4} is reported and EHMO calculations ofmore » the bonding in CpNbCl{sub 2}({mu}-SEt{sub 2})NiCp were discussed. 27 refs., 5 figs., 5 tabs.« less

Long-Range Intramolecular Electronic Communication in a Trinuclear Ruthenium Tropolonate Complex.

PubMed

Yoshida, Jun; Kuwahara, Kyohei; Suzuki, Kota; Yuge, Hidetaka

2017-02-20

Dinuclear and trinuclear ruthenium complexes, [Ru(trop) 2 (C 2 trop)Ru(dppe)Cp] [2b; trop = tropolonato, C 2 trop = ethynyltropolonato, dppe = 1,2-bis(diphenylphosphino)ethane] and [Ru(trop){(C 2 trop)Ru(dppe)Cp} 2 ] (3), were synthesized, and their electronic and electrochemical properties were investigated in comparison with our previously reported complex [Ru(acac) 2 (C 2 trop)Ru(dppe)Cp] (2a). The electron-donating Ru II (dppe)Cp unit and electron-accepting Ru III O 6 unit are connected by C 2 trop in these complexes. 2a incorporates acetylacetonate as an ancillary ligand, while 2b and 3 incorporate tropolonate as an ancillary ligand. Every complex, 2a, 2b, and 3, exhibits similar UV-vis-near-IR (NIR) absorption spectra, demonstrating the lack of explicit intramolecular electronic communication between the units at least in the neutral state. The weak NIR absorption in 2a further diminished upon electrochemical oxidation, indicating almost no electronic communication between the units. In contrast, 2b and 3 exhibit broad NIR absorptions upon oxidation. Additionally, 3 exhibits four stepwise redox couples in the electrochemical study, which are formally attributed to [Ru II (trop) 3 ] - /[Ru III (trop) 3 ], two [Ru II (dppe)Cp]/[Ru III (dppe)Cp] + , and [Ru III (trop) 3 ]/[Ru IV (trop) 3 ] + couples. Clear separation of the redox couples attributed to the two terminal [Ru(dppe)Cp] units demonstrates the thermodynamic stability of the intermediate oxidation states with respect to disproportionation. Further electrochemical studies using an electrolyte including perfluorinated weakly coordinating anions and density functional theory/time-dependent density functional theory calculations confirmed the effect of ancillary ligands, acetylacetonate and tropolonate. In the case of 2a, electronic delocalization over the whole complex, especially over the [Ru(acac) 2 (trop)] unit, appears to be small. In contrast, the electronic communication between [Ru(dppe)Cp] and [Ru(trop) 3 ] units in 3 seems to be enhanced upon oxidation, resulting in the long-range intramolecular electronic communication.

Structural impact of complete CpG methylation within target DNA on specific complex formation of the inducible transcription factor Egr-1.

PubMed

Zandarashvili, Levani; White, Mark A; Esadze, Alexandre; Iwahara, Junji

2015-07-08

The inducible transcription factor Egr-1 binds specifically to 9-bp target sequences containing two CpG sites that can potentially be methylated at four cytosine bases. Although it appears that complete CpG methylation would make an unfavorable steric clash in the previous crystal structures of the complexes with unmethylated or partially methylated DNA, our affinity data suggest that DNA recognition by Egr-1 is insensitive to CpG methylation. We have determined, at a 1.4-Å resolution, the crystal structure of the Egr-1 zinc-finger complex with completely methylated target DNA. Structural comparison of the three different methylation states reveals why Egr-1 can recognize the target sequences regardless of CpG methylation. Copyright © 2015 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Dehydrogenation, disproportionation and transfer hydrogenation reactions of formic acid catalyzed by molybdenum hydride compounds.

PubMed

Neary, Michelle C; Parkin, Gerard

2015-03-01

The cyclopentadienyl molybdenum hydride compounds, Cp R Mo(PMe 3 ) 3- x (CO) x H (Cp R = Cp, Cp*; x = 0, 1, 2 or 3), are catalysts for the dehydrogenation of formic acid, with the most active catalysts having the composition Cp R Mo(PMe 3 ) 2 (CO)H. The mechanism of the catalytic cycle is proposed to involve (i) protonation of the molybdenum hydride complex, (ii) elimination of H 2 and coordination of formate, and (iii) decarboxylation of the formate ligand to regenerate the hydride species. NMR spectroscopy indicates that the nature of the resting state depends on the composition of the catalyst. For example, (i) the resting states for the CpMo(CO) 3 H and CpMo(PMe 3 )(CO) 2 H systems are the hydride complexes themselves, (ii) the resting state for the CpMo(PMe 3 ) 3 H system is the protonated species [CpMo(PMe 3 ) 3 H 2 ] + , and (iii) the resting state for the CpMo(PMe 3 ) 2 (CO)H system is the formate complex, CpMo(PMe 3 ) 2 (CO)(κ 1 -O 2 CH), in the presence of a high concentration of formic acid, but CpMo(PMe 3 ) 2 (CO)H when the concentration of acid is low. While CO 2 and H 2 are the principal products of the catalytic reaction induced by Cp R Mo(PMe 3 ) 3- x (CO) x H, methanol and methyl formate are also observed. The generation of methanol is a consequence of disproportionation of formic acid, while methyl formate is a product of subsequent esterification. The disproportionation of formic acid is a manifestation of a transfer hydrogenation reaction, which may also be applied to the reduction of aldehydes and ketones. Thus, CpMo(CO) 3 H also catalyzes the reduction of a variety of ketones and aldehydes to alcohols by formic acid, via a mechanism that involves ionic hydrogenation.

Exosome-based tumor antigens-adjuvant co-delivery utilizing genetically engineered tumor cell-derived exosomes with immunostimulatory CpG DNA.

PubMed

Morishita, Masaki; Takahashi, Yuki; Matsumoto, Akihiro; Nishikawa, Makiya; Takakura, Yoshinobu

2016-12-01

For cancer immunotherapy via tumor antigen vaccination in combination with an adjuvant, major challenges include the identification of a particular tumor antigen and efficient delivery of the antigen as well as adjuvant to antigen-presenting cells. In this study, we proposed an efficient exosome-based tumor antigens-adjuvant co-delivery system using genetically engineered tumor cell-derived exosomes containing endogenous tumor antigens and immunostimulatory CpG DNA. Murine melanoma B16BL6 cells were transfected with a plasmid vector encoding a fusion streptavidin (SAV; a protein that binds to biotin with high affinity)-lactadherin (LA; an exosome-tropic protein) protein, yielding genetically engineered SAV-LA-expressing exosomes (SAV-exo). SAV-exo were combined with biotinylated CpG DNA to prepare CpG DNA-modified exosomes (CpG-SAV-exo). Fluorescent microscopic observation revealed the successful modification of exosomes with CpG DNA by SAV-biotin interaction. CpG-SAV-exo showed efficient and simultaneous delivery of exosomes with CpG DNA to murine dendritic DC2.4 cells in culture. Treatment with CpG-SAV-exo effectively activated DC2.4 cells and enhanced tumor antigen presentation capacity. Immunization with CpG-SAV-exo exhibited stronger in vivo antitumor effects in B16BL6 tumor-bearing mice than simple co-administration of exosomes and CpG DNA. Thus, genetically engineered CpG-SAV-exo is an effective exosome-based tumor antigens-adjuvant co-delivery system that will be useful for cancer immunotherapy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Rodent Hypoxia–Ischemia Models for Cerebral Palsy Research: A Systematic Review

PubMed Central

Rumajogee, Prakasham; Bregman, Tatiana; Miller, Steven P.; Yager, Jerome Y.; Fehlings, Michael G.

2016-01-01

Cerebral palsy (CP) is a complex multifactorial disorder, affecting approximately 2.5–3/1000 live term births, and up to 22/1000 prematurely born babies. CP results from injury to the developing brain incurred before, during, or after birth. The most common form of this condition, spastic CP, is primarily associated with injury to the cerebral cortex and subcortical white matter as well as the deep gray matter. The major etiological factors of spastic CP are hypoxia/ischemia (HI), occurring during the last third of pregnancy and around birth age. In addition, inflammation has been found to be an important factor contributing to brain injury, especially in term infants. Other factors, including genetics, are gaining importance. The classic Rice–Vannucci HI model (in which 7-day-old rat pups undergo unilateral ligation of the common carotid artery followed by exposure to 8% oxygen hypoxic air) is a model of neonatal stroke that has greatly contributed to CP research. In this model, brain damage resembles that observed in severe CP cases. This model, and its numerous adaptations, allows one to finely tune the injury parameters to mimic, and therefore study, many of the pathophysiological processes and conditions observed in human patients. Investigators can recreate the HI and inflammation, which cause brain damage and subsequent motor and cognitive deficits. This model further enables the examination of potential approaches to achieve neural repair and regeneration. In the present review, we compare and discuss the advantages, limitations, and the translational value for CP research of HI models of perinatal brain injury. PMID:27199883

MeCP2 deficiency in Rett syndrome causes epigenetic aberrations at the PWS/AS imprinting center that affects UBE3A expression.

PubMed

Makedonski, Kirill; Abuhatzira, Liron; Kaufman, Yotam; Razin, Aharon; Shemer, Ruth

2005-04-15

Rett syndrome (RS) is a severe and progressive neurodevelopmental disorder caused by heterozygous mutations in the X-linked methyl CpG binding protein 2 (MeCP2) gene. MeCP2 is a nuclear protein that binds specifically to methylated DNA and functions as a general transcription repressor in the context of chromatin remodeling complexes. RS shares clinical features with those of Angelman syndrome (AS), an imprinting neurodevelopmental disorder. In AS patients, the maternally expressed copy of UBE3A that codes for the ubiquitin protein ligase 3A (E6-AP) is repressed. The similar phenotype of these two syndromes led us to hypothesize that part of the RS phenotype is due to MeCP2-associated silencing of UBE3A. Indeed, UBE3A mRNA and protein are shown here to be significantly reduced in human and mouse MECP2 deficient brains. This reduced UBE3A level was associated with biallelic production of the UBE3A antisense RNA. In addition, MeCP2 deficiency resulted in elevated histone H3 acetylation and H3(K4) methylation and reduced H3(K9) methylation at the PWS/AS imprinting center, with no effect on DNA methylation or SNRPN expression. We conclude, therefore, that MeCP2 deficiency causes epigenetic aberrations at the PWS imprinting center. These changes in histone modifications result in loss of imprinting of the UBE3A antisense gene in the brain, increase in UBE3A antisense RNA level and, consequently reduction in UBE3A production.

Haploinsufficiency of MeCP2-interacting transcriptional co-repressor SIN3A causes mild intellectual disability by affecting the development of cortical integrity.

PubMed

Witteveen, Josefine S; Willemsen, Marjolein H; Dombroski, Thaís C D; van Bakel, Nick H M; Nillesen, Willy M; van Hulten, Josephus A; Jansen, Eric J R; Verkaik, Dave; Veenstra-Knol, Hermine E; van Ravenswaaij-Arts, Conny M A; Wassink-Ruiter, Jolien S Klein; Vincent, Marie; David, Albert; Le Caignec, Cedric; Schieving, Jolanda; Gilissen, Christian; Foulds, Nicola; Rump, Patrick; Strom, Tim; Cremer, Kirsten; Zink, Alexander M; Engels, Hartmut; de Munnik, Sonja A; Visser, Jasper E; Brunner, Han G; Martens, Gerard J M; Pfundt, Rolph; Kleefstra, Tjitske; Kolk, Sharon M

2016-08-01

Numerous genes are associated with neurodevelopmental disorders such as intellectual disability and autism spectrum disorder (ASD), but their dysfunction is often poorly characterized. Here we identified dominant mutations in the gene encoding the transcriptional repressor and MeCP2 interactor switch-insensitive 3 family member A (SIN3A; chromosome 15q24.2) in individuals who, in addition to mild intellectual disability and ASD, share striking features, including facial dysmorphisms, microcephaly and short stature. This phenotype is highly related to that of individuals with atypical 15q24 microdeletions, linking SIN3A to this microdeletion syndrome. Brain magnetic resonance imaging showed subtle abnormalities, including corpus callosum hypoplasia and ventriculomegaly. Intriguingly, in vivo functional knockdown of Sin3a led to reduced cortical neurogenesis, altered neuronal identity and aberrant corticocortical projections in the developing mouse brain. Together, our data establish that haploinsufficiency of SIN3A is associated with mild syndromic intellectual disability and that SIN3A can be considered to be a key transcriptional regulator of cortical brain development.

Cisplatin-induced cytotoxicity in BSO-exposed renal proximal tubular epithelial cells: sex, age, and species.

PubMed

Lu, Yongke; Kawashima, Akira; Horii, Ikuo; Zhong, Laifu

2005-01-01

Cisplatin (CP)-induced kidney damage and effects of DL-buthionine-(S,R)-sulfoximine (BSO) on it are species- and age-different. It remains unclear whether CP-induced cytotoxicity in renal proximal tubular epithelial cells (RTEC), the main target cells of CP, is also species- and age-different; and whether CP-induced cytotoxicity varies with the difference in age and species, if any, is one of the questions. In the present study, the effects of BSO on CP-induced cytotoxicity in primary cultures of RTEC isolated from monkeys and different age and sex rats were studied. The RTEC were isolated from 3-week-old, 2-month-old, or 5-month-old rats, and 6-8 year-old monkeys. After subculturing, RTEC was inoculated into type I collagen-coated 96-well culture plates; after preincubation, 40 microM BSO was added, 16 hours later, varying concentrations of CP were added. At that time, 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assays were performed to test cell viability. The concentrations of CP that inhibited 50% cell growth (IC50) of RTEC from rats and monkeys were 1.11 and 3.03 mM at 8 hours, and 0.51 and 1.24 mM at 24 hours, respectively. The BSO made the IC50s of RTEC from rats and monkeys lower, down to 0.07 and 0.48 mM at 8 hours, and 0.02 and 0.11 mM at 24 hours, respectively. The IC50s of RTEC from different sex and age rats were almost same. These results suggested that CP-induced cytotoxicity was concentration- and time-dependent, with species-dependent differences, rat RTEC were more susceptible to CP than monkey RTEC, rat RTEC were more dependent on glutathione (GSH) during the stress state were than monkey cells; CP-induced cytotoxicity was without sex- and age-dependent differences in rat RTEC.

The radiometal makes a difference. Synthesis and preliminary characterisation of DOTA-minigastrin analogue complexes with Ga, Lu and Y.

PubMed

Maurin, Michał; Garnuszek, Piotr; Baran, Piotr; Pawlak, Dariusz; Mikołajczak, Renata

2015-01-01

The minigastrin analogue - CP04: DOTA-(DGlu)6-Ala-Tyr-Gly-Trp-Met-Asp-Phe-NH2 has been developed for CCK2R targeting. This analogue can be radiolabelled with 111In or 68Ga for imaging, or with 90Y and 177Lu for therapy. However, affinity of the chelator-peptide conjugates to the cell membrane receptors may vary depending on the metal incorporated into the complex. So far, there are no such studies for the ligands of gastrin/cholecystokinin receptor CCK2R. It is supposed that the reason for the differentiation of receptor affinity to the respective receptors is in the changes of structure of chelating system and their influence on the bioactive conformations of the metal conjugated peptides. Herein, we report on the radiolabeling of CP04 with 90Y, 177Lu and 68Ga and synthesis of cold CP04 complexes with respective stable metals for further structural and physico-chemical and biological studies. From 200 to 600 MBq of 90Y, 177Lu or 68Ga were used for radiolabelling of 20 μg of CP04 dissolved in ascorbic acid solution (50 mg/mL, pH 4.5). Non-radioactive complexes with Lu and Ga were synthesized in milligram amounts starting from 0.5 mg up to 5 mg of CP04 dissolved in ascorbic acid solution (50 mg/mL, pH 4.5) when using 2-molar excess of the metal ions. Complex formation needed 5 min in microwave oven or 12 min in thermo-block at 95°C. RP-HPLC isocratic method (Kinetex 150/4.6 mm; 25% AcN/0.1% TFA, 1 mL/min) with UV/Vis and radiometric detection was developed for investigation of the radiolabelled and "cold" complexes. For LC-MS investigations, HPLC method was modified replacing TFA by formic acid. Yields of CP04 radiolabelling were greater than 90% for all three radionuclides. The HPLC method enabled identification of these radio-complexes based on comparison to their non-radioactive equivalents. In all cases, chromatograms revealed peaks that could be attributed to the metal-CP04 complexes and to impurities (including methionine oxidation). LC-MS analysis of Ga and Lu complexes revealed conformity of the observed molecular ions to the predicted formulas (m/z 2116 and 2220 Da for Ga and Lu, respectively). Different chromatographic behaviour observed for Ga-CP04 complex comparing to Lu- and Y- labelled peptide (relative retention to CP04: 1.08, 0.86 and 0.85, respectively) suggest different coordination of the metal ions. Therefore, further studies are planned using the non-radioactive complexes in order to assess their structural conformations.

Computational Modeling Approach in Probing the Effects of Cytosine Methylation on the Transcription Factor Binding to DNA.

PubMed

Tenayuca, John; Cousins, Kimberley; Yang, Shumei; Zhang, Lubo

2017-01-01

Cytosine methylation at CpG dinucleotides is a chief mechanism in epigenetic modification of gene expression patterns. Previous studies demonstrated that increased CpG methylation of Sp1 sites at -268 and -346 of protein kinase C ε promoter repressed the gene expression. The present study investigated the impact of CpG methylation on the Sp1 binding via molecular modeling and electrophoretic mobility shift assay. Each of the Sp1 sites contain two CpGs. Methylation of either CpG lowered the binding affinity of Sp1, whereas methylation of both CpGs produced a greater decrease in the binding affinity. Computation of van der Waals (VDW) energy of Sp1 in complex with the Sp1 sites demonstrated increased VDW values from one to two sites of CpG methylation. Molecular modeling indicated that single CpG methylation caused underwinding of the DNA fragment, with the phosphate groups at C1, C4 and C5 reoriented from their original positions. Methylation of both CpGs pinched the minor groove and increased the helical twist concomitant with a shallow, hydrophobic major groove. Additionally, double methylation eliminated hydrogen bonds on recognition helix residues located at positions -1 and 1, which were essential for interaction with O6/N7 of G-bases. Bonding from linker residues Arg565, Lys595 and Lys596 were also reduced. Methylation of single or both CpGs significantly affected hydrogen bonding from all three Sp1 DNA binding domains, demonstrating that the consequences of cytosine modification extend beyond the neighboring nucleotides. The results indicate that cytosine methylation causes subtle structural alterations in Sp1 binding sites consequently resulting in inhibition of side chain interactions critical for specific base recognition and reduction of the binding affinity of Sp1. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Blm10 facilitates nuclear import of proteasome core particles

PubMed Central

Weberruss, Marion H; Savulescu, Anca F; Jando, Julia; Bissinger, Thomas; Harel, Amnon; Glickman, Michael H; Enenkel, Cordula

2013-01-01

Short-lived proteins are degraded by proteasome complexes, which contain a proteolytic core particle (CP) but differ in the number of regulatory particles (RPs) and activators. A recently described member of conserved proteasome activators is Blm10. Blm10 contains 32 HEAT-like modules and is structurally related to the nuclear import receptor importin/karyopherin β. In proliferating yeast, RP-CP assemblies are primarily nuclear and promote cell division. During quiescence, RP-CP assemblies dissociate and CP and RP are sequestered into motile cytosolic proteasome storage granuli (PSG). Here, we show that CP sequestration into PSG depends on Blm10, whereas RP sequestration into PSG is independent of Blm10. PSG rapidly clear upon the resumption of cell proliferation and proteasomes are relocated into the nucleus. Thereby, Blm10 facilitates nuclear import of CP. Blm10-bound CP serves as an import receptor–cargo complex, as Blm10 mediates the interaction with FG-rich nucleoporins and is dissociated from the CP by Ran-GTP. Thus, Blm10 represents the first CP-dedicated nuclear import receptor in yeast. PMID:23982732

Cp[prime]M(NO)R[sub 2]: 16-electron piano-stool molecules of molybdenum and tungsten

DOE Office of Scientific and Technical Information (OSTI.GOV)

Legzdins, P.; Veltheer, J.E.

1993-02-01

A long-term goal of this research program is the development of organometallic nitrosyl complexes as specific reactants or selective catalysts for organic or organometallic transformations of practical significance. To attain this goal specifically with Cp[prime]M(NO)R[sub 2] system the authors developed new methods for their synthesis, established their characteristic physical and chemical properties, and are currently endeavoring to exploit those properties which are unique to the complexes. During our investigations, the authors have discovered that the Cp[prime]M(NO)R[sub 2] complexes react with a variety of small molecules, often in an unprecedented manner. The authors have also established several unique transformations that aremore » not exhibited by all members of this group of complexes. Indeed, the authors found that the chemical properties of these systems are often dependent on the metal, the nature of the R groups, and the type of Cp[prime] ligand. In this Account the authors summarize the synthesis, characterization, comparative reactivity, and distinctive chemical properties of the 16-electron Cp[prime]M(NO)R[sub 2] complexes known to date. 35 refs., 7 figs.« less

Nutrient digestibility and energy value of sheep rations differing in protein level, main protein source and non-forage fibre source.

PubMed

Milis, Ch; Liamadis, D

2008-02-01

Two in vivo digestion trials were conducted to evaluate the effects of diet's crude protein (CP) level, N degradability, and non-forage fibre source (NFFS) on nutrient digestibility and energy value of sheep rations. In each trial, rams were fed four isocaloric and isofibrous rations, differing in main protein and/or NFFS source. At the first trial, mean CP/metabolizable energy (ME) ratio of the diets was 17 g/MJ ME and at the second trial, 13 g/MJ ME. At both trials, the first ration contained cotton seed cake (CSC) and wheat bran (WB), the second CSC and corn gluten feed (CGF), the third corn gluten meal (CGM) and WB and the fourth CGM and CGF. Data of both trials were analysed in common as 2 x 2 x 2 factorial experimental design. Low N degradability (CGM) had positive effect on CP, neutral detergent fibre (NDF) and acid detergent fibre (ADF) digestibility of the ration. Those results suggest that an increase in rumen undegradable protein (RUP) content does not negatively affect nutrient digestibility of sheep rations. Corn gluten feed significantly elevated crude fibre (CF) digestibility, in comparison with WB. Rations having high CP/ME ratio had higher digestibility of CP in comparison with those having low CP/ME ratio; the opposite was true for ether extract, CF, NDF and ADF digestibilities. CP level x N degradability interaction negatively affected energy value of the rations that had high CP level and high N degradability. Former suggest that when CP content is high then N degradability should be low otherwise ration's ME is negatively affected. CP digestibility and coefficient q of the rations containing WB and having high N degradability (N degradability x NFFS interaction) were the lowest suggesting that the combination of CSC and WB negatively affected CP digestibility and energy value of the ration. This could be explained by a reduced microbial CP synthesis, or lower RUP digestibility or both.

Isolation and Compositional Analysis of a CP12-Associated Complex of Calvin Cycle Enzymes from Nicotiana tabacum

USDA-ARS?s Scientific Manuscript database

CP12 is a small intrinsically unstructured protein that forms a multiprotein complex with two Calvin Cycle enzymes, phosphoribulokinase (PRK) and NAD(P)-dependent glyceraldehyde-3-phosphate dehydrogenase (GAPDH). The complex can be reconstituted in vitro from recombinant proteins under conditions t...

Distinct Roles of Chromatin Insulator Proteins in Control of the Drosophila Bithorax Complex

PubMed Central

Savitsky, Mikhail; Kim, Maria; Kravchuk, Oksana; Schwartz, Yuri B.

2016-01-01

Chromatin insulators are remarkable regulatory elements that can bring distant genomic sites together and block unscheduled enhancer–promoter communications. Insulators act via associated insulator proteins of two classes: sequence-specific DNA binding factors and “bridging” proteins. The latter are required to mediate interactions between distant insulator elements. Chromatin insulators are critical for correct expression of complex loci; however, their mode of action is poorly understood. Here, we use the Drosophila bithorax complex as a model to investigate the roles of the bridging proteins Cp190 and Mod(mdg4). The bithorax complex consists of three evolutionarily conserved homeotic genes Ubx, abd-A, and Abd-B, which specify anterior–posterior identity of the last thoracic and all abdominal segments of the fly. Looking at effects of CTCF, mod(mdg4), and Cp190 mutations on expression of the bithorax complex genes, we provide the first functional evidence that Mod(mdg4) acts in concert with the DNA binding insulator protein CTCF. We find that Mod(mdg4) and Cp190 are not redundant and may have distinct functional properties. We, for the first time, demonstrate that Cp190 is critical for correct regulation of the bithorax complex and show that Cp190 is required at an exceptionally strong Fub insulator to partition the bithorax complex into two topological domains. PMID:26715665

Effectiveness of Adaptive Pretend Play on Affective Expression and Imagination of Children with Cerebral Palsy

ERIC Educational Resources Information Center

Hsieh, Hsieh-Chun

2012-01-01

Purpose: Children with cerebral palsy (CP) have difficulty participating in role-pretending activities. The concept of adaptive play makes play accessible by modifying play materials for different needs or treatment goals for children with CP. This study examines the affective expressions and imagination in children with CP as a function of…

Upper limb performance and the structuring of joint movement in teenagers with cerebral palsy: the reciprocal role of task demands and action capabilities.

PubMed

Figueiredo, Priscilla Rezende Pereira; Silva, Paula Lanna; Avelar, Bruna Silva; da Fonseca, Sérgio Teixeira; Bootsma, Reinoud J; Mancini, Marisa Cotta

2015-04-01

Individuals with unilateral cerebral palsy (CP) demonstrate reduced performance in upper limb tasks compared to typically developing (TD) peers. We examined whether task conditions modify differences between teenagers with and without CP during a reciprocal aiming task. Twenty teenagers (nine CP and 11 TD) moved a pointer between two targets as fast as possible without missing a target. Task conditions were manipulated by changing the targets' size, by modifying the inertial properties of the pointer and by varying the upper limb used to perform the task (preferred/non-affected and non-preferred/affected upper limbs). While compared to TD peers, CP teenagers exhibited lower performance (longer movement times). Such differences were attenuated when the task was performed with the preferred upper limb and when accuracy requirements were less stringent. CP teenagers were not differentially affected by the pointer inertia manipulation. Task conditions not only affected performance but also joint kinematics. CP teenagers revealed less movement at the elbow and more movement at the shoulder when performing the task with their less skilled upper limb. However, both CP and TD teenagers demonstrated a larger contribution of trunk movement when facing more challenging task conditions. The overall pattern of results indicated that the joint kinematics employed by individuals with unilateral CP constituted adaptive responses to task requirements. Thus, the explanation of the effects of unilateral CP on upper limb behavior needs to go beyond a context-indifferent manifestation of the brain injury to include the interaction between task demands and action capabilities.

Mapping the signal peptide binding and oligomer contact sites of the core subunit of the pea twin arginine protein translocase.

PubMed

Ma, Xianyue; Cline, Kenneth

2013-03-01

Twin arginine translocation (Tat) systems of thylakoid and bacterial membranes transport folded proteins using the proton gradient as the sole energy source. Tat substrates have hydrophobic signal peptides with an essential twin arginine (RR) recognition motif. The multispanning cpTatC plays a central role in Tat operation: It binds the signal peptide, directs translocase assembly, and may facilitate translocation. An in vitro assay with pea (Pisum sativum) chloroplasts was developed to conduct mutagenesis and analysis of cpTatC functions. Ala scanning mutagenesis identified mutants defective in substrate binding and receptor complex assembly. Mutations in the N terminus (S1) and first stromal loop (S2) caused specific defects in signal peptide recognition. Cys matching between substrate and imported cpTatC confirmed that S1 and S2 directly and specifically bind the RR proximal region of the signal peptide. Mutations in four lumen-proximal regions of cpTatC were defective in receptor complex assembly. Copurification and Cys matching analyses suggest that several of the lumen proximal regions may be important for cpTatC-cpTatC interactions. Surprisingly, RR binding domains of adjacent cpTatCs directed strong cpTatC-cpTatC cross-linking. This suggests clustering of binding sites on the multivalent receptor complex and explains the ability of Tat to transport cross-linked multimers. Transport of substrate proteins cross-linked to the signal peptide binding site tentatively identified mutants impaired in the translocation step.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non‐Polar Solvents by using Conductometry

PubMed Central

Iseda, Kazuya

2018-01-01

Abstract In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride (TBACl) ion‐pair salt to the free ions through complexation with meso‐octamethylcalix[4]pyrrole (CP), which is a well‐known receptor for chloride anions. In the presence of CP, the conductivity of TBACl increases in various non‐polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non‐polar solvents. In other words, CP recognizes chloride as an ion‐paired salt as well as a free anion in non‐polar solvents. Additionally, the TBA(CP–Cl) complex exhibited a considerably lower ion‐pairing constant (K ip) than TBACl in non‐polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli‐responsive soft materials in organic solvents using coulombic forces. PMID:29610717

Biodegradability of Chlorophenols in Surface Waters from the Urban Area of Buenos Aires.

PubMed

Gallego, A; Laurino Soulé, J; Napolitano, H; Rossi, S L; Vescina, C; Korol, S E

2018-04-01

Biodegradability of 2-Chlorophenol (2-CP), 3-Chlorophenol (3-CP), 4-Chlorophenol (4-CP), 2,4-Dichlorophenol (2,4-DCP) and 2,4,6 Trichlorophenol (2,4,6-TCP) has been tested in surface waters in the urban area of Buenos Aires. Samples were taken from the La Plata River and from the Reconquista and Matanza-Riachuelo basins, with a total amount of 18 sampling points. Water quality was established measuring chemical oxygen demand (COD), biochemical oxygen demand (BOD 5 ), and both Escherichia coli and Enterococcus counts. Biodegradability was carried out by a respirometric method, using a concentration of 20 mg L -1 of chlorophenol, and the surface water as inoculum. Chlorophenols concentration in the same water samples were simultaneously measured by a solid phase microextraction (SPME) procedure followed by gas chromatography-mass spectrometry (GC-MS). 2,4-DCP was the most degradable compound followed by 2,4,6-TCP, 4-CP, 3-CP and 2-CP. Biodegradability showed no correlation with compound concentration. At most sampling points the concentration was below the detection limit for all congeners. Biodegradability does not correlate even with COD, BOD 5 , or fecal contamination. Biodegradability assays highlighted information about bacterial exposure to contaminants that parameters routinely used for watercourse characterization do not reveal. For this reason, they might be a helpful tool to complete the characterization of a site.

Dispositions of enrofloxacin and its major metabolite ciprofloxacin in Thai swamp buffaloes

PubMed Central

RUENNARONG, Nitwarat; WONGPANIT, Kannika; SAKULTHAEW, Chainarong; GIORGI, Mario; KUMAGAI, Susumu; POAPOLATHEP, Amnart; POAPOLATHEP, Saranya

2015-01-01

Given the limited information available in this species, the aim of this study was to investigate the pharmacokinetic characteristics of enrofloxacin (ER) and its major metabolite ciprofloxacin (CP) in buffaloes, Bubalus bubalis. ER was administered intravenously (i.v.) or subcutaneously (s.c.) to buffaloes at doses of 5.0 and 7.5 mg/kg BW, and plasma, urine and fecal samples were collected until 48 hr post-administration. The concentrations of ER and CP in the plasma, urine and feces were analyzed using high-performance liquid chromatography equipped with a fluorescence detector. The plasma concentrations of ER and CP could be determined up to 24 hr and 32 hr after i.v. and s.c. administrations at doses of 5.0 and 7.5 mg/kg BW, respectively. CP concentrations were always lower than those of parental drug. The s.c. bioavailability of ER was 52.36 ± 4.24% and 72.12 ± 5.39% at doses of 5.0 and 7.5 mg/kg BW, respectively. Both ER and CP were detectable in urine and feces up to 24 hr. ER and CP were mainly excreted via the urine. Based on the pharmacokinetic data and PK-PD indices, s.c. administration of ER at doses of 5.0 and 7.5 mg/kg BW might be appropriate for the treatment of susceptible bacterial diseases in Thai swamp buffaloes. PMID:26596287

[Clinical analysis of 322 cases of non-epileptic cerebral palsy].

PubMed

Zhu, Deng-Na; Wang, Jun; Jia, Yan-Jie; Niu, Guo-Hui; Sun, Li; Xiong, Hua-Chun; Zhai, Hong-Yin; Chen, Hai; Li, Lin-Chen

2010-12-01

To study the clinical features of non-epileptic seizures associated with cerebral palsy (CP) in children. A total of 1 198 children with CP (age: 9 months to 6 years) were enrolled. The children with paroxysmal events were monitored by 24 hrs video-EEG (VEEG) to make sure the seizures were epileptic or non-epileptic. The symptoms, age, CP types and EEG features were observed in children with non-epileptic CP. Five hundred and seventy-eight children (48.24%) presented paroxysmal events. The seizures were epileptic in 231 children (19.28%) and non-epileptic in 322 cases (26.88%). In the 322 cases of non-epileptic CP, the paroxysmal events were of various kinds, including non-epileptic seizure tonic, seizure shake head, shrug shoulder or head hypsokinesis, cry or scream, panic attacks, sleep myoclonic and stereotyped movement. One hundred and fifty-eight (49.1%) out of the 322 children demonstrated nonspecific EEG abnormalities. One hundred and eleven children (34.5%) were misdiagnosed as epilepsy in primary hospitals. The CP children less than one year old showed higher frequency of non-epileptic seizures than the age groups over 1 year and 3 to 6 years. The frequency of non-epileptic seizures was the highest in children with spastic CP (168 cases, 52.2%), followed by dyskinetic CP (69 cases, 21.4%) and mixed type CP (65 cases, 20.2%). The paroxysmal events in children with CP partially are non-epileptic seizures and it is important to differentiate non-epileptic from epileptic seizures. The frequencies of non-epileptic seizures may be associated with a child's age and CP type.

Reducing the CP content in broiler feeds: impact on animal performance, meat quality and nitrogen utilization.

PubMed

Belloir, P; Méda, B; Lambert, W; Corrent, E; Juin, H; Lessire, M; Tesseraud, S

2017-11-01

Reducing the dietary CP content is an efficient way to limit nitrogen excretion in broilers but, as reported in the literature, it often reduces performance, probably because of an inadequate provision in amino acids (AA). The aim of this study was to investigate the effect of decreasing the CP content in the diet on animal performance, meat quality and nitrogen utilization in growing-finishing broilers using an optimized dietary AA profile based on the ideal protein concept. Two experiments (1 and 2) were performed using 1-day-old PM3 Ross male broilers (1520 and 912 for experiments 1 and 2, respectively) using the minimum AA:Lys ratios proposed by Mack et al. with modifications for Thr and Arg. The digestible Thr (dThr): dLys ratio was increased from 63% to 68% and the dArg:dLys ratio was decreased from 112% to 108%. In experiment 1, the reduction of dietary CP from 19% to 15% (five treatments) did not alter feed intake or BW, but the feed conversion ratio was increased for the 16% and 15% CP diets (+2.4% and +3.6%, respectively), while in experiment 2 (three treatments: 19%, 17.5% and 16% CP) there was no effect of dietary CP on performance. In both experiments, dietary CP content did not affect breast meat yield. However, abdominal fat content (expressed as a percentage of BW) was increased by the decrease in CP content (up to +0.5 and +0.2 percentage point, in experiments 1 and 2, respectively). In experiment 2, meat quality traits responded to dietary CP content with a higher ultimate pH and lower lightness and drip loss values for the low CP diets. Nitrogen retention efficiency increased when reducing CP content in both experiments (+3.5 points/CP percentage point). The main consequence of this higher efficiency was a decrease in nitrogen excretion (-2.5 g N/kg BW gain) and volatilization (expressed as a percentage of excretion: -5 points/CP percentage point). In conclusion, this study demonstrates that with an adapted AA profile, it is possible to reduce dietary CP content to at least 17% in growing-finishing male broilers, without altering animal performance and meat quality. Such a feeding strategy could therefore help improving the sustainability of broiler production as it is an efficient way to reduce environmental burden associated with nitrogen excretion.

High-precision robotic microcontact printing (R-μCP) utilizing a vision guided selectively compliant articulated robotic arm.

PubMed

McNulty, Jason D; Klann, Tyler; Sha, Jin; Salick, Max; Knight, Gavin T; Turng, Lih-Sheng; Ashton, Randolph S

2014-06-07

Increased realization of the spatial heterogeneity found within in vivo tissue microenvironments has prompted the desire to engineer similar complexities into in vitro culture substrates. Microcontact printing (μCP) is a versatile technique for engineering such complexities onto cell culture substrates because it permits microscale control of the relative positioning of molecules and cells over large surface areas. However, challenges associated with precisely aligning and superimposing multiple μCP steps severely limits the extent of substrate modification that can be achieved using this method. Thus, we investigated the feasibility of using a vision guided selectively compliant articulated robotic arm (SCARA) for μCP applications. SCARAs are routinely used to perform high precision, repetitive tasks in manufacturing, and even low-end models are capable of achieving microscale precision. Here, we present customization of a SCARA to execute robotic-μCP (R-μCP) onto gold-coated microscope coverslips. The system not only possesses the ability to align multiple polydimethylsiloxane (PDMS) stamps but also has the capability to do so even after the substrates have been removed, reacted to graft polymer brushes, and replaced back into the system. Plus, non-biased computerized analysis shows that the system performs such sequential patterning with <10 μm precision and accuracy, which is equivalent to the repeatability specifications of the employed SCARA model. R-μCP should facilitate the engineering of complex in vivo-like complexities onto culture substrates and their integration with microfluidic devices.

Health risks posed to infants in rural China by exposure to short- and medium-chain chlorinated paraffins in breast milk.

PubMed

Xia, Dan; Gao, Li-Rong; Zheng, Ming-Hui; Li, Jing-Guang; Zhang, Lei; Wu, Yong-Ning; Qiao, Lin; Tian, Qi-Chang; Huang, Hui-Ting; Liu, Wen-Bin; Su, Gui-Jin; Liu, Guo-Rui

2017-06-01

Chlorinated paraffins (CPs) are complex mixtures of synthetic chemicals found widely in environmental matrices. Short-chain CPs (SCCPs) are candidate persistent organic pollutants under the Stockholm Convention. There should be great concern about human exposure to SCCPs. Data on CP concentrations in human breast milk is scarce. This is the first study in which background SCCP and medium-chain CP (MCCP) body burdens in the general rural population of China have been estimated and health risks posed to nursing infants by CPs in breast milk assessed. The concentrations of 48 SCCP and MCCP formula congeners were determined in 24 pooled human milk samples produced from 1412 individual samples from eight provinces in 2007 and 16 provinces in 2011. The samples were analyzed by comprehensive two-dimensional gas chromatography electron capture negative ionization high-resolution time-of-flight mass spectrometry. The median SCCP and MCCP concentrations were 303 and 35.7ngg -1 lipid weight, respectively, for the 2007 samples and 360 and 45.4ngg -1 lipid weight, respectively, for the 2011 samples. The C 10 and C 14 homologs were the dominant CP carbon-chain-length groups, contributing 51% and 82% of the total SCCP and MCCP concentrations, respectively. There are probably multiple CP sources to the general Chinese population and numerous exposure pathways. The median estimated daily SCCP and MCCP intakes for nursing infants were 1310 and 152ngkg -1 d -1 , respectively, in 2007 and 1520 and 212ngkg -1 d -1 , respectively, in 2011. SCCPs do not currently pose significant risks to infants in China. However, it is necessary to continuously monitor CP concentrations and health risks because CP concentrations in Chinese human breast milk are increasing. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis of tripeptide derivatized cyclopentadienyl complexes of technetium and rhenium as radiopharmaceutical probes.

PubMed

Nadeem, Qaisar; Can, Daniel; Shen, Yunjun; Felber, Michael; Mahmood, Zaid; Alberto, Roger

2014-03-28

We describe the syntheses of half-sandwich complexes of the type [(η(5)-Cp(CONH-R))M(CO)3] with M = Re or (99m)Tc. The R group represents different tri-peptides (tpe) which display high binding affinities for oligopeptide transporters PEPT2. The (99m)Tc complexes were prepared directly from [(99m)Tc(OH2)3(CO)3](+) and Diels-Alder dimerized, cyclopentadienyl derivatized peptides in water. This approach corroborates the feasibility of metal-mediated retro Diels-Alder reactions for the preparation of not only small molecules but also peptides carrying a [(η(5)-Cp)(99m)Tc(CO)3] tag. We synthesized the Diels-Alder product [(HCpCONH-tpe)2] from Thiele's acid [(η(5)-HCpCOOH)2] via double peptide coupling. The Re-complexes [(η(5)-CpCONH-tpe)Re(CO)3] were obtained by attaching [(Cp-COOH)Re(CO)3] directly to the N-terminus of peptides as received from SPPS. The authenticity of the (99m)Tc-complexes is confirmed by chromatographic comparison with the corresponding rhenium complexes, fully characterized by spectroscopic techniques.

The chromosomal association/dissociation of the chromatin insulator protein Cp190 of Drosophila melanogaster is mediated by the BTB/POZ domain and two acidic regions.

PubMed

Oliver, Daniel; Sheehan, Brian; South, Heather; Akbari, Omar; Pai, Chi-Yun

2010-12-31

Chromatin insulators or boundary elements are a class of functional elements in the eukaryotic genome. They regulate gene transcription by interfering with promoter-enhancer communication. The Cp190 protein of Drosophila melanogaster is essential to the function of at least three-types of chromatin insulator complexes organized by Su(Hw), CTCF and BEAF32. We mapped functional regions of Cp190 in vivo and identified three domains that are essential for the insulator function and for the viability of flies: the BTB/POZ domain, an aspartic acid-rich (D-rich) region and a C-terminal glutamic acid-rich (E-rich) region. Other domains including the centrosomal targeting domain and the zinc fingers are dispensable. The N-terminal CP190BTB-D fragment containing the BTB/POZ domain and the D-rich region is sufficient to mediate association with all three types of insulator complexes. The fragment however is not sufficient for insulator activity or viability. The Cp190 and CP190BTB-D are regulated differently in cells treated with heat-shock. The Cp190 dissociated from chromosomes during heat-shock, indicating that dissociation of Cp190 with chromosomes can be regulated. In contrast, the CP190BTB-D fragment didn't dissociate from chromosomes in the same heat-shocked condition, suggesting that the deleted C-terminal regions have a role in regulating the dissociation of Cp190 with chromosomes. The N-terminal fragment of Cp190 containing the BTB/POZ domain and the D-rich region mediates association of Cp190 with all three types of insulator complexes and that the E-rich region of Cp190 is required for dissociation of Cp190 from chromosomes during heat-shock. The heat-shock-induced dissociation is strong evidence indicating that dissociation of the essential insulator protein Cp190 from chromosomes is regulated. Our results provide a mechanism through which activities of an insulator can be modulated by internal and external cues.

Reproducibility of Tactile Assessments for Children with Unilateral Cerebral Palsy

ERIC Educational Resources Information Center

Auld, Megan Louise; Ware, Robert S.; Boyd, Roslyn Nancy; Moseley, G. Lorimer; Johnston, Leanne Marie

2012-01-01

A systematic review identified tactile assessments used in children with cerebral palsy (CP), but their reproducibility is unknown. Sixteen children with unilateral CP and 31 typically developing children (TDC) were assessed 2-4 weeks apart. Test-retest percent agreements within one point for children with unilateral CP (and TDC) were…

η(4) -HBCC-σ,π-Borataallyl Complexes of Ruthenium Comprising an Agostic Interaction.

PubMed

Saha, Koushik; Joseph, Benson; Ramalakshmi, Rongala; Anju, R S; Varghese, Babu; Ghosh, Sundargopal

2016-06-01

Thermolysis of [Cp*Ru(PPh2 (CH2 )PPh2 )BH2 (L2 )] 1 (Cp*=η(5) -C5 Me5 ; L=C7 H4 NS2 ), with terminal alkynes led to the formation of η(4) -σ,π-borataallyl complexes [Cp*Ru(μ-H)B{R-C=CH2 }(L)2 ] (2 a-c) and η(2) -vinylborane complexes [Cp*Ru(R-C=CH2 )BH(L)2 ] (3 a-c) (2 a, 3 a: R=Ph; 2 b, 3 b: R=COOCH3 ; 2 c, 3 c: R=p-CH3 -C6 H4 ; L=C7 H4 NS2 ) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2 a-c are linked by a unique η(4) -interaction. Conversions of 1 into 3 a-c proceed through the formation of intermediates 2 a-c. Furthermore, in an attempt to expand the library of these novel complexes, chemistry of σ-borane complex [Cp*RuCO(μ-H)BH2 L] 4 (L=C7 H4 NS2 ) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the η(4) -σ,π-borataallyl complexes [Cp*Ru(μ-H)BH{R-C=CH2 }(L)] 5 and [Cp*Ru(μ-H)BH{HC=CH-R}(L)] 6 (R=COOCH3 ; L=C7 H4 NS2 ) by Markovnikov and anti-Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded η(4) -σ,π-borataallyl complex [Cp*Ru(μ-H)BH{R-C=CH-R}(L)] 7 (R=COOCH3 ; L=C7 H4 NS2 ). An agostic interaction was also found to be present in 2 a-c and 5-7, which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, (1) H, (11) B, (13) C NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2 b, 3 a-c and 5-7. DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlling of growth performance, lipid deposits and fatty acid composition of chicken meat through a probiotic, Lactobacillus johnsonii during subclinical Clostridium perfringens infection.

PubMed

Wang, Hesong; Ni, Xueqin; Liu, Lei; Zeng, Dong; Lai, Jing; Qing, Xiaodan; Li, Guangyao; Pan, Kangcheng; Jing, Bo

2017-02-10

Meat is considered as a major source of polyunsaturated fatty acid (PUFA) which is essential for humans, therefore its lipid level and fatty acid composition have drawn great attention. As no clinical sign can be found in chicks subclinically infected by Clostridium perfringens (CP), the meat may be purchased and eaten. The objective of the present study was to determine whether Lactobacillus johnsonii (LJ) can control the CP-caused impact on growth, lipid levels, fatty acid composition and other flavor or nutritional quality in the meat. 480 one-day-old chicks were divided into four groups and fed with basal diet (control and CP group). Supplemented with 1 × 10 5 (L-LJ) and 1 × 10 6 (H-LJ) colony-forming unit (cfu), CP diet was fed for 42 days. From day 19 to 22, birds of CP and LJ groups were administered with CP twice per day and the control was administered with liver broth. LJ-treated chickens were free from negative influences on growth performance and significant decrease of abdominal fat deposit., LJ inhibited CP-caused shearing force and drip loss increase and pH 40 min and 24 h decrease after sacrifice. In addition, LJ exhibited a positive effect on muscle lipid peroxidation by significantly increasing SOD, CAT and GSH-Px activity and decreasing MDA level. Besides, LJ attenuated the decrease of intramuscular fat, total cholesterol and triglyceride contents caused by CP infection. However, levels of total protein and most of amino acids were not changed. CP infection decreased C18:3n-3 (α-LA), C20:4n-6, C20:5n-3(EPA), C22:4n-6, C22:5n-3, C22:6n-3(DHA), total PUFA, n-3 PUFA and PUFA:SFA ratio and increased C14:0, total SFA and n-6:n-3 ratio. LJ was found to protect the muscle from these changes. Meanwhile, the 28-day gut permeability level was higher in CP group. These findings suggest that CP may affect the growth performance of chicks and negatively influence lipid content and fatty acid composition in chicken meat. Meanwhile, LJ treatment may be effective in controlling these changes by reducing the increased gut permeability caused by CP subclinical infection.

The impact of care pathways for exacerbation of Chronic Obstructive Pulmonary Disease: rationale and design of a cluster randomized controlled trial

PubMed Central

2010-01-01

Background Hospital treatment of chronic obstructive pulmonary disease (COPD) frequently does not follow published evidences. This lack of adherence can contribute to the high morbidity, mortality and readmissions rates. The European Quality of Care Pathway (EQCP) study on acute exacerbations of COPD (NTC00962468) is undertaken to determine how care pathways (CP) as complex intervention for hospital treatment of COPD affects care variability, adherence to evidence based key interventions and clinical outcomes. Methods An international cluster Randomized Controlled Trial (cRCT) will be performed in Belgium, Italy, Ireland and Portugal. Based on the power analysis, a sample of 40 hospital teams and 398 patients will be included in the study. In the control arm of the study, usual care will be provided. The experimental teams will implement a CP as complex intervention which will include three active components: a formative evaluation of the quality and organization of care, a set of evidence based key interventions, and support on the development and implementation of the CP. The main outcome will be six-month readmission rate. As a secondary endpoint a set of clinical outcome and performance indicators (including care process evaluation and team functioning indicators) will be measured in both groups. Discussion The EQCP study is the first international cRCT on care pathways. The design of the EQCP project is both a research study and a quality improvement project and will include a realistic evaluation framework including process analysis to further understand why and when CP can really work. Trial Registration number NCT00962468 PMID:21092098

Formation of virions is strictly required for turnip yellows virus long-distance movement in plants.

PubMed

Hipper, Clémence; Monsion, Baptiste; Bortolamiol-Bécet, Diane; Ziegler-Graff, Véronique; Brault, Véronique

2014-02-01

Viral genomic RNA of the Turnip yellows virus (TuYV; genus Polerovirus; family Luteoviridae) is protected in virions formed by the major capsid protein (CP) and the minor component, the readthrough (RT*) protein. Long-distance transport, used commonly by viruses to systemically infect host plants, occurs in phloem sieve elements and two viral forms of transport have been described: virions and ribonucleoprotein (RNP) complexes. With regard to poleroviruses, virions have always been presumed to be the long-distance transport form, but the potential role of RNP complexes has not been investigated. Here, we examined the requirement of virions for polerovirus systemic movement by analysing CP-targeted mutants that were unable to form viral particles. We confirmed that TuYV mutants that cannot encapsidate into virions are not able to reach systemic leaves. To completely discard the possibility that the introduced mutations in CP simply blocked the formation or the movement of RNP complexes, we tested in trans complementation of TuYV CP mutants by providing WT CP expressed in transgenic plants. WT CP was able to facilitate systemic movement of TuYV CP mutants and this observation was always correlated with the formation of virions. This demonstrated clearly that virus particles are essential for polerovirus systemic movement.

Syntheses of monomeric (. eta. sup 5 -pentamethylcyclopentadienyl)platinum(IV) methyl and bromo complexes and of (hydrotris(3,5-dimethyl-1-pyrazolyl)borato)trimethylplatinum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roth, S.; Ramamoorthy, V.; Sharp, P.R.

1990-09-05

The reaction of Cp*MgCl{center dot}THF (Cp* = C{sub 5}Me{sub 5}) with 1 equiv of PtMe{sub 3}I and PtMe{sub 2}Br{sub 2} produces Cp*PtMe{sub 3} (1) and Cp*PtMe{sub 2}Br (2), respectively. Reaction of 2 with Br{sub 2} produces Cp*PtMeBr{sub 2} (3) in good yield. The structures of 2 and 3 have been determined by x-ray crystallography, and the crystal structure data are reported. Complex 2 crystallizes in the monoclinic space group, P2{sub 1}/m, and complex 3 crystallizes in the monoclinic space group, P2{sub 1}/m. The molecules reside on mirror planes and are monomeric pseudotetrahedral Pt(IV) complexes with piano stool type geometries andmore » {eta}{sup 5}-Cp* groups. Both molecules have Br atoms on the mirror. This leads to a disorder of the Me and the second Br positions in complex 3. The average Pt-C(Cp*) bond length is 2.25 (7) {angstrom} in 2 and 2.22 (4) {angstrom} in 3. The Pt-C(Me) and Pt-Br bond lengths in 2 are 2.07 (2) and 2.498 (2) {angstrom}, respectively. The ordered Pt-Br bond length in 3 is 2.496 (2) {angstrom}. Treatment of 1 with halogens results in the cleavage of the Pt-Cp* bond. The reaction of PtMe{sub 3}I with KTp* (Tp* = (HB(3,5-dimethylpyrazolyl){sub 3}){sup {minus}}) in thf gives Tp*PtMe{sub 3} (4) in almost quantitative yield. The reaction of 4 with Br{sub 2} brominates the 4-position of the pyrazolyl ring only. 28 refs., 2 figs., 5 tabs.« less

The Craterostigma plantagineum glycine-rich protein CpGRP1 interacts with a cell wall-associated protein kinase 1 (CpWAK1) and accumulates in leaf cell walls during dehydration.

PubMed

Giarola, Valentino; Krey, Stephanie; von den Driesch, Barbara; Bartels, Dorothea

2016-04-01

Craterostigma plantagineum tolerates extreme desiccation. Leaves of this plant shrink and extensively fold during dehydration and expand again during rehydration, preserving their structural integrity. Genes were analysed that may participate in the reversible folding mechanism. Analysis of transcripts abundantly expressed in desiccated leaves identified a gene putatively coding for an apoplastic glycine-rich protein (CpGRP1). We studied the expression, regulation and subcellular localization of CpGRP1 and its ability to interact with a cell wall-associated protein kinase (CpWAK1) to understand the role of CpGRP1 in the cell wall during dehydration. The CpGRP1 protein accumulates in the apoplast of desiccated leaves. Analysis of the promoter revealed that the gene expression is mainly regulated at the transcriptional level, is independent of abscisic acid (ABA) and involves a drought-responsive cis-element (DRE). CpGRP1 interacts with CpWAK1 which is down-regulated in response to dehydration. Our data suggest a role of the CpGRP1-CpWAK1 complex in dehydration-induced morphological changes in the cell wall during dehydration in C. plantagineum. Cell wall pectins and dehydration-induced pectin modifications are predicted to be involved in the activity of the CpGRP1-CpWAK1 complex. © 2015 The Authors. New Phytologist © 2015 New Phytologist Trust.

Cognitive procedural learning among children and adolescents with or without spastic cerebral palsy: the differential effect of age.

PubMed

Gofer-Levi, M; Silberg, T; Brezner, A; Vakil, E

2014-09-01

Children learn to engage their surroundings skillfully, adopting implicit knowledge of complex regularities and associations. Probabilistic classification learning (PCL) is a type of cognitive procedural learning in which different cues are probabilistically associated with specific outcomes. Little is known about the effects of developmental disorders on cognitive skill acquisition. Twenty-four children and adolescents with cerebral palsy (CP) were compared to 24 typically developing (TD) youth in their ability to learn probabilistic associations. Performance was examined in relation to general cognitive abilities, level of motor impairment and age. Improvement in PCL was observed for all participants, with no relation to IQ. An age effect was found only among TD children. Learning curves of children with CP on a cognitive procedural learning task differ from those of TD peers and do not appear to be age sensitive. Copyright © 2014 Elsevier Ltd. All rights reserved.

Legacy Effect of Coronary Perforation Complicating Percutaneous Coronary Intervention for Chronic Total Occlusive Disease: An Analysis of 26 807 Cases From the British Cardiovascular Intervention Society Database.

PubMed

Kinnaird, Tim; Anderson, Richard; Ossei-Gerning, Nicholas; Cockburn, James; Sirker, Alex; Ludman, Peter; deBelder, Mark; Walsh, Simon; Smith, Elliot; Hanratty, Colm; Spratt, James; Strange, Julian; Hildick-Smith, David; Mamas, Mamas A

2017-05-01

Coronary perforation (CP) during chronic total occlusion percutaneous coronary intervention for stable angina (CTO-PCI) is a rare but serious event. The evidence base is limited, and the long-term effects are unclear. Using a national PCI database, the incidence, predictors, and outcomes of CP during CTO-PCI were defined. Data analyzed from the British Cardiovascular Intervention Society data set on all CTO-PCI procedures performed in England and Wales between 2006 and 2013. Multivariate logistic regressions and propensity scores were used to identify predictors of CP and its association with outcomes. A total of 376 CP were recorded from 26 807 CTO-PCI interventions (incidence of 1.40%) with an increase in frequency during the study period ( P =0.012). Patient-related factors associated with an increased risk of CP were age and female sex. Procedural factors indicative of complex CTO intervention strongly related to an increased risk of CP with a close relationship between the number of complex strategies used and CP evident ( P =0.008 for trend). Tamponade occurred in 16.6% and emergency surgery in 3.4% of cases. Adverse outcomes were frequent in those patients with perforation including bleeding, transfusion, myocardial infarction, and death. A legacy effect of perforation on mortality was evident, with an odds ratio for 12-month mortality of 1.60 for perforation survivors compared with matched nonperforation survivors without a CP ( P <0.0001). Many of the factors associated with an increased risk of CP were related to CTO complexity. Perforation was associated with adverse outcomes, with a legacy effect on later mortality after CP also observed. © 2017 American Heart Association, Inc.

Genetic variation in the chloroplast genome suggests multiple domestication of cultivated Asian rice (Oryza sativa L.).

PubMed

Kawakami, Shin-ichi; Ebana, Kaworu; Nishikawa, Tomotaro; Sato, Yo-ichiro; Vaughan, Duncan A; Kadowaki, Koh-ichi

2007-02-01

Two hundred and seventy-five accessions of cultivated Asian rice and 44 accessions of AA genome Oryza species were classified into 8 chloroplast (cp) genome types (A-H) based on insertion-deletion events at 3 regions (8K, 57K, and 76K) of the cp genome. The ancestral cp genome type was determined according to the frequency of occurrence in Oryza species and the likely evolution of the variable 57K region of the cp genome. When 2 nucleotide substitutions (AA or TT) were taken into account, these 8 cp types were subdivided into 11 cp types. Most indica cultivars had 1 of 3 cp genome types that were also identified in the wild relatives of rice, O. nivara and O. rufipogon, suggesting that the 3 indica cp types had evolved from distinct gene pools of the O. rufipogon - O. nivara complex. The majority of japonica cultivars had 1 of 3 different cp genome types. One of these 3 was identified in O. rufipogon, suggesting that at least 1 japonica type is derived from O. rufipogon with the same cp genome type. These results provide evidence to support a polyphyletic origin of cultivated Asian rice from at least 4 principal lineages in the O. rufipogon - O. nivara complex.

CenteringPregnancy-Africa: a pilot of group antenatal care to address Millennium Development Goals.

PubMed

Patil, Crystal L; Abrams, Elizabeth T; Klima, Carrie; Kaponda, Chrissie P N; Leshabari, Sebalda C; Vonderheid, Susan C; Kamanga, Martha; Norr, Kathleen F

2013-10-01

severe health worker shortages and resource limitations negatively affect quality of antenatal care (ANC) throughout sub-Saharan Africa. Group ANC, specifically CenteringPregnancy (CP), may offer an innovative approach to enable midwives to offer higher quality ANC. our overarching goal was to prepare to conduct a clinical trial of CenteringPregnancy-Africa (CP-Africa) in Malawi and Tanzania. In Phase 1, our goal was to determine the acceptability of CP as a model for ANC in both countries. In Phase 2, our objective was to develop CP-Africa session content consistent with the Essential Elements of CP model and with national standards in both Malawi and Tanzania. In Phase 3, our objective was to pilot CP-Africa in Malawi to determine whether sessions could be conducted with fidelity to the Centering process. Phases 1 and 2 took place in Malawi and Tanzania. Phase 3, the piloting of two sessions of CP-Africa, occurred at two sites in Malawi: a district hospital and a small clinic. we used an Action Research approach to promote partnerships among university researchers, the Centering Healthcare Institute, health care administrators, health professionals and women attending ANC to develop CP-Africa session content and pilot this model of group ANC. for Phases 1 and 2, members of the Ministries of Health, health professionals and pregnant women in Malawi and Tanzania were introduced to and interviewed about CP. In Phase 2, we finalised CP-Africa content and trained 13 health professionals in the Centering Healthcare model. In Phase 3, we conducted a small pilot with 24 pregnant women (12 at each site). participants enthusiastically embraced CP-Africa as an acceptable model of ANC health care delivery. The CP-Africa content met both CP and national standards. The pilot established that the CP model could be implemented with process fidelity to the 13 Essential Elements. Several implementation challenges and strategies to address these challenges were identified. preliminary data suggest that CP-Africa is feasible in resource-constrained, low-literacy, high-HIV settings in sub-Saharan Africa. By improving the quality of ANC delivery, midwives have an opportunity to make a contribution towards Millennium Development Goals (MDG) targeting improvements in child, maternal and HIV-related health outcomes (MDGs 4, 5 and 6). A clinical trial is needed to establish efficacy. CP-Africa also has the potential to reduce job-related stress and enhance job satisfaction for midwives in low income countries. If CP can be transferred with fidelity to process in sub-Saharan Africa and retain similar results to those reported in clinical trials, it has the potential to benefit pregnant women and their infants and could make a positive contribution to MGDs 4, 5 and 6. © 2013 Elsevier Ltd. All rights reserved.

Energy transfer in light-harvesting complexes LHCII and CP29 of spinach studied with three pulse echo peak shift and transient grating.

PubMed

Salverda, Jante M; Vengris, Mikas; Krueger, Brent P; Scholes, Gregory D; Czarnoleski, Adam R; Novoderezhkin, Vladimir; van Amerongen, Herbert; van Grondelle, Rienk

2003-01-01

Three pulse echo peak shift and transient grating (TG) measurements on the plant light-harvesting complexes LHCII and CP29 are reported. The LHCII complex is by far the most abundant light-harvesting complex in higher plants and fulfills several important physiological functions such as light-harvesting and photoprotection. Our study is focused on the light-harvesting function of LHCII and the very similar CP29 complex and reveals hitherto unresolved excitation energy transfer processes. All measurements were performed at room temperature using detergent isolated complexes from spinach leaves. Both complexes were excited in their Chl b band at 650 nm and in the blue shoulder of the Chl a band at 670 nm. Exponential fits to the TG and three pulse echo peak shift decay curves were used to estimate the timescales of the observed energy transfer processes. At 650 nm, the TG decay can be described with time constants of 130 fs and 2.2 ps for CP29, and 300 fs and 2.8 ps for LHCII. At 670 nm, the TG shows decay components of 230 fs and 6 ps for LHCII, and 300 fs and 5 ps for CP29. These time constants correspond to well-known energy transfer processes, from Chl b to Chl a for the 650 nm TG and from blue (670 nm) Chl a to red (680 nm) Chl a for the 670 nm TG. The peak shift decay times are entirely different. At 650 nm we find times of 150 fs and 0.5-1 ps for LHCII, and 360 fs and 3 ps for CP29, which we can associate mainly with Chl b <--> Chl b energy transfer. At 670 nm we find times of 140 fs and 3 ps for LHCII, and 3 ps for CP29, which we can associate with fast (only in LHCII) and slow transfer between relatively blue Chls a or Chl a states. From the occurrence of both fast Chl b <--> Chl b and fast Chl b --> Chl a transfer in CP29, we conclude that at least two mixed binding sites are present in this complex. A detailed comparison of our observed rates with exciton calculations on both CP29 and LHCII provides us with more insight in the location of these mixed sites. Most importantly, for CP29, we find that a Chl b pair must be present in some, but not all, complexes, on sites A(3) and B(3). For LHCII, the observed rates can best be understood if the same pair, A(3) and B(3), is involved in both fast Chl b <--> Chl b and fast Chl a <--> Chl a transfer. Hence, it is likely that mixed sites also occur in the native LHCII complex. Such flexibility in chlorophyll binding would agree with the general flexibility in aggregation form and xanthophyll binding of the LHCII complex and could be of use for optimizing the role of LHCII under specific circumstances, for example under high-light conditions. Our study is the first to provide spectroscopic evidence for mixed binding sites, as well as the first to show their existence in native complexes.

Transcriptome analysis reveals self-incompatibility in the tea plant (Camellia sinensis) might be under gametophytic control.

PubMed

Zhang, Cheng-Cai; Wang, Li-Yuan; Wei, Kang; Wu, Li-Yun; Li, Hai-Lin; Zhang, Fen; Cheng, Hao; Ni, De-Jiang

2016-05-17

Self-incompatibility (SI) is under genetic control and prevents inbreeding depression in angiosperms. SI mechanisms are quite complicated and still poorly understood in many plants. Tea (Camellia sinensis L.) belonging to the family of Theaceae, exhibits high levels of SI and high heterozygosity. Uncovering the molecular basis of SI of the tea plant may enhance breeding and simplify genomics research for the whole family. The growth of pollen tubes following selfing and crossing was observed using fluorescence microscopy. Self-pollen tubes grew slower than cross treatments from 24 h to 72 h after pollination. RNA-seq was employed to explore the molecular mechanisms of SI and to identify SI-related genes in C. sinensis. Self and cross-pollinated styles were collected at 24 h, 48 h and 72 h after pollination. Six RNA-seq libraries (SP24, SP48, SP72, CP24 CP48 and CP72; SP = self-pollinated, CP = cross-pollinated) were constructed and separately sequenced. In total, 299.327 million raw reads were generated. Following assembly, 63,762 unigenes were identified, and 27,264 (42.76 %) unigenes were annotated in five public databases: NR, KOG, KEGG, Swiss-Port and GO. To identify SI-related genes, the fragments per kb per million mapped reads (FPKM) values of each unigene were evaluated. Comparisons of CP24 vs. SP24, CP48 vs. SP48 and CP72 vs. SP72 revealed differential expression of 3,182, 3,575 and 3,709 genes, respectively. Consequently, several ubiquitin-mediated proteolysis, Ca(2+) signaling, apoptosis and defense-associated genes were obtained. The temporal expression pattern of genes following CP and SP was analyzed; 6 peroxidase, 1 polyphenol oxidase and 7 salicylic acid biosynthetic process-related genes were identified. The RNA-seq data were validated by qRT-PCR of 15 unigenes. Finally, a unigene (CL25983Contig1) with strong homology to the S-RNase was analyzed. It was mainly expressed in styles, with dramatically higher expression in self-pollinated versus cross-pollinated tissues at 24 h post-pollination. The present study reports the transcriptome of styles after cross- and self-pollination in tea and offers novel insights into the molecular mechanism behind SI in C. sinensis. We believe that this RNA-seq dataset will be useful for improvement in C. sinensis as well as other plants in the Theaceae family.

Measurement of CP--violating asymmetries in $$D^0\\to\\pi^+\\pi^-$$ and $$D^0\\to K^+K^-$$ decays at CDF

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aaltonen, T.; /Helsinki Inst. of Phys.; Alvarez Gonzalez, B.

2011-11-01

We report on a measurement of CP-violating asymmetries (A{sub CP}) in the Cabibbo-suppressed D{sup 0} {yields} {pi}{sup +}{pi}{sup -} and D{sup 0} {yields} K{sup +}K{sup -} decays reconstructed in a data sample corresponding to 5.9 fb{sup -1} of integrated luminosity collected by the upgraded Collider Detector at Fermilab. We use the strong decay D*{sup +} {yields} D{sup 0}{pi}{sup +} to identify the flavor of the charmed meson at production and exploit CP-conserving strong c{bar c} pair-production in p{bar p} collisions. High-statistics samples of Cabibbo-favored D{sup 0} {yields} K{sup -}{pi}{sup +} decays with and without a D*{sup {+-}} tag are usedmore » to correct for instrumental effects and significantly reduce systematic uncertainties. We measure A{sub CP}(D{sup 0} {yields} {pi}{sup +}{pi}{sup -}) = (+0.22 {+-} 0.24(stat) {+-} 0.11 (syst))% and A{sub CP}(D{sup 0} {yields} K{sup +}K{sup -}) = (-0.24 {+-} 0.22 (stat) {+-} 0.09 (syst))%, in agreement with CP conservation. These are the most precise determinations from a single experiment to date. Under the assumption of negligible direct CP violation in D{sup 0} {yields} {pi}{sup +}{pi}{sup -} and D{sup 0} {yields} K{sup +}K{sup -} decays, the results provide an upper limit to the CP-violating asymmetry in D{sup 0} mixing, |A{sub CP}{sup ind}(D{sup 0})| < 0.13% at the 90% confidence level.« less

75 FR 7454 - Notice of Commission Meeting and Public Hearing

Federal Register 2010, 2011, 2012, 2013, 2014

2010-02-19

..., Berks County, Pennsylvania. 3. Palmerton Borough, D-1981-024 CP-8. An application for the renewal of a... by Docket No. D-90-17 be included in the renewal of Docket No. D-81-24 CP-8. The existing surface... Protection Waters. 4. Antietam Valley Municipal Authority, D-1987-045 CP-3. An application for approval of...

Site-specific transmission of a floor-based, high-frequency, low-magnitude vibration stimulus in children with spastic cerebral palsy

PubMed Central

Singh, Harshvardhan; Whitney, Daniel G; Knight, Christopher A; Miller, Freeman; Manal, Kurt; Kolm, Paul; Modlesky, Christopher M

2016-01-01

Objective To determine the degree to which a high-frequency, low-magnitude vibration (HLV) signal emitted by a floor-based platform transmits to the distal tibia and distal femur of children with spastic cerebral palsy (CP) during standing. Design Cross-sectional study Setting University research laboratory Participants 4 to 12 year-old children with spastic CP who could stand independently (n=18) and typically developing children (n=10) participated in the study. Intervention Not applicable Main outcome measures The vibration signal at the HLV platform (~33 Hz and 0.3 g), distal tibia and distal femur was measured using accelerometers. Degree of plantar flexor spasticity was assessed using the Modified Ashworth Scale. Results The HLV signal was greater (p<0.001) at the distal tibia than at the platform in children with CP (0.36±0.06 vs. 0.29±0.05 g) and controls (0.40 ± 0.09 vs. 0.24 ± 0.07 g). Although the HLV signal was also higher at the distal femur (0.35±0.09 g, p<0.001) than at the platform in controls, it was lower in children with CP (0.20±0.07 g, p<0.001). The degree of spasticity was negatively related to the HLV signal transmitted to the distal tibia (rs=−0.547) and distal femur (rs=−0.566) in children with CP (both p<0.05). Conclusions An HLV signal from a floor-based platform was amplified at the distal tibia, attenuated at the distal femur and inversely related to the degree of muscle spasticity in children with spastic CP. Whether this transmission pattern affects the adaptation of their bones to HLV requires further investigation. PMID:26392035

Reaction of tin(iv) phthalocyanine dichloride with decamethylmetallocenes (M = CrII and CoII). Strong magnetic coupling of spins in (Cp*2Co+){SnIVCl2(Pc˙3-)}˙-·2C6H4Cl2.

PubMed

Konarev, Dmitri V; Troyanov, Sergey I; Shestakov, Alexander F; Yudanova, Evgeniya I; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N

2018-01-23

The reaction of tin(iv) phthalocyanine dichloride {Sn IV Cl 2 (Pc 2- )} with decamethylmetallocenes (Cp* 2 M, M = Co, Cr) has been studied. Decamethylcobaltocene reduces Sn IV Cl 2 (Pc 2- ) to form the (Cp* 2 Co + ){Sn IV Cl 2 (Pc˙ 3- )}˙ - ·2C 6 H 4 Cl 2 (1) complex. The negative charge of {Sn IV Cl 2 (Pc˙ 3- )}˙ - is delocalized over the Pc macrocycle providing the alternation of the C-N(imine) bonds, the appearance of new bands in the NIR range and a strong blue shift of both the Soret and Q-bands in the spectrum of 1. The magnetic moment of 1 is equal to 1.68μ B at 300 K, indicating the contribution of one S = 1/2 spin of the Pc˙ 3- macrocycles. These macrocycles form closely packed double stacks in 1 with effective π-π interactions providing strong antiferromagnetic coupling of spins at a Weiss temperature of -80 K. Decamethylchromocene initially also reduces Sn IV Cl 2 (Pc 2- ) to form the [(Cp* 2 Cr + ){Sn VI Cl 2 (Pc˙ 3- )}˙ - complex but further reaction between the ions is observed. This reaction is accompanied by the substitution of one Cp* ligand of Cp* 2 Cr by chloride anions originating from {Sn IV Cl 2 (Pc˙ 3- )}˙ - to form the complex {(Cp*CrCl 2 )(Sn IV (μ-Cl)(Pc 2- ))}·C 6 H 4 Cl 2 (2) in which the (Cp*CrCl 2 ) and {Sn IV (Pc 2- )} species are bonded through the μ-bridged Cl - anion. According to the DFT calculations, this reaction proceeds via an intermediate [(Cp* 2 CrCl)(SnClPc)] complex.

Muscle synergies and complexity of neuromuscular control during gait in cerebral palsy.

PubMed

Steele, Katherine M; Rozumalski, Adam; Schwartz, Michael H

2015-12-01

Individuals with cerebral palsy (CP) have impaired movement due to a brain injury near birth. Understanding how neuromuscular control is altered in CP can provide insight into pathological movement. We sought to determine if individuals with CP demonstrate reduced complexity of neuromuscular control during gait compared with unimpaired individuals and if changes in control are related to functional ability. Muscle synergies during gait were retrospectively analyzed for 633 individuals (age range 3.9-70y): 549 with CP (hemiplegia, n=122; diplegia, n=266; triplegia, n=73; quadriplegia, n=88) and 84 unimpaired individuals. Synergies were calculated using non-negative matrix factorization from surface electromyography collected during previous clinical gait analyses. Synergy complexity during gait was compared with diagnosis subtype, functional ability, and clinical examination measures. Fewer synergies were required to describe muscle activity during gait in individuals with CP compared with unimpaired individuals. Changes in synergies were related to functional impairment and clinical examination measures including selective motor control, strength, and spasticity. Individuals with CP use a simplified control strategy during gait compared with unimpaired individuals. These results were similar to synergies during walking among adult stroke survivors, suggesting similar neuromuscular control strategies between these clinical populations. © 2015 Mac Keith Press.

In Vitro Evaluation of Cell Compatibility of Dental Cements Used with Titanium Implant Components.

PubMed

Marvin, Jason C; Gallegos, Silvia I; Parsaei, Shaida; Rodrigues, Danieli C

2018-03-09

To evaluate the biocompatibility of five dental cement compositions after directly exposing human gingival fibroblast (HGF) and MC3T3-E1 preosteoblast cells to cement alone and cement applied on commercially pure titanium (cpTi) specimens. Nanostructurally integrated bioceramic (NIB), resin (R), resin-modified glass ionomer (RMGIC), zinc oxide eugenol (ZOE), and zinc phosphate (ZP) compositions were prepared according to the respective manufacturer's instructions. Samples were prepared in cylindrical Teflon molds or applied over the entire surface of polished cpTi discs. All samples were cured for 0.5, 1, 12, or 24 hours post-mixing. Direct contact testing was conducted according to ISO 10993 by seeding 6-well plates at 350,000 cells/well. Plates were incubated at 37°C in a humidified atmosphere with 5% CO 2 for 24 hours before individually plating samples and cpTi control discs. Plates were then incubated for an additional 24 hours. Microtetrazolium (MTT) cell viability assays were used to measure sample cytotoxicity. For samples that cured for 24 hours prior to direct contact exposure, only NIB and ZP cements when cemented on cpTi demonstrated cell viability percentages above the minimum biocompatibility requirement (≥70%) for both the investigative cell lines. R, RMGIC, and ZOE cements exhibited moderate to severe cytotoxic effects on both cell lines in direct contact and when cemented on cpTi specimens. For HGF cells, ZOE cemented-cpTi specimens exhibited significantly decreased cytotoxicity, whereas RMGIC cemented-cpTi specimens exhibited significantly increased cytotoxicity. Despite previous studies that showed enhanced cpTi corrosion activity for fluoride-containing compositions (NIB and ZP), there was no significant difference in cytotoxicity between cement alone and cemented-cpTi. In general, the MC3T3-E1 preosteoblast cells were more sensitive than HGF cells to cement composition. Ultimately, cement composition played a significant role in maintaining host cell compatibility. Results of this work help illustrate the impact of different cement formulations on host cell health and emphasize the need for understanding material properties when selecting certain formulations of dental cements, which can ultimately influence the survival of dental implant systems. © 2018 by the American College of Prosthodontists.

Age- and sex-related differences in nuclear lipid content and nucleoside triphosphatase activity in the JCR:LA-cp corpulent rat.

PubMed

Czubryt, M P; Russell, J C; Sarantopoulos, J; Gilchrist, J S; Pierce, G N

1997-11-01

The putative role of the nuclear nucleoside triphosphatase (NTPase) is to provide energy to the nuclear pore complex for poly A(+) mRNA export. Previous work has demonstrated that liver nuclear NTPase activity is greater in 6 month old corpulent (cp/cp) female JCR:LA rats, a hyperlipidemic rat model, compared to lean (+/?) animals. This increase appeared to be related to increases in nuclear membrane cholesterol content. The current study extended these initial data to compare NTPase activity as a function of age and sex in isolated JCR:LA-cp rat liver nuclei, to further test the hypothesis that nuclear membrane cholesterol may modulate NTPase activity. NTPase activity was increased in cp/cp female animals compared to +/? females at all ages studied, with Vmax values increased by 60-176%. Membrane integrity of cp/cp female nuclei was reduced compared to +/? female nuclei. Nuclear membrane cholesterol levels increased linearly with age by 50, 150 and 250% in 3, 6 and 9 month old cp/cp females over leans. In contrast, nuclei from cp/cp males exhibited only minor, isolated changes in NTPase activity. Furthermore, there were no significant changes in nuclear cholesterol content or membrane integrity in the less hyperlipidemic male animals at any age. These data suggest that altered lipid metabolism may lead to changes in nuclear membrane structure, which in turn may alter NTPase activity and functioning of the nuclear pore complex.

The inverse sandwich complex [(K(18-crown-6))2Cp][CpFe(CO)2]--unpredictable redox reactions of [CpFe(CO)2]I with the silanides Na[SiRtBu2] (R = Me, tBu) and the isoelectronic phosphanyl borohydride K[PtBu2BH3].

PubMed

Sänger, Inge; Kückmann, Theresa I; Dornhaus, Franz; Bolte, Michael; Wagner, Matthias; Lerner, Hans-Wolfram

2012-06-14

The dimeric iron carbonyl [CpFe(CO)(2)](2) and the iodosilanes tBu(2)RSiI were obtained from the reaction of [CpFe(CO)(2)]I with the silanides Na[SiRtBu(2)] (R = Me, tBu) in THF. By the reactions of [CpFe(CO)(2)]I and Na[SiRtBu(2)] (R = Me, tBu) the disilanes tBu(2)RSiSiRtBu(2) (R = Me, tBu) were additionally formed using more than one equivalent of the silanide. In this context it should be noted that reduction of [CpFe(CO)(2)](2) with Na[SitBu(3)] gives the disilanes tBu(3)SiSitBu(3) along with the sodium ferrate [(Na(18-crown-6))(2)Cp][CpFe(CO)(2)]. The potassium analogue [(K(18-crown-6))(2)Cp][CpFe(CO)(2)] (orthorhombic, space group Pmc2(1)), however, could be isolated as a minor product from the reaction of [CpFe(CO)(2)]I with [K(18-crown-6)][PtBu(2)BH(3)]. The reaction of [CpFe(CO)(2)](2) with the potassium benzophenone ketyl radical and subsequent treatment with 18-crown-6 yielded the ferrate [K(18-crown-6)][CpFe(CO)(2)] in THF at room temperature. The crown ether complex [K(18-crown-6)][CpFe(CO)(2)] was analyzed using X-ray crystallography (orthorhombic, space group Pna2(1)) and its thermal behaviour was investigated.

Antimutagenic effects of garlic extract on chromosomal aberrations.

PubMed

Shukla, Yogeshwer; Taneja, Pankaj

2002-02-08

Garlic (Allium sativum) has been used since ancient times, as a spice and also for its medicinal properties. In present set of investigations antimutagenic effect of garlic extract (GE) has been evaluated using 'in vivo chromosomal aberration assay' in Swiss albino mice. Cyclophosphamide (CP), a well-known mutagen, was given at a single dose of 25 mg/kg b.w. intraperitoneally. Pretreatment with 1, 2.5 and 5% of freshly prepared GE was given through oral intubation for 5 days prior to CP administration. Animals from all the groups were sacrificed at sampling times of 24 and 48 h and their bone marrow tissue was analyzed for chromosomal damage. The animals of the positive control group (CP alone) shows a significant increase in chromosomal aberrations both at 24 and 48 h sampling time. GE, alone did not significantly induced aberrations at either sampling time, confirming its non-mutagenicity. However in the GE pre-treated and CP post-treated groups, a dose dependent decrease in cytogenetic damage was recorded. A significant suppression in the chromosomal aberrations was recorded following pretreatment with 2.5 and 5% GE administration. The anticytotoxic effects of GE were also evident, as observed by significant increase in mitotic index, when compared to positive control group. Reduction in CP induced clastogenicity by GE was evident at 24 h and to a much greater extent at 48 h of cell cycle. Thus results of the present investigations revealed that GE has chemopreventive potential against CP induced chromosomal mutations in Swiss albino mice.

Quantification of short- and medium-chain chlorinated paraffins in environmental samples by gas chromatography quadrupole time-of-flight mass spectrometry.

PubMed

Gao, Wei; Wu, Jing; Wang, Yawei; Jiang, Guibin

2016-06-24

Chlorinated paraffins (CPs) are technical products produced and used in bulk for a number of purposes. However, the analysis of CPs is challenging, as they are complex mixtures of compounds and isomers. We herein report the development of an analytical method for the analysis of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) using quadrupole time-of-flight high-resolution mass spectrometry (GC-NCI-qTOF-HRMS). This method employs gas chromatography with a chemical ionization source working in negative mode. The linear relationship between chlorination and the CP total response factors was applied to quantify the CP content and the congener group distribution patterns. In a single injection, 24 SCCP formula groups and 24 MCCP formula groups were quantified. Extraction of accurate masses using qTOF-HRMS allowed the SCCPs and MCCPs to be distinguished, with interference from other chemicals (e.g., PCBs) being largely avoided. The SCCP and MCCP detection limits were 24-81ng/mL and 27-170ng/mL, respectively. Comparison of the obtained results with analytical results from gas chromatography coupled with electron capture negative ionization low-resolution mass spectrometry (GC-ECNI-LRMS) indicate that the developed technique is a more accurate and convenient method for the analysis of CPs in samples from a range of matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

Warming reinforces nonconsumptive predator effects on prey growth, physiology, and body stoichiometry.

PubMed

Janssens, Lizanne; Van Dievel, Marie; Stoks, Robby

2015-12-01

While nonconsumptive effects of predators may strongly affect prey populations, little is known how future warming will modulate these effects. Such information would be especially relevant with regard to prey physiology and resulting changes in prey stoichiometry. We investigated in Enallagma cyathigerum damselfly larvae the effects of a 4°C warming (20°C vs. 24°C) and predation risk on growth rate, physiology and body stoichiometry, for the first time including all key mechanisms suggested by the general stress paradigm (GSP) on how stressors shape changes in body stoichiometry. Growth rate and energy storage were higher at 24°C. Based on thermodynamic principles and the growth rate hypothesis, we could demonstrate predictable reductions in body C:P under warming and link these to the increase in P-rich RNA; the associated warming-induced decrease in C:N may be explained by the increased synthesis of N-rich proteins. Yet, under predation risk, growth rate instead decreased with warming and the warming-induced decreases in C:N and C:P disappeared. As predicted by the GSP, larvae increased body C:N and C:P at 24°C under predation risk. Notably, we did not detect the assumed GSP-mechanisms driving these changes: despite an increased metabolic rate there was neither an increase of C-rich biomolecules (instead fat and sugar contents decreased under predation risk), nor a decrease of N-rich proteins. We hypothesize that the higher C:N and N:P under predation risk are caused by a higher investment in morphological defense. This may also explain the stronger predator-induced increase in C:N under warming. The expected higher C:P under predation risk was only present under warming and matched the observed growth reduction and associated reduction in P-rich RNA. Our integrated mechanistic approach unraveled novel pathways of how warming and predation risk shape body stoichiometry. Key findings that (1) warming effects on elemental stoichiometry were predictable and only present in the absence of predation risk and that (2) warming reinforced the predator-induced effects on C:N:P, are pivotal in understanding how nonconsumptive predator effects under global warming will shape prey populations.

Single-molecule visualization of a formin-capping protein ‘decision complex' at the actin filament barbed end

PubMed Central

Bombardier, Jeffrey P.; Eskin, Julian A.; Jaiswal, Richa; Corrêa, Ivan R.; Xu, Ming-Qun; Goode, Bruce L.; Gelles, Jeff

2015-01-01

Precise control of actin filament length is essential to many cellular processes. Formins processively elongate filaments, whereas capping protein (CP) binds to barbed ends and arrests polymerization. While genetic and biochemical evidence has indicated that these two proteins function antagonistically, the mechanism underlying the antagonism has remained unresolved. Here we use multi-wavelength single-molecule fluorescence microscopy to observe the fully reversible formation of a long-lived ‘decision complex' in which a CP dimer and a dimer of the formin mDia1 simultaneously bind the barbed end. Further, mDia1 displaced from the barbed end by CP can randomly slide along the filament and later return to the barbed end to re-form the complex. Quantitative kinetic analysis reveals that the CP-mDia1 antagonism that we observe in vitro occurs through the decision complex. Our observations suggest new molecular mechanisms for the control of actin filament length and for the capture of filament barbed ends in cells. PMID:26566078

Does early communication mediate the relationship between motor ability and social function in children with cerebral palsy?

PubMed

Lipscombe, Belinda; Boyd, Roslyn N; Coleman, Andrea; Fahey, Michael; Rawicki, Barry; Whittingham, Koa

2016-01-01

Children diagnosed with neurodevelopmental conditions such as cerebral palsy (CP) are at risk of experiencing restrictions in social activities negatively impacting their subsequent social functioning. Research has identified motor and communication ability as being unique determinants of social function capabilities in children with CP, to date, no research has investigated whether communication is a mediator of the relationship between motor ability and social functioning. To investigate whether early communication ability at 24 months corrected age (ca.) mediates the relationship between early motor ability at 24 months ca. and later social development at 60 months ca. in a cohort of children diagnosed with cerebral palsy (CP). A cohort of 71 children (43 male) diagnosed with CP (GMFCS I=24, 33.8%, II=9, 12.7%, III=12, 16.9%, IV=10, 14.1%, V=16, 22.5%) were assessed at 24 and 60 months ca. Assessments included the Gross Motor Function Measure (GMFM), the Communication and Symbolic Behaviour Scales-Developmental Profile (CSBS-DP) Infant-Toddler Checklist and the Paediatric Evaluation of Disability Inventory (PEDI). A mediation model was examined using bootstrapping. Early communication skills mediated the relationship between early motor abilities and later social functioning, b=0.24 (95% CI=0.08-0.43 and the mediation model was significant, F (2, 68)=32.77, p<0.001, R(2)=0.49. Early communication ability partially mediates the relationship between early motor ability and later social function in children with CP. This demonstrates the important role of early communication in ongoing social development. Early identification of communication delay and enriched language exposure is crucial in this population. Copyright © 2016 Elsevier Ltd. All rights reserved.

Formation of cation-anion complexes in the photochemical reaction of molybdenocene dihydrode with iron pentacarbonyl. Crystal structures of (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ and (Cp/sub 2/Mo(CO)H)/sup +/(CoMo(CO)/sub 3/)/sup -/ (triclinic modification) (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antsyshkina, A.S.; Dikareva, L.M.; Porai-Koshits, M.A.

1985-11-01

The reaction of Cp/sub 2/MoH/sub 2/ with Fe(CO)/sub 5/ in boiling benzene under UV irradiation gives the ionic complexes (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ (I) and (Cp/sub 2/Mo(CO)H)/sup +/(CpMo(CO)/sub 3/)/sup -/ (II), whose structures were established by x-ray diffraction analysis (Syntex P2/sub 1/ automatic diffractometer, lambda Mo K/sub ..cap alpha../, graphite monochromator, theta/2theta scan technique, full-matrix least-squares method, isotropic variant for I on the basis of 2112 reflections to % = 0.11 and anisotropic variant for II on the basis of 3770 values of hkl to R = 0.052). In complexes I and II the (CpMo(CO)H)/sup +/ fragment ismore » a tapered sandwich with an eclipsed conformation of the rings. In complex I the angle between the rings is 33.9/sup 0/, the mean Mo-C(C/sub 5/H/sub 5/) distance is 2.28(3) A, the mean Mo-C(CO) distance is 2.03(3) A, and the mean Mo-H distance is 1.78(10) A. The corresponding parameters in complex II are: 32.4/sup 0/, 2.296(7), 2.020(6), and 1.87(7) A. The anion in complex I is based on a triangular cluster of Fe atoms, in which one Fe-Fe distance is significantly shorter (2.488(5) A) than the other two (2.702(5) and 2.697(5) A). The Fe atoms forming the short bond are joined additionally by hydride (Fe-H = 2.14 A) and carbonyl (Fe-C = 1.90(3) and 1.93(3) A) Bridges. The remaining groups are terminal. A probable scheme for the process of the formation of complexes I and II has been discussed.« less

Clinical Efficacy and Safety of First-Line Dasatinib Therapy and the Relevance of Velocity of BCR-ABL1 Transcript Decline for Achievement of Molecular Responses in Newly Diagnosed Chronic-Phase Chronic Myeloid Leukemia: Report from the Juntendo Yamanashi Cooperative Study Group.

PubMed

Takaku, Tomoiku; Iriyama, Noriyoshi; Mitsumori, Toru; Sato, Eriko; Gotoh, Akihiko; Kirito, Keita; Noguchi, Masaaki; Koike, Michiaki; Sakamoto, Junichi; Oba, Koji; Komatsu, Norio

2018-01-01

The use of tyrosine kinase inhibitors led to an improvement in the prognoses of patients with chronic myeloid leukemia (CML). The aims of this study were to investigate the efficacy and safety of dasatinib in Japanese patients and to explore the factors that affect the achievement of molecular responses. The primary endpoint was a major molecular response (MMR) by 12 months. The halving time for BCR-ABL1 transcripts was calculated using transcript levels. Thirty-two patients with chronic-phase CML (CML-CP) were enrolled and 30 received 100 mg dasatinib once daily. At 24 months of follow-up, 21 (72%) and 24 (83%) patients achieved an MMR by 12 and 24 months, respectively; the rates of a deep molecular response (DMR) by 12 and 24 months were 48 and 59%, respectively. A shorter halving time of BCR-ABL1 transcripts (≤10.6 days) accurately predicted both an MMR and a DMR. The incidence of pleural effusion was 50%. Our study reconfirmed the efficacy and safety of dasatinib treatment in Japanese patients with newly diagnosed CML-CP. In addition, the usefulness of the halving time of BCR-ABL1 transcripts was validated. These data emphasize the significance of an early treatment response in achieving a DMR during dasatinib therapy. © 2017 S. Karger AG, Basel.

Deep Defects Seen on Visual Fields Spatially Correspond Well to Loss of Retinal Nerve Fiber Layer Seen on Circumpapillary OCT Scans.

PubMed

Mavrommatis, Maria A; Wu, Zhichao; Naegele, Saskia I; Nunez, Jason; De Moraes, Carlos; Ritch, Robert; Hood, Donald C

2018-02-01

To examine the structure-function relationship in glaucoma between deep defects on visual fields (VF) and deep losses in the circumpapillary retinal nerve fiber layer (cpRNFL) on optical coherence tomography (OCT) circle scans. Thirty two glaucomatous eyes with deep VF defects, as defined by at least one test location worse than ≤ -15 dB on the 10-2 and/or 24-2 VF pattern deviation (PD) plots, were included from 87 eyes with "early" glaucoma (i.e., 24-2 mean deviation better than -6 dB). Using the location of the deep VF points and a schematic model, the location of local damage on an OCT circle scan was predicted. The thinnest location of cpRNFL (i.e., deepest loss) was also determined. In 19 of 32 eyes, a region of complete or near complete cpRNFL loss was observed. All 19 of these had deep VF defects on the 24-2 and/or 10-2. All of the 32 eyes with deep VF defects had abnormal cpRNFL regions (red, 1%) and all but 2 had a region of cpRNFL thickness <21 μm. The midpoint of the VF defect and the location of deepest cpRNFL had a 95% limit of agreement within approximately two-thirds of a clock-hour (or 30°) sector (between -22.1° to 25.2°). Individual fovea-to-disc angle (FtoDa) adjustment improved agreement in one eye with an extreme FtoDa. Although studies relating local structural (OCT) and functional (VF) measures typically show poor to moderate correlations, there is good qualitative agreement between the location of deep cpRNFL loss and deep defects on VFs.

Low Frequency Seismo-Acoustic Propagation in a Sloping Ocean Environment: Measured Results and Numerical Predictions

DTIC Science & Technology

1987-11-01

15407 - 1525,1 m/s Cp = 1900 m/ s , op = 0,2, p= 1.8 L . Cp = 2340 m/ s . Op = 02, p= 1,9 Cp = 3000 m/ s . Op = 02, P = 2,2 Cj = 1500 m/s, oj = 02 Cp...4300 m/ s , op = 005, p = 24 Cc = 2150 m/s, o^ = 01 20 Figure 5. Geoacoustic input parameters for SAFARI model. 0.0 10.0 30.0 30.0 RANGE IKM

Variables Affecting the Reporting of Pain Following an Acute Myocardial Infarction

DTIC Science & Technology

1991-05-01

research found which investigated the phenomenon of unreported CP. The experience of pain is a highly complex human experience with a multiplicity of...occur, and is persistent (Greer & Hoyt, 1990). Nociceptive fibers have cell bodies in the spinal ganglia , which enter the dorsal horn posteriorly, and...via the spinothalamic pathway, and stimulate somatic motor neurons on the anterior horn, or preganglionic neurons of the autonomic nervous system in the

Completing the Heterocubane Family [Cp*AlE]4 (E = O, S, Se, and Te) by Selective Oxygenation and Sulfuration of [Cp*Al]4: Density Functional Theory Calculations of [Cp*AlE]4 and Reactivity of [Cp*AlO]4 toward Hydrolysis.

PubMed

Stelzer, Adrian C; Hrobárik, Peter; Braun, Thomas; Kaupp, Martin; Braun-Cula, Beatrice

2016-05-16

The subvalent aluminum compound [Cp*Al]4 (1) reacts with dioxygen, N2O, or sulfur to yield the heterocubane complexes [Cp*AlX]4 [X = O (2) and S (3)]. Treatment of [Cp*AlO]4 (2) with (tBuO)3SiOH gave [(tBuO)3SiOAlO]4 (6) and Cp*H. The structures and spectroscopic data of the Al clusters are supported by density functional theory (DFT) calculations, which also demonstrate the importance of noncovalent interactions (NCI) in oligomeric Al(I) complexes as well as in [Cp*AlS]4 and the heavier homologues of Se and Te. The computed (27)Al NMR shifts indicate a deshielding at the Al centers with increasing electronegativity of the chalcogen atom as well as significant spin-orbit shielding effects within the heavier heterocubane [Al4E4] cores. Further hydrolysis of 6 with an additional amount of silanol in the presence of water resulted in the formation of [Al4(OH)6(OH2)2(OSiOtBu3)6] (7), which shows a structural motif found in boehmite and diaspore.

Feeding and Gastrointestinal Problems in Children with Cerebral Palsy

ERIC Educational Resources Information Center

Erkin, Gulten; Culha, Canan; Ozel, Sumru; Kirbiyik, Eylem Gulsen

2010-01-01

The aim of our study was to identify feeding and gastrointestinal system (GIS) problems in children with cerebral palsy (CP), and to evaluate the relationship between these problems and the severity of CP. A total of 120 children with CP were enrolled consecutively into the study (67 males, 53 females; mean age: 6.0[plus or minus]2.4 years; range:…

Is Interlimb Coordination during Walking Preserved in Children with Cerebral Palsy?

ERIC Educational Resources Information Center

Meyns, Pieter; Van Gestel, Leen; Bruijn, Sjoerd M.; Desloovere, Kaat; Swinnen, Stephan P.; Duysens, Jacques

2012-01-01

Arm movements during gait in children with cerebral palsy (CP) are altered compared to typically developing children (TD). We investigated whether these changes in arm movements alter interlimb coordination in CP gait. 3D gait analysis was performed in CP (diplegia [DI]: N = 15 and hemiplegia [HE]: N = 11) and TD (N = 24) children at preferred and…

Caspase Activation in Fetal Rat Brain Following Experimental Intrauterine Inflammation

PubMed Central

Sharangpani, Aditi; Takanohashi, Asako; Bell, Michael J.

2009-01-01

Intrauterine inflammation has been implicated in developmental brain injuries, including the development of periventricular leukomalacia (PVL) and cerebral palsy (CP). Previous studies in our rat model of intrauterine inflammation demonstrated apoptotic cell death in fetal brains within the first 5 days after lipopolysaccharide (LPS) administration to mothers and eventual dysmyelination. Cysteine-containing, aspartate-specific proteases, or caspases, are proteins involved with apoptosis through both intracellular (intrinsic pathway) and extracellular (extrinsic pathway) mechanisms. We hypothesized that cell death in our model would occur mainly via activation of the extrinsic pathway. We further hypothesized that Fas, a member of the tumor necrosis factor receptor (TNFR) superfamily, would be increased and the death inducing signaling complex (DISC) would be detectable. Pregnant rats were injected intracervically with LPS at E15 and immunoblotting, immunohistochemical and immunoprecipitation analyses were performed. The presence of the activated form of the effector caspase (caspase-3) was observed 24 h after LPS administration. Caspase activity assays demonstrated rapid increases in (i) caspases-9 and -10 within 1 h, (ii) caspase-8 at 2 h and (iii) caspase-3 at 4 h. At 24 h after LPS, activated caspase-3+/Fas+ cells were observed within the developing white matter. Lastly, the DISC complex (caspase-8, Fas and Fas-associated Death Domain (FADD)) was observed within 30 min by immunoprecipitation. Apoptosis in our model occurs via both extrinsic and intrinsic pathways, and activation of Fas may play a role. Understanding the mechanisms of cell death in models of intrauterine inflammation may affect development of future strategies to mitigate these injuries in children. PMID:18289516

Antisense Suppression of the Small Chloroplast Protein CP12 in Tobacco Alters Carbon Partitioning and Severely Restricts Growth1[W

PubMed Central

Howard, Thomas P.; Fryer, Michael J.; Singh, Prashant; Metodiev, Metodi; Lytovchenko, Anna; Obata, Toshihiro; Fernie, Alisdair R.; Kruger, Nicholas J.; Quick, W. Paul; Lloyd, Julie C.; Raines, Christine A.

2011-01-01

The thioredoxin-regulated chloroplast protein CP12 forms a multienzyme complex with the Calvin-Benson cycle enzymes phosphoribulokinase (PRK) and glyceraldehyde-3-phosphate dehydrogenase (GAPDH). PRK and GAPDH are inactivated when present in this complex, a process shown in vitro to be dependent upon oxidized CP12. The importance of CP12 in vivo in higher plants, however, has not been investigated. Here, antisense suppression of CP12 in tobacco (Nicotiana tabacum) was observed to impact on NAD-induced PRK and GAPDH complex formation but had little effect on enzyme activity. Additionally, only minor changes in photosynthetic carbon fixation were observed. Despite this, antisense plants displayed changes in growth rates and morphology, including dwarfism and reduced apical dominance. The hypothesis that CP12 is essential to separate oxidative pentose phosphate pathway activity from Calvin-Benson cycle activity, as proposed in cyanobacteria, was tested. No evidence was found to support this role in tobacco. Evidence was seen, however, for a restriction to malate valve capacity, with decreases in NADP-malate dehydrogenase activity (but not protein levels) and pyridine nucleotide content. Antisense repression of CP12 also led to significant changes in carbon partitioning, with increased carbon allocation to the cell wall and the organic acids malate and fumarate and decreased allocation to starch and soluble carbohydrates. Severe decreases were also seen in 2-oxoglutarate content, a key indicator of cellular carbon sufficiency. The data presented here indicate that in tobacco, CP12 has a role in redox-mediated regulation of carbon partitioning from the chloroplast and provides strong in vivo evidence that CP12 is required for normal growth and development in plants. PMID:21865489

Site-Specific Transmission of a Floor-Based, High-Frequency, Low-Magnitude Vibration Stimulus in Children With Spastic Cerebral Palsy.

PubMed

Singh, Harshvardhan; Whitney, Daniel G; Knight, Christopher A; Miller, Freeman; Manal, Kurt; Kolm, Paul; Modlesky, Christopher M

2016-02-01

To determine the degree to which a high-frequency, low-magnitude vibration signal emitted by a floor-based platform transmits to the distal tibia and distal femur of children with spastic cerebral palsy (CP) during standing. Cross-sectional study. University research laboratory. Children with spastic CP who could stand independently (n=18) and typically developing children (n=10) (age range, 4-12y) participated in the study (N=28). Not applicable. The vibration signal at the high-frequency, low-magnitude vibration platform (approximately 33Hz and 0.3g), distal tibia, and distal femur was measured using accelerometers. The degree of plantar flexor spasticity was assessed using the Modified Ashworth Scale. The high-frequency, low-magnitude vibration signal was greater (P<.001) at the distal tibia than at the platform in children with CP (.36±.06g vs .29±.05g) and controls (.40±.09g vs .24±.07g). Although the vibration signal was also higher at the distal femur (.35±.09g, P<.001) than at the platform in controls, it was lower in children with CP (.20±.07g, P<.001). The degree of spasticity was negatively related to the vibration signal transmitted to the distal tibia (Spearman ρ=-.547) and distal femur (Spearman ρ=-.566) in children with CP (both P<.05). A high-frequency, low-magnitude vibration signal from a floor-based platform was amplified at the distal tibia, attenuated at the distal femur, and inversely related to the degree of muscle spasticity in children with spastic CP. Whether this transmission pattern affects the adaptation of the bones of children with CP to high-frequency, low-magnitude vibration requires further investigation. Copyright © 2016 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

Child characteristics, caregiver characteristics, and environmental factors affecting the quality of life of caregivers of children with cerebral palsy.

PubMed

Tseng, Mei-Hui; Chen, Kuan-Lin; Shieh, Jeng-Yi; Lu, Lu; Huang, Chien-Yu; Simeonsson, Rune J

2016-12-01

The study aimed to investigate comprehensively the determinants of the quality of life (QOL) of caregivers of children with cerebral palsy (CP) based on the International Classification of Functioning, Disability and Health for Children and Youth (ICF-CY). A total of 167 children with CP (mean age 9.06 years, SD 2.61 years) and their caregivers (mean age 40.24 years, SD 5.43 years) participated in this study. The QOL of caregivers was measured with the World Health Organization Quality of Life-BREF-Taiwan version (WHOQOL-BREF-TW). The potential determinants of QOL were collected, including child characteristics, caregiver characteristics, and environmental factors from all dimensions of the ICF-CY and analysed using multiple regression models. Four multiple regression models revealed that determinants of the QOL of caregivers of children with CP was multidimensional, encompassing child characteristics (age, type of CP, fine motor impairment, other diseases, behaviour and emotions, visual impairment, hearing impairment), caregiver characteristics (general mental health, parenting stress, marital status, family coping patterns, and socio-economic status), and environmental factors (child's medication, school setting, and current rehabilitation service, caregiver's spouse's age, family life impacts, and domestic helper). Knowledge of the determinants of QOL could serve as a guide in a holistic approach to evaluation and intervention and help plan interventions targeted at these determinants to improve the QOL of caregivers of children with CP. Implications for Rehabilitation Caregivers of children with CP had lower QOL, except the environment QOL. The QOL determinants of caregivers of children with CP are multidimensional, including child characteristics, caregiver characteristics, and environmental factors. In addition to child characteristics of severity of fine motor impairments and emotional and behavioural problems, caregiver characteristics of general mental health, parenting stress, and coping patterns, and environmental factors of family life impacts, and school setting demonstrated important relationships with caregiver QOL.

Stimulation of Chronic Lymphocytic Leukemia (CLL) Cells with CpG Oligodeoxynucleotide (ODN) Gives Consistent Karyotypic Results among Laboratories: a CLL Research Consortium (CRC)h Study

PubMed Central

Heerema, Nyla A.; Byrd, John C.; Cin, Paola Dal; Dell’ Aquila, Marie L.; Koduru, Prasad; Aviram, Ayala; Smoley, Stephanie; Rassenti, Laura Z.; Greaves, Andrew W.; Brown, Jennifer R.; Rai, Kanti R.; Kipps, Thomas J.; Kay, Neil E.; van Dyke, Daniel

2010-01-01

Cytogenetic abnormalities in CLL are important prognostic indicators. Historically, only interphase cytogenetics was clinically useful in CLL because traditional mitogens are not effective mitotic stimulants. Recently, CpG-oligodeoxynucleotide (ODN) stimulation has shown effectiveness in CLL. The CLL Research Consortium (CRC) tested the effectiveness and reproducibility of CpG-ODN stimulation to detect chromosomally abnormal clones by five laboratories. More clonal abnormalities were observed after culture of CLL cells with CpG-ODN than with pokeweed mitogen (PWM)+12-O-tetradecanoyl-phorobol-13-acetate (TPA). All clonal abnormalities in PWM+TPA cultures were observed in CpG-ODN cultures, whereas CpG-ODN identified some clones not found by PWM+TPA. CpG-ODN stimulation of one normal control and 12 CLL samples showed that excepting clones of del(13q) in low frequencies and one translocation, results in all five laboratories were consistent, and all abnormalities were concordant with FISH. Thus, abnormal clones in CLL are more readily detected with CpG-ODN stimulation than with traditional B-cell mitogens. After CpG-ODN stimulation, abnormalities were reproducible among cytogenetic laboratories. CpG-ODN did not appear to induce aberrations in cell culture and enhanced detection of abnormalities and complexity in CLL. Since karyotypic complexity is prognostic and is not detectable by standard FISH analyses, stimulation with CpG-ODN is useful to identify this additional prognostic factor in CLL. PMID:21156225

Application of calcium peroxide activated with Fe(II)-EDDS complex in trichloroethylene degradation.

PubMed

Zhang, Xiang; Gu, Xiaogang; Lu, Shuguang; Miao, Zhouwei; Xu, Minhui; Fu, Xiaori; Qiu, Zhaofu; Sui, Qian

2016-10-01

This study was conducted to assess the application of calcium peroxide (CP) activated with Fe(II) chelated by (S,S)-ethylenediamine-N,N'-disuccinic acid (EDDS) to enhance trichloroethylene (TCE) degradation in aqueous solution. It was indicated that EDDS prevented soluble iron from precipitation, and the optimum molar ratio of Fe(II)/EDDS to accelerate TCE degradation was 1/1. The influences of initial TCE, CP and Fe(II)-EDDS concentration were also investigated. The combination of CP and Fe(II)-EDDS complex rendered the efficient degradation of TCE at near neutral pH range. Chemical probe and scavenger tests identified that TCE degradation mainly owed to the oxidation of HO while O2(-) promoted HO generation. Cl(-), HCO3(-) and humic acid were found to inhibit CP/Fe(II)-EDDS performance on different levels. In conclusion, the application of CP activated with Fe(II)-EDDS complex is a promising technology in chemical remediation of groundwater, while further research in practical implementation is needed. Copyright © 2016 Elsevier Ltd. All rights reserved.

The role of the [CpM(CO)2](-) chromophore in the optical properties of the [Cp2ThMCp(CO)2](+) complexes, where M = Fe, Ru and Os. A theoretical view.

PubMed

Cantero-López, Plinio; Le Bras, Laura; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

2015-12-14

The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2](+) complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2](-) chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

A Heterobimetallic Complex With an Unsupported Uranium(III)-Aluminum(I) Bond: (CpSiMe3)3U-AlCp* (Cp* = C5Me5)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minasian, Stefan; Krinsky Ph.D., Jamin; Williams, Valerie

2008-07-23

The discovery of molecular metal-metal bonds has been of fundamental importance to the understanding of chemical bonding. For the actinides, examples of unsupported metal-metal bonds are relatively uncommon, consisting of Cp{sub 3}U-SnPh{sub 3}, and several actinide-transition metal complexes. Traditionally, bonding in the f-elements has been described as electrostatic; however, elucidating the degree of covalency is a subject of recent research. In carbon monoxide complexes of the trivalent uranium metallocenes, decreased {nu}{sub CO} values relative to free CO suggest that the U(III) atom acts as a {pi}-donor. Ephritikhine and coworkers have demonstrated that {pi}-accepting ligands can differentiate trivalent lanthanide and actinidemore » ions, an effect that renders this chemistry of interest in the context of nuclear waste separation technology.« less

Neurodevelopmental comorbidities and seizure control 24 months after a first unprovoked seizure in children.

PubMed

Jason, Eva Åndell; Tomson, Torbjörn; Carlsson, Sofia; Tedroff, Kristina; Åmark, Per

2018-07-01

To follow children with newly diagnosed unprovoked seizures to determine (1) whether the prevalence of neurodevelopmental comorbidities and cerebral palsy (CP) changed after the initial seizure, and (2) the association between studied comorbidities and seizures 13-24 months after seizure onset or initiation of treatment. Analyses were based on 750 children (28 days-18 years) with a first unprovoked seizure (index) included in a population-based Incidence Registry in Stockholm between 2001 and 2006. The children were followed for two years and their medical records were examined for a priori defined neurodevelopmental/psychiatric comorbidities and CP and seizure frequency. Baseline information was collected from medical records from before, and up to six months after, the index seizure. Odds ratios (OR) of repeated seizures 13-24 months after the first seizure or after initiation of anti-epileptic drug treatment was calculated by logistic regression and adjusted for age and sex. At baseline, 32% of the children had neurodevelopmental/psychiatric comorbidities or CP compared to 35%, 24 months later. Children with such comorbidities more often experienced seizures 13-24 months after the index seizure (OR 2.87, CI 2.07-3.99) with the highest OR in those with CP or attention deficit hyperactivity disorder (ADHD). Children diagnosed at age <1 year exhibited the highest prevalence of comorbidities as well as OR for repeated seizures. A combination of young age and comorbidity was associated with an OR for repeated seizures of 5.12 (CI 3.03-8.65). Among the children without comorbidities 76% were seizure free 13-24 months after the index seizure or after initiation of AED treatment compared to 53% of children with comorbidities. This study indicates that neurodevelopmental comorbidities and CP in children with epilepsy tend to be present already at seizure onset and that such comorbidities are strong indicators of poor outcome regarding seizure control with or without treatment. Copyright © 2018 Elsevier B.V. All rights reserved.

Cationic and Neutral Cp*M(NO)(κ2-Ph2PCH2CH2PPh2) Complexes of Molybdenum and Tungsten: Lewis-Acid-Induced Intramolecular C-H Activation.

PubMed

Handford, Rex C; Wakeham, Russell J; Patrick, Brian O; Legzdins, Peter

2017-03-20

Treatment of CH 2 Cl 2 solutions of Cp*M(NO)Cl 2 (Cp* = η 5 -C 5 (CH 3 ) 5 ; M = Mo, W) first with 2 equiv of AgSbF 6 in the presence of PhCN and then with 1 equiv of Ph 2 PCH 2 CH 2 PPh 2 affords the yellow-orange salts [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 in good yields (M = Mo, W). Reduction of [Cp*M(NO)(PhCN)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 )](SbF 6 ) 2 with 2 equiv of Cp 2 Co in C 6 H 6 at 80 °C produces the corresponding 18e neutral compounds, Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) which have been isolated as analytically pure orange-red solids. The addition of 1 equiv of the Lewis acid, Sc(OTf) 3 , to solutions of Cp*M(NO)(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) at room temperature results in the immediate formation of thermally stable Cp*M(NO→Sc(OTf) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes in which one of the phenyl substituents of the Ph 2 PCH 2 CH 2 PPh 2 ligands has undergone intramolecular orthometalation. In a similar manner, addition of BF 3 produces the analogous Cp*M(NO→BF 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ) complexes. In contrast, B(C 6 F 5 ) 3 forms the 1:1 Lewis acid-base adducts, Cp*M(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) in CH 2 Cl 2 at room temperature. Upon warming to 80 °C, Cp*Mo(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) converts cleanly to the orthometalated product Cp*Mo(NO→B(C 6 F 5 ) 3 )(H)(κ 3 -(C 6 H 4 )PhPCH 2 CH 2 PPh 2 ), but Cp*W(NO→B(C 6 F 5 ) 3 )(κ 2 -Ph 2 PCH 2 CH 2 PPh 2 ) generates a mixture of products whose identities remain to be ascertained. Attempts to extend this chemistry to include related Ph 2 PCH 2 PPh 2 compounds have had only limited success. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

The risk of fractures among patients with cirrhosis or chronic pancreatitis.

PubMed

Bang, Ulrich Christian; Benfield, Thomas; Bendtsen, Flemming; Hyldstrup, Lars; Beck Jensen, Jens-Erik

2014-02-01

Cirrhosis and chronic pancreatitis (CP) are accompanied by inflammation and malnutrition. Both conditions can have negative effects on bone metabolism and promote fractures. We evaluated the risk of fractures among patients with CP or cirrhosis and determined the effect of fat malabsorption on fracture risk among patients with CP. We performed a retrospective cohort study using the Danish National Patient Register to identify patients diagnosed with CP or cirrhosis. We analyzed data collected from January 1, 1995, to December 31, 2010, on 20,769 patients (35.5% women with cirrhosis and 11,972 patients (33.5% women) with CP. Each patient was compared with 10 age- and sex-matched controls. We also assessed the risk of fractures among patients with CP who received pancreatic enzyme substitution (PES) for fat malabsorption. During the study period, bone fractures occurred in 3954 patients with cirrhosis and 2594 patients with CP. The adjusted hazard ratio (HR) for any fracture was 2.4 in patients with cirrhosis (95% confidence interval [CI], 2.2-2.5) and 1.7 in patients with CP (95% CI, 1.6-1.8). The relative risk of low-trauma fractures was highest among individuals younger than 50 years old. Alcohol as an etiology was associated with an increased risk of fracture compared with patients with nonalcoholic cirrhosis (HR, 2.4 vs 1.5; P < .0001) and CP (HR, 2.0 vs 1.5; P < .0001). Patients with CP receiving PES for fat malabsorption had a lower risk of fractures than other CP patients (HR, 0.8; 95% CI, 0.7-0.9). However, increasing the duration of treatment with PES was associated with an increased risk of fracture. Patients, especially younger patients, with cirrhosis or CP have an increased risk of fractures of all types. Copyright © 2014 AGA Institute. Published by Elsevier Inc. All rights reserved.

RE-PERG, a new procedure for electrophysiologic diagnosis of glaucoma that may improve PERG specificity.

PubMed

Mavilio, Alberto; Sisto, Dario; Ferreri, Paolo; Cardascia, Nicola; Alessio, Giovanni

2017-01-01

A significant variability of the second harmonic (2ndH) phase of steady-state pattern electroretinogram (SS-PERG) in intrasession retest has been recently described in glaucoma patients (GP), which has not been found in healthy subjects. To evaluate the reliability of phase variability in retest (a procedure called RE-PERG or REPERG) in the presence of cataract, which is known to affect standard PERG, we tested this procedure in GP, normal controls (NC), and cataract patients (CP). The procedure was performed on 50 GP, 35 NC, and 27 CP. All subjects were examined with RE-PERG and SS-PERG and also with spectral domain optical coherence tomography and standard automated perimetry. Standard deviation of phase and amplitude value of 2ndH were correlated by means of one-way analysis of variance and Pearson correlation, with the mean deviation and pattern standard deviation assessed by standard automated perimetry and retinal nerve fiber layer and the ganglion cell complex thickness assessed by spectral domain optical coherence tomography. Receiver operating characteristics were calculated in cohort populations with and without cataract. Standard deviation of phase of 2ndH was significantly higher in GP with respect to NC ( P <0.001) and CP ( P <0.001), and it correlated with retinal nerve fiber layer ( r =-0.5, P <0.001) and ganglion cell complex ( r =-0.6, P <0.001) defects in GP. Receiver operating characteristic evaluation showed higher specificity of RE-PERG (86.4%; area under the curve 0.93) with respect to SS-PERG (54.5%; area under the curve 0.68) in CP. RE-PERG may improve the specificity of SS-PERG in clinical practice in the discrimination of GP.

Supported metallocene catalysts by surface organometallic chemistry. Synthesis, characterization, and reactivity in ethylene polymerization of oxide-supported mono- and biscyclopentadienyl zirconium alkyl complexes: establishment of structure/reactivity relationships.

PubMed

Jezequel, M; Dufaud, V; Ruiz-Garcia, M J; Carrillo-Hermosilla, F; Neugebauer, U; Niccolai, G P; Lefebvre, F; Bayard, F; Corker, J; Fiddy, S; Evans, J; Broyer, J P; Malinge, J; Basset, J M

2001-04-18

The reactions of CpZr(CH(3))(3), 1, and Cp(2)Zr(CH(3))(2), 2, with partially dehydroxylated silica, silica-alumina, and alumina surfaces have been carried out with careful identification of the resulting surface organometallic complexes in order to probe the relationship between catalyst structure and polymerization activity. The characterization of the supported complexes has been achieved in most cases by in situ infrared spectroscopy, surface microanalysis, qualitative and quantitative analysis of evolved gases during surface reactions with labeled surface, solid state (1)H and (13)C NMR using (13)C-enriched compounds, and EXAFS. 1 and 2 react with silica(500) and silica-alumina(500) by simple protonolysis of one Zr-Me bond by surface silanols with formation of a single well-defined neutral compound. In the case of silica-alumina, a fraction of the supported complexes exhibits some interactions with electronically unsaturated surface aluminum sites. 1 and 2 also react with the hydroxyl groups of gamma-alumina(500), leading to several surface structures. Correlation between EXAFS and (13)C NMR data suggests, in short, two main surface structures having different environments for the methyl group: [Al](3)-OZrCp(CH(3))(2) and [Al](2)-OZrCp(CH(3))(mu-CH(3))-[Al] for the monoCp series and [Al](2)-OZrCp(2)(CH(3)) and [Al]-OZrCp(2)(mu-CH(3))-[Al] for the bisCp series. Ethylene polymerization has been carried out with all the supported complexes under various reaction conditions. Silica-supported catalysts in the absence of any cocatalyst exhibited no activity whatsoever for ethylene polymerization. When the oxide contained Lewis acidic sites, the resulting surface species were active. The activity, although improved by the presence of additional cocatalysts, remained very low by comparison with that of the homogeneous metallocene systems. This trend has been interpreted on the basis of various possible parameters, including the (p-pi)-(d-pi) back-donation of surface oxygen atoms to the zirconium center.

Distinctive activation and functionalization of hydrocarbon C-H bonds initiated by Cp*W(NO)(η(3)-allyl)(CH2CMe3) complexes.

PubMed

Baillie, Rhett A; Legzdins, Peter

2014-02-18

Converting hydrocarbon feedstocks into value-added chemicals continues to offer challenges to contemporary preparative chemists. A particularly important remaining challenge is the selective activation and functionalization of the C(sp(3))-H linkages of alkanes, which are relatively abundant but chemically inert. This Account outlines the discovery and development of C-H bond functionalization mediated by a family of tungsten organometallic nitrosyl complexes. Specifically, it describes how gentle thermolyses of any of four 18-electron Cp*W(NO)(η(3)-allyl)(CH2CMe3) complexes (Cp* = η(5)-C5Me5; η(3)-allyl = η(3)-H2CCHCHMe, η(3)-H2CCHCHSiMe3, η(3)-H2CCHCHPh, or η(3)-H2CCHCMe2) results in the loss of neopentane and the transient formation of a 16-electron intermediate species, Cp*W(NO)(η(2)-allene) and/or Cp*W(NO)(η(2)-diene). We have never detected any of these species spectroscopically, but we infer their existence based on trapping experiments with trimethylphosphine (PMe3) and labeling experiments using deuterated hydrocarbon substrates. This Account first summarizes the syntheses and properties of the four chiral Cp*W(NO)(η(3)-allyl)(CH2CMe3) complexes. It then outlines the various types of C-H activations we have effected with each of the 16-electron (η(2)-allene) or (η(2)-diene) intermediate nitrosyl complexes, and presents the results of mechanistic investigations of some of these processes. It next describes the characteristic chemical properties of the Cp*W(NO)(η(3)-allyl)(η(1)-hydrocarbyl) compounds formed by the single activations of C(sp(3))-H bonds, with particular emphasis on those reactions that result in the selective functionalization of the original hydrocarbon substrate. We are continuing development of methods to release the acyl ligands from the metal centers while keeping the Cp*W(NO)(η(3)-allyl) fragments intact, with the ultimate aim of achieving these distinctive conversions of alkanes into functionalized organics in a catalytic manner.

Role of Su(Hw) zinc finger 10 and interaction with CP190 and Mod(mdg4) proteins in recruiting the Su(Hw) complex to chromatin sites in Drosophila.

PubMed

Melnikova, Larisa; Kostyuchenko, Margarita; Parshikov, Alexander; Georgiev, Pavel; Golovnin, Anton

2018-01-01

Su(Hw) belongs to the class of proteins that organize chromosome architecture and boundaries/insulators between regulatory domains. This protein contains a cluster of 12 zinc finger domains most of which are responsible for binding to three different modules in the consensus site. Su(Hw) forms a complex with CP190 and Mod(mdg4)-67.2 proteins that binds to well-known Drosophila insulators. To understand how Su(Hw) performs its activities and binds to specific sites in chromatin, we have examined the previously described su(Hw)f mutation that disrupts the 10th zinc finger (ZF10) responsible for Su(Hw) binding to the upstream module. The results have shown that Su(Hw)f loses the ability to interact with CP190 in the absence of DNA. In contrast, complete deletion of ZF10 does not prevent the interaction between Su(Hw)Δ10 and CP190. Having studied insulator complex formation in different mutant backgrounds, we conclude that both association with CP190 and Mod(mdg4)-67.2 partners and proper organization of DNA binding site are essential for the efficient recruitment of the Su(Hw) complex to chromatin insulators.

CENTERING PREGANCY- AFRICA: A PILOT OF GROUP ANTENATAL CARE TO ADDRESS MILLENIUM DEVELOPMENT GOALS

PubMed Central

Patil, Crystal L.; Abrams, Elizabeth T.; Klima, Carrie; Kaponda, Chrissie P.N.; Leshabari, Sebalda C.; Vonderheid, Susan C.; Kamaga, Martha; Norr, Kathleen F.

2013-01-01

Background Severe health worker shortages and resource limitations negatively affect quality of antenatal care (ANC) throughout sub-Saharan Africa. Group ANC, specifically CenteringPregnancy (CP), may offer an innovative approach to enable midwives to offer higher quality ANC. Objective Our overarching goal was to prepare to conduct a clinical trial of CenteringPregnancy – Africa (CP-Africa) in Malawi and Tanzania. In Phase 1, our goal was to determine the acceptability of CP as model for ANC in both countries. In Phase 2, our objective was to develop CP-Africa session content consistent with the Essential Elements of CP model and with national standards in both Malawi and Tanzania. In Phase 3, our objective was to pilot CP-Africa in Malawi to determine whether sessions could be conducted with fidelity to the Centering process. Setting Phase 1 and 2 took place in Malawi and Tanzania. Phase 3, the piloting of two sessions of CP-Africa, occurred at two sites in Malawi: a district hospital and a small clinic. Design We used an Action Research approach to promote partnerships among university researchers, the Centering Healthcare Institute, healthcare administrators, health professionals and women attending ANC to develop CP-Africa session content and pilot this model of group ANC. Participants For Phases 1 and 2, members of the Ministries of Health, health professionals and pregnant women in Malawi and Tanzania were introduced to and interviewed about CP. In Phase 2, we finalized CP-Africa content and trained thirteen health professionals in the Centering Healthcare model. In Phase 3, we conducted a small pilot with 24 pregnant women (12 at each site). Measurements and Findings Participants enthusiastically embraced CP-Africa as an acceptable model of ANC healthcare delivery. The CP-Africa content met both CP and national standards. The pilot established that the CP model could be implemented with process fidelity to the 13 Essential Elements. Several implementation challenges and strategies to address these challenges were identified. Key Conclusions Preliminary data suggest that CP-Africa is feasible in resource-constrained, low-literacy, high-HIV settings in sub-Saharan Africa. By improving the quality of ANC delivery, midwives have an opportunity to make a contribution towards Millennium Development Goals (MDG) targeting improvements in child, maternal and HIV-related health outcomes (MDGs 4, 5 and 6). A clinical trial is needed to establish efficacy. Implications for Practice CP-Africa also has the potential to reduce job-related stress and enhance job satisfaction for midwives in low income countries. If CP can be transferred with fidelity to process in sub-Saharan Africa and retain similar results to those reported in clinical trials, it has the potential to benefit pregnant women and their infants and could make a positive contribution to MGDs 4, 5 and .6. PMID:23871278

Time- and concentration-dependent increases in cell proliferation in rats and mice administered vinyl acetate in drinking water.

PubMed

Valentine, Rudolph; Bamberger, J R; Szostek, B; Frame, S R; Hansen, J F; Bogdanffy, M S

2002-06-01

Chronic administration of vinyl acetate (VA) in drinking water to rats and mice has produced upper digestive tract neoplasms. These tumors were believed to arise from the intracellular metabolism of VA by carboxylesterases to cytotoxic and genotoxic compounds. We hypothesized that prolonged VA exposure at high concentrations would induce cytotoxicity and a restorative cell proliferation (CP). These endpoints were measured in F-344 rats and BDF1 mice administered drinking water containing 0, 1000, 5000, 10,000, or 24,000 ppm VA for 92 days. On test days, Days 1, 8, 29, and 92, upper digestive tract histopathology and oral cavity CP (pulsed 5-bromodeoxyuridine [BrdU] to measure S-phase DNA synthesis) were evaluated. Analysis of test solutions showed that VA spontaneously hydrolyzed, slowly releasing acetic acid and thereby lowering pH. Statistically significant, concentration-related increases in CP occurred in basal cells of the mandibular oral cavity mucosa of mice at 10,000 and 24,000 ppm but only after 92 days. CP increases were approximately 2.4- and 3.4-fold above controls and were considered to be toxicologically significant. Some statistically significant increases in CP were also measured in the oral cavity mucosa of rats; however, these changes were considered to be of equivocal biological relevance. No histopathological evidence of mucosal injury was seen in either species. The absence of cytotoxicity in the upper digestive tract mucosa suggests that the increased CP at high administered VA concentrations may be due to a mitogenic response, ostensibly from the loss of cell growth controls in oral cavity mucosa.

Polyubiquitination of the B-cell translocation gene 1 and 2 proteins is promoted by the SCF ubiquitin ligase complex containing βTrCP.

PubMed

Sasajima, Hitoshi; Nakagawa, Koji; Kashiwayanagi, Makoto; Yokosawa, Hideyoshi

2012-01-01

B-cell translocation gene 1 and 2 (BTG1 and BTG2) are members of the BTG/Tob antiproliferative protein family, which is able to regulate the cell cycle and cell proliferation. We previously reported that BTG1, BTG2, Tob, and Tob2 are degraded via the ubiquitin-proteasome pathway. In this study, we investigated the mechanism of polyubiquitination of BTG1 and BTG2. Since the Skp1-Cdc53/Cullin 1-F-box protein (SCF) complex functions as one of the major ubiquitin ligases for cell cycle regulation, we first examined interactions between BTG proteins and components of the SCF complex, and found that BTG1 and BTG2 were capable of interacting with the SCF complex containing Cullin-1 (a scaffold protein) and Skp1 (a linker protein). As the SCF complex can ubiquitinate various target proteins by substituting different F-box proteins as subunits that recognize different target proteins, we next examined which F-box proteins could bind the two BTG proteins, and found that Skp2, β-transducin repeat-containing protein 1 (βTrCP1), and βTrCP2 were able to associate with both BTG1 and BTG2. Furthermore, we obtained evidence showing that βTrCP1 enhanced the polyubiquitination of both BTG1 and BTG2 more efficiently than Skp2 did, and that an F-box truncated mutant of βTrCP1 had a dominant negative effect on this polyubiquitination. Thus, we propose that BTG1 and BTG2 are subjected to polyubiquitination, more efficiently when it is mediated by SCFβTrCP than by SCFSkp2.

Ethanolic extract of Moringa oleifera Lam. leaves protect the pre-pubertal spermatogonial cells from cyclophosphamide-induced damage.

PubMed

Nayak, Guruprasad; Honguntikar, Sachin D; Kalthur, Sneha Guruprasad; D'Souza, Antony Sylvan; Mutalik, Srinivas; Setty, Manjunath M; Kalyankumar, Raksha; Krishnamurthy, Hanumanthappa; Kalthur, Guruprasad; Adiga, Satish Kumar

2016-04-22

Moringa oleifera Lam. is widely cultivated in Asian and African countries for its medicinal and dietary significance. The leaves are highly nutritious and are known to possess various biological activities. Pre-pubertal Swiss albino male mice were injected with single dose of cyclophosphamide (CP, 200mg/kg body weight) or ethanolic extract of Moringa oleifera leaves (MOE, 100mg/kg body weight) intraperitoneally. In combination group, MOE was administered 24h prior to CP injection. CP induced a significant decrease in testicular weight (p<0.01) and depletion of germ cells (p<0.001) and higher level of DNA damage (p<0.001) compared to control. The expression of P53, Bax, Cytochrome C (Cyt C) was increased while there was a decrease in the expression of Bcl2, c-Kit and Oct4. Administration of MOE 24h prior to CP treatment ameliorated the depletion (p<0.001), DNA damage (p<0.001) and apoptosis (p<0.01) of germ cells induced by CP. The mitigating effect of MOE appears to be mediated by up-regulating the expression of c-Kit and Oct4 transcripts in P53-independent manner. MOE protects the spermatogonial cells from CP-induced damage by modulating the apoptotic response elicited by CP and therefore can be considered as an efficient method of male fertility preservation. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Synthesis of Carboxylate Cp*Zr(IV) Species: Toward the Formation of Novel Metallocavitands.

PubMed

Daigle, Maxime; Bi, Wenhua; Légaré, Marc-André; Morin, Jean-François; Fontaine, Frédéric-Georges

2015-06-01

With the intent of generating metallocavitands isostructural to species [(CpZr)3(μ(3)-O)(μ(2)-OH)3(κO,O,μ(2)-O2C(R))3](+), the reaction of Cp*2ZrCl2 and Cp*ZrCl3 with phenylcarboxylic acids was carried out. Depending on the reaction conditions, five new complexes were obtained, which consisted of Cp*2ZrCl(κ(2)-OOCPh) (1), (Cp*ZrCl(κ(2)-OOCPh))2(μ-κ(2)-OOCPh)2 (2), [(Cp*Zr(κ(2)-OOCPh))2(μ-κ(2)-OOCPh)2(μ(2)-OH)2]·Et2O (3·Et2O), [[Cp*ZrCl2](μ-Cl)(μ-OH)(μ-O2CC6H5)[Cp*Zr

Reconfiguration of the proteasome during chaperone-mediated assembly

PubMed Central

Park, Soyeon; Li, Xueming; Kim, Ho Min; Singh, Chingakham Ranjit; Tian, Geng; Hoyt, Martin A.; Lovell, Scott; Battaile, Kevin P.; Zolkiewski, Michal; Coffino, Philip; Roelofs, Jeroen; Cheng, Yifan; Finley, Daniel

2013-01-01

The proteasomal ATPase ring, comprising Rpt1-Rpt6, associates with the heptameric α ring of the proteasome core particle (CP) in the mature proteasome, with the Rpt C-terminal tails inserting into pockets of the α ring1–4. Rpt ring assembly is mediated by four chaperones, each binding a distinct Rpt subunit5–10. We report that the base subassembly of the proteasome, which includes the Rpt ring, forms a high affinity complex with the CP. This complex is subject to active dissociation by the chaperones Hsm3, Nas6, and Rpn14. Chaperone-mediated dissociation was abrogated by a nonhydrolyzable ATP analog, indicating that chaperone action is coupled to nucleotide hydrolysis by the Rpt ring. Unexpectedly, synthetic Rpt tail peptides bound α pockets with poor specificity, except for Rpt6, which uniquely bound the α2/α3 pocket. Although the Rpt6 tail is not visualized within an α pocket in mature proteasomes2–4, it inserts into the α2/α3 pocket in the base-CP complex and is important for complex formation. Thus, the Rpt-CP interface is reconfigured when the lid complex joins the nascent proteasome to form the mature holoenzyme. PMID:23644457

Process for functionalizing alkanes

DOEpatents

Bergman, Robert G.; Janowicz, Andrew H.; Periana-Pillai, Roy A.

1985-01-01

Process for functionalizing saturated hydrocarbons selectively in the terminal position comprising: (a) reacting said saturated hydrocarbons of the formula: RH where: H represents a hydrogen atom, and R represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRhPMe.sub.3 H.sub.2 where: Cp represents a pentamethylated cyclopentadienyl radical, Rh represents a rhodium atom, P represents a phosphorous atom, Me represents a methyl group, H represents a hydrogen atom, in the presence of ultraviolet radiation at a temperature maintained at about -60.degree. to -17.degree. C. to form a hydridoalkyl complex of the formula: CpRhPMe.sub.3 RH (b) reacting said hydridoalkyl complex with a haloform of the formula: CHX.sub.3 where: X represents a bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula: CpRhPMe.sub.3 RX; and, (c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e. ambient) to form a functional haloalkyl compound.

Charge transfer complexes of metal-free phthalocyanine radical anions with decamethylmetallocenium cations: (Cp*2Co+)(H2Pc˙-)·solvent and (Cp*2Cr+)(H2Pc˙-)·4C6H4Cl2.

PubMed

Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2017-03-14

Charge transfer complexes (Cp* 2 Co + )(H 2 Pc˙ - )·0.5C 6 H 4 Cl 2 ·0.7C 6 H 5 CN·0.3C 6 H 14 (1) and (Cp* 2 Cr + )(H 2 Pc˙ - )·4C 6 H 4 Cl 2 (2) have been obtained as single crystals. Both complexes contain metal-free phthalocyanine (Pc) radical anions and decamethylmetallocenium cations. Reduction of the Pc macrocycle leads to the appearance of new bands at 1026-1030 nm in the NIR range and blue shifts of both Soret and Q-bands of H 2 Pc in the spectra of 1 and 2. The geometry of the Pc macrocycles supports the formation of H 2 Pc˙ - by the alternation of shorter and longer C-N(imine) bonds in the macrocycles in 2. Complex 1 contains pairs of H 2 Pc˙ - having effective π-π interactions with two sandwiched Cp* 2 Co + cations, whereas complex 2 contains stacks composed of alternating Cp* 2 Cr + and H 2 Pc˙ - ions. The magnetic moment of 1 is 1.64 μ B at 300 K due to the contribution of the H 2 Pc˙ - spins with the S = 1/2 state and diamagnetism of Cp* 2 Co + . This is supported by the observation of a narrow EPR signal of 1 with g = 2.0032-2.0036 characteristic of H 2 Pc˙ - . Strong antiferromagnetic coupling of spins with a Weiss temperature of -23 K is observed between H 2 Pc˙ - in 1. This coupling is probably mediated by the Cp* 2 Co + cations. The magnetic moment of 2 is 4.18 μ B at 300 K indicating the contribution of both paramagnetic H 2 Pc˙ - (S = 1/2) and Cp* 2 Cr + (S = 3/2) species. In spite of the presence of stacks of alternating ions in 2, only weak magnetic coupling is observed with a Weiss temperature of -4 K most probably due to ineffective π-π interactions between Cp* 2 Cr + and H 2 Pc˙ - . The EPR spectrum of 2 contains an asymmetric signal attributed to Cr III (g 1 = 3.9059-3.9220) and a narrow Lorentzian signal from H 2 Pc˙ - with g 2 = 1.9943-1.9961. In addition to these signals, a broad EPR signal grows in intensity below 80 K with g 4 = 2.1085-2.2438 which can be attributed to both paramagnetic Cp* 2 Cr + and H 2 Pc˙ - species having exchange interactions.

Texas Red transport across rat and dogfish shark (Squalus acanthias) choroid plexus.

PubMed

Reichel, Valeska; Miller, David S; Fricker, Gert

2008-10-01

Confocal microscopy and image analysis were used to compare driving forces, specificity, and regulation of transport of the fluorescent organic anion, Texas Red (sulforhodamine 101 free acid; TR), in lateral choroid plexus (CP) isolated from rat and an evolutionarily ancient vertebrate, dogfish shark (Squalus acanthias). CP from both species exhibited concentrative, specific, and metabolism-dependent TR transport from bath to subepithelial/vascular space; at steady state, TR accumulation in vascular/subepithelial space was substantially higher than in epithelial cells. In rat CP, steady-state TR accumulation in subepithelial/vascular spaces was reduced by Na(+)-replacement, but was not affected by a 10-fold increase in buffer K(+). In shark CP, Na(+)-replacement did not alter TR accumulation in either tissue compartment; subepithelial/vascular space levels of TR were reduced in high-K(+) medium. In both species, steady-state TR accumulation was not affected by p-aminohippurate or leukotriene C4, suggesting that neither organic anion transporters (SLC22A family) nor multidrug resistance-associated proteins (ABCC family) contributed. In rat CP, digoxin was without effect, indicating that organic anion transporting polypeptide isoform 2 was not involved. Several organic anions reduced cellular and subepithelial/vascular space TR accumulation in both tissues, including estrone sulfate, taurocholate, and the Mrp1 inhibitor MK571. In rat CP, TR accumulation in subepithelial/vascular spaces increased with PKA activation (forskolin), but was not affected by PKC activation (phorbol ester). In shark, neither PKA nor PKC activation specifically affected TR transport. Thus, rat and dogfish shark CP transport TR but do so using different basic mechanisms that respond to different regulatory signals.

Chemistry of vinylidene complexes. XXIV. A new μ-vinylidene complex containing RePt core, and platinum-bound carbonyl ligand. Spectroscopic, structural and electrochemical study

NASA Astrophysics Data System (ADS)

Verpekin, Victor V.; Vasiliev, Alexander D.; Kondrasenko, Alexander A.; Burmakina, Galina V.; Chudin, Oleg S.; Pavlenko, Nina I.; Zimonin, Dmitry V.; Rubaylo, Anatoly I.

2018-07-01

The novel heterobinuclear μ-vinylidene complex [Cp(CO)2Re(μ-C=CHPh)Pt(PPh3)(CO)] (1) was isolated from the reaction mixture of [Cp(CO)2Re(μ-C=CHPh)Fe(CO)4] and Pt(PPh3)4 for the first time. Alternative high-yield synthetic approaches to 1 were developed including the reactions of [Cp(CO)2Re(μ-C=CHPh)Pt(PPh3)2] (2) with Co2(CO)8 and Rh(acac)(CO)2. The complex was characterized by IR and 1H, 13C and 31P NMR spectroscopy, a molecular structure of 1 was determined by X-ray diffraction analysis. The electrochemical behavior of the new complex was studied by cyclic voltammetry at platinum or glassed carbon electrodes and by dc polarography at a dropping mercury electrode.

Registration of ‘CP 07-2137’ sugarcane

USDA-ARS?s Scientific Manuscript database

‘CP 07-2137’ (Reg. No.__; PI__) sugarcane (a complex hybrid of Saccharum spp.) was released in September 2014 to be cultivated on sandy (mineral) soils in Florida. CP 07-2137 was developed through a collaborative cultivar development program of the USDA-ARS, the University of Florida, and the Florid...

Registration of 'CP 09-2392' Sugarcane

USDA-ARS?s Scientific Manuscript database

CP 09-2392’ (Reg. No.____; PI _____) sugarcane, a complex hybrid of Saccharum spp, was developed through cooperative research conducted by the USDA-ARS, the University of Florida, and the Florida Sugar Cane League, Inc., and was released to growers in June 2016. ‘CP 09-2392’ was selected from a cro...

Russian sturgeon cultured in a subtropical climate shows weaken innate defences and a chronic stress response.

PubMed

Castellano, Mauricio; Silva-Álvarez, Valeria; Fernández-López, Elena; Mauris, Verónica; Conijeski, Daniel; Villarino, Andrea; Ferreira, Ana M

2017-09-01

Russian sturgeon (Acipenser gueldenstaedtii) has been successfully farmed in Uruguay for the past ten years. However, during the Uruguayan summer fish endure high water temperatures and increased bacterial infections that threaten aquaculture. Our understanding of sturgeon's immune system and its interplay with environmental factors like temperature is almost unknown. This study analysed the way in which seasonal variations affect enzymatic blood components of Russian sturgeon's innate defences, including the serum alternative complement pathway (ACP), ceruloplasmin (Cp) and lysozyme activities. Results showed that summertime conditions in the farm altered these defences in different ways, inducing a significant decrease in ACP and Cp, and an increase in lysozyme. In addition, serum levels of total protein and cortisol decreased in summer, suggesting a chronic stress response was induced in parallel. Subsequently, we analysed whether the increase in water river temperature during summer could account for the observed results. To that end, we acclimated juvenile sturgeons to mild (18 °C) or warm (24 °C) temperatures for 37 days. Like in summer, sturgeons exposed to 24 °C showed lower levels of serum ACP, Cp and total proteins, together with a progressive decrease in body weight and increased fish mortality. Administration of an immunostimulant containing Se and Zn slightly reverted the temperature-induced effects on sturgeon's defences. Altogether, our study provides novel data on various physiological parameters of the Russian sturgeon and highlights the impact warm temperature has on stress and innate immunity in this chondrostean fish. Copyright © 2017 Elsevier Ltd. All rights reserved.

Geometries and properties of bimetallic phosphido-bridged complex Cp(CO) 2W(μ-PPh 2)W(CO) 5 and Cp(CO) 3W(μ-PPh 2)W(CO) 5

NASA Astrophysics Data System (ADS)

Wang, Fang; Yang, Hongmei; Yang, Zuoyin; Zhang, Jingchang; Cao, Weiliang

2007-01-01

Complete geometry optimizations were carried out by HF and DFT methods to study the molecular structure of binuclear transition-metal compounds (Cp(CO) 3W(μ-PPh 2)W(CO) 5) (I) and (Cp(CO) 2W(μ-PPh 2)W(CO) 5) (II). A comparison of the experimental data and calculated structural parameters demonstrates that the most accurate geometry parameters are predicted by the MPW1PW91/LANL2DZ among the three DFT methods. Topological properties of molecular charge distributions were analyzed with the theory of atoms in molecules. (3, -1) critical points, namely bond critical point, were found between the two tungsten atoms, and between W1 and C10 in complex II, which confirms the existence of the metal-metal bond and a semi-bridging CO between the two tungsten atoms. The result provided a theoretical guidance of detailed study on the binuclear phosphido-bridged complex containing transition metal-metal bond, which could be useful in the further study of the heterobimetallic phosphido-bridged complexes.

Influence of central metalloligand geometry on electronic communication between metals: syntheses, crystal structures, MMCT properties of isomeric cyanido-bridged Fe2Ru complexes, and TDDFT calculations.

PubMed

Ma, Xiao; Lin, Chen-Sheng; Hu, Sheng-Min; Tan, Chun-Hong; Wen, Yue-Hong; Sheng, Tian-Lu; Wu, Xin-Tao

2014-06-02

To investigate how the central metalloligand geometry influences distant or vicinal metal-to-metal charge-transfer (MMCT) properties of polynuclear complexes, cis- and trans-isomeric heterotrimetallic complexes, and their one- and two-electron oxidation products, cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CN-Fe(II)(dppe)Cp][PF6]2 (cis/trans-1[PF6]2), cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CNFe(III)-(dppe)Cp][PF6]3 (cis/trans-1[PF6]3) and cis/trans-[Cp(dppe)Fe(III)NCRu(II)(phen)2CN-Fe(III)(dppe)Cp][PF6]4 (cis/trans-1[PF6]4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external Fe(II) atoms of the cis- and trans-isomeric complexes cis/trans-1[PF6]2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans-1[PF6]3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the Ru(II)-CN-Fe(II) subunit to a Fe(III) d orbital with some contributions from the co-ligands. Moreover, the NIR transition energy in trans-1[PF6]3 is lower than that in cis-1[PF6]3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two-electron oxidized complexes show that trans-1[PF6]4 possesses lower vicinal Ru(II) → Fe(III) MMCT transition energy than cis-1[PF6]4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Validation of Demographics, Etiology, and Risk Factors for Chronic Pancreatitis in the USA: A Report of the North American Pancreas Study (NAPS) Group.

PubMed

Conwell, Darwin L; Banks, Peter A; Sandhu, Bimaljit S; Sherman, Stuart; Al-Kaade, Samer; Gardner, Timothy B; Anderson, Michelle A; Wilcox, C Mel; Lewis, Michele D; Muniraj, Thiruvengadam; Forsmark, Christopher E; Cote, Gregory A; Guda, Nalini M; Tian, Ye; Romagnuolo, Joseph; Wisniewski, Stephen R; Brand, Randall; Gelrud, Andres; Slivka, Adam; Whitcomb, David C; Yadav, Dhiraj

2017-08-01

Our aim was to validate recent epidemiologic trends and describe the distribution of TIGAR-O risk factors in chronic pancreatitis (CP) patients. The NAPS-2 Continuation and Validation (NAPS2-CV) study prospectively enrolled 521 CP patients from 13 US centers from 2008 to 2012. CP was defined by definitive changes in imaging, endoscopy, or histology. Data were analyzed after stratification by demographic factors, physician-defined etiology, participating center, and TIGAR-O risk factors. Demographics and physician-defined etiology in the NAPS2-CV study were similar to the original NAPS2 study. Mean age was 53 years (IQR 43, 62) with 55% males and 87% white. Overall, alcohol was the single most common etiology (46%) followed by idiopathic etiology (24%). Alcohol etiology was significantly more common in males, middle-aged (35-65 years), and non-whites. Females and elderly (≥65 years) were more likely to have idiopathic etiology, while younger patients (<35 years) to have genetic etiology. Variability in etiology was noted by participating centers (e.g., alcohol etiology ranged from 27 to 67% among centers enrolling ≥25 patients). Smoking was the most commonly identified (59%) risk factor followed by alcohol (53%), idiopathic (30%), obstructive (19%), and hyperlipidemia (13%). The presence of multiple TIGAR-O risk factors was common, with 1, 2, ≥3 risk factors observed in 27.6, 47.6, and 23.6% of the cohort, respectively. Our data validate the current epidemiologic trends in CP. Alcohol remains the most common physician-defined etiology, while smoking was the most commonly identified TIGAR-O risk factor. Identification of multiple risk factors suggests CP to be a complex disease.

Electronic effects on the catalytic disproportionation of formic acid to methanol by [Cp*Ir(III)(R-bpy)Cl]Cl complexes.

PubMed

Sasayama, A F; Moore, C E; Kubiak, C P

2016-02-14

A series of [Cp*Ir(III)(R-bpy)Cl]Cl (R-bpy = 4,4'-di-R-2,2'-bipyridine; R = CF3, H, Me, tBu, OMe) complexes was prepared and studied for catalytic formic acid disproportionation. The relationship between the electron donating strength of the bipyridine substituents and methanol production of the corresponding complexes was analyzed; the unsubstituted (R = H) complex was the most selective for methanol formation.

Synthesis of [Fe(Leq)(Lax)] n coordination polymer nanoparticles using blockcopolymer micelles.

PubMed

Göbel, Christoph; Klimm, Ottokar; Puchtler, Florian; Rosenfeldt, Sabine; Förster, Stephan; Weber, Birgit

2017-01-01

Spin-crossover compounds are a class of materials that can change their spin state from high spin (HS) to low spin (LS) by external stimuli such as light, pressure or temperature. Applications demand compounds with defined properties concerning the size and switchability that are maintained when the compound is integrated into composite materials. Here, we report the synthesis of [Fe(L eq )(L ax )] n coordination polymer (CP) nanoparticles using self-assembled polystyrene- block -poly(4-vinylpyridine) (PS- b -P4VP) block copolymer (BCP) micelles as template. Variation of the solvent (THF and toluene) and the rigidity of the axial ligand L ax (L ax = 1,2-di(pyridin-4-yl)ethane) (bpea), trans -1,2-di(pyridin-4-yl)ethene (bpee), and 1,2-di(pyridin-4-yl)ethyne) (bpey); L eq = 1,2-phenylenebis(iminomethylidyne)-bis(2,4-pentanedionato)(2-)) allowed the determination of the preconditions for the selective formation of nanoparticles. A low solubility of the CP in the used solvent and a high stability of the Fe-L bond with regard to ligand exchange are necessary for the formation of composite nanoparticles where the BCP micelle is filled with the CP, as in the case of the [FeL eq (bpey)] n @BCP. Otherwise, in the case of more flexible ligands or ligands that lead to high spin complexes, the formation of microcrystals next to the CP-BCP nanoparticles is observed above a certain concentration of [Fe(L eq )(L ax )] n . The core of the nanoparticles is about 45 nm in diameter due to the templating effect of the BCP micelle, independent of the used iron complex and [Fe(L eq )(L ax )] n concentration. The spin-crossover properties of the composite material are similar to those of the bulk for FeL eq (bpea)] n @BCP while pronounced differences are observed in the case of [FeL eq (bpey)] n @BCP nanoparticles.

Inter-species variation in the oligomeric states of the higher plant Calvin cycle enzymes glyceraldehyde-3-phosphate dehydrogenase and phosphoribulokinase

PubMed Central

Lloyd, Julie C.; Raines, Christine A.

2011-01-01

In darkened leaves the Calvin cycle enzymes glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK) form a regulatory multi-enzyme complex with the small chloroplast protein CP12. GAPDH also forms a high molecular weight regulatory mono-enzyme complex. Given that there are different reports as to the number and subunit composition of these complexes and that enzyme regulatory mechanisms are known to vary between species, it was reasoned that protein–protein interactions may also vary between species. Here, this variation is investigated. This study shows that two different tetramers of GAPDH (an A2B2 heterotetramer and an A4 homotetramer) have the capacity to form part of the PRK/GAPDH/CP12 complex. The role of the PRK/GAPDH/CP12 complex is not simply to regulate the ‘non-regulatory’ A4 GAPDH tetramer. This study also demonstrates that the abundance and nature of PRK/GAPDH/CP12 interactions are not equal in all species and that whilst NAD enhances complex formation in some species, this is not sufficient for complex formation in others. Furthermore, it is shown that the GAPDH mono-enzyme complex is more abundant as a 2(A2B2) complex, rather than the larger 4(A2B2) complex. This smaller complex is sensitive to cellular metabolites indicating that it is an important regulatory isoform of GAPDH. This comparative study has highlighted considerable heterogeneity in PRK and GAPDH protein interactions between closely related species and the possible underlying physiological basis for this is discussed. PMID:21498632

Inter-species variation in the oligomeric states of the higher plant Calvin cycle enzymes glyceraldehyde-3-phosphate dehydrogenase and phosphoribulokinase.

PubMed

Howard, Thomas P; Lloyd, Julie C; Raines, Christine A

2011-07-01

In darkened leaves the Calvin cycle enzymes glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK) form a regulatory multi-enzyme complex with the small chloroplast protein CP12. GAPDH also forms a high molecular weight regulatory mono-enzyme complex. Given that there are different reports as to the number and subunit composition of these complexes and that enzyme regulatory mechanisms are known to vary between species, it was reasoned that protein-protein interactions may also vary between species. Here, this variation is investigated. This study shows that two different tetramers of GAPDH (an A2B2 heterotetramer and an A4 homotetramer) have the capacity to form part of the PRK/GAPDH/CP12 complex. The role of the PRK/GAPDH/CP12 complex is not simply to regulate the 'non-regulatory' A4 GAPDH tetramer. This study also demonstrates that the abundance and nature of PRK/GAPDH/CP12 interactions are not equal in all species and that whilst NAD enhances complex formation in some species, this is not sufficient for complex formation in others. Furthermore, it is shown that the GAPDH mono-enzyme complex is more abundant as a 2(A2B2) complex, rather than the larger 4(A2B2) complex. This smaller complex is sensitive to cellular metabolites indicating that it is an important regulatory isoform of GAPDH. This comparative study has highlighted considerable heterogeneity in PRK and GAPDH protein interactions between closely related species and the possible underlying physiological basis for this is discussed.

Physiological and comfort effects of a commercial "cooling cap" worn under protective helmets.

PubMed

Wickwire, P J; Bishop, P A; Green, J M; Richardson, M T; Lomax, R G; Casaru, C; Curtner-Smith, M

2009-08-01

Ballistic protective helmets can impair heat dissipation. A cooling device in the helmet (cooling pad, CP) could help prevent heat problems in military personnel and potentially enhance comfort. This study examined the effects of CP on rectal and skin temperatures, heart rate, percent change in plasma volume, urine specific gravity, rating of perceived exertion, and other subjective measures while performing light work in a hot environment. It was hypothesized that the CP would act as an insulator to the head, which would not positively affect any physiological variable but could positively affect wearer subjective comfort or temperature. Participants performed a work protocol for approximately 2 hr. A ballistic vest, slacks, short-sleeved button-up shirt, and a ballistic helmet (one trial with CP and one trial without) were worn. Repeated measures analysis of variance (ANOVA) showed no differences (p > 0.05) between wearing and not wearing the CP for any physiological parameter. However, participants perceived the CP as cooler (p = 0.002). Other trends in perceptual data such as thermal strain and helmet comfort indicated the CP felt cooler. However, based on forehead temperature and participant comments, the CP lost its cooling ability relatively quickly (within approximately 30 min).

Comparative Genotypes, Staphylococcal Cassette Chromosome mec (SCCmec) Genes and Antimicrobial Resistance amongst Staphylococcus epidermidis and Staphylococcus haemolyticus Isolates from Infections in Humans and Companion Animals.

PubMed

McManus, Brenda A; Coleman, David C; Deasy, Emily C; Brennan, Gráinne I; O' Connell, Brian; Monecke, Stefan; Ehricht, Ralf; Leggett, Bernadette; Leonard, Nola; Shore, Anna C

2015-01-01

This study compares the characteristics of Staphylococcus epidermidis (SE) and Staphylococcus haemolyticus (SH) isolates from epidemiologically unrelated infections in humans (Hu) (28 SE-Hu; 8 SH-Hu) and companion animals (CpA) (12 SE-CpA; 13 SH-CpA). All isolates underwent antimicrobial susceptibility testing, multilocus sequence typing and DNA microarray profiling to detect antimicrobial resistance and SCCmec-associated genes. All methicillin-resistant (MR) isolates (33/40 SE, 20/21 SH) underwent dru and mecA allele typing. Isolates were predominantly assigned to sequence types (STs) within a single clonal complex (CC2, SE, 84.8%; CC1, SH, 95.2%). SCCmec IV predominated among MRSE with ST2-MRSE-IVc common to both Hu (40.9%) and CpA (54.5%). Identical mecA alleles and nontypeable dru types (dts) were identified in one ST2-MRSE-IVc Hu and CpA isolate, however, all mecA alleles and 2/4 dts detected among 18 ST2-MRSE-IVc isolates were closely related, sharing >96.5% DNA sequence homology. Although only one ST-SCCmec type combination (ST1 with a non-typeable [NT] SCCmec NT9 [class C mec and ccrB4]) was common to four MRSH-Hu and one MRSH-CpA, all MRSH isolates were closely related based on similar STs, SCCmec genes (V/VT or components thereof), mecA alleles and dts. Overall, 39.6% of MR isolates harbored NT SCCmec elements, and ACME was more common amongst MRSE and CpA isolates. Multidrug resistance (MDR) was detected among 96.7% of isolates but they differed in the prevalence of specific macrolide, aminoglycoside and trimethoprim resistance genes amongst SE and SH isolates. Ciprofloxacin, rifampicin, chloramphenicol [fexA, cat-pC221], tetracycline [tet(K)], aminoglycosides [aadD, aphA3] and fusidic acid [fusB] resistance was significantly more common amongst CpA isolates. SE and SH isolates causing infections in Hu and CpA hosts belong predominantly to STs within a single lineage, harboring similar but variable SCCmec genes, mecA alleles and dts. Host and staphylococcal species-specific characteristics were identified in relation to antimicrobial resistance genes and phenotypes, SCCmec and ACME.

Comparative Genotypes, Staphylococcal Cassette Chromosome mec (SCCmec) Genes and Antimicrobial Resistance amongst Staphylococcus epidermidis and Staphylococcus haemolyticus Isolates from Infections in Humans and Companion Animals

PubMed Central

McManus, Brenda A.; Coleman, David C.; Deasy, Emily C.; Brennan, Gráinne I.; O’ Connell, Brian; Monecke, Stefan; Ehricht, Ralf; Leggett, Bernadette; Leonard, Nola; Shore, Anna C.

2015-01-01

This study compares the characteristics of Staphylococcus epidermidis (SE) and Staphylococcus haemolyticus (SH) isolates from epidemiologically unrelated infections in humans (Hu) (28 SE-Hu; 8 SH-Hu) and companion animals (CpA) (12 SE-CpA; 13 SH-CpA). All isolates underwent antimicrobial susceptibility testing, multilocus sequence typing and DNA microarray profiling to detect antimicrobial resistance and SCCmec-associated genes. All methicillin-resistant (MR) isolates (33/40 SE, 20/21 SH) underwent dru and mecA allele typing. Isolates were predominantly assigned to sequence types (STs) within a single clonal complex (CC2, SE, 84.8%; CC1, SH, 95.2%). SCCmec IV predominated among MRSE with ST2-MRSE-IVc common to both Hu (40.9%) and CpA (54.5%). Identical mecA alleles and nontypeable dru types (dts) were identified in one ST2-MRSE-IVc Hu and CpA isolate, however, all mecA alleles and 2/4 dts detected among 18 ST2-MRSE-IVc isolates were closely related, sharing >96.5% DNA sequence homology. Although only one ST-SCCmec type combination (ST1 with a non-typeable [NT] SCCmec NT9 [class C mec and ccrB4]) was common to four MRSH-Hu and one MRSH-CpA, all MRSH isolates were closely related based on similar STs, SCCmec genes (V/VT or components thereof), mecA alleles and dts. Overall, 39.6% of MR isolates harbored NT SCCmec elements, and ACME was more common amongst MRSE and CpA isolates. Multidrug resistance (MDR) was detected among 96.7% of isolates but they differed in the prevalence of specific macrolide, aminoglycoside and trimethoprim resistance genes amongst SE and SH isolates. Ciprofloxacin, rifampicin, chloramphenicol [fexA, cat-pC221], tetracycline [tet(K)], aminoglycosides [aadD, aphA3] and fusidic acid [fusB] resistance was significantly more common amongst CpA isolates. SE and SH isolates causing infections in Hu and CpA hosts belong predominantly to STs within a single lineage, harboring similar but variable SCCmec genes, mecA alleles and dts. Host and staphylococcal species-specific characteristics were identified in relation to antimicrobial resistance genes and phenotypes, SCCmec and ACME. PMID:26379051

Diphosphine- and CO-Induced Fragmentation of Chloride-bridged Dinuclear Complex and Cp*Ir(mu-Cl)(3)Re(CO)(3) and Attempted Synthesis of Cp*Ir(mu-Cl)(3)Mn(CO)(3): Spectroscopic Data and X-ray Diffraction Structures of the Pentamethylcyclopentadienyl Compounds [Cp*IrCl{(Z)-Ph2PCH = CHPPh2}][Cl]center dot 2CHCl(3) and Cp*Ir(CO)Cl-2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hammons, Casey; Wang, Xiaoping; Nesterov, Vladimir

2010-01-01

The confacial bioctahedral compound Cp*Ir(mu-Cl)(3)Re(CO)(3) (1) undergoes rapid fragmentation in the presence of the unsaturated diphosphine ligand (Z)-Ph2PCH = CHPPh2 to give the mononuclear compounds [Cp*IrCl {(Z)-Ph2PCH = CHPPh2}][Cl] (2) and fac-ClRe(CO)(3)[(Z)-Ph2PCH = CHPPh2] (3). 2 has been characterized by H-1 and P-31 NMR spectroscopy and X-ray diffraction analysis. 2 center dot 2CHCl(3) crystallizes in the monoclinic space group C2/c, a = 35.023 (8) angstrom, b = 10.189 (2) angstrom, c = 24.003 (6) angstrom, b = 103.340 (3), V = 8,335 (3) angstrom 3, Z = 8, and d(calc) = 1.647 Mg/m(3); R = 0.0383, R-w = 0.1135 formore » 8,178 reflections with I> 2 sigma(I). The Ir(III) center in 2 exhibits a six-coordinate geometry and displays a chelating diphosphine group. Compound 1 reacts with added CO with fragmentation to yield the known compounds Cp*Ir(CO)Cl-2 (4) and ClRe(CO)(5) (5) in near quantitative yield by IR spectroscopy. Using the protocol established by our groups for the synthesis of 1, we have explored the reaction of [Cp*IrCl2](2) with ClMn(CO)(5) as a potential route to Cp*Ir(mu-Cl)(3)Mn(CO)(3); unfortunately, 4 was the only product isolated from this reaction. The solid-state structure of 4 was determined by X-ray diffraction analysis. 4 crystallizes in the triclinic space group P-1, a = 7.4059 (4) angstrom, b = 7.8940 (4) angstrom, c = 11.8488 (7) angstrom, alpha = 80.020 (1), beta = 79.758 (1), gamma = 68.631 (1), V = 630.34 (6) angstrom(3), Z = 2, and d(calc) = 2.246 Mg/m(3); R = 0.0126, R-w = 0.0329 for 2,754 reflections with I> 2 sigma(I). The expected three-legged piano-stool geometry in 4 has been crystallographically confirmed.« less

Contemporary Management of Chronic Prostatitis/Chronic Pelvic Pain Syndrome.

PubMed

Magistro, Giuseppe; Wagenlehner, Florian M E; Grabe, Magnus; Weidner, Wolfgang; Stief, Christian G; Nickel, J Curtis

2016-02-01

Chronic prostatitis/chronic pelvic pain syndrome (CP/CPPS) is a common condition that causes severe symptoms, bother, and quality-of-life impact in the 8.2% of men who are believed to be affected. Research suggests a complex pathophysiology underlying this syndrome that is mirrored by its heterogeneous clinical presentation. Management of patients diagnosed with CP/CPPS has always been a formidable task in clinical practice. Due to its enigmatic etiology, a plethora of clinical trials failed to identify an efficient monotherapy. A comprehensive review of published randomized controlled trials (RCTs) on the treatment of CP/CPPS and practical best evidence recommendations for management. Medline and the Cochrane database were screened for RCTs on the treatment of CP/CPPS from 1998 to December 2014, using the National Institutes of Health Chronic Prostatitis Symptom Index as an objective outcome measure. Published data in concert with expert opinion were used to formulate a practical best evidence statement for the management of CP/CPPS. Twenty-eight RCTs identified were eligible for this review and presented. Trials evaluating antibiotics, α-blockers, anti-inflammatory and immune-modulating substances, hormonal agents, phytotherapeutics, neuromodulatory drugs, agents that modify bladder function, and physical treatment options failed to reveal a clear therapeutic benefit. With its multifactorial pathophysiology and its various clinical presentations, the management of CP/CPPS demands a phenotypic-directed approach addressing the individual clinical profile of each patient. Different categorization algorithms have been proposed. First studies applying the UPOINTs classification system provided promising results. Introducing three index patients with CP/CPPS, we present practical best evidence recommendations for management. Our current understanding of the pathophysiology underlying CP/CPPS resulting in this highly variable syndrome does not speak in favor of a monotherapy for management. No efficient monotherapeutic option is available. The best evidence-based management of CP/CPPS strongly suggests a multimodal therapeutic approach addressing the individual clinical phenotypic profile. Chronic prostatitis/chronic pelvic pain syndrome presents a variable syndrome. Successful management of this condition is challenging. It appears that a tailored treatment strategy addressing individual patient characteristics is more effective than one single therapy. Copyright © 2015 European Association of Urology. Published by Elsevier B.V. All rights reserved.

Molecular structures and excited states of CpM(CO)(2) (Cp = eta(5)-C(5)H(5); M = Rh, Ir) and [Cl(2)Rh(CO)(2)](-). Theoretical evidence for a competitive charge transfer mechanism.

PubMed

Hu, Zhenming; Boyd, Russell J; Nakatsuji, Hiroshi

2002-03-20

Molecular structures and excited states of CpM(CO)(2) (Cp = eta(5)-C(5)H(5); M = Rh, Ir) and [Cl(2)Rh(CO)(2)](-) complexes have been investigated using the B3LYP and the symmetry-adapted cluster (SAC)/SAC-configuration interaction (SAC-CI) theoretical methods. All the dicarbonyl complexes have singlet ground electronic states with large singlet-triplet separations. Thermal dissociations of CO from the parent dicarbonyls are energetically unfavorable. CO thermal dissociation is an activation process for [Cl(2)Rh(CO)(2)](-) while it is a repulsive potential for CpM(CO)(2). The natures of the main excited states of CpM(CO)(2) and [Cl(2)Rh(CO)(2)](-) are found to be quite different. For [Cl(2)Rh(CO)(2)](-), all the strong transitions are identified to be metal to ligand CO charge transfer (MLCT) excitations. A significant feature of the excited states of CpM(CO)(2) is that both MLCT excitation and a ligand Cp to metal and CO charge transfer excitation are strongly mixed in the higher energy states with the latter having the largest oscillator strength. A competitive charge transfer excited state has therefore been identified theoretically for CpRh(CO)(2) and CpIr(CO)(2). The wavelength dependence of the quantum efficiencies for the photoreactions of CpM(CO)(2) reported by Lees et al. can be explained by the existence of two different types of excited states. The origin of the low quantum efficiencies for the C-H/S-H bond activations of CpM(CO)(2) can be attributed to the smaller proportion of the MLCT excitation in the higher energy states.

HIV-1 gp120 neurotoxicity proximally and at a distance from the point of exposure: protection by rSV40 delivery of antioxidant enzymes.

PubMed

Louboutin, Jean-Pierre; Agrawal, Lokesh; Reyes, Beverly A S; Van Bockstaele, Elisabeth J; Strayer, David S

2009-06-01

Toxicity of HIV-1 envelope glycoprotein (gp120) for substantia nigra (SN) neurons may contribute to the Parkinsonian manifestations often seen in HIV-1-associated dementia (HAD). We studied the neurotoxicity of gp120 for dopaminergic neurons and potential neuroprotection by antioxidant gene delivery. Rats were injected stereotaxically into their caudate-putamen (CP); CP and (substantia nigra) SN neuron loss was quantified. The area of neuron loss extended several millimeters from the injection site, approximately 35% of the CP area. SN neurons, outside of this area of direct neurotoxicity, were also severely affected. Dopaminergic SN neurons (expressing tyrosine hydroxylase, TH, in the SN and dopamine transporter, DAT, in the CP) were mostly affected: intra-CP gp120 caused approximately 50% DAT+ SN neuron loss. Prior intra-CP gene delivery of Cu/Zn superoxide dismutase (SOD1) or glutathione peroxidase (GPx1) protected SN neurons from intra-CP gp120. Thus, SN dopaminergic neurons are highly sensitive to HIV-1 gp120-induced neurotoxicity, and antioxidant gene delivery, even at a distance, is protective.

Cp*Co(III) catalysts with proton-responsive ligands for carbon dioxide hydrogenation in aqueous media.

PubMed

Badiei, Yosra M; Wang, Wan-Hui; Hull, Jonathan F; Szalda, David J; Muckerman, James T; Himeda, Yuichiro; Fujita, Etsuko

2013-11-04

New water-soluble pentamethylcyclopentadienyl cobalt(III) complexes with proton-responsive 4,4'- and 6,6'-dihydroxy-2,2'-bipyridine (4DHBP and 6DHBP, respectively) ligands have been prepared and were characterized by X-ray crystallography, UV-vis and NMR spectroscopy, and mass spectrometry. These cobalt(III) complexes with proton-responsive ligands predominantly exist in their deprotonated [Cp*Co(DHBP-2H(+))(OH2)] forms with stronger electron-donating properties in neutral and basic solutions, and are active catalysts for CO2 hydrogenation in aqueous bicarbonate media at moderate temperature under a total 4-5 MPa (CO2:H2 1:1) pressure. The cobalt complexes containing 4DHBP ligands ([1-OH2](2+) and [1-Cl](+), where 1 = Cp*Co(4DHBP)) display better thermal stability and exhibit notable catalytic activity for CO2 hydrogenation to formate in contrast to the catalytically inactive nonsubstituted bpy analogues [3-OH2](2+) (3 = Cp*Co(bpy)). While the catalyst Cp*Ir(6DHBP)(OH2)(2+) in which the pendent oxyanion lowers the barrier for H2 heterolysis via proton transfer through a hydrogen-bonding network involving a water molecule is remarkably effective (ACS Catal. 2013, 3, 856-860), cobalt complexes containing 6DHBP ligands ([2-OH2](2+) and [2-Cl](+), 2 = Cp*Co(6DHBP)) exhibit lower TOF and TON for CO2 hydrogenation than those with 4DHBP. The low activity is attributed to thermal instability during the hydrogenation of CO2 as corroborated by DFT calculations.

From Structural Complexity to Structure-Property Relationships in Intermetallics: Development of Density Functional Theory-Chemical Pressure Analysis

NASA Astrophysics Data System (ADS)

Engelkemier, Joshua

The unparalleled structural diversity of intermetallic compounds provides nearly unlimited potential for the discovery and optimization of materials with useful properties, such as thermoelectricity, superconductivity, magnetism, hydrogen storage, superelasticity, and catalysis. This same diversity, however, creates challenges for understanding and controlling the unpredictable structure of intermetallic phases. Moreover, the fundamental design principles that have proven so powerful in molecular chemistry do not have simple analogues for metallic, solid state materials. One of these basic principles is the concept of atomic size effects. Especially in densely packed crystal structures where the need to fill space is in competition with the atoms' preferences for ideal interatomic distances, substitution of one element in a compound for another with similar chemical properties yet different atomic size can have dramatic effects on the ordering of the atoms (which in turn affects the electronic structure, vibrational properties, and materials properties). But because the forces that hold metallic phases together are less easily understood from a local perspective than covalent or ionic interactions in other kinds of materials, it is usually unclear whether the atoms are organized to optimize stabilizing, bonding interactions or rather forced to be close together despite repulsive, steric interactions. This dissertation details the development of a theoretical method, called Density Functional Theory-Chemical Pressure (DFT-CP) analysis, to address this issue. It works by converting the distribution of total energy density from a DFT calculation into a map of chemical pressure through a numerical approximation of the first derivative of energy with respect to voxel volume. The CP distribution is then carefully divided into contact volumes between neighboring atoms, from which it is possible to determine whether atoms are too close together (positive CP) or too far away from each other (negative CP). This technique is used in combination with the concept of structural plasticity (Berns, 2014) to demonstrate how complex intermetallic phases can be understood as a response of simpler structure types to the destabilizing buildup of CP. From this point of view, interfaces created in complex structures relieve the CP manifest in the more basic, parent structures. This is shown specifically for Ca36Sn23 relative to a hypothetical W5Si3-type Ca5Sn3 phase, LnMn xGa3 (Ln = Ho-Tm, x < 0.15) compared to unstuffed AuCu3-type LnGa3 structures, and structural derivatives of CaCu5- and HoCoGa5-type compounds. As a direct result of the technical developments necessitated by these analyses on structural complexity in intermetallics, a further connection is made in this thesis between the calculated CP schemes and the frequencies of vibrational modes in MgCu2-type CaPd2, the Cr 3Si-type superconductor Nb3Ge, and CaCu5-type CaPd5. Local chemical interactions revealed by DFT-CP analysis are used to identify structure-property relationships for the pseudogap in the phonon density of states (DOS) of CaPd2, the higher critical temperature of Nb3Ge vs. Nb3Sn, and the wide diversity of structures based on the CaCu5 type.

Protonation of metal hydrides by strong acids. Formation of an equilibrium mixture of dihydride and dihydrogen complexes from protonation of Cp{sup *}Os(CO){sub 2}H. Structural characterization of [CpW(CO){sub 2}(PMe{sub 3})(H){sub 2}]{sup +}OTf{sup -}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bullock, R.M.; Song, J.S.; Szalda, D.J.

1996-05-14

Cp{sup *}Os(CO){sub 2}H is protonated by triflic acid (HOTf) in CD{sub 2} Cl{sub 2} solution to give an equilibrium mixture (87:13) of the dihydride [Cp{sup *}Os(CO){sub 2}(H){sub 2}]{sup +}OTf{sup -} and the dihydrogen complex [Cp{sup *}Os(CO){sub 2}({eta}{sup 2}-H{sub 2})]{sup +}OTf{sup -}. The acidity of these protonated species is roughly comparable to HOTf, since only partial protonation was observed. In the absence of acid, the T{sub 1} of the hydride ligand of Cp{sup *}Os(CO){sub 2}H is 5.9 s at -80{degree}C. When all of the Cp{sup *}Os(CO){sub 2}H is protonated by excess HOTf,the T{sub l} (-80{degree}C) of the terminal hydride ligands ofmore » [Cp{sup *}Os(CO){sub 2}(H){sub 2}]{sup +}OTf{sup -} is 2.8 s, while the T{sub l} of the dihydrogen ligand of [Cp{sup *}Os(CO){sub 2}({eta}{sup 2}-H{sub 2})]{sup +} OTf{sup -} is 19 ms, (-80{degree}C). The observed T{sub l} values of the Os-H resonance of Cp{sup *}Os(CO){sub 2}H decreased significantly under conditions of partial protonation, indicating intermolecular proton transfer among [Cp{sup *}Os(CO){sub 2}({eta}{sup 2}H{sub 2})]{sup +}OTf{sup -}, [Cp{sup *}Os(CO){sub 2}(H){sub 2}]{sup +}OTf{sup -}, Cp{sup *}Os(CO){sub 2}H, and HOTf. IR spectra indicate that the two CO ligands of [Cp{sup *}Os(CO){sub 2}(H){sub 2}]{sup +} (and hence the hydrides as well) are trans to each other in the four-legged piano stool geometry. 62 refs., 6 figs., 8 tabs.« less

The mechanistic bases of the power–time relationship: muscle metabolic responses and relationships to muscle fibre type

PubMed Central

Black, Matthew I.; DiMenna, Fred J.; Blackwell, Jamie R.; Schmidt, Jakob Friis; Thompson, Christopher; Wylie, Lee J.; Mohr, Magni; Bangsbo, Jens; Krustrup, Peter; Jones, Andrew M.

2016-01-01

Key points The power‐asymptote (critical power; CP) of the hyperbolic power–time relationship for high‐intensity exercise defines a threshold between steady‐state and non‐steady‐state exercise intensities and the curvature constant (W′) indicates a fixed capacity for work >CP that is related to a loss of muscular efficiency.The present study reports novel evidence on the muscle metabolic underpinnings of CP and W′ during whole‐body exercise and their relationships to muscle fibre type.We show that the W′ is not correlated with muscle fibre type distribution and that it represents an elevated energy contribution from both oxidative and glycolytic/glycogenolytic metabolism.We show that there is a positive correlation between CP and highly oxidative type I muscle fibres and that muscle metabolic steady‐state is attainable CP.Our findings indicate a mechanistic link between the bioenergetic characteristics of muscle fibre types and the power–time relationship for high‐intensity exercise. Abstract We hypothesized that: (1) the critical power (CP) will represent a boundary separating steady‐state from non‐steady‐state muscle metabolic responses during whole‐body exercise and (2) that the CP and the curvature constant (W′) of the power–time relationship for high‐intensity exercise will be correlated with type I and type IIx muscle fibre distributions, respectively. Four men and four women performed a 3 min all‐out cycling test for the estimation of CP and constant work rate (CWR) tests slightly >CP until exhaustion (T lim), slightly CP T lim isotime to test the first hypothesis. Eleven men performed 3 min all‐out tests and donated muscle biopsies to test the second hypothesis. Below CP, muscle [PCr] [42.6 ± 7.1 vs. 49.4 ± 6.9 mmol (kg d.w.)−1], [La−] [34.8 ± 12.6 vs. 35.5 ± 13.2 mmol (kg d.w.)−1] and pH (7.11 ± 0.08 vs. 7.10 ± 0.11) remained stable between ∼12 and 24 min (P > 0.05 for all), whereas these variables changed with time >CP such that they were greater [[La−] 95.6 ± 14.1 mmol (kg d.w.)−1] and lower [[PCr] 24.2 ± 3.9 mmol (kg d.w.)−1; pH 6.84 ± 0.06] (P < 0.05) at T lim (740 ± 186 s) than during the

Interaction of DRD4 Methylation and Phthalate Metabolites Affects Continuous Performance Test Performance in ADHD.

PubMed

Kim, Johanna Inhyang; Kim, Jae-Won; Shin, Inkyung; Kim, Bung-Nyun

2018-05-01

We investigated the interaction effect between the methylation of dopamine receptor D4 (DRD4) and phthalate exposure in ADHD on continuous performance test (CPT) variables. Urine concentrations of mono-(2-ethyl-5-hydroxyhexyl) phthalate (MEHHP), mono-(2-ethyl-5-oxohexyl) phthalate (MEOHP), and mono-n-butyl phthalate (MBP) were tested. The methylation status was analyzed for CpG sites of DRD4. Multivariable linear regression models were applied to investigate the interaction effects of methylation and phthalate levels. There was a significant interaction effect of the methylation of CpG26 and CpG28 with the MEHHP level on omission errors in ADHD patients, but not in controls. The post hoc analysis revealed a significant correlation between the MEHHP concentration and omission errors in the methylated group, but not in the unmethylated group. The interaction between the methylation status of CpG sites of DRD4, particularly CpG26 and CpG28, and phthalate metabolite levels affects the attention level in ADHD patients.

Cyclodextrin inclusion complex formation and solid-state characterization of the natural antioxidants alpha-tocopherol and quercetin.

PubMed

Koontz, John L; Marcy, Joseph E; O'Keefe, Sean F; Duncan, Susan E

2009-02-25

Cyclodextrin (CD) complexation procedures are relatively simple processes, but these techniques often require very specific conditions for each individual guest molecule. Variations of the coprecipitation from aqueous solution technique were optimized for the CD complexation of the natural antioxidants alpha-tocopherol and quercetin. Solid inclusion complex products of alpha-tocopherol/beta-CD and quercetin/gamma-CD had molar ratios of 1.7:1, which were equivalent to 18.1% (w/w) alpha-tocopherol and 13.0% (w/w) quercetin. The molar reactant ratios of CD/antioxidant were optimized at 8:1 to improve the yield of complexation. The product yields of alpha-tocopherol/beta-CD and quercetin/gamma-CD complexes from their individual reactants were calculated as 24 and 21% (w/w), respectively. ATR/FT-IR, 13C CP/MAS NMR, TGA, and DSC provided evidence of antioxidant interaction with CD at the molecular level, which indicated true CD inclusion complexation in the solid state. Natural antioxidant/CD inclusion complexes may serve as novel additives in controlled-release active packaging to extend the oxidative stability of foods.

Superior vena caval pressure elevation causes pleural effusion formation in sheep.

PubMed

Allen, S J; Laine, G A; Drake, R E; Gabel, J C

1988-09-01

The effect of superior vena caval pressure (SVCP) elevation on the formation of pleural effusions (PE) was studied in sheep. Through a right thoracotomy, a Silastic cuff was placed around the superior vena cava. Catheters for monitoring SVCP and pulmonary artery pressure (PAP) were also placed. After a 1- to 3-wk recovery period, we measured the SVCP, PAP, cardiac output, and plasma protein concentration (Cp). We then elevated the SVCP to various levels from base line [5.3 +/- 2.6 (SD) mmHg] to 33 mmHg. The cardiac output, PAP, and Cp were remeasured 1-2 h and 24 h after SVCP elevation. At the end of the 24-h period, the animals were killed. The PE volume and pleural fluid protein concentration (Cpl) were measured, and the Cpl/Cp was calculated. PE generally did not occur until the SVCP was elevated above 15 mmHg. To study the effect of the thoracotomy on the subsequent pleural effusion, we studied six additional sheep in which we did not perform a thoracotomy. In these animals, the SVCP was elevated to between 5 and 28 mmHg for 24 h by use of a 16-Fr balloon catheter placed via a left external jugular vein and a right carotid-external jugular shunt. We found that the PE volume, for a given SVCP elevation, was similar to that present in sheep that received a thoracotomy. For all sheep the volume of PE was related to SVCP by the equation PE (ml) = 0.24e0.26SVCP, r = 0.85. In the sheep without a thoracotomy, Cpl/Cp rose with increasing volume of PE. Our data demonstrate that elevation of SVCP greater than 15 mmHg for 24 h results in the formation of PE. The rise in Cpl/Cp with PE volume suggests that filtration through the pleural vessels is not the major contributor to PE formation.

Endogenous and exogenous porphyrins as photosensitizers in the Hep-2 human carcinoma cell line.

PubMed

Alvarez, M G; Milanesio, M; Rivarola, V; Durantini, E; Batlle, A; Fukuda, H

2009-07-01

The photodynamic activity of three photosensitizers (PS): AL-induced PPIX, the porphyrin derivative 5-(4-trimethylammoniumphenyl)-10, 5, 20-tris (2,4,6- trimethoxyphenyl) porphyrin (CP) and the molecular dyad porphyrin-C(60) (P-C(60)), the last two incorporated into liposomal vesicles, was evaluated on Hep-2 human larynx carcinoma cell line. ALA-induced accumulation of the endogenous PS PPIX, reached saturation values between 5 and 24 h incubation time; the maximal PPIX content was 5.7 nmol/106 cells. The same intracellular level was accumulated when the cationic porphyrin CP was used, while the amount of P-C(60) attained was 1.5 nmol/106 cells. Under violet-blue exciting light, the fluorescence of PPIX and P-C(60) was found in the cytoplasm showing a granular appearance indicating lysosomal localization. CP was mainly detected as a filamentous pattern characteristic of mitochondrial localization. No dark cytotoxicity was observed using 1mM ALA, 5 microM CP and 1 microM P-C(60) after 24 h incubation. Cell morphology was analyzed using Hoechst-33258, toluidine blue staining, TUNEL assay and DNA fragmentation, 24 h after irradiation with 54 J/cm2. When photosensitized with ALA and P-C(60), chromatine condensation characteristic of apoptotic cell death was found; instead, 58 % of necrotic cells were observed with CP. The results show that in the Hep-2 cells, of the three PS analyzed, the molecular dyad P-C(60) was more efficient than CP and PPIX, and confirm that PDT can induce different mechanisms of cell death depending on the PS and the irradiation dose.

Chemoprotection by D-methionine against cisplatin-induced side-effects: insight from in vitro studies using human plasma.

PubMed

Sooriyaarachchi, Melani; White, Wade M; Narendran, Aru; Gailer, Jürgen

2014-03-01

Animal studies have shown that the nephrotoxicity and ototoxicity of the anti-cancer drug cisplatin (CP) can be ameliorated by the co-administration with D-methionine. The molecular mechanisms of this activity, however, are not well understood. Since CP is intravenously administered, the underlying chemistry may involve the interaction of CP-derived Pt-species with D-methionine in the bloodstream. Our previous studies have shown that the chemoprotective agents N-acetyl-l-cysteine and sodium thiosulfate modulate the metabolism of CP in human plasma in vitro, albeit in a different manner. Using a metallomics approach, we show that the incubation of human plasma with D-methionine and CP (molar ratio of 20 : 1) leads to the formation of a Pt-D-methionine complex independent of the order of addition. These results were corroborated by analogous experiments that were carried out using PBS-buffer instead of plasma. In addition, CP and D-methionine were added simultaneously to PBS-buffer and samples were analyzed at certain time intervals by the same metallomics method and LC-ESI-MS over a ∼21 h time period. Whereas the intermediate [Pt(NH3)Cl(D-methionine)](+) species was detected between 1-4 h, only the terminal [Pt(D-methionine)2](+) complex was present 21 h later. Combined, these studies demonstrate that in plasma and at the 20 : 1 D-methionine : CP molar ratio, an early CP hydrolysis product reacts with D-methionine to form a 1 : 1 complex that is followed by the formation of a 2 : 1 compound at a later time point. The formation of these Pt-D-methionine species may therefore play an important role in the processes by which D-methionine protects mammalian organisms against CP-induced toxicities.

Understanding the factors affecting the activation of alkane by Cp′Rh(CO)2 (Cp′ = Cp or Cp*)

PubMed Central

George, Michael W.; Hall, Michael B.; Jina, Omar S.; Portius, Peter; Sun, Xue-Zhong; Towrie, Michael; Wu, Hong; Yang, Xinzheng; Zarić, Snežana D.

2010-01-01

Fast time-resolved infrared spectroscopic measurements have allowed precise determination of the rates of activation of alkanes by Cp′Rh(CO) (Cp′ = η5-C5H5 or η5-C5Me5). We have monitored the kinetics of C─H activation in solution at room temperature and determined how the change in rate of oxidative cleavage varies from methane to decane. The lifetime of CpRh(CO)(alkane) shows a nearly linear behavior with respect to the length of the alkane chain, whereas the related Cp*Rh(CO)(alkane) has clear oscillatory behavior upon changing the alkane. Coupled cluster and density functional theory calculations on these complexes, transition states, and intermediates provide the insight into the mechanism and barriers in order to develop a kinetic simulation of the experimental results. The observed behavior is a subtle interplay between the rates of activation and migration. Unexpectedly, the calculations predict that the most rapid process in these Cp′Rh(CO)(alkane) systems is the 1,3-migration along the alkane chain. The linear behavior in the observed lifetime of CpRh(CO)(alkane) results from a mechanism in which the next most rapid process is the activation of primary C─H bonds (─CH3 groups), while the third key step in this system is 1,2-migration with a slightly slower rate. The oscillatory behavior in the lifetime of Cp*Rh(CO)(alkane) with respect to the alkane’s chain length follows from subtle interplay between more rapid migrations and less rapid primary C─H activation, with respect to CpRh(CO)(alkane), especially when the CH3 group is near a gauche turn. This interplay results in the activation being controlled by the percentage of alkane conformers. PMID:21048088

Texas Red transport across rat and dogfish shark (Squalus acanthias) choroid plexus

PubMed Central

Reichel, Valeska; Miller, David S.; Fricker, Gert

2008-01-01

Confocal microscopy and image analysis were used to compare driving forces, specificity, and regulation of transport of the fluorescent organic anion, Texas Red (sulforhodamine 101 free acid; TR), in lateral choroid plexus (CP) isolated from rat and an evolutionarily ancient vertebrate, dogfish shark (Squalus acanthias). CP from both species exhibited concentrative, specific, and metabolism-dependent TR transport from bath to subepithelial/vascular space; at steady state, TR accumulation in vascular/subepithelial space was substantially higher than in epithelial cells. In rat CP, steady-state TR accumulation in subepithelial/vascular spaces was reduced by Na+-replacement, but was not affected by a 10-fold increase in buffer K+. In shark CP, Na+-replacement did not alter TR accumulation in either tissue compartment; subepithelial/vascular space levels of TR were reduced in high-K+ medium. In both species, steady-state TR accumulation was not affected by p-aminohippurate or leukotriene C4, suggesting that neither organic anion transporters (SLC22A family) nor multidrug resistance-associated proteins (ABCC family) contributed. In rat CP, digoxin was without effect, indicating that organic anion transporting polypeptide isoform 2 was not involved. Several organic anions reduced cellular and subepithelial/vascular space TR accumulation in both tissues, including estrone sulfate, taurocholate, and the Mrp1 inhibitor MK571. In rat CP, TR accumulation in subepithelial/vascular spaces increased with PKA activation (forskolin), but was not affected by PKC activation (phorbol ester). In shark, neither PKA nor PKC activation specifically affected TR transport. Thus, rat and dogfish shark CP transport TR but do so using different basic mechanisms that respond to different regulatory signals. PMID:18650317

The Safety of Intravenous Cyclophosphamide in the Treatment of Rheumatic Diseases.

PubMed

Woytala, Patryk J; Morgiel, Ewa; Łuczak, Anna; Czesak-Woytala, Katarzyna; Wiland, Piotr

2016-01-01

The therapeutic effects of cyclophosphamide (CP) in the treatment of systemic rheumatic diseases are related to its immune suppressive activity. However effective, the application of CP is restricted due to multiple adverse effects. This retrospective study was conducted to determine the frequency of adverse effects attributed to CP toxicity. The study involved 65 patients (17 male; 48 female) receiving intravenous CP between October 2007 and December 2010. The mean age at onset was 51.2 years (range 19-77 years). The most common diagnoses were systemic sclerosis (20), systemic lupus erythematosus (13) and vasculitis (13). The indications for treatment with CP were interstitial lung disease in the course of systemic diseases (33), vasculitis (24), glomerulonephritis (5) and changes in the central nervous system (3). The patients were administered 400-1000 mg CP in intravenous infusions at 2-16 week intervals, with the addition of sodium 2-sulfanylethanesulfonate (mesna) before and after each pulse. Out of 65 patients 40 (60%) reported adverse effects: infections in 24 (37%), nausea in 19 (29%), vomiting in 11 (17%), abdominal pain in 7 (11%) and pancytopenia in one, leading to cessation of the therapy. No association was found between the frequency of side effects and the treatment duration (p = 0.632), age (p = 0.852), diagnosis (p = 0.171) or nominal dose (p = 0.321). As knowledge about CP continues to increase, this medication remains a safe way to treat many rheumatic diseases.

Translation of near infrared brain imaging to assess children with cerebral palsy

NASA Astrophysics Data System (ADS)

Alexandrakis, George; Khan, Bilal; Tian, Fenghua; Asanani, Nayan; Behbehani, Khosrow; Delgado, Mauricio R.; Liu, Hanli

2009-02-01

Cerebral palsy (CP) is the most common motor disorder of central origin in childhood and affects at least 2 children per 1000 live births every year. Neuroimaging techniques are needed to study neuroplastic rearrangements in the human brain in vivo as a result of CP. Unfortunately, accurate imaging from currently available techniques often requires the patients' complete body confinement, steadiness and minimal noise for a long period of time, which limits the success rate to less than 50% for normal children and worse for CP-affected ones. In this work we show that functional near infrared (fNIR) imaging is robust to motion artifacts and has excellent potential as a sensitive diagnostic tool for this motor disorder. We have analyzed data from pediatric normal and CP patients performing finger-tapping and handwaving motor cortex activation tasks. From these analyses we have identified both spatial and temporal metrics of NIR-based motor cortex activation patterns that can clearly distinguish between normal and CP patients. We also present data from additional patients where signal processing methods are applied to filter out concurrently recorded hemodynamic signals due to breathing and cardiac pulsation. It is shown that filtering can substantially improve the quality of activation data, thus enabling more accurate comparison of activation patterns between normal and CP-affected children.

Comparison of sublingual tablets with nitroglycerin complexed with beta-cyclodextrin or titrated with crosspovidone--technological approach.

PubMed

Centkowska, Katarzyna; Sznitowska, Małgorzata

2008-01-01

Fast disintegrating sublingual tablets containing nitroglycerin either complexed with beta-cyclodextrin (NTG-CD) or titrated with crosspovidone (NTG-CP) were prepared using Starch 1500 or StarLac as disintegrants. Regarding disintegration time and stability of the active substance Starch 1500 was more appropriate for NTG-CD while for NTG-CP StarLac was suitable. Stability of NTG was better in NTG-CD tablets than in NTG-CP tablets, however, within 12 months of storage at 25 degrees C the loss of NTG in all formulations was still greater than 10%.

ULTRAFINE CARBON PARTICLE (UFCP) INHALATION AFFECTS CARDIOVASCULAR PERFORMANCE IN HYPERTENSIVE RATS (SHR)

EPA Science Inventory

Inhaled UfCP affect cardiovascular performance in healthy rats (Harder et al. Inhal Toxicol 2005; 17:29-42) without apparent pulmonary damage. To assess whether geriatric cardiovascular compromised rats are more susceptible to UfCP effects, male adult (6months) and geriatric (13m...

cpSRP43 Is a Novel Chaperone Specific for Light-harvesting Chlorophyll a,b-binding Proteins*

PubMed Central

Falk, Sebastian; Sinning, Irmgard

2010-01-01

The biosynthesis of most membrane proteins is directly coupled to membrane insertion, and therefore, molecular chaperones are not required. The light-harvesting chlorophyll a,b-binding proteins (LHCPs) present a prominent exception as they are synthesized in the cytoplasm, and after import into the chloroplast, they are targeted and inserted into the thylakoid membrane. Upon arrival in the stroma, LHCPs form a soluble transit complex with the chloroplast signal recognition particle (cpSRP) consisting of an SRP54 homolog and the unique cpSRP43 composed of three chromodomains and four ankyrin repeats. Here we describe that cpSRP43 alone prevents aggregation of LHCP by formation of a complex with nanomolar affinity, whereas cpSRP54 is not required for this chaperone activity. Other stromal chaperones like trigger factor cannot replace cpSRP43, which implies that LHCPs require a specific chaperone. Although cpSRP43 does not have an ATPase activity, it can dissolve aggregates of LHCPs similar to chaperones of the Hsp104/ClpB family. We show that the LHCP-cpSRP43 interaction is predominantly hydrophobic but strictly depends on an intact DPLG motif between the second and third transmembrane region. The cpSRP43 ankyrin repeats that provide the binding site for the DPLG motif are sufficient for the chaperone function, whereas the chromodomains are dispensable. Taken together, we define cpSRP43 as a highly specific chaperone for LHCPs in addition to its established function as a targeting factor for this family of membrane proteins. PMID:20498370

The mCpG-binding domain of human MBD3 does not bind to mCpG but interacts with NuRD/Mi2 components HDAC1 and MTA2.

PubMed

Saito, Motoki; Ishikawa, Fuyuki

2002-09-20

Although mammalian MBD3 contains the mCpG-binding domain (MBD) and is highly homologous with the authentic mCpG-binding protein MBD2, it was reported that the protein does not bind to mCpG specifically. Using recombinant human wild type and mutant MBD3 proteins, we demonstrated that atypical amino acids found in MBD3 MBD, namely, His-30 and Phe-34, are responsible for the inability of MBD3 to bind to mCpG. Interestingly, although H30K/F34Y MBD3 mutant protein binds to mCpG efficiently in vitro, it was not localized at the mCpG-rich pericentromeric regions in mouse cells. We also showed that Y34F MBD2b MBD, which possesses not the mCpG-specific DNA-binding activity but the nonspecific DNA-binding activity, was localized at the pericentromeric regions. These results suggested that the mCpG-specific DNA-binding activity is largely dispensable, and another factor(s) is required for the localization of MBD proteins in vivo. MBD3 was identified as a component of the NuRD/Mi2 complex that shows chromatin remodeling and histone deacetylase activities. We demonstrated that MBD3 MBD is necessary and sufficient for binding to HDAC1 and MTA2, two components of the NuRD/Mi2 complex. It was therefore suggested that mCpG-binding-defective MBD3 has evolutionarily conserved its MBD because of the secondary role played by the MBD in protein-protein interactions.

Activation of the Early B-Cell-Specific mb-1 (Ig-α) Gene by Pax-5 Is Dependent on an Unmethylated Ets Binding Site

PubMed Central

Maier, Holly; Colbert, Jeff; Fitzsimmons, Daniel; Clark, Dawn R.; Hagman, James

2003-01-01

Methylation of cytosine in CpG dinucleotides promotes transcriptional repression in mammals by blocking transcription factor binding and recruiting methyl-binding proteins that initiate chromatin remodeling. Here, we use a novel cell-based system to show that retrovirally expressed Pax-5 protein activates endogenous early B-cell-specific mb-1 genes in plasmacytoma cells, but only when the promoter is hypomethylated. CpG methylation does not directly affect binding of the promoter by Pax-5. Instead, methylation of an adjacent CpG interferes with assembly of ternary complexes comprising Pax-5 and Ets proteins. In electrophoretic mobility shift assays, recruitment of Ets-1 is blocked by methylation of the Ets site (5′CCGGAG) on the antisense strand. In transfection assays, selective methylation of a single CpG within the Pax-5-dependent Ets site greatly reduces mb-1 promoter activity. Prior demethylation of the endogenous mb-1 promoter is required for its activation by Pax-5 in transduced cells. Although B-lineage cells have only unmethylated mb-1 genes and do not modulate methylation of the mb-1 promoter during development, other tissues feature high percentages of methylated alleles. Together, these studies demonstrate a novel DNA methylation-dependent mechanism for regulating transcriptional activity through the inhibition of DNA-dependent protein-protein interactions. PMID:12612069

A rare male patient with classic Rett syndrome caused by MeCP2_e1 mutation.

PubMed

Tokaji, Narumi; Ito, Hiromichi; Kohmoto, Tomohiro; Naruto, Takuya; Takahashi, Rizu; Goji, Aya; Mori, Tatsuo; Toda, Yoshihiro; Saito, Masako; Tange, Shoichiro; Masuda, Kiyoshi; Kagami, Shoji; Imoto, Issei

2018-03-01

Rett syndrome (RTT) is a severe neurodevelopmental disorder typically affecting females. It is mainly caused by loss-of-function mutations that affect the coding sequence of exon 3 or 4 of methyl-CpG-binding protein 2 (MECP2). Severe neonatal encephalopathy resulting in death before the age of 2 years is the most common phenotype observed in males affected by a pathogenic MECP2 variant. Mutations in MECP2 exon 1 affecting the MeCP2_e1 isoform are relatively rare causes of RTT in females, and only one case of a male patient with MECP2-related severe neonatal encephalopathy caused by a mutation in MECP2 exon 1 has been reported. This is the first reported case of a male with classic RTT caused by a 5-bp duplication in the open-reading frame of MECP2 exon 1 (NM_001110792.1:c.23_27dup) that introduced a premature stop codon [p.(Ser10Argfs*36)] in the MeCP2_e1 isoform, which has been reported in one female patient with classic RTT. Therefore, both males and females displaying at least some type of MeCP2_e1 mutation may exhibit the classic RTT phenotype. © 2018 Wiley Periodicals, Inc.

Process for functionalizing alkanes

DOEpatents

Bergman, Robert G.; Janowicz, Andrew H.; Periana, Roy A.

1988-01-01

Process for functionalizing saturated hydrocarbons comprising: (a) reacting said saturated hydrocarbons of the formula: R.sub.1 H wherein H represents a hydrogen atom; and R.sub.1 represents a saturated hydrocarbon radical, with a metal complex of the formula: CpRh[P(R.sub.2).sub.3 ]H.sub.2 wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical; Rh represents a rhodium atom; P represents a phosphorus atom; R.sub.2 represents a hydrocarbon radical; H represents a hydrogen atom, in the presence of ultraviolet radiation to form a hydridoalkyl complex of the formula: CpRh[P(R.sub.2).sub.3 ](R.sub.1)H (b) reacting said hydridoalkyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X''X'''X'''' or CHX'X''X''' wherein X', X'', X'", X"" represent halogens selected from bromine, iodine or chlorine atom, at a temperature in the range of about -60.degree. to -17.degree. C. to form the corresponding haloalkyl complex of step (a) having the formula: CpRhPMe.sub.3 RX; and, (c) reacting said haloalkyl complex formed in (b) with halogen (X.sub.2) at a temperature in the range of about -60.degree. to 25.degree. C. (i.e., ambient) to form a functional haloalkyl compound.

Effects of Static or Oscillating Dietary Crude Protein Levels on Fermentation Dynamics of Beef Cattle Diets Using a Dual-Flow Continuous Culture System

PubMed Central

Benedeti, Pedro Del Bianco; da Silva, Lorrayny Galoro; de Paula, Eduardo Marostegan; Monteiro, Hugo Fernando; Shenkoru, Teshome; Santos, Stefanie Alvarenga; Poulson, Simon Roger

2016-01-01

The objective of this study was to evaluate the effects of increasing dietary crude protein (CP) levels and also comparing the effects of static versus oscillating dietary CP on ruminal nutrient digestibility, ruminal fermentation, nitrogen (N) metabolism, and microbial efficiency in beef cattle diets using a dual-flow continuous culture system. Eight fermenters (1,223 ± 21 mL) were used in a replicated 4 x 4 Latin square design with periods lasting 12 d each (8 d for adaptation and 4 d for sampling). Dietary treatments were: 1) 10% CP, 2) 12% CP, 3) 14% CP, and 4) 10 and 14% CP diets oscillating at 48-h intervals. Experimental diets consisted of 50% orchard hay and 50% concentrate. Fermenters were fed 72 g/d and solid and liquid dilution rates were adjusted to 5.5 and 11%/h, respectively. Data were analyzed using the MIXED procedure in SAS with α = 0.05. Apparent and true ruminal digestibilities of dry matter and organic matter were not affected (P > 0.05) by increasing dietary CP, nor by oscillating dietary CP. Total volatile fatty acids concentration and molar proportions of acetate, propionate, butyrate, valerate, iso-butyrate and iso-valerate were not affected (P > 0.05) by increasing or oscillating dietary CP. Ruminal NH3-N concentration increased linearly (P < 0.01) in response to increasing dietary CP. Total N, non-ammonia N, and rumen undegraded protein flows did not differ among treatments or between oscillating dietary CP and static 12% CP. Microbial N and NH3-N flows and microbial efficiency did not differ when comparing oscillating versus static CP (P > 0.05). However, there was a quadratic effect (P < 0.05) for these variables when dietary CP was increased. These results indicate that either ruminal microorganisms do not respond to oscillating CP levels or are capable of coping with 48-h periods of undernourishment. PMID:28036405

Synthesis, characterization and biological evaluation of a (67)Ga-labeled (η(6)-Tyr)Ru(η(5)-Cp) peptide complex with the HAV motif.

PubMed

Bihari, Zsolt; Vultos, Filipe; Fernandes, Célia; Gano, Lurdes; Santos, Isabel; Correia, João D G; Buglyó, Péter

2016-07-01

Heterobimetallic complexes with the evolutionary, well-preserved, histidyl-alanyl-valinyl (HAV) sequence for cadherin targeting, an organometallic Ru core with anticancer activity and a radioactive moiety for imaging may hold potential as theranostic agents for cancer. Visible-light irradiation of the HAVAY-NH2 pentapeptide in the presence of [(η(5)-Cp)Ru(η(6)-naphthalene)](+) resulted in the formation of a full sandwich type complex, (η(6)-Tyr-RuCp)-HAVAY-NH2 in aqueous solution, where the metal ion is connected to the Tyr (Y) unit of the peptide. Conjugation of this complex to 2,2'-(7-(1-carboxy-4-((4-isothiocyanatobenzyl)amino)-4-oxobutyl)-1,4,7-triazonane-1,4-diyl)diacetic acid (NODA-GA) and subsequent metalation of the resulting product with stable ((nat)Ga) and radioactive ((67)Ga) isotope yielded (nat)Ga/(67)Ga-NODA-GA-[(η(6)-Tyr-RuCp)-HAVAY-NH2]. The non-radioactive compounds were characterized by NMR spectroscopy and Mass Spectrometry. The cellular uptake and cytotoxicity of the radioactive and non-radioactive complexes, respectively, were evaluated in various human cancer cell lines characterized by different levels of N- or E-cadherins expression. Results from these studies indicate moderate cellular uptake of the radioactive complexes. However, the inhibition of the cell proliferation was not relevant. Copyright © 2016 Elsevier Inc. All rights reserved.

Hydridomethyl iridium complex

DOEpatents

Bergman, Robert G.; Buchanan, J. Michael; Stryker, Jeffrey M.; Wax, Michael J.

1989-01-01

A process for functionalizing methane comprising: (a) reacting methane with a hydridoalkyl metal complex of the formula: CpIr[P(R.sub.1).sub.3 ]H(R.sub.2) wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical having from 1 to 5 carbon atoms; Ir represents an iridium atom; P represents a phosphorus atom; R.sub.1 represents an alkyl group; R.sub.2 represents an alkyl group having at least two carbon atoms; and H represents a hydrogen atom, in the presence of a liquid alkane R.sub.3 H having at least three carbon atoms to form a hydridomethyl complex of the formula: CpIr[P(R.sub.1).sub.3 ]HMe where Me represents a methyl radical. (b) reacting said hydridomethyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X"X'"X"" or CHX'X"X'"; wherein X', X", X"', and X"" represent halogens selected from bromine, iodine and chlorine, to halomethyl complex of step (a) having the formula: CpIr[P(R.sub.1).sub.3 ]MeX: (c) reacting said halomethyl complex with a mercuric halide of the formula HgX.sub.2 to form a methyl mercuric halide of the formula HgMeX; and (d) reacting said methyl mercuric halide with a molecular halogen of the formula X.sub.2 to form methyl halide.

RECOVERY ACT - Thylakoid Assembly and Folded Protein Transport by the Tat Pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dabney-Smith, Carole

Assembly of functional photosystems complete with necessary intrinsic (membrane-bound) and extrinsic proteins requires the function of at least 3 protein transport pathways in thylakoid membranes. Our research focuses on one of those pathways, a unique and essential protein transport pathway found in the chloroplasts of plants, bacteria, and some archaebacteria, the Twin arginine translocation (Tat) system. The chloroplast Tat (cpTat) system is thought to be responsible for the proper location of ~50% of thylakoid lumen proteins, several of which are necessary for proper photosystem assembly, maintenance, and function. Specifically, cpTat systems are unique because they transport fully folded and assembledmore » proteins across ion tight membranes using only three membrane components, Tha4, Hcf106, and cpTatC, and the protonmotive force generated by photosynthesis. Despite the importance of the cpTat system in plants, the mechanism of transport of a folded precursor is not well known. Our long-term goal is to investigate the role protein transport systems have on organelle biogenesis, particularly the assembly of membrane protein complexes in thylakoids of chloroplasts. The objective of this proposal is to correlate structural changes in the membrane-bound cpTat component, Tha4, to the mechanism of translocation of folded-precursor substrates across the membrane bilayer by using a cysteine accessibility and crosslinking approach. Our central hypothesis is that the precursor passes through a proteinaceous pore of assembled Tha4 protomers that have undergone a conformational or topological change in response to transport. This research is predicated upon the observations that Tha4 exists in molar excess in the membrane relative to the other cpTat components; its regulated assembly to the precursor-bound receptor; and our data showing oligomerization of Tha4 into very large complexes in response to transport. Our rationale for these studies is that understanding cpTat system mechanism in chloroplasts will lead to a better understanding of the biogenesis of photosynthetic membranes potentially providing a means to engineer photosynthetic complexes into synthetic membranes for energy production. We are especially well prepared to undertake this project because we have developed a novel functional replacement assay, which was used to demonstrate a correlation of Tha4 oligomerization to transport. Thylakoids of plant chloroplasts provide a very robust, reliable assay to gain mechanistic detail about cpTat systems, providing most of the biochemical analyses to date. We plan to test our central hypothesis and accomplish the overall objective of this proposal by (1) Identifying the cpTat component(s) that interact with the mature domain of precursor during transport, (2) Determining the organization of the cpTat translocon, and (3) Comparing Tha4 topology in thylakoids during active transport and at rest. The proposed studies are innovative due to our ability to correlate structural changes in cpTat protein complexes during the transport of precursor. At the completion of this project, we expect to know the cpTat component(s) that interacts directly with the mature domain of the precursor, important because it is not known which components comprise the pore for passage of the mature domain. We also expect to know the arrangement of the components in the cpTat transport complex through direct interaction between Tha4 and the other CpTat components, a key point to establishing the mechanism of translocation. Lastly, we expect to correlate topological changes of Tha4 with precursor transport, key to establishing Tha4's role in the transport process. The successful completion of these studies is expected to have an important impact in understanding chloroplast biogenesis and assembly of photosynthetic complexes in plants and photosynthetic bacteria.« less

Cyclopentadienylniobium and -molybdenum phosphorodithioate complexes. X-ray crystal structures of CpNbCl sub 3 (S sub 2 P(OPr sup i ) sub 2 ), CpNbCl(. mu. -Cl) sub 2 Nb(S sub 2 P(OPr sup i ) sub 2 )Cp, and cis-Cp prime Mo(CO) sub 2 (S sub 2 P(OPr sup i ) sub 2 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woodward, S.; Riaz, U.; Curtis, M.D.

1990-10-01

Reaction of CpNbCl{sub 4} (Cp = {eta}-C{sub 5}H{sub 5}) with (Pr{sup i}O){sub 2}P(S)(SH) in the presence of NEt{sub 3} yields CpNbCl{sub 3}(S{sub 2}P(S{sub 2}Pr{sup i}){sub 2}) (1). Reduction of 1 with Na/Hg affords the Nb-Nb-bonded complex CpNbCl({mu}-Cl){sub 2}Nb(S{sub 2}P(OR){sub 2})Cp (2). In refluxing toluene, (Pr{sup i}O){sub 2}P(S)(SH) with (Cp{prime}Mo(CO){sub 3}){sub 2} (Cp{prime} = {eta}-C{sub 5}H{sub 4}Me) gives cis-Cp{prime}Mo(CO){sub 2}(S{sub 2}P(OPr{sup i}){sub 2}) (3). Oxidation of 3 with I{sub 2} affords Cp{prime}MoI{sub 2}(CO)(S{sub 2}P(OPr{sup i}){sub 2}) (4). The crystal structures of 1-3 are compared. For 1, triclinic, P{bar 1}, a = 7.122 (3) {angstrom}, b = 11.365 (4) {angstrom}, c =more » 12.532 (4) {angstrom}, {alpha} = 77.38 (3){degree}, {beta} = 89.08 (3){degree}, {gamma} = 72.87 (3){degree}, V = 944.5 (8) {angstrom}{sup 3}. For 2, triclinic, P{bar 1}, a = 7.251 (3) {angstrom}, b = 12.386 (5) {angstrom}, c = 13.988 (5) {angstrom}, {alpha} = 102.66 (3){degree}, {beta} = 103.56 (3){degree}, {gamma} = 94.66 (3){degree}, V = 1180.0 (8) {angstrom}{sup 3}, Z = 2. For 3, orthorhombic, Pbca, a = 12.703 (3) {angstrom}, b = 16.707 (4) {angstrom}, c = 18.398 (4) {angstrom}, V = 3904.4 (17) {angstrom}{sup 3}, Z = 8.« less

A structural study of [CpM(CO)3H] (M = Cr, Mo and W) by single-crystal X-ray diffraction and DFT calculations: sterically crowded yet surprisingly flexible molecules.

PubMed

Burchell, Richard P L; Sirsch, Peter; Decken, Andreas; McGrady, G Sean

2009-08-14

The single-crystal X-ray structures of the complexes [CpCr(CO)3H] 1, [CpMo(CO)3H] 2 and [CpW(CO)3H] 3 are reported. The results indicate that 1 adopts a structure close to a distorted three-legged piano stool geometry, whereas a conventional four-legged piano stool arrangement is observed for 2 and 3. Further insight into the equilibrium geometries and potential energy surfaces of all three complexes was obtained by DFT calculations. These show that in the gas phase complex 1 also prefers a geometry close to a four-legged piano stool in line with its heavier congeners, and implying strong packing forces at work for 1 in the solid state. Comparison with their isolelectronic group 7 tricarbonyl counterparts [CpM(CO)3] (M = Mn 4 and Re 5) illustrates that 1, 2 and 3 are sterically crowded complexes. However, a surprisingly soft bending potential is evident for the M-H moiety, whose order (1 approximately = 2 < 3) correlates with the M-H bond strength rather than with the degree of congestion at the metal centre, indicating electronic rather than steric control of the potential. The calculations also reveal cooperative motions of the hydride and carbonyl ligands in the M(CO)3H unit, which allow the M-H moiety to move freely, in spite of the closeness of the four basal ligands, helping to explain the surprising flexibility of the crowded coordination sphere observed for this family of high CN complexes.

Arsenic removal from water by coupling photocatalysis and complexation-ultrafiltration processes: A preliminary study.

PubMed

Molinari, R; Argurio, P

2017-02-01

Inorganic As removal from contaminated water has been studied by off-line coupling of photocatalysis and complexation-ultrafiltration (CP-UF), showing that this combination permits to obtain a quite complete arsenic removal from the treated water. Two commercial polymers, poly(dimethylamine-coepichlorohydrin-coethylenediamine) (PDEHED) and poly(diallyl dimethyl amnmonium chloride) (PolyDADMAC) have been tested in the CP-UF process. The operating conditions (pH and polymer/As weight ratio) for As(V) complexation were determined finding values of 7.5/20 and 9.2/30 for PDEHED and polyDADMAC, respectively. The UF tests were performed by continuous diafiltration and diafiltration with volume reduction modes. The latter method permits to save the volume of washing solution during polymer regeneration. As(III) was not complexed, operating under the As(V) complexation conditions, thus a pre-oxidation step by using the photocatalytic approach was carried out to remove As(III) species. As(III) conversion to As(V) was evaluated by As speciation by using the CP-UF process for analytical purposes. Photocatalytic oxidation was successfully performed under UV radiation by using TiO 2 (0.05 mg L -1 ), O 2 and pH = 9. The oxidation was very fast during the first 10 min following a zero order kinetics (k = 0.83 mg L -1  min -1 ) and reaching 90% As(III) oxidation. A conceptual scheme coupling photocatalysis and CP-UF and some criteria to operate the CP-UF process, useful to address it towards application, are reported. Copyright © 2016 Elsevier Ltd. All rights reserved.

Does smoking affect gingival crevicular fluid LL-37 levels following non-surgical periodontal treatment in chronic periodontitis?

PubMed

Türkoğlu, Oya; Eren, Gülnihal; Emingil, Gülnur; Azarsız, Elif; Kutukculer, Necil; Atilla, Gül

2016-01-01

LL-37 contributes to maintaining the balance between health and disease. Smoking is a risk factor for periodontitis that impairs neutrophil functions. The aim of the present study was to comparatively evaluate gingival crevicular fluid (GCF) LL-37 levels in smoker and non-smoker chronic periodontitis (CP) patients and controls, as well as the effect of non-surgical periodontal treatment on GCF LL-37 levels. Thirty-one CP patients (16 smokers, 15 non-smokers) and thirty-one controls (16 smokers, 15 non-smokers) were included in the study. CP patients received non-surgical treatment. GCF LL-37 levels and periodontal parameters were assessed at baseline, 1 and 3 months after completion of non-surgical periodontal treatment. GCF LL-37 levels were analyzed by ELISA. No significant difference was observed in GCF LL-37 levels between smoker and non-smoker controls (p>0.05). Smoker CP group had significantly lower GCF LL-37 level than non-smoker CP group at baseline (p<0.05). GCF LL-37 levels significantly decreased in non-smoker CP group at first week, 1 and 3 months after completion of non-surgical periodontal treatment (p<0.05) although no significant decrease in GCF LL-37 levels was observed in smoker CP group (p>0.05). Periodontal parameters were correlated with GCF LL-37 levels in non-smoker CP group (p<0.05), but not in smoker CP group (p>0.05). GCF LL-37 levels do not seem to be affected from smoking in periodontal health. However, smoking might have a suppressive effect on GCF LL-37 levels in CP. Non-surgical treatment is effective in decreasing GCF LL-37 levels in non-smoker CP patients but not in smokers with CP. Copyright © 2015. Published by Elsevier Ltd.

SU94. Allele-Specific and Trauma-Related Epigenetic Changes in the FKBP5 Gene: Differences Between Psychotic Patients and Healthy Controls

PubMed Central

Mihaljevic, Marina; Franic, Dusica; Soldatovic, Ivan; Andric, Sanja; Mirjanic, Tijana; Novakovic, Ivana; Adzic, Miroslav; Maric, Nadja

2017-01-01

Abstract Background: Hypothalamic-pituitary-adrenal (HPA) axis dysregulation is a proposed etiological mechanism of psychosis. Recent studies highlighted impact of the FKBP5 gene and its functional variant rs1360780, which risk (T) allele affects the activity of HPA axis following stress exposure, on psychotic patients exposed to early trauma (1). Additionally, risk allele and trauma dependent FKBP5 demethylation in intron 7 was observed in traumatized individuals (2). Thus, the purpose of this pilot study was to investigate influence of the risk allele and trauma on FKBP5 DNA methylation levels at intron 7 in psychotic patients and to compare it with healthy individuals. Methods: The sample consisted of 24 psychosis spectrum patients and 24 controls matched by age and gender. All participants were genotyped for rs1360780 and divided into 2 groups depending on the presence of the risk allele (risk and nonrisk group). DNA methylation levels at 3 CpG sites (CpG1, CpG2, and CpG3) in intron 7 were analyzed by Sanger sequencing. Early-life adversities were measured by Childhood Trauma Questionnaire. Pearson correlation and t test were performed as appropriate. Results: Analyses revealed decreased FKBP5 methylation at targeted CpG sites and averaged methylation level (AML) at intron 7 in patients compared to controls (P = .026, P = .017, P = .027, and P = .003, respectively). Decreased AML and methylation at CpG3 were observed comparing risk and nonrisk patients’ groups (P = .018 and P = .016, respectively). Additionally, decreased methylation was found in risk patients’ group compared to risk controls’ group. No differences were found comparing nonrisk groups. Furthermore, strong negative associations between trauma and methylation at CpG3 and AML were observed only in risk controls’ group (r = −0.707, P = .007; r = −0.741, P = .004, respectively). Conclusion: Our preliminary results revealed allele-specific epigenetic changes of the FKBP5 gene in psychotic patients, which is in line with previous reports in traumatized individuals. Trauma-related demethylation in risk controls’ group supports the hypothesis that psychotic and stress-related conditions could share common neurobiological underlying mechanism, such as HPA axis dysregulation, particularly in individuals with genetic predisposition for altered stress response. References 1.Daskalakis NP, Binder EB. Schizophrenia in the spectrum of gene-stress interactions: the FKBP5 example. Schizophr Bull. 2015;41:323–329. 2.Klengel T, Mehta D, Anacker C et al. Allele-specific FKBP5 DNA demethylation mediates gene-childhood trauma interactions. Nat Neurosci. 2013;16:33–41.

Proton Order-Disorder Phenomena in a Hydrogen-Bonded Rhodium-η(5)-Semiquinone Complex: A Possible Dielectric Response Mechanism.

PubMed

Mitsumi, Minoru; Ezaki, Kazunari; Komatsu, Yuuki; Toriumi, Koshiro; Miyatou, Tatsuya; Mizuno, Motohiro; Azuma, Nobuaki; Miyazaki, Yuji; Nakano, Motohiro; Kitagawa, Yasutaka; Hanashima, Takayasu; Kiyanagi, Ryoji; Ohhara, Takashi; Nakasuji, Kazuhiro

2015-06-26

A newly synthesized one-dimensional (1D) hydrogen-bonded (H-bonded) rhodium(II)-η(5)-semiquinone complex, [Cp*Rh(η(5)-p-HSQ-Me4)]PF6 ([1]PF6; Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl; HSQ = semiquinone) exhibits a paraelectric-antiferroelectric second-order phase transition at 237.1 K. Neutron and X-ray crystal structure analyses reveal that the H-bonded proton is disordered over two sites in the room-temperature (RT) phase. The phase transition would arise from this proton disorder together with rotation or libration of the Cp* ring and PF6(-) ion. The relative permittivity εb' along the H-bonded chains reaches relatively high values (ca., 130) in the RT phase. The temperature dependence of (13)C CP/MAS NMR spectra demonstrates that the proton is dynamically disordered in the RT phase and that the proton exchange has already occurred in the low-temperature (LT) phase. Rate constants for the proton exchange are estimated to be 10(-4)-10(-6) s in the temperature range of 240-270 K. DFT calculations predict that the protonation/deprotonation of [1](+) leads to interesting hapticity changes of the semiquinone ligand accompanied by reduction/oxidation by the π-bonded rhodium fragment, producing the stable η(6)-hydroquinone complex, [Cp*Rh(3+)(η(6)-p-H2Q-Me4)](2+) ([2](2+)), and η(4)-benzoquinone complex, [Cp*Rh(+)(η(4)-p-BQ-Me4)] ([3]), respectively. Possible mechanisms leading to the dielectric response are discussed on the basis of the migration of the protonic solitons comprising of [2](2+) and [3], which would be generated in the H-bonded chain. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The length of an internal poly(A) tract of hibiscus latent Singapore virus is crucial for its replication.

PubMed

Niu, Shengniao; Cao, Shishu; Huang, Li-Jing; Tan, Kelvin Chee-Leong; Wong, Sek-Man

2015-01-01

Hibiscus latent Singapore virus (HLSV) mutants were constructed to study roles of its internal poly(A) tract (IPAT) in viral replication and coat protein (CP) expression. Shortening of the IPAT resulted in reduced HLSV RNA accumulation and its minimal length required for HLSV CP expression in plants was 24 nt. Disruption of a putative long range RNA-RNA interacting structure between 5' and 3' untranslated regions of HLSV-22A and -24A resulted in reduced viral RNA and undetectable CP accumulation in inoculated leaves. Replacement of the IPAT in HLSV with an upstream pseudoknot domain (UPD) of Tobacco mosaic virus (TMV) or insertion of the UPD to the immediate downstream of a 24 nt IPAT in HLSV resulted in drastically reduced viral RNA replication. Plants infected with a TMV mutant by replacement of the UPD with 43 nt IPAT exhibited milder mosaic symptoms without necrosis. We have proposed a model for HLSV replication. Copyright © 2014 Elsevier Inc. All rights reserved.

WORLD PORT INDEX Nineteenth Edition

DTIC Science & Technology

2009-01-01

SABLE US 4424N 08319W CP06 14863 V RN E N N Y Y Y Q N Q M Y N 4460 OSCODA US 4425N 08319W CP06 14863 V RN E N N Y Y Y Q N Q M Y N 4470 ALPENA US 4504N... ALPENA US CP06 04470 ALSEA 16810 * ALTA NO 182 21130 ALTAMIRA MX 148 09355 ALTATA MX 153 15820 ALUMINA MARINE TERM 10772 * ALUSHTA UP BA24 43810

Comparison of Re-irradiation Outcomes for Charged Particle Radiotherapy and Robotic Stereotactic Radiotherapy Using CyberKnife for Recurrent Head and Neck Cancers: A Multi-institutional Matched-cohort Analysis.

PubMed

Yamazaki, Hideya; Demizu, Yusuke; Okimoto, Tomoaki; Ogita, Mikio; Himei, Kengo; Nakamura, Satoaki; Suzuki, Gen; Yoshida, Ken; Kotsuma, Tadayuki; Yoshioka, Yasuo

2016-10-01

To compare survival outcomes for charged particle radiotherapy (CP) and stereotactic body radiotherapy using CyberKnife (CK) in patients who had undergone re-irradiation for head and neck cancers. We conducted a retrospective multi-institutional matched-cohort analysis on 25 patients treated with CP and 25 matched patients treated with CK according to three prognostic factors (nasopharyngeal cancer or not, interval between initial radiotherapy and re-irradiation, and planning target volume). CP was used more often to treat non-squamous cell cancer ((non-SCC): 52% vs. 0%) with a higher prescribed dose (median=57.6 Gy(RBE)/16 fractions) than CK (32 Gy/5 fractions). The local control rate (LC) for patients treated with CP was 71.2% at 1 year and that for patients treated with CK was 63.8% (p=0.24). The 1-year overall survival (OS) rates were 67.1% for CP and 36.3% for CK (p=0.0002), respectively. Non-SCC patients showed better OS rates at 1 year than SCC patients. In the SCC sub-group analysis, the 1-year LC, OS rates were 65%, 58.3% in the CP group and 64%, 36.3% in the CK group (p=0.81, p=0.02), respectively. A total of 16 patients (32%) experienced grade 3 or worse toxicities (24% in CK and 40% in CP, p=0.36), including six grade 5 toxicities. CP produced higher survival rates than CK, treated more non-SCC patients and used a higher prescribed dose. On the other hand, severe toxicities occurred in both groups, which, however, require further investigation. Copyright© 2016 International Institute of Anticancer Research (Dr. John G. Delinassios), All rights reserved.

Virus-like nanostructures for tuning immune response

NASA Astrophysics Data System (ADS)

Mammadov, Rashad; Cinar, Goksu; Gunduz, Nuray; Goktas, Melis; Kayhan, Handan; Tohumeken, Sehmus; Topal, Ahmet E.; Orujalipoor, Ilghar; Delibasi, Tuncay; Dana, Aykutlu; Ide, Semra; Tekinay, Ayse B.; Guler, Mustafa O.

2015-11-01

Synthetic vaccines utilize viral signatures to trigger immune responses. Although the immune responses raised against the biochemical signatures of viruses are well characterized, the mechanism of how they affect immune response in the context of physical signatures is not well studied. In this work, we investigated the ability of zero- and one-dimensional self-assembled peptide nanostructures carrying unmethylated CpG motifs (signature of viral DNA) for tuning immune response. These nanostructures represent the two most common viral shapes, spheres and rods. The nanofibrous structures were found to direct immune response towards Th1 phenotype, which is responsible for acting against intracellular pathogens such as viruses, to a greater extent than nanospheres and CpG ODN alone. In addition, nanofibers exhibited enhanced uptake into dendritic cells compared to nanospheres or the ODN itself. The chemical stability of the ODN against nuclease-mediated degradation was also observed to be enhanced when complexed with the peptide nanostructures. In vivo studies showed that nanofibers promoted antigen-specific IgG production over 10-fold better than CpG ODN alone. To the best of our knowledge, this is the first report showing the modulation of the nature of an immune response through the shape of the carrier system.

Differentiation of Constriction and Restriction: Complex Cardiovascular Hemodynamics.

PubMed

Geske, Jeffrey B; Anavekar, Nandan S; Nishimura, Rick A; Oh, Jae K; Gersh, Bernard J

2016-11-29

Differentiation of constrictive pericarditis (CP) from restrictive cardiomyopathy (RCM) is a complex and often challenging process. Because CP is a potentially curable cause of heart failure and therapeutic options for RCM are limited, distinction of these 2 conditions is critical. Although different in regard to etiology, prognosis, and treatment, CP and RCM share a common clinical presentation of predominantly right-sided heart failure, in the absence of significant left ventricular systolic dysfunction or valve disease, due to impaired ventricular diastolic filling. Fundamental to the diagnosis of either condition is a clear understanding of the underlying hemodynamic principles and pathophysiology. We present a contemporary review of the pathophysiology, hemodynamics, diagnostic assessment, and therapeutic approach to patients presenting with CP and RCM. Copyright © 2016 American College of Cardiology Foundation. Published by Elsevier Inc. All rights reserved.

Insight into Oxide-Bridged Heterobimetallic Al/Zr Olefin Polymerization Catalysts.

PubMed

Boulho, Cédric; Zijlstra, Harmen S; Hofmann, Alexander; Budzelaar, Peter H M; Harder, Sjoerd

2016-11-21

Reaction of (TBBP)AlMe⋅THF with [Cp* 2 Zr(Me)OH] gave [(TBBP)Al(THF)-O-Zr(Me)Cp* 2 ] (TBBP=3,3',5,5'-tetra-tBu-2,2'-biphenolato). Reaction of [DIPPnacnacAl(Me)-O-Zr(Me)Cp 2 ] with [PhMe 2 NH] + [B(C 6 F 5 ) 4 ] - gave a cationic Al/Zr complex that could be structurally characterized as its THF adduct [(DIPPnacnac)Al(Me)-O-Zr(THF)Cp 2 ] + [B(C 6 F 5 ) 4 ] - (DIPPnacnac=HC[(Me)C=N(2,6-iPr 2 -C 6 H 3 )] 2 ). The first complex polymerizes ethene in the presence of an alkylaluminum scavenger but in the absence of methylalumoxane (MAO). The adduct cation is inactive under these conditions. Theoretical calculations show very high energy barriers (ΔG=40-47 kcal mol -1 ) for ethene insertion with a bridged AlOZr catalyst. This is due to an unfavorable six-membered-ring transition state, in which the methyl group bridges the metal and ethene with an obtuse metal-Me-C angle that prevents synchronized bond-breaking and making. A more-likely pathway is dissociation of the Al-O-Zr complex into an aluminate and the active polymerization catalyst [Cp* 2 ZrMe] + . © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Medical service use in children with cerebral palsy: The role of child and family factors characteristics.

PubMed

Meehan, Elaine M; Reid, Susan M; Williams, Katrina J; Freed, Gary L; Sewell, Jillian R; Reddihough, Dinah S

2016-06-01

The aim of the study was to investigate the patterns of medical service use in children with cerebral palsy (CP), taking into account child and family characteristics. Nine hundred and one parents and carers of children registered with the Victorian CP Register were invited to complete a survey. Participants were asked about their child's appointments with general practitioners and public and private paediatric medical specialists over the preceding 12 months. Information on family characteristics and finances was also collected. Data on CP severity and complexity were extracted from the CP Register. Three hundred and fifty parents and carers (39%) participated. Of these, 83% reported that their child had ≥1 appointment with a general practitioner over the preceding 12 months, while 84% had ≥1 appointment with a public or private paediatric medical specialist. Overall, 58% of children saw 2-5 different paediatric medical specialists, while 9% had appointments with ≥6 clinicians. Children with severe and complex CP were more likely to have had ≥1 appointment with a publically funded paediatric medical specialist and had seen a greater number of different clinicians over the study period. Family characteristics were not associated with service use. Children with CP are managed by a number of paediatric medical specialists, and they continue to see a range of specialists throughout adolescence. In Victoria, differences in service use are not based on family characteristics; instead the highest service users are those with severe and complex CP. For this group, care co-ordination and information sharing between treating clinicians are important, if gaps in care are to be avoided. © 2016 Paediatrics and Child Health Division (The Royal Australasian College of Physicians).

Polycomb-like proteins link the PRC2 complex to CpG islands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Haojie; Liefke, Robert; Jiang, Junyi

The Polycomb repressive complex 2 (PRC2) mainly mediates transcriptional repression1,2 and has essential roles in various biological processes including the maintenance of cell identity and proper differentiation. Polycomb-like (PCL) proteins, such as PHF1, MTF2 and PHF19, are PRC2-associated factors that form sub-complexes with PRC2 core components3, and have been proposed to modulate the enzymatic activity of PRC2 or the recruitment of PRC2 to specific genomic loci4,5,6,7,8,9,10,11,12,13. Mammalian PRC2-binding sites are enriched in CG content, which correlates with CpG islands that display a low level of DNA methylation14. However, the mechanism of PRC2 recruitment to CpG islands is not fully understood.more » Here we solve the crystal structures of the N-terminal domains of PHF1 and MTF2 with bound CpG-containing DNAs in the presence of H3K36me3-containing histone peptides. We show that the extended homologous regions of both proteins fold into a winged-helix structure, which specifically binds to the unmethylated CpG motif but in a completely different manner from the canonical winged-helix DNA recognition motif. We also show that the PCL extended homologous domains are required for efficient recruitment of PRC2 to CpG island-containing promoters in mouse embryonic stem cells. Our research provides the first, to our knowledge, direct evidence to demonstrate that PCL proteins are crucial for PRC2 recruitment to CpG islands, and further clarifies the roles of these proteins in transcriptional regulation in vivo.« less

More introgression with less gene flow: chloroplast vs. mitochondrial DNA in the Picea asperata complex in China, and comparison with other Conifers.

PubMed

Du, Fang K; Petit, Rémy J; Liu, Jian Quan

2009-04-01

Recent work has suggested that rates of introgression should be inversely related to levels of gene flow because introgressed populations cannot be 'rescued' by intraspecific gene flow if it is too low. Mitochondrial and chloroplast DNA (mtDNA and cpDNA) experience very different levels of gene flow in conifers due to their contrasted maternal and paternal modes of transmission, hence the prediction that mtDNA should introgress more readily than cpDNA in this group. Here, we use sequence data from both mtDNA and cpDNA to test this hypothesis in a group of closely related spruces species, the Picea asperata complex from China. Nine mitochondrial and nine chloroplast haplotypes were recovered from 459 individuals in 46 natural populations belonging to five species of the Picea asperata complex. Low variation was found in the two mtDNA introns along with a high level of differentiation among populations (G(ST) = 0.90). In contrast, we detected higher variation and lower differentiation among populations at cpDNA markers (G(ST) = 0.56), a trend shared by most conifer species studied so far. We found that cpDNA variation, although far from being fully diagnostic, is more species-specific than mtDNA variation: four groups of populations were identified using cpDNA markers, all of them related to species or groups of species, whereas for mtDNA, geographical variation prevails over species differentiation. The literature suggests that mtDNA haplotypes are often shared among related conifer species, whereas cpDNA haplotypes are more species-specific. Hence, increased intraspecific gene flow appears to decrease differentiation within species but not among species.

Microbiota-Mediated Modulation of Organophosphate Insecticide Toxicity by Species-Dependent Interactions with Lactobacilli in a Drosophila melanogaster Insect Model.

PubMed

Daisley, Brendan A; Trinder, Mark; McDowell, Tim W; Collins, Stephanie L; Sumarah, Mark W; Reid, Gregor

2018-05-01

Despite the benefits to the global food supply and agricultural economies, pesticides are believed to pose a threat to the health of both humans and wildlife. Chlorpyrifos (CP), a commonly used organophosphate insecticide, has poor target specificity and causes acute neurotoxicity in a wide range of species via the suppression of acetylcholinesterase. This effect is exacerbated 10- to 100-fold by chlorpyrifos oxon (CPO), a principal metabolite of CP. Since many animal-associated symbiont microorganisms are known to hydrolyze CP into CPO, we used a Drosophila melanogaster insect model to investigate the hypothesis that indigenous and probiotic bacteria could affect CP metabolism and toxicity. Antibiotic-treated and germfree D. melanogaster insects lived significantly longer than their conventionally reared counterparts when exposed to 10 μM CP. Drosophila melanogaster gut-derived Lactobacillus plantarum , but not Acetobacter indonesiensis , was shown to metabolize CP. Liquid chromatography tandem-mass spectrometry confirmed that the L. plantarum isolate preferentially metabolized CP into CPO when grown in CP-spiked culture medium. Further experiments showed that monoassociating germfree D. melanogaster with the L. plantarum isolate could reestablish a conventional-like sensitivity to CP. Interestingly, supplementation with the human probiotic Lactobacillus rhamnosus GG (a strain that binds but does not metabolize CP) significantly increased the survival of the CP-exposed germfree D. melanogaster This suggests strain-specific differences in CP metabolism may exist among lactobacilli and emphasizes the need for further investigation. In summary, these results suggest that (i) CPO formation by the gut microbiota can have biologically relevant consequences for the host, and (ii) probiotic lactobacilli may be beneficial in reducing in vivo CP toxicity. IMPORTANCE An understudied area of research is how the microbiota (microorganisms living in/on an animal) affects the metabolism and toxic outcomes of environmental pollutants such as pesticides. This study focused specifically on how the microbial biotransformation of chlorpyrifos (CP; a common organophosphate insecticide) affected host exposure and toxicity parameters in a Drosophila melanogaster insect model. Our results demonstrate that the biotransformation of CP by the gut microbiota had biologically relevant and toxic consequences on host health and that certain probiotic lactobacilli may be beneficial in reducing CP toxicity. Since inadvertent pesticide exposure is suspected to negatively impact the health of off-target species, these findings may provide useful information for wildlife conservation and environmental sustainability planning. Furthermore, the results highlight the need to consider microbiota composition differences between beneficial and pest insects in future insecticide designs. More broadly, this study supports the use of beneficial microorganisms to modulate the microbiota-mediated biotransformation of xenobiotics. Copyright © 2018 American Society for Microbiology.

Mechanism-Based Condition Screening for Sustainable Catalysis in Single-Electron Steps by Cyclic Voltammetry.

PubMed

Liedtke, Theresa; Spannring, Peter; Riccardi, Ludovico; Gansäuer, Andreas

2018-04-23

A cyclic-voltammetry-based screening method for Cp 2 TiX-catalyzed reactions is introduced. Our mechanism-based approach enables the study of the influence of various additives on the electrochemically generated active catalyst Cp 2 TiX, which is in equilibrium with catalytically inactive [Cp 2 TiX 2 ] - . Thioureas and ureas are most efficient in the generation of Cp 2 TiX in THF. Knowing the precise position of the equilibrium between Cp 2 TiX and [Cp 2 TiX 2 ] - allowed us to identify reaction conditions for the bulk electrolysis of Cp 2 TiX 2 complexes and for Cp 2 TiX-catayzed radical arylations without having to carry out the reactions. Our time- and resource-efficient approach is of general interest for the design of catalytic reactions that proceed in single-electron steps. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of replacing fish meal with soy cake in a diet based on urea-treated rice straw on performance of growing Laisind beef cattle.

PubMed

Van Nhiem, Duong; Berg, Jan; Kjos, Nils Petter; Trach, Nguyen Xuan; Tuan, Bui Quang

2013-04-01

The present study was to test if different ratios of fish meal to soy cake as protein supplements in the diet are not significantly different in effects on feed intakes and performance of growing beef cattle fed urea-treated rice straw (URTRS) as basal diet under local conditions in North Vietnam. Thirty-six male cattle of Laisind (50% local Yellow cattle and 50% Sindhi, both Bos indicus) at around 12 months of age with an average live weight of 124 ± 12 kg at start were used in six groups of the experiment. Six diets named A, B, C, D, E, and F used in the experiment were similar in crude protein (CP) level, except for diet A with no supplementation, but different in fish meal/soy cake ratio based on CP content as follows: diet A 0/0, diet B 100/0, diet C 75/25, diet D 50/50, diet E 25/75, and diet F 0/100. Following a 4-week adaptation period, a comparison period lasted 24 weeks. The total intakes of dry matter (DM), DM from roughage, metabolizable energy (ME), and CP were 6, 7, 6, and 20% higher in diets B-F than diet A with P values ≤ 0.05, 0.05, 0.05, and 0.001, respectively. The average daily gain (ADG) was 50% higher (P<0.001) in diets B-F than that in diet A. Compared to diet A, diets B-F had lower feed conversion ratio (FCR)DM, FCRME, and FCRCP by 30, 20, and 30%, respectively (all at P<0.001). There were no significant differences between diets B-F in the intakes, FCRs, and ADG. The apparent digestibility of CP was 12 to 24% higher (P<0.001) in diets B-F than that in diet A. There was a tendency that the apparent digestibilities of DM, CP, and CF were increasing with increasing level of soy cake in this study. The ratio of fish meal to soy cake did not significantly affect feed intakes, ADG, FCR, and apparent nutrient digestibilities of the cattle. Soy cake can therefore be used to partially or fully replace fish meal as a protein supplement in the diet of growing beef cattle fed URTRS without any negative effects on animal performance.

Activation of C-H bonds by rare-earth metallocene-butyl complexes.

PubMed

Grindell, Richard; Day, Benjamin M; Guo, Fu-Sheng; Pugh, Thomas; Layfield, Richard A

2017-09-05

The stable metallocene-butyl complexes [(Cp Me ) 2 M( n Bu)] 2 (M = Y, Dy) were synthesized and their reactivity towards to ferrocene and bulky N-heterocyclic carbenes investigated. Selective mono-deprotonation of ferrocene and a benzylic methyl group of IMes were observed, whereas a control reaction of (Cp Me ) 3 M with IMes resulted in a normal-to-abnormal NHC rearrangement.

Molecular orbital studies of the bonding in heavy element organometallics: Progress report

NASA Astrophysics Data System (ADS)

Bursten, B. E.

1988-03-01

Over the past two years we have made considerable progress in the understanding of the bonding in heavy element mononuclear and binuclear complexes. For mononuclear complexes, our strategy has been to study the orbital interactions between the actinide metal center and the surrounding ligands. One particular system which has been studied extensively is X sub 3 AnL (where X = Cp, Cl, NH sub 2 ; An = actinide; and L = neutral or anionic ligand). We are interested not only in the mechanics of the An-X orbital interactions, but also how the relative donor characteristics of X may influence coordination of the fourth ligand L to the actinide. For binuclear systems, we are interested not only in homobimetallic complexes, but also in heterobimetallic complexes containing actinides and transition metals. In order to make the calculations of such large systems tractable, we have transferred the X-alpha-SW codes to the newly acquired Cray XMP24 at the Ohio Supercomputer Center. This has resulted in significant savings of money and time.

Characterization of EEG patterns in brain-injured subjects and controls after a Snoezelen(®) intervention.

PubMed

Gómez, Carlos; Poza, Jesús; Gutiérrez, María T; Prada, Esther; Mendoza, Nuria; Hornero, Roberto

2016-11-01

The aim of this study was to assess the changes induced in electroencephalographic (EEG) activity by a Snoezelen(®) intervention on individuals with brain-injury and control subjects. EEG activity was recorded preceding and following a Snoezelen(®) session in 18 people with cerebral palsy (CP), 18 subjects who have sustained traumatic brain-injury (TBI) and 18 controls. EEG data were analyzed by means of spectral and nonlinear measures: median frequency (MF), individual alpha frequency (IAF), sample entropy (SampEn) and Lempel-Ziv complexity (LZC). Our results showed decreased values for MF, IAF, SampEn and LZC as a consequence of the therapy. The main changes between pre-stimulation and post-stimulation conditions were found in occipital and parietal brain areas. Additionally, these changes are more widespread in controls than in brain-injured subjects, which can be due to cognitive deficits in TBI and CP groups. Our findings support the notion that Snoezelen(®) therapy affects central nervous system, inducing a slowing of oscillatory activity, as well as a decrease of EEG complexity and irregularity. These alterations seem to be related with higher levels of relaxation of the participants. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

18F-Flortaucipir Binding in Choroid Plexus: Related to Race and Hippocampus Signal.

PubMed

Lee, Christopher M; Jacobs, Heidi I L; Marquié, Marta; Becker, John A; Andrea, Nicolas V; Jin, David S; Schultz, Aaron P; Frosch, Matthew P; Gómez-Isla, Teresa; Sperling, Reisa A; Johnson, Keith A

2018-01-01

On target 18F-Flortaucipir (FTP) binding of Alzheimer's disease tau aggregates and off-target binding of melanocytes have been demonstrated with autoradiography. We aimed to investigate the hypothesis that if binding in choroid plexus (CP) is due to melanocytes, the signal would be elevated in Black/African American (B/AA) compared to White (W) participants. In addition, we examined whether CP signal affects measurements in adjacent regions, and whether correcting for spill-in effects has an influence on associations between hippocampus (HC) FTP and amyloid or cognition. FTP race differences in 147 Harvard Aging Brain Study participants (23 B/AA, 124W) were examined in CP, HC, HC covaried for CP, amygdala, inferior temporal gyrus, entorhinal cortex, and fusiform regions. Associations between CP FTP and other regions-of-interest (ROIs) were probed to assess spill-in effects. A statistical regression approach to attenuate CP spill-in was tested by relating adjusted HC SUVR residuals and unadjusted HC SUVR to race, cognition and amyloid. All analyses were covaried for age, sex, education and amyloid deposition, and Bonferroni-corrected for multiple comparisons. B/AA individuals had elevated CP and HC SUVR (p < 0.007), whereas other ROI SUVR and HC SUVR covaried for CP SUVR did not show race differences (p > 0.05). CP SUVR was associated with HC SUVR (p < 10-14), but with no other ROI SUVR (p > 0.05). When adjusting HC SUVR for CP SUVR, no race differences in residual HC SUVR were detected, and relationships with amyloid and memory became apparent. Melanocyte FTP binding may account partially for high CP signal. This off-target binding affects mainly HC FTP measurements, which should be interpreted with caution.

18F-Flortaucipir Binding in Choroid Plexus: Related to Race and Hippocampus Signal

PubMed Central

Lee, Christopher M.; Jacobs, Heidi I.L.; Marquié, Marta; Becker, John A.; Andrea, Nicolas V.; Jin, David S.; Schultz, Aaron P.; Frosch, Matthew P.; Gómez-Isla, Teresa; Sperling, Reisa A.; Johnson, Keith A.

2018-01-01

Background On target 18F-Flortaucipir (FTP) binding of Alzheimer’s disease tau aggregates and off-target binding of melanocytes have been demonstrated with autoradiography. Objective We aimed to investigate the hypothesis that if binding in choroid plexus (CP) is due to melanocytes, the signal would be elevated in Black/African American (B/AA) compared to White (W) participants. In addition, we examined whether CP signal affects measurements in adjacent regions, and whether correcting for spill-in effects has an influence on associations between hippocampus (HC) FTP and amyloid or cognition. Methods FTP race differences in 147 Harvard Aging Brain Study participants (23 B/AA, 124W) were examined in CP, HC, HC covaried for CP, amygdala, inferior temporal gyrus, entorhinal cortex, and fusiform regions. Associations between CP FTP and other regions-of-interest (ROIs) were probed to assess spill-in effects. A statistical regression approach to attenuate CP spill-in was tested by relating adjusted HC SUVR residuals and unadjusted HC SUVR to race, cognition and amyloid. All analyses were covaried for age, sex, education and amyloid deposition, and Bonferroni-corrected for multiple comparisons. Results B/AA individuals had elevated CP and HC SUVR (p < 0.007), whereas other ROI SUVR and HC SUVR covaried for CP SUVR did not show race differences (p > 0.05). CP SUVR was associated with HC SUVR (p < 10−14), but with no other ROI SUVR (p > 0.05). When adjusting HC SUVR for CP SUVR, no race differences in residual HC SUVR were detected, and relationships with amyloid and memory became apparent. Conclusion Melanocyte FTP binding may account partially for high CP signal. This off-target binding affects mainly HC FTP measurements, which should be interpreted with caution. PMID:29614677

Complete Chloroplast Genome Sequences of Important Oilseed Crop Sesamum indicum L

PubMed Central

Yi, Dong-Keun; Kim, Ki-Joong

2012-01-01

Sesamum indicum is an important crop plant species for yielding oil. The complete chloroplast (cp) genome of S. indicum (GenBank acc no. JN637766) is 153,324 bp in length, and has a pair of inverted repeat (IR) regions consisting of 25,141 bp each. The lengths of the large single copy (LSC) and the small single copy (SSC) regions are 85,170 bp and 17,872 bp, respectively. Comparative cp DNA sequence analyses of S. indicum with other cp genomes reveal that the genome structure, gene order, gene and intron contents, AT contents, codon usage, and transcription units are similar to the typical angiosperm cp genomes. Nucleotide diversity of the IR region between Sesamum and three other cp genomes is much lower than that of the LSC and SSC regions in both the coding region and noncoding region. As a summary, the regional constraints strongly affect the sequence evolution of the cp genomes, while the functional constraints weakly affect the sequence evolution of cp genomes. Five short inversions associated with short palindromic sequences that form step-loop structures were observed in the chloroplast genome of S. indicum. Twenty-eight different simple sequence repeat loci have been detected in the chloroplast genome of S. indicum. Almost all of the SSR loci were composed of A or T, so this may also contribute to the A-T richness of the cp genome of S. indicum. Seven large repeated loci in the chloroplast genome of S. indicum were also identified and these loci are useful to developing S. indicum-specific cp genome vectors. The complete cp DNA sequences of S. indicum reported in this paper are prerequisite to modifying this important oilseed crop by cp genetic engineering techniques. PMID:22606240

Synthesis and Structure of Vanadium Halide Complexes Containing Diphosphine Ligands with Pendant Amines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Egbert, Jonathan D.; Labios, Liezel A.; Darmon, Jonathan M.

2016-02-18

A series of vanadium(III) diiodide complexes of the formula CpV(P RN R'P R)I 2 (Cp = 5-C 5H 5; P RN R'P R = (R 2PCH 2) 2N(R)), where R = Et, R = Me (1a), R = Ph (1b); R = Ph, R = Me (1c)) is reported. The corresponding vanadium(II) monoiodide complexes of the formula CpV(P RN R' PR)I, where R = Et, R = Me (2a), R = Ph (2b); R = Ph, R = Me (2c)) were prepared in THF by reduction of 1a-c with Zn powder. The paramagnetic complexes 1a-c and 2a-c are characterized bymore » elemental analysis, 1H NMR spectroscopy, and by cyclic voltammetry for complexes 2b and 4b. Complexes 1c and 2a-c were also characterized in the single crystal by X-ray crystallography. We report the preparation of the vanadium(II) complexes CpV(P Ph 2N Ph 2)I (3) (P Ph 2N Ph 2 = 1,5-diphenyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) and trans-[VCl 2(PEtNMePEt)2] (4a) and trans-[VCl 2(PEtNPhPEt) 2] (4b). These complexes represent initial coordination chemistry of vanadium complexes with P RN R'P R and P Ph 2N Ph 2 diphosphine ligands, which contain a pendant amine in the second coordination sphere. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

DOE PAGES

Brown, Alexandra C.; Altman, Alison B.; Lohrey, Trevor D.; ...

2017-05-31

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp 2TiCl and KH 3AlC(TMS) 3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp 2Ti(μ-H) 2(H)AlC(TMS) 3 (2) or trimetallic (Cp 2Ti) 2(μ-H) 3(H)AlC(TMS) 3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The naturemore » of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.« less

CpG methylation at the USF binding site mediates cell-specific transcription of human ascorbate transporter SVCT2 exon 1a

PubMed Central

Qiao, Huan; May, James M.

2013-01-01

SVCT2 is the major transporter mediating vitamin C uptake in most organs. Its expression is driven by two promoters (CpG-poor exon 1a promoter and CpG-rich exon 1b promoter). In this work we mapped discrete elements within the proximal CpG-poor promoter responsible for the exon 1a transcription. We identified two E boxes for USF binding and one Y box for NF-Y binding. We further show that the formation of an NFY/USF complex on the exon 1a promoter amplifies each other's ability to bind to the promoter in a cooperativity-dependent manner and is absolutely required for the full activity of the exon 1a promoter. The analysis of the CpG site located at the upstream USF binding site in the promoter showed a strong correlation between expression and demethylation. It was also shown that the exon 1a transcription was induced in cell culture treated with demethylating agent decitabine. The specific methylation of this CpG site impaired both the binding of USF and the formation of the functional NF-Y/USF complex as well as promoter activity, suggesting its importance for the cell-specific transcription. Thus CpG methylation at the upstream USF binding site functions in establishing and maintaining cell-specific transcription from the CpG-poor SVCT2 exon 1a promoter. PMID:21770893

Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2 }2 {μ-η2 :η2 -B2 H4 }] and [{Cp*M(CO)2 }2 B2 H2 M(CO)4 ], M=Mo,W.

PubMed

Mondal, Bijan; Bag, Ranjit; Ghorai, Sagar; Bakthavachalam, K; Jemmis, Eluvathingal D; Ghosh, Sundargopal

2018-07-02

The reaction of [(Cp*Mo) 2 (μ-Cl) 2 B 2 H 6 ] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO) 2 } 2 {μ-η 2 :η 2 -B 2 H 4 }] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged C s structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum-alkyne complex [{CpMo(CO) 2 } 2 C 2 H 2 ]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO) 4 ] fragment, [{Cp*Mo(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (3) was isolated upon treatment with [W(CO) 5 ⋅thf]. Compound 3 shows the intriguing presence of [B 2 H 2 ] with a short B-B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (4) and [{Cp*W(CO) 2 } 2 B 2 H 2 Mo(CO) 4 ] (5), which provided direct proof of the existence of the tungsten analogue of 2. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

SU-F-P-64: The Impact of Plan Complexity Parameters On the Plan Quality and Deliverability of Volumetric Modulated Arc Therapy with Canonical Correlation Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, X; Yi, J; Xie, C

Purpose: To evaluate the impact of complexity indices on the plan quality and deliverability of volumetric modulated arc therapy (VMAT), and to determine the most significant parameters in the generation of an ideal VMAT plan. Methods: A multi-dimensional exploratory statistical method, canonical correlation analysis (CCA) was adopted to study the correlations between VMAT parameters of complexity, quality and deliverability, as well as their contribution weights with 32 two-arc VMAT nasopharyngeal cancer (NPC) patients and 31 one-arc VMAT prostate cancer patients. Results: The MU per arc (MU/Arc) and MU per control point (MU/CP) of NPC were 337.8±25.2 and 3.7±0.3, respectively, whichmore » were significantly lower than those of prostate cancer patients (MU/Arc : 506.9±95.4, MU/CP : 5.6±1.1). The plan complexity indices indicated that two-arc VMAT plans were more complex than one-arc VMAT plans. Plan quality comparison confirmed that one-arc VMAT plans had a high quality than two-arc VMAT plans. CCA results implied that plan complexity parameters were highly correlated with plan quality with the first two canonical correlations of 0.96, 0.88 (both p<0.001) and significantly correlated with deliverability with the first canonical correlation of 0.79 (p<0.001), plan quality and deliverability was also correlated with the first canonical correlation of 0.71 (p=0.02). Complexity parameters of MU/CP, segment area (SA) per CP, percent of MU/CP less 3 and planning target volume (PTV) were weighted heavily in correlation with plan quality and deliveability . Similar results obtained from individual NPC and prostate CCA analysis. Conclusion: Relationship between complexity, quality, and deliverability parameters were investigated with CCA. MU, SA related parameters and PTV volume were found to have strong effect on the plan quality and deliverability. The presented correlation among different quantified parameters could be used to improve the plan quality and the efficiency of the radiotherapy process when creating a complex VMAT plan.« less

Photoresponsive Molecular Memory Films Composed of Sequentially Assembled Heterolayers Containing Ruthenium Complexes.

PubMed

Nagashima, Takumi; Ozawa, Hiroaki; Suzuki, Takashi; Nakabayashi, Takuya; Kanaizuka, Katsuhiko; Haga, Masa-Aki

2016-01-26

Photoresponsive molecular memory films were fabricated by a layer-by-layer (LbL) assembling of two dinuclear Ru complexes with tetrapodal phosphonate anchors, containing either 2,3,5,6-tetra(2-pyridyl)pyrazine or 1,2,4,5-tetra(2-pyridyl)benzene as a bridging ligand (Ru-NP and Ru-CP, respectively), using zirconium phosphonate to link the layers. Various types of multilayer homo- and heterostructures were constructed. In the multilayer heterofilms such as ITO||(Ru-NP)m |(Ru-CP)n , the difference in redox potentials between Ru-NP and Ru-CP layers was approximately 0.7 V, which induced a potential gradient determined by the sequence of the layers. In the ITO||(Ru-NP)m |(Ru-CP)n multilayer heterofilms, the direct electron transfer (ET) from the outer Ru-CP layers to the ITO were observed to be blocked for m>2, and charge trapping in the outer Ru-CP layers became evident from the appearance of an intervalence charge transfer (IVCT) band at 1140 nm from the formation of the mixed-valent state of Ru-CP units, resulting from the reductive ET mediation of the inner Ru-NP layers. Therefore, the charging/discharging ("1"and "0") states in the outer Ru-CP layers could be addressed and interconverted by applying potential pulses between -0.5 and +0.7 V. The two states could be read out by the direction of the photocurrent (anodic or cathodic). The molecular heterolayer films thus represent a typical example of a photoresponsive memory device; that is, the writing process may be achieved by the applied potential (-0.5 or +0.7 V), while the readout process is achieved by measuring the direction of the photocurrent (anodic or cathodic). Sequence-sensitive multilayer heterofilms, using redox-active complexes as building blocks, thus demonstrate great potential for the design of molecular functional devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Eye injuries in the elderly from consumer products in the United States: 2001-2007.

PubMed

Chen, Allison J; Kim, Julia G; Linakis, James G; Mello, Michael J; Greenberg, Paul B

2013-03-01

To quantify and characterize eye injuries related to consumer products in elderly patients (≥ 65) treated in United States (US) hospital emergency departments (EDs) in 2001-2007. Retrospective study. The study comprised 1,455 patient cases. Descriptive analysis of consumer-product (CP)-related eye injury data derived from the National Electronic Injury Surveillance System, a probability sample of 100 hospitals nationwide with 24-hour EDs. Narrative data was used to assign each case with the CP causing the eye injury, correcting for cases with misclassified CP codes. The proportions of eye injury visits were calculated by age, gender, diagnosis, disposition, locale of incident, and CP categories. The patient population included ocular injuries of all severity levels. We examined data for all non-fatal eye injuries in elderly patients (≥ 65) treated in US EDs in 2001-2007. Age, gender, diagnosis, case disposition, locale of incident, CP causing the injury. There were an estimated 67,864 visits to United States EDs by patients >65 years for CP-related eye injuries during the study period, of which 64 % (43,105; 95 % confidence interval [CI], 40,739-45,472) were by males; 70 % (CI, 44,837-49,496) occurred at home. Chemicals (22 %; 15,236; CI, 13,482-16,989), followed by cutting tools/construction (21 %; 14,524; CI, 12,777-16,272), furniture (15 %; 10,145; CI, 8,724-11,566), and gardening (14 %; 9,467; CI, 8,021-10,912) were the most common causes of eye injury. The CP categories with the greatest proportion of preventable injuries were cutting tools/construction (90 %), gardening (88 %), and household tools (71 %). Contusions or abrasions (39 %; 26,968; CI, 24,850-29,086) were the most common diagnoses. This study suggests that most CP-related elderly eye injuries in the U.S. occur at home and in men. Chemicals are the most common cause of injury. Further research is needed to determine effective strategies to minimize CP-related eye injuries in the elderly.

Dyslipidemia rather than Type 2 Diabetes Mellitus or Chronic Periodontitis Affects the Systemic Expression of Pro- and Anti-Inflammatory Genes.

PubMed

Nepomuceno, Rafael; Villela, Bárbara Scoralick; Corbi, Sâmia Cruz Tfaile; Bastos, Alliny De Souza; Dos Santos, Raquel Alves; Takahashi, Catarina Satie; Orrico, Silvana Regina Perez; Scarel-Caminaga, Raquel Mantuaneli

2017-01-01

A high percentage of type 2 diabetes mellitus (T2D) patients are also affected by dyslipidemia and chronic periodontitis (CP), but no studies have determined the gene expression in patients that are simultaneously affected by all three diseases. We investigated the systemic expression of immune-related genes in T2D, dyslipidemia, and CP patients. One hundred and fifty patients were separated into five groups containing 30 individuals each: (G1) poorly controlled T2D with dyslipidemia and CP; (G2) well-controlled T2D with dyslipidemia and CP; (G3) normoglycemic individuals with dyslipidemia and CP; (G4) healthy individuals with CP; (G5) systemic and periodontally healthy individuals. Blood analyses of lipid and glycemic profiles were carried out. The expression of genes, including IL10, JAK1, STAT3, SOCS3, IP10, ICAM1, IFNA, IFNG, STAT1, and IRF1, was investigated by RT-qPCR. Patients with dyslipidemia demonstrated statistically higher expression of the IL10 and IFNA genes, while IFNG, IP10, IRF1, JAK1, and STAT3 were lower in comparison with nondyslipidemic patients. Anti-inflammatory genes, such as IL10 , positively correlated with parameters of glucose, lipid, and periodontal profiles, while proinflammatory genes, such as IFNG , were negatively correlated with these parameters. We conclude that dyslipidemia appears to be the primary disease that is associated with gene expression of immune-related genes, while parameters of T2D and CP were correlated with the expression of these important immune genes.

CP Violation (4/4)

ScienceCinema

Raven, G.

2018-05-23

Existence of antimatter is a consequence of the combination of special relativity and quantum mechanics. No 'primordial' antimatter's observed, need CP violation. CP broken by the charged weak interaction. The weak and mass eigenstates of quarks are different, and this difference is described by the CKM matrix. There is a clear (and unexplained!) hierarchical structure to the CKM matrix...with 3 (or more families, one can have a complex phase(s) in the CKM matrix, and this allows for CP violation! Measurements show that CKM describes the dominant (only?) source of CP violation (at the EW scale). But it doesn't explain the matter--antimatter asymmetry of the universe.

Chronic pancreatitis in Eastern India: Experience from a tertiary care center.

PubMed

Jha, Ashish Kumar; Goenka, Mahesh Kumar; Goenka, Usha

2017-03-01

There is a wide variation in the clinical presentation of chronic pancreatitis (CP) in the different parts of India. Data regarding the clinical profile of CP from eastern India are scarce. We describe the clinical and demographic profiles of patients with CP in eastern India. Consecutive patients were evaluated for the clinical presentation, etiology and complication of CP. One hundred and thirty-nine patients with CP (mean age 39.57±14.88 years; M/F 3.48:1) were included. Idiopathic CP (50.35%) was the most common etiology followed by alcohol (33.81%); 68.34% had calcific CP and 31.65% had noncalcific CP. The median duration of symptoms was 24 (1-240) months. Pain was the most common symptom, being present in 93.52% of the patients. Diabetes, steatorrhea and pseudocyst were present in 45.32%, 14.38% and 7.19% of the cases, respectively. Moderate to severe anemia was revealed in 16.53% of the patients. Benign biliary stricture was diagnosed in 19.42% of the cases (symptomatic in 6.47%). The common radiological findings were the following: pancreatic calculi (68.34%), dilated pancreatic duct (PD) (58.99%), parenchymal atrophy (25.89%) and PD stricture (23.74%). In our center, idiopathic CP followed by alcoholic CP was the most frequent form of CP. Tropical CP was distinctly uncommon.

MeCP2 SUMOylation rescues Mecp2-mutant-induced behavioural deficits in a mouse model of Rett syndrome

PubMed Central

Tai, Derek J. C.; Liu, Yen C.; Hsu, Wei L.; Ma, Yun L.; Cheng, Sin J.; Liu, Shau Y.; Lee, Eminy H. Y.

2016-01-01

The methyl-CpG-binding protein 2 (MeCP2) gene, MECP2, is an X-linked gene encoding the MeCP2 protein, and mutations of MECP2 cause Rett syndrome (RTT). However, the molecular mechanism of MECP2-mutation-caused RTT is less known. Here we find that MeCP2 could be SUMO-modified by the E3 ligase PIAS1 at Lys-412. MeCP2 phosphorylation (at Ser-421 and Thr-308) facilitates MeCP2 SUMOylation, and MeCP2 SUMOylation is induced by NMDA, IGF-1 and CRF in the rat brain. MeCP2 SUMOylation releases CREB from the repressor complex and enhances Bdnf mRNA expression. Several MECP2 mutations identified in RTT patients show decreased MeCP2 SUMOylation. Re-expression of wild-type MeCP2 or SUMO-modified MeCP2 in Mecp2-null neurons rescues the deficits of social interaction, fear memory and LTP observed in Mecp2 conditional knockout (cKO) mice. These results together reveal an important role of MeCP2 SUMOylation in social interaction, memory and synaptic plasticity, and that abnormal MeCP2 SUMOylation is implicated in RTT. PMID:26842955

Arabidopsis CP12 mutants have reduced levels of phosphoribulokinase and impaired function of the Calvin–Benson cycle

PubMed Central

Elena López-Calcagno, Patricia; Omar Abuzaid, Amani; Lawson, Tracy

2017-01-01

Abstract CP12 is a small, redox-sensitive protein, the most detailed understanding of which is the thioredoxin-mediated regulation of the Calvin–Benson cycle, where it facilitates the formation of a complex between glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK) in response to changes in light intensity. In most organisms, CP12 proteins are encoded by small multigene families, where the importance of each individual CP12 gene in vivo has not yet been reported. We used Arabidopsis thaliana T-DNA mutants and RNAi transgenic lines with reduced levels of CP12 transcript to determine the relative importance of each of the CP12 genes. We found that single cp12-1, cp12-2, and cp12-3 mutants do not develop a severe photosynthetic or growth phenotype. In contrast, reductions of both CP12-1 and CP12-2 transcripts lead to reductions in photosynthetic capacity and to slower growth and reduced seed yield. No clear phenotype for CP12-3 was evident. Additionally, the levels of PRK protein are reduced in the cp12-1, cp12-1/2, and multiple mutants. Our results suggest that there is functional redundancy between CP12-1 and CP12-2 in Arabidopsis where these proteins have a role in determining the level of PRK in mature leaves and hence photosynthetic capacity. PMID:28430985

The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study

DOE PAGES

Lukens, W. W.; Speldrich, M.; Yang, P.; ...

2016-01-01

The electronic structures of 4f 3/5f 3Cp" 3M and Cp"sub>3M·alkylisocyanide complexes, where Cp" is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal–ligand interactions.

Influence of pedal cadence on the respiratory compensation point and its relation to critical power.

PubMed

Broxterman, R M; Ade, C J; Barker, T; Barstow, T J

2015-03-01

It is not known if the respiratory compensation point (RCP) is a distinct work rate (Watts (W)) or metabolic rate V̇(O2) and if the RCP is mechanistically related to critical power (CP). To examine these relationships, 10 collegiate men athletes performed cycling incremental and constant-power tests at 60 and 100 rpm to determine RCP and CP. RCP work rate was significantly (p≤0.05) lower for 100 than 60 rpm (197±24 W vs. 222±24 W), while RCP V̇(O2) was not significantly different (3.00±0.33 l min(-1) vs. 3.12±0.41 l min(-1)). CP at 60 rpm (214±51 W; V̇(O2): 3.01±0.69 l min(-1)) and 100 rpm (196±46 W; V̇(O2): 2.95±0.54 l min(-1)) were not significantly different from RCP. However, RCP and CP were not significantly correlated. These findings demonstrate that RCP represents a distinct metabolic rate, which can be achieved at different power outputs, but that RCP and CP are not equivalent parameters and should not, therefore, be used synonymously. Copyright © 2014 Elsevier B.V. All rights reserved.

Stage of lactation and corresponding diets affect in situ protein degradation by dairy cows.

PubMed

Schadt, I; Mertens, D R; Van Soest, P J; Azzaro, G; Licitra, G

2014-12-01

The influence of stage of lactation and corresponding diets on rates of protein degradation (kd) is largely unstudied. Study objectives were to measure and compare in situ ruminal kd of crude protein (CP) and estimate rumen CP escape (rumen-undegradable protein; RUP) of selected feeds by cows at 3 stages of lactation fed corresponding diets, and to determine the incubation times needed in an enzymatic in vitro procedure, using 0.2 units of Streptomyces griseus protease per percent of true CP, that predicted in situ RUP. Residue CP was measured after in situ fermentation for 4, 8, 12, 24, 36, 48, and 72 h of 5 protein sources and 3 total mixed rations, which were fed to the in situ cows. Two nonlactating (dry) cows and 2 cows each at 190 (mid) and 90 (peak) days of lactation were used. Each pair of cows was offered free-choice diets that differed in composition to meet their corresponding nutrient requirements. Diets had decreasing proportions of forages and contained (dry matter basis) 11.9, 15.1 and 16.4% CP and 54.3, 40.3 and 35.3% neutral detergent fiber, for dry, mid, and peak TMR (TMR1, TMR2, and TMR3), respectively. Intakes were 10.3, 21.4, and 23.8kg of dry matter/d, respectively. Kinetic CP fractions (extractable, potentially degradable, undegradable, or slowly degradable) were unaffected by treatment. Lag time and kd varied among feeds. The kd was faster for all feeds (0.136/h) when incubated in dry-TMR1 cows compared with mid-TMR2 (0.097/h) or peak-TMR3 (0.098/h) cows, and no differences in lag time were detected. Calculated RUP, using estimated passage rates for each cow based on intake, differed between dry-TMR1 (0.382) and mid-TMR2 (0.559) or peak-TMR3 (0.626) cows, with a tendency for mid-TMR2 to be different from peak-TMR3. Using the average kd and lag time obtained from dry-TMR1 to calculate RUP for mid-TMR2 and peak-TMR3 cows using their passage rates reduced RUP values by 6.3 and 9.5 percentage units, respectively. Except for that of herring meal, in vitro residue CP at 6, 12, and 48h of enzymatic hydrolysis was correlated (r=0.90) with in situ RUP of peak-TMR3, mid-TMR2, and dry-TMR1, respectively. Although confounded within treatments, stage of lactation, diet, and intake appeared to affect CP degradation parameters and RUP. Using kd from nonlactating cows, or the RUP calculated from them, may bias diet evaluation or ration formulation for lactating cows. In addition, enzymatic in vitro predictions of RUP should be measured using incubation times that are appropriate for lactating cows. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Cp2 TiX Complexes for Sustainable Catalysis in Single-Electron Steps.

PubMed

Richrath, Ruben B; Olyschläger, Theresa; Hildebrandt, Sven; Enny, Daniel G; Fianu, Godfred D; Flowers, Robert A; Gansäuer, Andreas

2018-04-25

We present a combined electrochemical, kinetic, and synthetic study with a novel and easily accessible class of titanocene catalysts for catalysis in single-electron steps. The tailoring of the electronic properties of our Cp 2 TiX-catalysts that are prepared in situ from readily available Cp 2 TiX 2 is achieved by varying the anionic ligand X. Of the complexes investigated, Cp 2 TiOMs proved to be either equal or substantially superior to the best catalysts developed earlier. The kinetic and thermodynamic properties pertinent to catalysis have been determined. They allow a mechanistic understanding of the subtle interplay of properties required for an efficient oxidative addition and reduction. Therefore, our study highlights that efficient catalysts do not require the elaborate covalent modification of the cyclopentadienyl ligands. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitric acid passivation does not affect in vitro biocompatibility of titanium.

PubMed

Faria, Adriana C L; Beloti, Márcio M; Rosa, Adalberto L

2003-01-01

In general, both chemical composition and surface features of implants affect cell response. The aim of this study was to evaluate the effect of titanium (Ti) passivation on the response of rat bone marrow cells, considering cell attachment, cell morphology, cell proliferation, total protein content, alkaline phosphatase (ALP) activity, and bonelike nodule formation. Cells were cultured on both commercially pure titanium (cpTi) and titanium-aluminium-vanadium alloy (Ti-6Al-4V) discs, either passivated or not. For attachment evaluation, cells were cultured for 4 and 24 hours. Cell morphology was evaluated after 4 days. After 7, 14, and 21 days, cell proliferation, total protein content, and ALP activity were evaluated. Bonelike nodule formation was evaluated after 21 days. Data were compared by analysis of variance and the Duncan multiple range test. Cell attachment, cell morphology, cell proliferation, total protein content, ALP activity, and bonelike nodule formation all were unaffected by Ti composition or passivation. Although the protocol for passivation used here could interfere with the pattern of ions released from Ti-6Al-4V and cpTi surfaces, the present study did not show any effect of this surface treatment on in vitro biocompatibility of Ti as evaluated by osteoblast attachment, proliferation, and differentiation.

A two-state computational investigation of methane C--H and ethane C--C oxidative addition to [CpM(PH3)]n+ (M = Co, Rh, Ir; n = 0, 1).

PubMed

Petit, Alban; Richard, Philippe; Cacelli, Ivo; Poli, Rinaldo

2006-01-11

Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordination sphere. No local sigma-CH(4) minimum was found for the Ir system. The energetic profiles agree with the nonexistence of the Co(III) methyl hydride complex and with the greater thermal stability of the Ir complex relative to the Rh complex. Reductive elimination of methane from the related oxidized complexes [CpM(PH(3))(CH(3))(H)](+) (M = Rh, Ir) proceeds entirely on the spin doublet PES, because the 15-electron [CpM(PH(3))](+) products have a doublet ground state. This process is thermodynamically favored by about 25 kcal mol(-1) relative to the corresponding neutral system. It is essentially barrierless for the Rh system and has a relatively small barrier (ca. 7.5 kcal mol(-1)) for the Ir system. In both cases, the reaction involves a sigma-CH(4) intermediate. Reductive elimination of ethane from [CpM(PH(3))(CH(3))(2)](+) (M = Rh, Ir) shows a similar thermodynamic profile, but is kinetically quite different from methane elimination from [CpM(PH(3))(CH(3))(H)](+): the reductive elimination barrier is much greater and does not involve a sigma-complex intermediate. The large difference in the calculated activation barriers (ca. 12.0 and ca. 30.5 kcal mol(-1) for the Rh and Ir systems, respectively) agrees with the experimental observation, for related systems, of oxidatively induced ethane elimination when M = Rh, whereas the related Ir systems prefer to decompose by alternative pathways.

Vascular wall function in insulin-resistant JCR:LA-cp rats: role of male and female sex.

PubMed

O'Brien, S F; Russell, J C; Dolphin, P J; Davidge, S T

2000-08-01

Vascular wall function was assessed in obese insulin-resistant (cp/cp) and lean normal (+/?), male and female, JCR:LA-cp rats. Both male and female cp/cp rats showed enhanced maximum contractility in response to norepinephrine; impaired smooth muscle in response to sodium nitroprusside, a nitric oxide (NO) donor; and impaired relaxation in response to acetylcholine (ACh), compared with their lean counterparts. The abnormalities were similar in male and female cp/cp rats. The NO synthase inhibitor, Nomega-nitro-L-arginine methyl ester (L-NAME), inhibited ACh-mediated relaxation significantly in male rats, both cp/cp and +/?. The inhibition of ACh-mediated relaxation by L-NAME in +/? females was less, with no reduction in maximal relaxation, and was absent in cp/cp females. These effects suggest that the relative importance of NO in the endothelial modulation of smooth muscle contractility is greater in male rats. The results are consistent with a decreased role for endothelial NO in the cp/cp rats of both sexes and a reduction in NO-independent cholinergic relaxation in the male cp/cp rat. This NO-independent mechanism is not affected in the female cp/cp rats. The relatively small differences between males and females in smooth muscle cell and vascular function may contribute to sex-related differences in the atherogenesis, vasospasm, and ischemic damage associated with the obese insulin-resistant state.

Microstructural white matter alterations and hippocampal volumes are associated with cognitive deficits in craniopharyngioma.

PubMed

Fjalldal, S; Follin, C; Svärd, D; Rylander, L; Gabery, S; Petersén, Å; van Westen, D; Sundgren, P C; Björkman-Burtscher, I M; Lätt, J; Ekman, B; Johanson, A; Erfurth, E M

2018-06-01

Patients with craniopharyngioma (CP) and hypothalamic lesions (HL) have cognitive deficits. Which neural pathways are affected is unknown. To determine whether there is a relationship between microstructural white matter (WM) alterations detected with diffusion tensor imaging (DTI) and cognition in adults with childhood-onset CP. A cross-sectional study with a median follow-up time of 22 (6-49) years after operation. The South Medical Region of Sweden (2.5 million inhabitants). Included were 41 patients (24 women, ≥17 years) surgically treated for childhood-onset CP between 1958-2010 and 32 controls with similar age and gender distributions. HL was found in 23 patients. Subjects performed cognitive tests and magnetic resonance imaging, and images were analyzed using DTI of uncinate fasciculus, fornix, cingulum, hippocampus and hypothalamus as well as hippocampal volumetry. Right uncinate fasciculus was significantly altered ( P  ≤ 0.01). Microstructural WM alterations in left ventral cingulum were significantly associated with worse performance in visual episodic memory, explaining approximately 50% of the variation. Alterations in dorsal cingulum were associated with worse performance in immediate, delayed recall and recognition, explaining 26-38% of the variation, and with visuospatial ability and executive function, explaining 19-29%. Patients who had smaller hippocampal volume had worse general knowledge ( P  = 0.028), and microstructural WM alterations in hippocampus were associated with a decline in general knowledge and episodic visual memory. A structure to function relationship is suggested between microstructural WM alterations in cingulum and in hippocampus with cognitive deficits in CP. © 2018 The authors.

Decreased absorption as a possible cause for the lower bioavailability of a sustained-release propranolol.

PubMed

Takahashi, H; Ogata, H; Warabioka, R; Kashiwada, K; Ohira, M; Someya, K

1990-03-01

The influence of sustained absorption on the oral availability of propranolol (P) and the metabolic disposition of P were investigated by obtaining the partial metabolic clearances (CLm) following long-acting P (LA) dosing in comparison with the conventional propranolol tablet (CP). Ten healthy volunteers were given a single oral dose of an LA capsule (60 mg) and CP (20 mg x 3) using a crossover design. Blood and urine samples were collected over 24- and 48-h postdose periods, respectively. Concentrations of P, propranolol glucuronide (PG), 4-hydroxypropranolol (4P), 4-hydroxypropranolol glucuronide (4PG), 4-hydroxypropranolol sulfate (4PS), and naphthoxylactic acid (NLA) were determined by HPLC with fluorescence and UV detection. Significant differences were observed between LA and CP in the area under the plasma concentration-time curves (AUCs) for P, PG, and NLA and in the amounts excreted into urine (Ae) for all measured metabolites (i.e., PG, 4P, 4PG, 4PS, and NLA). The parallel decrease of the AUC for P and the excreted amounts of all measured metabolites following LA dosing resulted in partial metabolic clearances (CLm) and renal clearances (CL) for P and its metabolites that were similar to those observed for CP. Therefore, the hepatic metabolism of P would not be affected by the slower absorption at a single oral dose of 60 mg. These results indicate that the poor absorption of P from the gastrointestinal tract might be one of the factors causing the low bioavailability of P observed after administration of the sustained-release formulation.

Solvent Dynamical Effects in Electron Transfer: Comparisons of Self-Exchange Kinetics for Cobaltocenium-Cobaltocene and Related Redox Couples with Theoretical Predictions.

DTIC Science & Technology

1988-02-17

prepared by oxidizing CP2Fe and Cp2 Fe, respectively, with nitrosonium tetrafluoroborate (Lancaster Synthesis, Ltd.) in dichloromethane...generally agreed to within 10%. As noted above, most kex measurements for CP2Co+ / ° and Cp’Co+ /° employed ca. 0.04 M cobalticenium ions together...and Weaver, M. J., J. Phys. Chem. 1984, 88, 1860. 33. For example, see (a) Taube, H., "Electron Transfer Reactions of N N ,~ %WIN 33 Complex Ions in

De-masking oxytocin-deficiency in craniopharyngioma and assessing its link with affective function.

PubMed

Gebert, Dorothea; Auer, Matthias K; Stieg, Mareike R; Freitag, Martin T; Lahne, Madlén; Fuss, Johannes; Schilbach, Katharina; Schopohl, Jochen; Stalla, Günter K; Kopczak, Anna

2018-02-01

Despite the high prevalence of panhypopituitarism and diabetes insipidus in patients with craniopharyngioma (CP), little is known about the functioning of the neuropeptide oxytocin in these patients. This is of special interest as tumor-associated lesions often impair sites critical for oxytocin production and release, and affective dysfunction in CP links with elsewhere reported prosocial, antidepressant and anxiolytic oxytocin effects. Using a prospective study-design, we tested whether oxytocin is reduced in CP-patients, and whether altered oxytocin levels account for affective and emotional dysfunction. 26 adult CP-patients and 26 healthy controls matched in sex and age underwent physical exercise, a stimulus previously shown to induce oxytocin release. Baseline and stimulated salivary oxytocin levels, as well as empathy, depression and anxiety scores were measured. Results showed that patients overall did not present with lower baseline oxytocin levels than controls (F[1,30]=0.21, p=0.649), but baseline oxytocin levels were indeed reduced in patients with hypothalamic damage, as assessed by MRI-based grading (F[2,9.79]=4.54, p=0.040). In response to exercise-induced stimulation, all CP-patients showed a blunted oxytocin-release compared to controls (F[1,30]=9.36, p=0.005). DI was not associated with oxytocin levels. Regarding affective function, unexpectedly, higher baseline oxytocin was related to higher trait anxiety (b=2.885, t(43)=2.421, p=0.020, CI[.478; 5.292]); the positive link with higher depression failed to reach statistical significance (b=1.928, t(43)=1.949, p=0.058, CI[-0.070; 3.927]). A blunted oxytocin-release was linked with higher state anxiety (b=-0.133, t(43)=-2.797, p=0.008, CI[-0.230; -0.037]). Empathy was not associated with oxytocin measures. In conclusion, we observed reduced baseline oxytocin levels only in CP-patients with hypothalamic damage. Exercise-induced stimulation de-masked an oxytocin-deficiency in all CP-patients. Baseline oxytocin levels and stimulated OT-responses might have different effects on affective function, which should be considered in future substitution paradigms. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cerebral Palsy

MedlinePlus

... her strength. Recommend on Facebook Tweet Share Compartir Cerebral palsy (CP) is a group of disorders that affect a ... ability to move and maintain balance and posture. CP is the most common motor disability in childhood. ...

Transition-state charge transfer reveals electrophilic, ambiphilic, and nucleophilic carbon-hydrogen bond activation.

PubMed

Ess, Daniel H; Nielsen, Robert J; Goddard, William A; Periana, Roy A

2009-08-26

Absolutely localized molecular orbital energy decomposition analysis of C-H activation transition states (TSs), including Pt, Au, Ir, Ru, W, Sc, and Re metal centers, shows an electrophilic, ambiphilic, and nucleophilic charge transfer (CT) continuum irrespective of the bonding paradigm (oxidative addition, sigma-bond metathesis, oxidative hydrogen migration, 1,2-substitution). Pt(II) insertion and Au(III) substitution TSs are highly electrophilic and dominated by C-H bond to metal/ligand orbital stabilization, while Ir-X and Ru-X (X = R, NH(2), OR, or BOR(2)) substitution TSs are ambiphilic in nature. In this ambiphilic activation regime, an increase in one direction of CT typically leads to a decrease in the reverse direction. Comparison of Tp(CO)Ru-OH and Tp(CO)Ru-NH(2) complexes showed no evidence for the classic d(pi)-p(pi) repulsion model. Complexes such as and Cp(CO)(2)W-B(OR)(2), (PNP)Ir(I), Cp(2)ScMe, and (acac-kappaO,kappaO)(2)Re(III)-OH were found to mediate nucleophilic C-H activation, where the CT is dominated by the metal/ligand orbital to C-H antibonding orbital interaction. This CT continuum ultimately affects the metal-alkyl intermediate polarization and possible functionalization reactions. This analysis will impact the design of new activation reactions and stimulate the discovery of more nucleophilic activation complexes.

Longitudinal development of communication in children with cerebral palsy between 24 and 53 months: Predicting speech outcomes.

PubMed

Hustad, Katherine C; Allison, Kristen M; Sakash, Ashley; McFadd, Emily; Broman, Aimee Teo; Rathouz, Paul J

2017-08-01

To determine whether communication at 2 years predicted communication at 4 years in children with cerebral palsy (CP); and whether the age a child first produces words imitatively predicts change in speech production. 30 children (15 males) with CP participated and were seen 5 times at 6-month intervals between 24 and 53 months (mean age at time 1 = 26.9 months (SD 1.9)). Variables were communication classification at 24 and 53 months, age that children were first able to produce words imitatively, single-word intelligibility, and longest utterance produced. Communication at 24 months was highly predictive of abilities at 53 months. Speaking earlier led to faster gains in intelligibility and length of utterance and better outcomes at 53 months than speaking later. Inability to speak at 24 months indicates greater speech and language difficulty at 53 months and a strong need for early communication intervention.

Identification of host factors potentially involved in RTM-mediated resistance during potyvirus long distance movement.

PubMed

Sofer, Luc; Cabanillas, Daniel Garcia; Gayral, Mathieu; Téplier, Rachèle; Pouzoulet, Jérôme; Ducousso, Marie; Dufin, Laurène; Bréhélin, Claire; Ziegler-Graff, Véronique; Brault, Véronique; Revers, Frédéric

2017-07-01

The long distance movement of potyviruses is a poorly understood step of the viral cycle. Only factors inhibiting this process, referred to as "Restricted TEV Movement" (RTM), have been identified in Arabidopsis thaliana. On the virus side, the potyvirus coat protein (CP) displays determinants required for long-distance movement and for RTM-based resistance breaking. However, the potyvirus CP was previously shown not to interact with the RTM proteins. We undertook the identification of Arabidopsis factors which directly interact with either the RTM proteins or the CP of lettuce mosaic virus (LMV). An Arabidopsis cDNA library generated from companion cells was screened with LMV CP and RTM proteins using the yeast two-hybrid system. Fourteen interacting proteins were identified. Two of them were shown to interact with CP and the RTM proteins suggesting that a multiprotein complex could be formed between the RTM proteins and virions or viral ribonucleoprotein complexes. Co-localization experiments in Nicotiana benthamiana showed that most of the viral and cellular protein pairs co-localized at the periphery of chloroplasts which suggests a putative role for plastids in this process.

Prompt and easy activation by specific thioredoxins of calvin cycle enzymes of Arabidopsis thaliana associated in the GAPDH/CP12/PRK supramolecular complex.

PubMed

Marri, Lucia; Zaffagnini, Mirko; Collin, Valérie; Issakidis-Bourguet, Emmanuelle; Lemaire, Stéphane D; Pupillo, Paolo; Sparla, Francesca; Miginiac-Maslow, Myroslawa; Trost, Paolo

2009-03-01

The Calvin cycle enzymes glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK) can form under oxidizing conditions a supramolecular complex with the regulatory protein CP12. Both GAPDH and PRK activities are inhibited within the complex, but they can be fully restored by reduced thioredoxins (TRXs). We have investigated the interactions of eight different chloroplast thioredoxin isoforms (TRX f1, m1, m2, m3, m4, y1, y2, x) with GAPDH (A(4), B(4), and B(8) isoforms), PRK and CP12 (isoform 2), all from Arabidopsis thaliana. In the complex, both A(4)-GAPDH and PRK were promptly activated by TRX f1, or more slowly by TRXs m1 and m2, but all other TRXs were ineffective. Free PRK was regulated by TRX f1, m1, or m2, while B(4)- and B(8)-GAPDH were absolutely specific for TRX f1. Interestingly, reductive activation of PRK caged in the complex was much faster than reductive activation of free oxidized PRK, and activation of A(4)-GAPDH in the complex was much faster (and less demanding in terms of reducing potential) than activation of free oxidized B(4)- or B(8)-GAPDH. It is proposed that CP12-assembled supramolecular complex may represent a reservoir of inhibited enzymes ready to be released in fully active conformation following reduction and dissociation of the complex by TRXs upon the shift from dark to low light. On the contrary, autonomous redox-modulation of GAPDH (B-containing isoforms) would be more suited to conditions of very active photosynthesis.

First report of an unusual novel double mutation affecting the transcription repression domain of MeCP2 and causing a severe phenotype of Rett syndrome: Molecular analyses and computational investigation.

PubMed

Ghorbel, Rania; Ghorbel, Raouia; Rouissi, Aida; Fendri-Kriaa, Nourhene; Ben Salah, Ghada; Belguith, Neila; Ammar-Keskes, Leila; Gouider-Khouja, Neziha; Fakhfakh, Faiza

2018-02-26

Rett syndrome is an X-linked neurodevelopmental disorder that develops a profound intellectual and motor disability and affects 1 from 10 000 to 15 000 live female births. This disease is characterized by a period of apparently normal development until 6-18 months of age when motor and communication abilities regress which is caused by mutations occurred in the X-linked MECP2 gene, encoding the methyl-CpG binding protein 2. This research study reports a molecular analysis via an exhaustive gene sequencing which reveals an unusual novel double mutation (c.695 G > T; c.880C > T) located in a highly conserved region in MECP2 gene affecting the transcription repression domain (TRD) of MeCP2 protein and leading for the first time to a severe phenotype of Rett syndrome. Moreover, a computational investigation of MECP2 mutations demonstrates that the novel mutation c.695 G > T is highly deleterious which affects the MeCP2 protein showing also an adverse impact on MECP2 gene expression and resulting in an affected folding and decreased stability of MECP2 structures. Thus, the altered TRD domain engenders a disrupted process of MECP2 functions. Therefore, this is the first study which highlights a novel double mutation among the transcription repression domain (TRD) of MeCP2 protein in Rett patient with a severe clinical phenotype in North Africa region. Copyright © 2018 Elsevier Inc. All rights reserved.

Does the stoichiometric carbon:phosphorus knife edge apply for predaceous copepods?

PubMed

Laspoumaderes, Cecilia; Modenutti, Beatriz; Elser, James J; Balseiro, Esteban

2015-06-01

Recent work has indicated that stoichiometric food quality in terms of the carbon:phosphorus (C:P) ratio affects consumers whether the imbalance involves a deficit or an excess of nutrients; hence, organisms exist on a "stoichiometric knife edge". While previous studies have focused primarily on autotroph-herbivore trophic transfer, nutritional imbalances may also affect the interactions between species at higher trophic levels. Since the foods of carnivores are normally stoichiometrically similar to the body compositions of those carnivores, they may be more severely affected than herbivores if imbalances become pronounced. We analysed the response of the predatory copepod Parabroteas sarsi to monospecific diet treatments consisting of high and low C:P prey items. These dietary treatments strongly affected the predator's elemental composition and growth, although prey selection, excretion, egestion, and respiration rates were not affected. We suggest that, due to their low threshold elemental ratio and a narrow C:P stoichiometric knife edge, these predators are highly vulnerable to stoichiometric imbalances, whether an excess or a deficit of nutrients is involved. Our results demonstrating this high sensitivity to prey C:P ratio show that the stoichiometric knife edge may apply to not only herbivores but also higher trophic levels. Thus, predators such as P. sarsi, with a much narrower range of food quality, may also be strongly affected by fluctuations in the quality of their prey, with negative consequences for their secondary production.

Zirconocene mediated acetylboron chemistry.

PubMed

Jian, Zhongbao; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

2018-05-31

The methyl zirconocene complex Cp*2Zr(Me)OMes reacts with H3C-B(C6F5)2 and CO to give the respective acetyl(methyl)borate Zr complex. Cp*2Zr(H)OMes reacts with H3C-B(C6F5)2 and CO to give the respective acetyl(hydrido)borate Zr product, admixed with a minor amount of the formyl(methyl)borate Zr complex isomer. Prolonged exposure to CO under close to ambient conditions results in the uptake of another CO equivalent to yield the corresponding borata-β-lactone zirconocene product.

PiiL: visualization of DNA methylation and gene expression data in gene pathways.

PubMed

Moghadam, Behrooz Torabi; Zamani, Neda; Komorowski, Jan; Grabherr, Manfred

2017-08-02

DNA methylation is a major mechanism involved in the epigenetic state of a cell. It has been observed that the methylation status of certain CpG sites close to or within a gene can directly affect its expression, either by silencing or, in some cases, up-regulating transcription. However, a vertebrate genome contains millions of CpG sites, all of which are potential targets for methylation, and the specific effects of most sites have not been characterized to date. To study the complex interplay between methylation status, cellular programs, and the resulting phenotypes, we present PiiL, an interactive gene expression pathway browser, facilitating analyses through an integrated view of methylation and expression on multiple levels. PiiL allows for specific hypothesis testing by quickly assessing pathways or gene networks, where the data is projected onto pathways that can be downloaded directly from the online KEGG database. PiiL provides a comprehensive set of analysis features that allow for quick and specific pattern searches. Individual CpG sites and their impact on host gene expression, as well as the impact on other genes present in the regulatory network, can be examined. To exemplify the power of this approach, we analyzed two types of brain tumors, Glioblastoma multiform and lower grade gliomas. At a glance, we could confirm earlier findings that the predominant methylation and expression patterns separate perfectly by mutations in the IDH genes, rather than by histology. We could also infer the IDH mutation status for samples for which the genotype was not known. By applying different filtering methods, we show that a subset of CpG sites exhibits consistent methylation patterns, and that the status of sites affect the expression of key regulator genes, as well as other genes located downstream in the same pathways. PiiL is implemented in Java with focus on a user-friendly graphical interface. The source code is available under the GPL license from https://github.com/behroozt/PiiL.git .

The poly(rC)-binding protein αCP2 is a noncanonical factor in X. laevis cytoplasmic polyadenylation

PubMed Central

Vishnu, Melanie R.; Sumaroka, Marina; Klein, Peter S.; Liebhaber, Stephen A.

2011-01-01

Post-transcriptional control of mRNA stability and translation is central to multiple developmental pathways. This control can be linked to cytoplasmic polyadenylation in certain settings. In maturing Xenopus oocytes, specific mRNAs are targeted for polyadenylation via recruitment of the Cytoplasmic Polyadenylation Element (CPE) binding protein (CPEB) to CPE(s) within the 3′ UTR. Cytoplasmic polyadenylation is also critical to early embryonic events, although corresponding determinants are less defined. Here, we demonstrate that the Xenopus ortholog of the poly(rC) binding protein αCP2 can recruit cytoplasmic poly(A) polymerase activity to mRNAs in Xenopus post-fertilization embryos, and that this recruitment relies on cis sequences recognized by αCP2. We find that the hα-globin 3′ UTR, a validated mammalian αCP2 target, constitutes an effective target for cytoplasmic polyadenylation in Xenopus embryos, but not during Xenopus oocyte maturation. We further demonstrate that the cytoplasmic polyadenylation activity is dependent on the action of the C-rich αCP-binding site in conjunction with the adjacent AAUAAA. Consistent with its ability to target mRNA for poly(A) addition, we find that XαCP2 associates with core components of the Xenopus cytoplasmic polyadenylation complex, including the cytoplasmic poly(A) polymerase XGLD2. Furthermore, we observe that the C-rich αCP-binding site can robustly enhance the activity of a weak canonical oocyte maturation CPE in early embryos, possibly via a direct interaction between XαCP2 and CPEB1. These studies establish XαCP2 as a novel cytoplasmic polyadenylation trans factor, indicate that C-rich sequences can function as noncanonical cytoplasmic polyadenylation elements, and expand our understanding of the complexities underlying cytoplasmic polyadenylation in specific developmental settings. PMID:21444632

Using a non-spin flip model to rationalize the irregular patterns observed in the activation of the C-H and Si-H bonds of small molecules by CpMCO (M = Co, Rh) complexes.

PubMed

Castro, Guadalupe; Colmenares, Fernando

2017-09-20

The activation of the C-H and Si-H bonds of CH(CH 3 ) 3 and SiH(CH 3 ) 3 molecules by organometallic compounds CpMCO (M = Co, Rh) has been investigated through DFT and CASSCF-MRMP2 calculations. In particular, we have analyzed the pathways joining the lowest-lying triplet and singlet states of the reactants with the products arising from the insertion of the metal atom into the C-H or Si-H bonds of the organic molecules. Channels connecting the reactants with the inserted structure Cp(CO)H-M-C(CH 3 ) 3 through the oxidative addition of the C-H bond of the organic molecule to the metal fragment were found only for the reaction CpRhCO + CH(CH 3 ) 3 . However, inserted structures could also be obtained for the interactions of SiH(CH 3 ) 3 with CpCoCO and CpRhCO by two sequential reactions involving the formation and rebounding of the radical fragments Cp(CO)H-M + Si(CH 3 ) 3 . According to this two-step reaction scheme, the complex CpCoCO is unable to activate the C-H bond of the CH(CH 3 ) 3 molecule due to the high energy at which the radical fragments Cp(CO)H-M + C(CH 3 ) 3 are located. The picture attained for these interactions is consistent with the available experimental data for this kind of reaction and allows rationalization of the differences in the reactivity patterns determined for them without using spin-flip models, as has been proposed in previous studies.

Cyclosporine A and azathioprine are equipotent in chronic kidney allograft rejection.

PubMed

Hamar, P; Liu, S; Viklický, O; Szabó, A; Múller, V; Heemann, U

2000-04-15

Chronic rejection is the major cause of graft loss after kidney transplantation. Various immunosuppressive protocols have been used to ameliorate this process. We investigated whether cyclosporin A- (CyA) or azathioprine- (Aza) based immunosuppression is better able to slow the progression of chronic rejection. Fisher kidneys were transplanted into bilaterally nephrectomized Lewis rats. Recipients received CyA (1.5 mg/kg/day, s.c.) for 10 days, and were treated from day 11 with either CyA (1.5 mg/kg)+pred (0.15 mg/kg) (C+P),Aza (2 mg/kg)+pred (A+P), vehicle+pred (P), or vehicle alone (controls) (n = 8/group). Proteinuria was regularly assessed and grafts were harvested for morphological, immunohistological, and molecular biological analysis at week 24. By week 12 proteinuria had increased to significant levels. At week 24, proteinuria was significantly lower and creatinine clearance was significantly higher in C+P and A+P, than in P or controls. Morphological analysis supported these functional results: at week 24, glomerulopathy, tubular atrophy and intimal proliferation (as assessed according to the BANFF score) were less pronounced in C+P and A+P, as compared with P or controls. These morphological parameters were accompanied by a reduced infiltration of ED-1+ macrophages and CD-5+ T lymphocytes. In P or controls the synthesis of IL-2Ralpha mRNA was markedly elevated at this time. In parallel to the reduced cellular infiltration, IL-2Ralpha mRNA expression was markedly inhibited, both, in C+P and A+P. There were no significant differences between C+P and A+P regarding the parameters studied. In conclusion, both C+P and A+P reduced the infiltration of activated T lymphocytes, and the pace of chronic kidney allograft rejection. The outcome of C+P and A+P based therapy did not differ significantly.

Targeted-bisulfite sequence analysis of the methylation of CpG islands in genes encoding PNPLA3, SAMM50, and PARVB of patients with non-alcoholic fatty liver disease.

PubMed

Kitamoto, Takuya; Kitamoto, Aya; Ogawa, Yuji; Honda, Yasushi; Imajo, Kento; Saito, Satoru; Yoneda, Masato; Nakamura, Takahiro; Nakajima, Atsushi; Hotta, Kikuko

2015-08-01

The pathogenesis of non-alcoholic fatty liver disease (NAFLD) is affected by epigenetic factors as well as by genetic variation. We performed targeted-bisulfite sequencing to determine the levels of DNA methylation of 4 CpG islands (CpG99, CpG71, CpG26, and CpG101) in the regulatory regions of PNPLA3, SAMM50, PARVB variant 1, and PARVB variant 2, respectively. We compared the levels of methylation of DNA in the livers of the first and second sets of patients with mild (fibrosis stages 0 and 1) or advanced (fibrosis stages 2 to 4) NAFLD and in those of patients with mild (F0 to F2) or advanced (F3 and F4) chronic hepatitis C infection. The hepatic mRNA levels of PNPLA3, SAMM50, and PARVB were measured using qPCR. CpG26, which resides in the regulatory region of PARVB variant 1, was markedly hypomethylated in the livers of patients with advanced NAFLD. Conversely, CpG99 in the regulatory region of PNPLA3 was substantially hypermethylated in these patients. These differences in DNA methylation were replicated in a second set of patients with NAFLD or chronic hepatitis C. PNPLA3 mRNA levels in the liver of the same section of a biopsy specimen used for genomic DNA preparation were lower in patients with advanced NAFLD compared with those with mild NAFLD and correlated inversely with CpG99 methylation in liver DNA. Moreover, the levels of CpG99 methylation and PNPLA3 mRNA were affected by the rs738409 genotype. Hypomethylation of CpG26 and hypermethylation of CpG99 may contribute to the severity of fibrosis in patients with NAFLD or chronic hepatitis C infection. Copyright © 2015 European Association for the Study of the Liver. Published by Elsevier B.V. All rights reserved.

A "TNM" classification system for cancer pain: the Edmonton Classification System for Cancer Pain (ECS-CP).

PubMed

Fainsinger, Robin L; Nekolaichuk, Cheryl L

2008-06-01

The purpose of this paper is to provide an overview of the development of a "TNM" cancer pain classification system for advanced cancer patients, the Edmonton Classification System for Cancer Pain (ECS-CP). Until we have a common international language to discuss cancer pain, understanding differences in clinical and research experience in opioid rotation and use remains problematic. The complexity of the cancer pain experience presents unique challenges for the classification of pain. To date, no universally accepted pain classification measure can accurately predict the complexity of pain management, particularly for patients with cancer pain that is difficult to treat. In response to this gap in clinical assessment, the Edmonton Staging System (ESS), a classification system for cancer pain, was developed. Difficulties in definitions and interpretation of some aspects of the ESS restricted acceptance and widespread use. Construct, inter-rater reliability, and predictive validity evidence have contributed to the development of the ECS-CP. The five features of the ECS-CP--Pain Mechanism, Incident Pain, Psychological Distress, Addictive Behavior and Cognitive Function--have demonstrated value in predicting pain management complexity. The development of a standardized classification system that is comprehensive, prognostic and simple to use could provide a common language for clinical management and research of cancer pain. An international study to assess the inter-rater reliability and predictive value of the ECS-CP is currently in progress.

The demise of chloroplast DNA in Arabidopsis.

PubMed

Rowan, Beth A; Oldenburg, Delene J; Bendich, Arnold J

2004-09-01

Although it might be expected that chloroplast DNA (cpDNA) would be stably maintained in mature leaves, we report the surprising observation that cpDNA levels decline during plastid development in Arabidopsis thaliana (Col.) until most of the leaves contain little or no DNA long before the onset of senescence. We measured the cpDNA content in developing cotyledons, rosette leaves, and cauline leaves. The amount of cpDNA per chloroplast decreases as the chloroplasts develop, reaching undetectable levels in mature leaves. In young cauline leaves, most individual molecules of cpDNA are found in complex, branched forms. In expanded cauline leaves, cpDNA is present in smaller branched forms only at the base of the leaf and is virtually absent in the distal part of the leaf. We conclude that photosynthetic activity may persist long after the demise of the cpDNA. Copyright 2004 Springer-Verlag

[Regulatory B cells activated by CpG-ODN combined with anti-CD40 monoclonal antibody inhibit CD4(+)T cell proliferation].

PubMed

Wang, Keng; Tao, Lei; Su, Jianbing; Zhang, Yueyang; Zou, Binhua; Wang, Yiyuan; Li, Xiaojuan

2016-09-01

Objective To observe the immunosuppressive function of regulatory B cells (Bregs) in vitro after activated by CpG oligodeoxynucleotide (CpG-ODN) and anti-CD40 mAb. Methods Mice splenic CD5(+)CD1d(high)B cells and CD5(-)CD1d(low)B cells were sorted by flow cytometry. These B cells were first stimulated with CpG-ODN combined with anti-CD40 mAb for 24 hours, and then co-cultured with purified CD4(+)T cells. The interleukin 10 (IL-10) expression in the activated Bregs and other B cell subset, as well as the proliferation and interferon γ (IFN-γ) expression in the CD4(+) T cells activated by anti-CD3 mAb plus anti-CD28 mAb were determined by flow cytometry. Results CD5(+)CD1d(high) B cells activated by CpG-ODN plus anti-CD40 mAb blocked the up-regulated CD4(+)T proliferation and significantly reduced the IFN-γ level. At the same time, activated CD5(-)CD1d(low)B cells showed no inhibitory effect on CD4(+)T cells. Further study revealed that IL-10 expression in the CD5(+)CD1d(high) B cells were much higher than that in the CD5(-)CD1d(low)B cells after stimulated with CpG-ODN combined with anti-CD40 mAb for 24 hours. Conclusion CD5(+)CD1d(high) B cells activated by CpG-ODN combined with anti-CD40 mAb have immune inhibitory effects on CD4(+)T cell activation in vitro , which possibly due to IL-10 secretion.

Saponin and non-saponin fractions of red ginseng ameliorate cisplatin-induced pica in rats.

PubMed

Sathyanath, Rekha; Hanumantha Rao, Balaji Raghavendran; Kim, Hyeong-Geug; Cho, Jung-Hyo; Son, Chang-Gue

2013-08-01

Nausea and vomiting are considered as the foremost unpleasant side effects of chemotherapy experienced by 20-90% of cancer patients. In the present study, the effects of Korean Panax ginseng C.A. Meyer (Araliaceae) (RG), ginseng saponin (GS) and non-saponin (GNS) on cisplatin (CP)-induced pica and gastric damage in rats were investigated. Rats were treated with RG (25, 50, 100 mg/kg b.wt.), GS (5 and 10 mg/kg 100 mg/kg b.wt.) and GNS (50 and 100 mg/kg b.wt.) before or after a single intraperitoneal injection of CP (6 mg/kg b.wt.). Kaolin together with normal food intake, normal food alone, body weight, histological examination of stomach and small intestine were used as indices of CP-induced pica in rats. Pre-treatment with RG (50 and 100 mg/kg b.wt.) attenuated CP-induced kaolin intake at 24 h. CP-induced kaolin intake decreased upon post-treatment of rats with RG (50 and 100 mg/kg b.wt.) at 48 h. The incidence of body weight reduction at 48 and 72 h diminished in rats post-treated with RG (50 mg/kg b.wt.). Pre-treatment with GS (5 and 10 mg/kg b.wt.) and GNS (50 and 100 mg/kg b.wt.) attenuated CP-induced kaolin intake while normal food intake was not improved in 24 and 48 h. The gastro-protective effects of RG, GS and GNS were further confirmed by histopathological (damage in glandular portion and villi with dilated appearance) findings. The study indicates that both the red GS and GNS improve feeding behavior against CP-induced pica in rats.

2-Phenylbenzothiazole conjugated with cyclopentadienyl tricarbonyl [CpM(CO)3] (M = Re, (99m)Tc) complexes as potential imaging probes for β-amyloid plaques.

PubMed

Jia, Jianhua; Cui, Mengchao; Dai, Jiapei; Liu, Boli

2015-04-14

Technetium-99m-labeled cyclopentadienyl tricarbonyl complexes conjugated with the 2-phenylbenzothiazole binding motif were synthesized. The rhenium surrogates , , and were demonstrated to have moderate to high affinities for Aβ1-42 aggregates with Ki values of 142, 76, 64 and 24 nM, respectively. During the fluorescence staining of brain sections of transgenic mice and patients with Alzheimer's disease, these rhenium complexes demonstrated perfect and intense labeling of Aβ plaques. Moreover, in in vitro autoradiography, (99m)Tc-labeled complexes clearly detected β-amyloid plaques on sections of brain tissue from transgenic mice, which confirmed the sufficient affinity of these tracers for Aβ plaques. However, these compounds did not show desirable properties in vivo, especially showing poor brain uptake (below 0.5% ID g(-1)), which will hinder the further development of these tracers as brain imaging agents. Nonetheless, it is encouraging that these (99m)Tc-labeled complexes designed by a conjugate approach displayed sufficient affinities for Aβ plaques.

A set of plastid loci for use in multiplex fragment length genotyping for intraspecific variation in Pinus (Pinaceae)1

PubMed Central

Wofford, Austin M.; Finch, Kristen; Bigott, Adam; Willyard, Ann

2014-01-01

• Premise of the study: Recently released Pinus plastome sequences support characterization of 15 plastid simple sequence repeat (cpSSR) loci originally published for P. contorta and P. thunbergii. This allows selection of loci for single-tube PCR multiplexed genotyping in any subsection of the genus. • Methods: Unique placement of primers and primer conservation across the genus were investigated, and a set of six loci were selected for single-tube multiplexing. We compared interspecific variation between cpSSRs and nucleotide sequences of ycf1 and tested intraspecific variation for cpSSRs using 911 samples in the P. ponderosa species complex. • Results: The cpSSR loci contain mononucleotide and complex repeats with additional length variation in flanking regions. They are not located in hypervariable regions, and most primers are conserved across the genus. A single PCR per sample multiplexed for six loci yielded 45 alleles in 911 samples. • Discussion: The protocol allows efficient genotyping of many samples. The cpSSR loci are too variable for Pinus phylogenies but are useful for the study of genetic structure within and among populations. The multiplex method could easily be extended to other plant groups by choosing primers for cpSSR loci in a plastome alignment for the target group. PMID:25202625

Structural and Computational Studies of Cp(CO)2(PCy3)MoFBF3, a Complex with a Bound BF4- Ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Tan-Yun; Szalda, David J.; Franz, James A.

2010-02-15

Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BF4 gives Cp(CO)2(PCy3)MoFBF3, and the crystal structure of this complex was determined. In the weakly bound FBF3 ligand, the B-F(bridging) bond length is 1.475(8) Å, which is 0.15 Å longer than the average length of the three B-F(terminal) bonds. The PCy3 and FBF3 ligands are cis to each other in the four-legged piano stool structure. Electronic structure (DFT) calculations predict the trans isomer of Cp(CO)2(PCy3)MoFBF3 to be 9.5 kcal/mol (in ΔGog,298)) less stable than the cis isomer that was crystallographically characterized. Hydride transfer from Cp(CO)2(PCy3)MoH to Ph3C+BAr'4 [Ar' = 3,5-bis(trifluoromethyl)phenyl] in CH2Cl2 solvent produces [Cp(CO)2(PCy3)Mo(ClCH2Cl)]+[BAr'4]more » , in which CH2Cl2 is coordinated to the metal. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.« less

Maternal BMI as a predictor of methylation of obesity-related genes in saliva samples from preschool-age Hispanic children at-risk for obesity.

PubMed

Oelsner, Kathryn Tully; Guo, Yan; To, Sophie Bao-Chieu; Non, Amy L; Barkin, Shari L

2017-01-09

The study of epigenetic processes and mechanisms present a dynamic approach to assess complex individual variation in obesity susceptibility. However, few studies have examined epigenetic patterns in preschool-age children at-risk for obesity despite the relevance of this developmental stage to trajectories of weight gain. We hypothesized that salivary DNA methylation patterns of key obesogenic genes in Hispanic children would 1) correlate with maternal BMI and 2) allow for identification of pathways associated with children at-risk for obesity. Genome-wide DNA methylation was conducted on 92 saliva samples collected from Hispanic preschool children using the Infinium Illumina HumanMethylation 450 K BeadChip (Illumina, San Diego, CA, USA), which interrogates >484,000 CpG sites associated with ~24,000 genes. The analysis was limited to 936 genes that have been associated with obesity in a prior GWAS Study. Child DNA methylation at 17 CpG sites was found to be significantly associated with maternal BMI, with increased methylation at 12 CpG sites and decreased methylation at 5 CpG sites. Pathway analysis revealed methylation at these sites related to homocysteine and methionine degradation as well as cysteine biosynthesis and circadian rhythm. Furthermore, eight of the 17 CpG sites reside in genes (FSTL1, SORCS2, NRF1, DLC1, PPARGC1B, CHN2, NXPH1) that have prior known associations with obesity, diabetes, and the insulin pathway. Our study confirms that saliva is a practical human tissue to obtain in community settings and in pediatric populations. These salivary findings indicate potential epigenetic differences in Hispanic preschool children at risk for pediatric obesity. Identifying early biomarkers and understanding pathways that are epigenetically regulated during this critical stage of child development may present an opportunity for prevention or early intervention for addressing childhood obesity. The clinical trial protocol is available at ClinicalTrials.gov ( NCT01316653 ). Registered 3 March 2011.

Formic acid acting as an efficient oxygen scavenger in four-electron reduction of oxygen catalyzed by a heterodinuclear iridium-ruthenium complex in water.

PubMed

Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

2010-09-01

A heterodinuclear iridium-ruthenium complex [Ir(III)(Cp*)(H(2)O)(bpm)Ru(II)(bpy)(2)](SO(4))(2) (Cp* = eta(5)-pentamethyl-cyclopentadienyl, bpm = 2,2'-bipyrimidine, bpy = 2,2'-bipyridine) acts as an effective catalyst for removal of dissolved O(2) by the four-electron reduction of O(2) with formic acid in water at an ambient temperature.

Direction to practical production of hydrogen by formic acid dehydrogenation with Cp*Ir complexes bearing imidazoline ligands

DOE PAGES

Onishi, Naoya; Ertem, Mehmed Z.; Xu, Shaoan; ...

2016-11-10

In a Cp*Ir complex with a bidentate pyridyl-imidazoline ligand achieved the evolution of 1.02 m 3 of H 2/CO 2 gases by formic acid dehydrogenation without any additives or adjustments in the solution system. Furthermore, the pyridyl-imidazoline moieties provided the optimum pH to be 1.7, resulting in high activity and stability even at very acidic conditions.

Direction to practical production of hydrogen by formic acid dehydrogenation with Cp*Ir complexes bearing imidazoline ligands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Onishi, Naoya; Ertem, Mehmed Z.; Xu, Shaoan

In a Cp*Ir complex with a bidentate pyridyl-imidazoline ligand achieved the evolution of 1.02 m 3 of H 2/CO 2 gases by formic acid dehydrogenation without any additives or adjustments in the solution system. Furthermore, the pyridyl-imidazoline moieties provided the optimum pH to be 1.7, resulting in high activity and stability even at very acidic conditions.

A possible molecular basis for photoprotection in the minor antenna proteins of plants.

PubMed

Fox, Kieran F; Ünlü, Caner; Balevičius, Vytautas; Ramdour, Baboo Narottamsing; Kern, Carina; Pan, Xiaowei; Li, Mei; van Amerongen, Herbert; Duffy, Christopher D P

2018-07-01

The bioenergetics of light-harvesting by photosynthetic antenna proteins in higher plants is well understood. However, investigation into the regulatory non-photochemical quenching (NPQ) mechanism, which dissipates excess energy in high light, has led to several conflicting models. It is generally accepted that the major photosystem II antenna protein, LHCII, is the site of NPQ, although the minor antenna complexes (CP24/26/29) are also proposed as alternative/additional NPQ sites. LHCII crystals were shown to exhibit the short excitation lifetime and several spectral signatures of the quenched state. Subsequent structure-based models showed that this quenching could be explained by slow energy trapping by the carotenoids, in line with one of the proposed models. Using Fluorescence Lifetime Imaging Microscopy (FLIM) we show that the crystal structure of CP29 corresponds to a strongly quenched conformation. Using a structure-based theoretical model we show that this quenching may be explained by the same slow, carotenoid-mediated quenching mechanism present in LHCII crystals. Copyright © 2018 Elsevier B.V. All rights reserved.

Fulminant massive gas gangrene caused by Clostridium perfringens.

PubMed

Kuroda, Shoji; Okada, Yumi; Mita, Masaki; Okamoto, Yasuo; Kato, Hirotaka; Ueyama, Shigemitsu; Fujii, Ikuzo; Morita, Sumiharu; Yoshida, Yasuaki

2005-05-01

Clostridium perfringens (C.P) gas gangrene is one of the most fulminant infectious diseases. We encountered fulminant massive gas gangrene in a 56- year-old man with alcoholic liver cirrhosis. The patient died 14 hours after diagnosis of gas gangrene (54 hours after admission). Dramatic changes in abdominal CT imaging revealed development of a massive volume of gas in the intra-portal vein, retroperitoneum and abdominal subcutaneous tissue within 24 hours. We also proved C.P infection by immunohistological staining, leading to a diagnosis of C.P gas gangrene.

Electroosmotic pump performance is affected by concentration polarizations of both electrodes and pump

PubMed Central

Suss, Matthew E.; Mani, Ali; Zangle, Thomas A.; Santiago, Juan G.

2010-01-01

Current methods of optimizing electroosmotic (EO) pump performance include reducing pore diameter and reducing ionic strength of the pumped electrolyte. However, these approaches each increase the fraction of total ionic current carried by diffuse electric double layer (EDL) counterions. When this fraction becomes significant, concentration polarization (CP) effects become important, and traditional EO pump models are no longer valid. We here report on the first simultaneous concentration field measurements, pH visualizations, flow rate, and voltage measurements on such systems. Together, these measurements elucidate key parameters affecting EO pump performance in the CP dominated regime. Concentration field visualizations show propagating CP enrichment and depletion fronts sourced by our pump substrate and traveling at order mm/min velocities through millimeter-scale channels connected serially to our pump. The observed propagation in millimeter-scale channels is not explained by current propagating CP models. Additionally, visualizations show that CP fronts are sourced by and propagate from the electrodes of our system, and then interact with the EO pump-generated CP zones. With pH visualizations, we directly detect that electrolyte properties vary sharply across the anode enrichment front interface. Our observations lead us to hypothesize possible mechanisms for the propagation of both pump- and electrode-sourced CP zones. Lastly, our experiments show the dynamics associated with the interaction of electrode and membrane CP fronts, and we describe the effect of these phenomena on EO pump flow rates and applied voltages under galvanostatic conditions. PMID:21516230

The effect of enamel bleaching on the shear bond strengths of metal and ceramic brackets.

PubMed

Oztaş, E; Bağdelen, G; Kiliçoğlu, H; Ulukapi, H; Aydin, I

2012-04-01

The aim of this study was to evaluate the effects of bleaching and delayed bonding on the shear bond strengths of metal and ceramic brackets bonded with light and chemically cure composite resin to human enamel. One hundred and twenty extracted human premolar teeth were randomly divided into three groups of 40 each. The first two groups were bleached with 20 per cent carbamide peroxide (CP) at-home bleaching agent. No bleaching procedures were applied to the third group and served as control. The first two and control groups were divided into equal subgroups according to different adhesive-bracket combinations. Specimens in group 1 (n = 40) were bonded 24 hours after bleaching process was completed while the specimens in group 2 (n = 40) were bonded 14 days after. The specimens in all groups were debonded with a Universal testing machine while the modified adhesive remnant index was used to evaluate fracture properties. No statistically significant differences were found between the shear bond strengths of metal and ceramic brackets bonded to bleached enamel after 24 hours, 14 days, and unbleached enamel with light or chemical cure adhesives (P > 0.05). The mode of failure was mostly at the bracket/adhesive interface and cohesive failures within the resin were also observed. Our findings indicated that at-home bleaching agents that contain 20 per cent CP did not significantly affect the shear bond strength of metal and ceramic orthodontic brackets to enamel when bonding is performed 24 hours or 14 days after bleaching.

Sex differences in cerebral palsy on neuromotor outcome: a critical review.

PubMed

Romeo, Domenico M; Sini, Francesca; Brogna, Claudia; Albamonte, Emilio; Ricci, Daniela; Mercuri, Eugenio

2016-08-01

Sex differences have been reported in children with cerebral palsy (CP), with males having a higher risk of developing CP, but it is not entirely clear whether sex may also affect the severity of motor impairment. The aim of the present study was to critically review the existing literature on sex influence on neuromotor outcome in children with CP. The published papers confirm that CP occurs more frequently in males than in females. Within different types of CP or individual level of impairment, however, there was limited evidence that sex also had an effect on their performance. © 2016 Mac Keith Press.

7 CFR 915.332 - Florida avocado maturity regulation.

Code of Federal Regulations, 2010 CFR

2010-01-01

...-24 18 37/16 11-07 Herman 10-03 16 39/16 10-17 14 36/16 10-31 Pinkerton (CP) 10-03 13 33/16 10-17 11... Reed (CP) 12-12 12 34/16 12-26 10 33/16 1-09 9 30/16 1-23 1 Avocados of the West Indian type varieties...

7 CFR 915.332 - Florida avocado maturity regulation.

Code of Federal Regulations, 2011 CFR

2011-01-01

...-24 18 37/16 11-07 Herman 10-03 16 39/16 10-17 14 36/16 10-31 Pinkerton (CP) 10-03 13 33/16 10-17 11... Reed (CP) 12-12 12 34/16 12-26 10 33/16 1-09 9 30/16 1-23 1 Avocados of the West Indian type varieties...

7 CFR 915.332 - Florida avocado maturity regulation.

Code of Federal Regulations, 2013 CFR

2013-01-01

...-24 18 37/16 11-07 Herman 10-03 16 39/16 10-17 14 36/16 10-31 Pinkerton (CP) 10-03 13 33/16 10-17 11... Reed (CP) 12-12 12 34/16 12-26 10 33/16 1-09 9 30/16 1-23 1 Avocados of the West Indian type varieties...

7 CFR 915.332 - Florida avocado maturity regulation.

Code of Federal Regulations, 2014 CFR

2014-01-01

...-24 18 37/16 11-07 Herman 10-03 16 39/16 10-17 14 36/16 10-31 Pinkerton (CP) 10-03 13 33/16 10-17 11... Reed (CP) 12-12 12 34/16 12-26 10 33/16 1-09 9 30/16 1-23 1 Avocados of the West Indian type varieties...

7 CFR 915.332 - Florida avocado maturity regulation.

Code of Federal Regulations, 2012 CFR

2012-01-01

...-24 18 37/16 11-07 Herman 10-03 16 39/16 10-17 14 36/16 10-31 Pinkerton (CP) 10-03 13 33/16 10-17 11... Reed (CP) 12-12 12 34/16 12-26 10 33/16 1-09 9 30/16 1-23 1 Avocados of the West Indian type varieties...

Giant Rugby Ball [{CpBnFe(η5-P5)}24Cu96Br96] Derived from Pentaphosphaferrocene and CuBr2

PubMed Central

2015-01-01

The self-assembly of [CpBnFe(η5-P5)] (CpBn = η5-C5(CH2Ph)5) with CuBr2 leads to the formation of an unprecedented rugby ball-shaped supramolecule consisting of 24 units of the pentaphosphaferrocene and an extended CuBr framework, which does not follow the fullerene topology. The resulting scaffold of 312 noncarbon atoms reveals three different coordination modes of the cyclo-P5 ligand including a novel π-coordination. The outer dimensions of 3.7 × 4.6 nm of the sphere approach the range of the size of proteins. With a value of 32.1 nm3, it is 62 times larger in volume than a C60 molecule. Surprisingly, this giant rugby ball is also slightly soluble in CH2Cl2. PMID:26280785

Aging reduces the neuroprotective capacity, VEGF secretion, and metabolic activity of rat choroid plexus epithelial cells.

PubMed

Emerich, Dwaine F; Schneider, Patricia; Bintz, Briannan; Hudak, Jebecka; Thanos, Christopher G

2007-01-01

Delivery of neurotrophic molecules to the brain has potential for preventing neuronal loss in neurodegenerative disorders. Choroid plexus (CP) epithelial cells secrete numerous neurotrophic factors, and encapsulated CP transplants are neuroprotective in models of stroke and Huntington's disease (HD). To date, all studies examining the neuroprotective potential of CP transplants have used cells isolated from young donor animals. Because the aging process significantly impacts the cytoarchitecture and function of the CP the following studies determined whether age-related impairments occur in its neuroprotective capacity. CP was isolated from either young (3-4 months) or aged (24 months) rats. In vitro, young CP epithelial cells secreted more VEGF and were metabolically more active than aged CP epithelial cells. Additionally, conditioned medium from cultured aged CP was less potent than young CP at enhancing the survival of serum-deprived neurons. Finally, encapsulated CP was tested in an animal model of HD. Cell-loaded or empty alginate capsules (control group) were transplanted unilaterally into the rat striatum. Seven days later, the animals received an injection of quinolinic acid (QA; 225 nmol) adjacent to the implant site. Animals were tested for motor function 28 days later. In the control group, QA lesions severely impaired function of the contralateral forelimb. Implants of young CP were potently neuroprotective as rats receiving CP transplants were not significantly impaired when tested for motor function. In contrast, implants of CP from aged rats were only modestly effective and were much less potent than young CP transplants. These data are the first to directly link aging with diminished neuroprotective capacity of CP epithelial cells.

Kinetics and Mechanism of the Hydrogenation of CpCr(CO)3•/[CpCr(CO)3]2 Equilibrium to CpCr(CO)3H

DOE Office of Scientific and Technical Information (OSTI.GOV)

Norton, Jack R.; Spataru, Tudor; Camaioni, Donald M.

2014-05-26

The kinetics of the hydrogenation of 2 CpCr(CO)3•/[CpCr(CO)3]2 to CpCr(CO)3H has been investigated. The reaction is second-order in Cr and first-order in H2, with a rate constant of 45 M 2s 1 at 25 °C in benzene. DFT calculations rule out an H2 complex as an intermediate, and suggest (a) end-on approach of H2 to one Cr of [CpCr(CO)3]2 as the Cr-Cr bond undergoes heterolytic cleavage, (b) heterolytic cleavage of the coordinated H2 between O and Cr, and (c) isomerization of the resulting O-protonated CpCr(CO)2(COH) to CpCr(CO)3H. The work at Pacific Northwest National Laboratory (PNNL) was supported by the U.S.more » Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences; Battelle operates PNNL for DOE.« less

Recent advances in MeCP2 structure and function1

PubMed Central

Hite, Kristopher C.; Adams, Valerie H.; Hansen, Jeffrey C.

2010-01-01

Mutations in methyl DNA binding protein 2 (MeCP2) cause the neurodevelopmental disorder Rett syndrome (RTT). The mechanism(s) by which the native MeCP2 protein operates in the cell are not well understood. Historically, MeCP2 has been characterized as a proximal gene silencer with 2 functional domains: a methyl DNA binding domain and a transcription repression domain. However, several lines of new data indicate that MeCP2 structure and function relationships are more complex. In this review, we first discuss recent studies that have advanced understanding of the basic structural biochemistry of MeCP2. This is followed by an analysis of cell-based experiments suggesting MeCP2 is a regulator, rather than a strict silencer, of transcription. The new data establish MeCP2 as a multifunctional nuclear protein, with potentially important roles in chromatin architecture, regulation of RNA splicing, and active transcription. We conclude by discussing clinical correlations between domain-specific mutations and RTT pathology to stress that all structural domains of MeCP2 are required to properly mediate cellular function of the intact protein. PMID:19234536

Carbon-hydrogen activation of cycloalkanes by cyclopentadienylcarbonylrhodium--a lifetime enigma.

PubMed

Pitts, Amanda L; Wriglesworth, Alisdair; Sun, Xue-Zhong; Calladine, James A; Zarić, Snežana D; George, Michael W; Hall, Michael B

2014-06-18

Carbon-hydrogen bond activation reactions of four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) by the Cp'Rh(CO) fragments (Cp' = η(5)-C5H5 (Cp) or η(5)-C5Me5 (Cp*)) were modeled theoretically by combining density functional and coupled cluster theories, and their reaction rates were measured by fast time-resolved infrared spectroscopy. The reaction has two steps, starting with the formation of a σ-complex intermediate, followed by oxidative addition of the C-H bond by the rhodium. A range of σ-complex stabilities among the electronically unique C-H bonds in a cycloalkane were calculated and are related to the individual strengths of the C-H bond's interactions with the Rh fragment and the steric repulsion that is incurred upon forming the specific σ-complex. The unexpectedly large increase in the lifetimes of the σ-complexes from cyclohexane to cycloheptane was predicted to be due to the large range of stabilities of the different σ-complexes found for cycloheptane. The reaction lifetimes were simulated with two mechanisms, with and without migrations among the different σ-complexes, to determine if ring migrations prior to C-H activation were influencing the rate. Both mechanisms predicted similar lifetimes for cyclopentane, cyclohexane, and, to a lesser extent, cycloheptane, suggesting ring migrations do not have a large impact on the rate of C-H activation for these cycloalkanes. For cyclooctane, the inclusion of ring migrations in the reaction mechanism led to a more accurate prediction of the lifetime, indicating that ring migrations did have an effect on the rate of C-H activation for this alkane, and that migration among the σ-complexes is faster than the C-H activation for this larger cycloalkane.

Association of red complex, A. actinomycetemcomitans and non-oral bacteria with periodontal diseases.

PubMed

da Silva-Boghossian, Carina Maciel; do Souto, Renata Martins; Luiz, Ronir R; Colombo, Ana Paula Vieira

2011-09-01

Pathogens related to systemic infections have been detected in the periodontal microbiota. The relationship amongst these pathogens, periodontal bacteria and periodontal clinical status is poorly understood. This study evaluated the association amongst red complex, A. actinomycetemcomitans (A.a) and non-oral pathogenic bacteria in subjects with good periodontal health (PH), gingivitis (G), chronic (CP) and aggressive (AP) periodontitis. Subgingival biofilm samples were obtained from 51 PH, 42 G, 219 CP and 90 AP subjects. The presence and levels of A.a, red complex (Porphyromonas gingivalis, Tannerella forsythia, Treponema denticola), Acinetobacter baumannii, Escherichia coli, Enterococcus faecalis, Pseudomonas aeruginosa, and Staphylococcus aureus were determined by DNA probes and DNA-DNA hybridization technique. CP and AP subjects presented significantly higher prevalence and levels of A.a, red complex and A. baumannii than G and PH individuals (p<0.01), whereas S. aureus was detected in lower frequency and counts in AP as compared to the other groups (p<0.001). The predictor variables age, prevalence of red complex, and the presence of A. baumannii and P. aeruginosa were strongly associated with the frequency of sites with PD and CAL ≥5 mm. Increasing age (OR 1.08), high frequency of red complex (OR 6.10), and the presence of A.a with P. aeruginosa (OR 1.90) were associated with periodontal disease (p<0.001). Subjects harbouring a high prevalence of A.a, A. baumannii, and red complex with P. aeruginosa were more likely to have AP than CP (p<0.001). Putative periodontal pathogens and non-oral bacteria alone or in association were strongly associated with periodontitis. Copyright © 2011 Elsevier Ltd. All rights reserved.

Low-protein diets affect ileal amino acid digestibility and gene expression of digestive enzymes in growing and finishing pigs.

PubMed

He, Liuqin; Wu, Li; Xu, Zhiqi; Li, Tiejun; Yao, Kang; Cui, Zhijie; Yin, Yulong; Wu, Guoyao

2016-01-01

The objective of this study was to evaluate effects of dietary crude protein (CP) intake on ileal amino acid digestibilities and expression of genes for digestive enzymes in growing and finishing pigs. In Experiment 1, 18 growing pigs (average initial BW = 36.5 kg) were assigned randomly into one of three treatments (n = 6/treatment group) representing normal (18 % CP), low (15 % CP), and very low (12 % CP) protein intake. In Experiment 2, 18 finishing pigs (average initial BW = 62.3 kg) were allotted randomly into one of three treatments (n = 6/treatment group), representing normal (16 % CP), low (13 % CP) and very low (10 % CP) protein intake. In both experiments, diets with low and very low CP were supplemented with crystalline amino acids to achieve equal content of standardized ileal digestible Lys, Met, Thr, and Trp, and were provided to pigs ad libitum. Daily feed intake, BW, and feed/gain ratios were determined. At the end of each experiment, all pigs were slaughtered to collect pancreas, small-intestine samples, and terminal ileal chymes. Samples were used for determining expression of genes for digestive enzymes and ileal amino acid digestibilities. Growing pigs fed the 12 % CP and 15 % CP diets had lower final body weight (P < 0.01) and ADG (P < 0.0001) when compared with pigs fed the 18 % dietary CP diet. Growing pigs fed with the 12 % CP diet showed higher digestibilities for CP (P < 0.05), DM (P < 0.05), Lys (P < 0.0001), Met (P < 0.01), Cys (P < 0.01), Thr (P < 0.01), Trp (P < 0.05), Val (P < 0.05), Phe (P < 0.05), Ala (P < 0.05), Cys (P < 0.01), and Gly (P < 0.05) than those fed the 18 % CP diet. Finishing pigs fed the 16 % CP diet had a higher (P < 0.01) final body weight than those fed the 10 % CP diet. mRNA levels for digestive enzymes (trypsinogen, chymotrypsin B, and dipeptidases-II and III) differed among the three groups of pigs (P < 0.05), and no difference was noted in the genes expression between control group and lower CP group. These results indicated that a reduction of dietary CP by a six-percentage value limited the growth performance of growing-finishing pigs and that a low-protein diet supplemented with deficient amino acids could reduce the excretion of nitrogen into the environment without affecting weight gain.

[Relationship between chronic prostatitis and prostatic calculus].

PubMed

Chen, Hong-jie; Yang, Ning-gang; Zhang, Ju-jie; Wang, Jun; Zhang, Xiang-jun; Zhang, Jun; Yu, Xin-ning; Zhang, Dian-ting

2011-01-01

To explore the relationship between chronic prostatitis (CP) and prostatic calculus (PC). We used transperineal ultrasonography (TPUS) to detect PC in 500 normal volunteers and 491 CP patients, and divided them into a CP and a CP + PC group according to the ultrasonographic results. Then we analyzed the NIH-CPSI scores, duration of symptoms and white blood cell count in the expressed prostate secretion (ESP). PC was found in 19.8% of the normal controls, 5% (5/100), 12% (12/100), 19% (19/100), 27% (27/100) and 36% (36/100) in the 20-30 yr, 31-40 yr, 41-50 yr, 51-60 yr and > 60 yr groups, respectively. In comparison, PC was detected in 42.2% of the CP patients, 15.8% (12/76), 30.1% (69/215), 55.7% (59/109), 66.2% (43/65) and 82.8% (24/29) in the above five age groups, respectively, with statistically significant differences between the control and CP groups (P < 0.01). The CP and CP + PC groups showed significant differences in the duration of symptoms and white blood cell count in ESP (P < 0.01) but not in CPSI scores (P < 0.05). The incidence of PC is higher in CP patients than in healthy men, and it is associated with inflammation, aging and symptom duration, but not with CPSI scores.

Association Between Chloroplast DNA and Mitochondrial DNA Haplotypes in Prunus spinosa L. (Rosaceae) Populations across Europe

PubMed Central

MOHANTY, APARAJITA; MARTÍN, JUAN PEDRO; GONZÁLEZ, LUIS MIGUEL; AGUINAGALDE, ITZIAR

2003-01-01

Chloroplast DNA (cpDNA) and mitochondrial DNA (mtDNA) were studied in 24 populations of Prunus spinosa sampled across Europe. The cpDNA and mtDNA fragments were amplified using universal primers and subsequently digested with restriction enzymes to obtain the polymorphisms. Combinations of all the polymorphisms resulted in 33 cpDNA haplotypes and two mtDNA haplotypes. Strict association between the cpDNA haplotypes and the mtDNA haplotypes was detected in most cases, indicating conjoint inheritance of the two genomes. The most frequent and abundant cpDNA haplotype (C20; frequency, 51 %) is always associated with the more frequent and abundant mtDNA haplotype (M1; frequency, 84 %). All but two of the cpDNA haplotypes associated with the less frequent mtDNA haplotype (M2) are private haplotypes. These private haplotypes are phylogenetically related but geographically unrelated. They form a separate cluster on the minimum‐length spanning tree. PMID:14534199

An ultra-wide bandwidth-based range/GPS tight integration approach for relative positioning in vehicular ad hoc networks

NASA Astrophysics Data System (ADS)

Shen, Feng; Wayn Cheong, Joon; Dempster, Andrew G.

2015-04-01

Relative position awareness is a vital premise for the implementation of emerging intelligent transportation systems, such as collision warning. However, commercial global navigation satellite systems (GNSS) receivers do not satisfy the requirements of these applications. Fortunately, cooperative positioning (CP) techniques, through sharing the GNSS measurements between vehicles, can improve the performance of relative positioning in a vehicular ad hoc network (VANET). In this paper, while assuming there are no obstacles between vehicles, a new enhanced tightly coupled CP technique is presented by adding ultra-wide bandwidth (UWB)-based inter-vehicular range measurements. In the proposed CP method, each vehicle fuses the GPS measurements and the inter-vehicular range measurements. Based on analytical and experimental results, in the full GPS coverage environment, the new tight integration CP method outperforms the INS-aided tight CP method, tight CP method, and DGPS by 11%, 15%, and 24%, respectively; in the GPS outage scenario, the performance improvement achieves 60%, 65%, and 73%, respectively.

Electron transfer protein complexes in the thylakoid membranes of heterocysts from the cyanobacterium Nostoc punctiforme.

PubMed

Cardona, Tanai; Battchikova, Natalia; Zhang, Pengpeng; Stensjö, Karin; Aro, Eva-Mari; Lindblad, Peter; Magnuson, Ann

2009-04-01

Filamentous, heterocystous cyanobacteria are capable of nitrogen fixation and photoautotrophic growth. Nitrogen fixation takes place in heterocysts that differentiate as a result of nitrogen starvation. Heterocysts uphold a microoxic environment to avoid inactivation of nitrogenase, e.g. by downregulation of oxygenic photosynthesis. The ATP and reductant requirement for the nitrogenase reaction is considered to depend on Photosystem I, but little is known about the organization of energy converting membrane proteins in heterocysts. We have investigated the membrane proteome of heterocysts from nitrogen fixing filaments of Nostoc punctiforme sp. PCC 73102, by 2D gel electrophoresis and mass spectrometry. The membrane proteome was found to be dominated by the Photosystem I and ATP-synthase complexes. We could identify a significant amount of assembled Photosystem II complexes containing the D1, D2, CP43, CP47 and PsbO proteins from these complexes. We could also measure light-driven in vitro electron transfer from Photosystem II in heterocyst thylakoid membranes. We did not find any partially disassembled Photosystem II complexes lacking the CP43 protein. Several subunits of the NDH-1 complex were also identified. The relative amount of NDH-1M complexes was found to be higher than NDH-1L complexes, which might suggest a role for this complex in cyclic electron transfer in the heterocysts of Nostoc punctiforme.

Contemporary treatment options for chronic prostatitis/chronic pelvic pain syndrome.

PubMed

Ismail, M; Mackenzie, K; Hashim, H

2013-07-01

The prostate gland, about the size a walnut, forms part of the male reproductive system and sits directly underneath the bladder surrounding the urethra. It is a fibromuscular exocrine gland that secretes a complex proteolytic fluid which constitutes one-third of the volume of the seminal fluid. Prostatitis refers to a group of disorders that affect the prostate and cause genitourinary pain, dysuria, urinary frequency and sexual dysfunction. The prevalence of prostatitis in the United States has been estimated to be around 9%, while the worldwide prevalence ranges from 2 to 10%, and 15% of men experience prostatitis-like symptoms at some point in their lives. There are a number of treatments which have been used for chronic prostatitis/chronic pelvic pain syndrome (CP/CPPS), with only a small amount of high-level evidence. The current recommended treatment for CP/CPPS is predominantly a multimodal approach using a combination of antibiotics, α-blockers, antimuscarinic and anti-inflammatory drugs. The response to treatment and improvement in symptoms is very variable; therefore, as the evidence evolves, it is likely that treatment will become symptom specific rather than a generic, 'one strategy fits all' treatment for CP/CPPS. Copyright 2013 Prous Science, S.A.U. or its licensors. All rights reserved.

[Adaptation of control mechanisms involved in upright undisturbed stance maintenance during prolonged darkness].

PubMed

Rougier, P

2003-04-01

To assess to which extent the non visual somato-sensorial information may, through a recalibration process, induce a reorganisation by the central nervous system to control undisturbed upright stance. Ten healthy adults were placed in complete darkness for a 24 min period. Their postural performance was recorded through a force platform on which they were required to stand still at regular intervals. Centre of Pressure (CP) displacements, recorded from the platform, were modelled as fractional brownian motion. Through this analysis, one may objectively assess from which distance and for how long the corrective process is initiated with the aim of slowing and retrace its steps. In addition, the degree to which the CP trajectories are successively controlled was determined. Once in complete darkness, an increase of the mean time intervals (Delta(t)) before the corrective process intervenes was observed, the effect being mostly significant for the mediolateral direction. In parallel, the mean distances covered at this Delta(t) were slightly affected for both mediolateral and anteroposterior directions. Lastly, the degree to which the CP trajectories are controlled tended to decrease. These data suggest a reorganisation of the control mechanisms called into play for maintaining an undisturbed upright stance, thus implying participation of the central nervous system. This short-term adaptation is discussed on the basis of our knowledge of long term adaptations previously observed in blind individuals, and also in a rehabilitation perspective.

Effects of inclusion levels of banana (Musa spp.) peelings on feed degradability and rumen environment of cattle fed basal elephant grass.

PubMed

Nambi-Kasozi, Justine; Sabiiti, Elly Nyambobo; Bareeba, Felix Budara; Sporndly, Eva; Kabi, Fred

2016-04-01

The effect of feeding varying banana peeling (BP) levels on rumen environment and feed degradation characteristics was evaluated using three rumen fistulated steers in four treatments. The steers were fed BP at 0, 20, 40, and 60% levels of the daily ration with basal elephant grass (EG) to constitute four diets. Maize bran, cotton seed cake, and Gliricidia sepium were offered to make the diets iso-nitrogenous. The nylon bag technique was used to measure BP and EG dry matter (DM), crude protein (CP), and neutral detergent fiber (NDF) degradabilities at 0, 6, 12, 24, 48, 72, 96, and 120 h. Rumen fluid samples were collected to determine pH and volatile fatty acid (VFA) concentrations. Effective DM, CP, and NDF degradabilities of BP ranged between 574 and 807, 629-802, and 527-689 g/kg, respectively, being lower at higher BP levels. Elephant grass degradability behaved similarly with relatively high effective CP degradability (548-569 g/kg) but low effective DM and NDF degradability (381-403 and 336-373 g/kg, respectively). Rumen pH and VFA reduced with increasing BP in the diets. Rumen pH dropped to 5.8 and 5.9 at the 40 and 60% BP feeding levels, respectively. Banana peelings were better degraded than EG but higher BP levels negatively affected feed degradability and rumen environment.

Aggression in Children with Conduct Problems and Callous-Unemotional Traits: Social Information Processing and Response to Peer Provocation.

PubMed

Helseth, Sarah A; Waschbusch, Daniel A; King, Sara; Willoughby, Michael T

2015-11-01

Callous/unemotional traits (CU) moderate children's conduct problems (CP) in numerous domains, including social functioning. The present study examined whether CU traits also moderate the aggressiveness of children's social information processing (SIP) and responses to varying intensities of peer provocation. Sixty elementary school-age children (46 males) were grouped into those without CP or CU (controls, n = 32), those with CP but not CU (CP-only; n = 14), and those with both CP and CU (CPCU, n = 14). Participants completed a task that measured two aspects of SIP (response generation and hostile attribution bias) and a computerized reaction time task (CRTT) that measured behavior, affect, and communication before and after provocation under instrumental and hostile aggressive conditions. Children with CPCU generated more aggressive responses than controls on measures of SIP. On the CRTT, all children exhibited reactive aggression following high provocation, but only children with CPCU exhibited proactive aggression, and reactive aggression following low provocation; no differences in affect were found. In a series of exploratory analyses, CPCU children communicated antisocially, while CP-only communicated prosocially. Finally, children with CPCU did not seem to hold a grudge following the final instance of provocation, instead gradually returning to baseline like their non-CU peers. These distinct social cognitive and behavioral profiles hint at different etiologies of CP and CPCU, underscoring the variability of aggression in these populations.

Rapid eye movement sleep behaviour disorder and striatal dopamine depletion in patients with Parkinson's disease.

PubMed

Chung, S J; Lee, Y; Lee, J J; Lee, P H; Sohn, Y H

2017-10-01

Rapid eye movement sleep behaviour disorder (RBD) is related to striatal dopamine depletion. This study was performed to confirm whether clinically probable RBD (cpRBD) in patients with Parkinson's disease (PD) is associated with a specific pattern of striatal dopamine depletion. A prospective survey was conducted using the RBD Screening Questionnaire (RBDSQ) in 122 patients with PD who had undergone dopamine transporter (DAT) positron emission tomography scan. Patients with cpRBD (RBDSQ ≥ 7) exhibited greater motor deficits, predominantly in the less-affected side and axial symptoms, and were prescribed higher levodopa-equivalent doses at follow-up than those without cpRBD (RBDSQ ≤ 4), despite their similar disease and treatment durations. Compared to patients without cpRBD, those with cpRBD showed lower DAT activities in the putamen, particularly in the less-affected side in all putaminal subregions, and a tendency to be lower in the ventral striatum. In addition, greater motor deficits in patients with cpRBD than in those without cpRBD remained significant after controlling for DAT binding in the putamen and other confounding variables. These results demonstrated that the presence of RBD in patients with PD is associated with different patterns of both motor deficit distribution and striatal DAT depletion, suggesting that the presence of RBD represents a distinct PD subtype with a malignant motor parkinsonism. © 2017 EAN.

Computer-based analysis of general movements reveals stereotypies predicting cerebral palsy.

PubMed

Philippi, Heike; Karch, Dominik; Kang, Keun-Sun; Wochner, Katarzyna; Pietz, Joachim; Dickhaus, Hartmut; Hadders-Algra, Mijna

2014-10-01

To evaluate a kinematic paradigm of automatic general movements analysis in comparison to clinical assessment in 3-month-old infants and its prediction for neurodevelopmental outcome. Preterm infants at high risk (n=49; 26 males, 23 females) and term infants at low risk (n=18; eight males, 10 females) of developmental impairment were recruited from hospitals around Heidelberg, Germany. Kinematic analysis of general movements by magnet tracking and clinical video-based assessment of general movements were performed at 3 months of age. Neurodevelopmental outcome was evaluated at 2 years. By comparing the general movements of small samples of children with and without cerebral palsy (CP), we developed a kinematic paradigm typical for infants at risk of developing CP. We tested the validity of this paradigm as a tool to predict CP and neurodevelopmental impairment. Clinical assessment correctly identified almost all infants with neurodevelopmental impairment including CP, but did not predict if the infant would be affected by CP or not. The kinematic analysis, in particular the stereotypy score of arm movements, was an excellent predictor of CP, whereas stereotyped repetitive movements of the legs predicted any neurodevelopmental impairment. The automatic assessment of the stereotypy score by magnet tracking in 3-month-old spontaneously moving infants at high risk of developmental abnormalities allowed a valid detection of infants affected and unaffected by CP. © 2014 Mac Keith Press.

Effects of dietary fiber and reduced crude protein on nitrogen balance and egg production in laying hens.

PubMed

Roberts, S A; Xin, H; Kerr, B J; Russell, J R; Bregendahl, K

2007-08-01

Ammonia emission is a major concern for the poultry industry and can be lowered by dietary inclusion of fibrous ingredients and by lowering the dietary CP content. The objectives of this research were to determine the effects of dietary fiber and reduced-CP diets, which may lower NH(3) emission, on egg production and N balance in laying hens. A total of 256 Hy-Line W-36 hens were fed diets with 2 contents of CP (normal and reduced) and 4 fiber treatments in a 2 x 4 factorial arrangement from 23 to 58 wk of age. The fiber treatments included a corn and soybean meal-based control diet and diets formulated with either 10.0% corn dried distillers grains with solubles (DDGS), 7.3% wheat middlings (WM), or 4.8% soybean hulls (SH) added to contribute equal amounts of neutral detergent fiber. The CP contents of the reduced-CP diets were approximately 1 percentage unit lower than that of the normal-CP diets. All diets were formulated on a digestible amino acid basis to be isoenergetic. There were no effects (P > 0.05) of including corn DDGS, WM, or SH in the diet on egg production, egg weight, egg mass, yolk color, feed consumption, feed utilization, or BW gain. Although the corn DDGS and WM diets resulted in an increase (P < 0.001) in N consumption, N excretion was not affected (P > 0.10) compared with hens fed the control diet. The reduced-CP diets did not affect egg weight, feed consumption, or BW gain (P > 0.05); however, egg production, egg mass, feed utilization, N consumption, and N excretion were lower than that from the hens fed the normal-CP diets (P < 0.05). The results of this study show that the diets containing 10% corn DDGS, 7% WM, or 5% SH did not affect egg production or N excretion. However, the 1% lower CP diets caused a lower egg production and lower N excretion.

Physical and Mental Quality of Life (QOL) in Chronic Pancreatitis(CP): A Case-Control Study from the NAPS2 cohort

PubMed Central

Amann, Stephen T.; Yadav, Dhiraj; Barmada, M. Micheal; O’Connell, Michael; Kennard, Elizabeth D.; Anderson, Michelle; Baillie, John; Sherman, Stuart; Romagnuolo, Joseph; Hawes, Robert H.; AlKaade, Samer; Brand, Randall E.; Lewis, Michele D.; Gardner, Timothy B.; Gelrud, Andres; Money, Mary E.; Banks, Peter A.; Slivka, Adam; Whitcomb, David C

2012-01-01

Objectives Define the Quality of Life (QOL) in chronic pancreatitis (CP) subjects Methods We studied 443 well phenotyped CP subjects and 611 controls prospectively enrolled from 20 US centers between 2000–2006 in the North American Pancreatitis Study 2 (NAPS2). Responses to the SF-12 questionnaire were used to calculate the Mental (MCS) and Physical component summary scores (PCS) with norm based scoring (normal ≥50). QOL in CP subjects was compared with controls after controlling for demographic factors, drinking history, smoking and medical conditions. QOL in CP was also compared with known scores for several chronic conditions. Results Both PCS (38±11.5 vs. 52±9.4) and MCS (44±11.5 vs. 51±9.2) were significantly lower in CP compared with controls (p<0.001). On multivariable analyses, compared to controls, a profound decrease in physical QOL (PCS 12.02 points lower) and a clinically significant decrease in mental QOL (MCS 4.24 points lower) was seen due to CP. QOL in CP was similar to (heart, kidney, liver, lung disease) or worse than (non-skin cancers, diabetes mellitus, hypertension, rheumatoid arthritis) other chronic conditions. Conclusions The impact of CP on QOL appears substantial. The QOL in CP subjects appears to be worse or similar to the QOL of many other chronic conditions. PMID:23357924

Aqueous organometallic chemistry. 2. {sup 1}H NMR spectroscopic, synthetic, and structural study of the chemo- and diastereoselective reactions of [Cp{sup *}Rh(H{sub 2}O){sub 3}]{sup 2+} with nitrogen ligands as a function of pH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ogo, Seiji; Chen, H.; Fish, R.H.

The reactions of a new Cp{sup *}Rh aqua synthon, [Cp{sup *}Rh(H{sub 2}O){sub 3}]{sup 2+} (1), at acidic pH values (2-6) with aniline (2), pyridine (3), and L-phenylalanine (4) have provided interesting chemo- and diastereoselectivities as studied by {sup 1}H NMR, FAB/MS, and single-crystal X-ray crystallography. The reaction of 2 and aqua complex 1, at pH values from 4 to 6, quantitatively provided [Cp{sup *}Rh({eta}{sup 6}-aniline)]{sup 2+} (5); the structure of 5 was unequivocally determined by a single-crystal X-ray analysis, which also showed an approximate 25% {eta}{sup 5} component. Compound 3 reacted with 1, at pH 2-6, to selectively provide [Cp{supmore » *}Rh({eta}{sup 1}-pyridine){sub n} (H{sub 2}O){sub 3-n}]{sup 2+} (n = 1-3) complexes 6a-c as a function of pH. Surprisingly, complex 1 reacted with 4, from pH 4 to 6, to provide only one diastereomer of the known cyclic trimer [(Cp{sup *}Rh)({mu}-{eta}{sup 1}-(OCO):{eta}{sup 2}-(N,OCO)-L-phe nylalanine)]{sub 3}{sup 3+} (7; S{sub C},S{sub C},S{sub C},S{sub Rh},S{sub Rh},S{sub Rh},) an example of a one-step, highly diastereoselective reaction in H{sub 2}O. 8 refs., 4 figs., 2 tabs.« less

Multicenter Approach to Recurrent Acute and Chronic Pancreatitis in the United States: The North American Pancreatitis Study 2 (NAPS2)

PubMed Central

Whitcomb, David C.; Yadav, Dhiraj; Adam, Slivka; Hawes, Robert H.; Brand, Randall E.; Anderson, Michelle A.; Money, Mary E.; Banks, Peter A.; Bishop, Michele D.; Baillie, John; Sherman, Stuart; DiSario, James; Burton, Frank R.; Gardner, Timothy B.; Amann, Stephen T.; Gelrud, Andres; Lo, Simon K.; DeMeo, Mark T.; Steinberg, William M.; Kochman, Michael L.; Etemad, Babak; Forsmark, Christopher E.; Elinoff, Beth; Greer, Julia B.; O’Connell, Michael; Lamb, Janette; Barmada, M. Michael

2008-01-01

Background Recurrent acute pancreatitis (RAP) and chronic pancreatitis (CP) are complex syndromes associated with numerous etiologies, clinical variables and complications. We developed the North American Pancreatitis Study 2 (NAPS2) to be sufficiently powered to understand the complex environmental, metabolic and genetic mechanisms underlying RAP and CP. Methods Between August 2000 and September 2006, a consortium of 20 expert academic and private sites prospectively ascertained 1,000 human subjects with RAP or CP, plus 695 controls (spouse, family, friend or unrelated). Standardized questionnaires were completed by both the physicians and study subjects and blood was drawn for genomic DNA and biomarker studies. All data were double-entered into a database and systematically reviewed to minimize errors and include missing data. Results A total of 1,000 subjects (460 RAP, 540 CP) and 695 controls who completed consent forms and questionnaires and donated blood samples comprised the final dataset. Data were organized according to diagnosis, supporting documentation, etiological classification, clinical signs and symptoms (including pain patterns and duration, and quality of life), past medical history, family history, environmental exposures (including alcohol and tobacco use), medication use and therapeutic interventions. Upon achieving the target enrollment, data were organized and classified to facilitate future analysis. The approaches, rationale and datasets are described, along with final demographic results. Conclusion The NAPS2 consortium has successfully completed a prospective ascertainment of 1,000 subjects with RAP and CP from the USA. These data will be useful in elucidating the environmental, metabolic and genetic conditions, and to investigate the complex interactions that underlie RAP and CP. PMID:18765957

Rhodium-catalyzed enantioselective cyclizations of γ-alkynylaldehydes with acyl phosphonates: ligand- and substituent-controlled C-P or C-H bond cleavage.

PubMed

Masuda, Kengo; Sakiyama, Norifumi; Tanaka, Rie; Noguchi, Keiichi; Tanaka, Ken

2011-05-11

It has been established that a cationic rhodium(I)/(R)-H(8)-BINAP or (R)-Segphos complex catalyzes two modes of enantioselective cyclizations of γ-alkynylaldehydes with acyl phosphonates via C-P or C-H bond cleavage. The ligands of the Rh(I) complexes and the substitutents of both γ-alkynylaldehydes and acyl phosphonates control these two different pathways. © 2011 American Chemical Society

The long-term health, social, and financial burden of hypoxic-ischaemic encephalopathy.

PubMed

Eunson, Paul

2015-04-01

Infants who suffer hypoxic-ischaemic encephalopathy (HIE) at term are at risk of dying or developing severe cerebral palsy (CP). Children with severe CP often have other neurodevelopmental disabilities, which may affect their quality of life as much as the CP itself. New treatments for HIE, such as cooling, may improve motor outcomes, but affected infants may still have significant cognitive or communication problems. Infants who have experienced HIE and develop CP will require significant medical input throughout childhood and adult life. The costs of this medical input are high, but the indirect costs to the child, his or her family, and the relevant social services and education systems are many times greater. When demonstrating the cost-effectiveness of interventions aimed at preventing or treating HIE, these additional costs should be taken into account. © The Authors. Journal compilation © 2015 Mac Keith Press.

Epigenetic Silencing of the Proapoptotic Gene BIM in Anaplastic Large Cell Lymphoma through an MeCP2/SIN3a Deacetylating Complex12

PubMed Central

Piazza, Rocco; Magistroni, Vera; Mogavero, Angela; Andreoni, Federica; Ambrogio, Chiara; Chiarle, Roberto; Mologni, Luca; Bachmann, Petra S; Lock, Richard B; Collini, Paola; Pelosi, Giuseppe; Gambacorti-Passerini, Carlo

2013-01-01

BIM is a proapoptotic member of the Bcl-2 family. Here, we investigated the epigenetic status of the BIM locus in NPM/ALK+ anaplastic large cell lymphoma (ALCL) cell lines and in lymph node biopsies from NPM/ALK+ ALCL patients. We show that BIM is epigenetically silenced in cell lines and lymph node specimens and that treatment with the deacetylase inhibitor trichostatin A restores the histone acetylation, strongly upregulates BIM expression, and induces cell death. BIM silencing occurs through recruitment of MeCP2 and the SIN3a/histone deacetylase 1/2 (HDAC1/2) corepressor complex. This event requires BIM CpG methylation/demethylation with 5-azacytidine that leads to detachment of the MeCP2 corepressor complex and reacetylation of the histone tails. Treatment with the ALK inhibitor PF2341066 or with an inducible shRNA targeting NPM/ALK does not restore BIM locus reacetylation; however, enforced expression of NPM/ALK in an NPM/ALK-negative cell line significantly increases the methylation at the BIM locus. This study demonstrates that BIM is epigenetically silenced in NPM/ALK-positive cells through recruitment of the SIN3a/HDAC1/2 corepressor complex and that NPM/ALK is dispensable to maintain BIM epigenetic silencing but is able to act as an inducer of BIM methylation. PMID:23633923

Potential Anticancer Heterometallic Fe-Au and Fe-Pd Agents: Initial Mechanistic Insights

PubMed Central

Lease, Nicholas; Vasilevski, Vadim; Carreira, Monica; de Almeida, Andreia; Sanaú, Mercedes; Hirva, Pipsa; Casini, Angela; Contel, Maria

2013-01-01

A series of gold(III) and palladium(II) heterometallic complexes with new iminophosphorane ligands derived from ferrocenyl-phosphanes [{Cp-P(Ph2)=N-Ph}2Fe] (1), [{Cp-P(Ph2)=N-CH2-2-NC5H4}2Fe] (2) and [{Cp-P(Ph2)=N-CH2-2-NC5H4}Fe(Cp)] (3) have been synthesized and structurally characterized. Ligands 2 and 3 afford stable coordination complexes [AuCl2(3)]ClO4, [{AuCl2}2(2)](ClO4)2, [PdCl2(3)] and [{PdCl2}2(2)]. The complexes have been evaluated for their antripoliferative properties in human ovarian cancer cells sensitive and resistant to cisplatin (A2780S/R), in human breast cancer cells (MCF7) and in a non-tumorigenic human embryonic kidney cell line (HEK-293T). The highly cytotoxic trimetallic derivatives M2Fe (M = Au, Pd) are more cytotoxic to cancer cells than their corresponding monometallic fragments. Moreover, these complexes were significantly more cytotoxic than cisplatin in the resistant A2780R and the MCF7 cell lines. Studies of the interactions of the trimetallic compounds with DNA and the zinc-finger protein PARP-1 indicate that they exert anticancer effects in vitro based on different mechanisms of actions with respect to cisplatin. PMID:23786413

Morphological correlation between caloric tests and vestibular hydrops in Ménière's disease using intravenous Gd enhanced inner ear MRI.

PubMed

Choi, Ji Eun; Kim, Yi-Kyung; Cho, Young Sang; Lee, Kieun; Park, Hyun Woo; Yoon, Sung Hoon; Kim, Hyung-Jin; Chung, Won-Ho

2017-01-01

The purpose of this study was to prove the hypothesis that caloric response in Ménière's disease (MD) is reduced by hydropic expansion of the vestibular labyrinth, not by vestibular hypofunction, by evaluating the correlation morphologically using an intravenous Gadolinium (IV-Gd) inner ear MRI. In study I, the prevalence of abnormal video Head Impulse Test (vHIT) results among the patients with definite unilateral MD (n = 24) and vestibular neuritis (VN) (n = 22) were investigated. All patients showed abnormal canal paresis (CP) (> 26%) on caloric tests. The prevalence of abnormal vHIT in patients with abnormal CP was significantly lower in MD patients (12.5%) than that in VN patients (81.8%) (p < 0.001). In study II, morphological correlation between caloric tests and vestibular hydrops level was evaluated in unilateral MD patients (n = 16) who had normal vHIT results. Eleven patients (61%) had abnormal CP. After taking the images of IV-Gd inner ear MRI, the vestibular hydrops ratio (endolymph volume/total lymph volume = %VH) was measured. In addition, the relative vestibular hydrops ratio (%RVH = (%VHaffected ear-%VHunaffected ear) / (%VHaffected ear + %VHunaffected ear)) was calculated. Each ratio (%VH and %RVH) was compared with average peak slow phase velocity (PSPV) and CP, respectively. In the MD patients, %VH of the affected ear correlated significantly with mean PSPV on the same side (rs = -0.569, p = 0.024), while %RVH correlated significantly with CP (rs = 0.602, p = 0.014). In most MD patients (87.5%) compared to VN patients, vHIT results were normal even though the caloric function was reduced. In addition, the reduced caloric function with normal vHIT was related to the severity of the vestibular hydrops measured by the IV-Gd inner ear MRI. These findings concluded that the abnormal caloric tests with normal vHIT in MD indicated severe endolymphatic hydrops rather than vestibular hypofunction.

Tang-Nai-Kang Alleviates Pre-diabetes and Metabolic Disorders and Induces a Gene Expression Switch toward Fatty Acid Oxidation in SHR.Cg-Leprcp/NDmcr Rats

PubMed Central

Li, Linyi; Yoshitomi, Hisae; Wei, Ying; Qin, Lingling; Zhou, Jingxin; Xu, Tunhai; Wu, Xinli; Zhou, Tian; Sun, Wen; Guo, Xiangyu; Wu, Lili; Wang, Haiyan; Zhang, Yan; Li, Chunna; Liu, Tonghua; Gao, Ming

2015-01-01

Increased energy intake and reduced physical activity can lead to obesity, diabetes and metabolic syndrome. Transcriptional modulation of metabolic networks has become a focus of current drug discovery research into the prevention and treatment of metabolic disorders associated with energy surplus and obesity. Tang-Nai-Kang (TNK), a mixture of five herbal plant extracts, has been shown to improve abnormal glucose metabolism in patients with pre-diabetes. Here, we report the metabolic phenotype of SHR.Cg-Lepr cp/NDmcr (SHR/cp) rats treated with TNK. Pre-diabetic SHR/cp rats were randomly divided into control, TNK low-dose (1.67 g/kg) and TNK high-dose (3.24 g/kg) groups. After high-dose treatment for 2 weeks, the serum triglycerides and free fatty acids in SHR/cp rats were markedly reduced compared to controls. After 3 weeks of administration, the high dose of TNK significantly reduced the body weight and fat mass of SHR/cp rats without affecting food consumption. Serum fasting glucose and insulin levels in the TNK-treated groups decreased after 6 weeks of treatment. Furthermore, TNK-treated rats exhibited obvious improvements in glucose intolerance and insulin resistance. The improved glucose metabolism may be caused by the substantial reduction in serum lipids and body weight observed in SHR/cp rats starting at 3 weeks of TNK treatment. The mRNA expression of NAD+-dependent deacetylase sirtuin 1 (SIRT1) and genes related to fatty acid oxidation was markedly up-regulated in the muscle, liver and adipose tissue after TNK treatment. Furthermore, TNK promoted the deacetylation of two well-established SIRT1 targets, PPARγ coactivator 1α (PGC1α) and forkhead transcription factor 1 (FOXO1), and induced the phosphorylation of AMP-activated protein kinase (AMPK) and acetyl-CoA carboxylase (ACC) in different tissues. These observations suggested that TNK may be an alternative treatment for pre-diabetes and metabolic syndrome by inducing a gene expression switch toward fat oxidation through the activation of SIRT1 and AMPK signaling. PMID:25874615

Safety and immunogenicity of a live recombinant canarypox virus expressing HIV type 1 gp120 MN MN tm/gag/protease LAI (ALVAC-HIV, vCP205) followed by a p24E-V3 MN synthetic peptide (CLTB-36) administered in healthy volunteers at low risk for HIV infection. AGIS Group and L'Agence Nationale de Recherches sur Le Sida.

PubMed

Salmon-Céron, D; Excler, J L; Finkielsztejn, L; Autran, B; Gluckman, J C; Sicard, D; Matthews, T J; Meignier, B; Valentin, C; El Habib, R; Blondeau, C; Raux, M; Moog, C; Tartaglia, J; Chong, P; Klein, M; Milcamps, B; Heshmati, F; Plotkin, S

1999-05-01

A live recombinant canarypox vector expressing HIV-1 gpl20 MN tm/gag/protease LAI (ALVAC-HIV, vCP205) alone or boosted by a p24E-V3 MN synthetic peptide (CLTB-36) was tested in healthy volunteers at low risk for HIV infection for their safety and immunogenicity. Both antigens were well tolerated. ALVAC-HIV (vCP205) induced low levels of neutralizing antibodies against HIV-1 MN in 33% of the volunteers. None of them had detectable neutralizing antibodies against a nonsyncytium-inducing HIV-1 clade B primary isolate (Bx08). After the fourth injection of vCP205, CTL activity was detected in 33% of the volunteers and was directed against Env, Gag, and Pol. This activity was mediated by both CD4+ and CD8+ lymphocytes. On the other hand, the CLTB-36 peptide was poorly immunogenic and induced no neutralizing antibodies or CTLs. Although the ALVAC-HIV (vCP205) and CLTB-36 prime-boost regimen was not optimal, further studies with ALVAC-HIV (vCP205) are warranted because of its clear induction of a cellular immune response and utility as a priming agent for other subunit antigens such as envelope glycoproteins, pseudoparticles, or new peptides.

Effect of Laser Power and Scan Speed on Melt Pool Characteristics of Commercially Pure Titanium (CP-Ti)

NASA Astrophysics Data System (ADS)

Kusuma, Chandrakanth; Ahmed, Sazzad H.; Mian, Ahsan; Srinivasan, Raghavan

2017-07-01

Selective laser melting (SLM) is an additive manufacturing technique that creates complex parts by selectively melting metal powder layer-by-layer using a laser. In SLM, the process parameters decide the quality of the fabricated component. In this study, single beads of commercially pure titanium (CP-Ti) were melted on a substrate of the same material using an in-house built SLM machine. Multiple combinations of laser power and scan speed were used for single bead fabrication, while the laser beam diameter and powder layer thickness were kept constant. This experimental study investigated the influence of laser power, scan speed, and laser energy density on the melt pool formation, surface morphology, geometry (width and height), and hardness of solidified beads. In addition, the observed unfavorable effect such as inconsistency in melt pool width formation is discussed. The results show that the quality, geometry, and hardness of solidified melt pool are significantly affected by laser power, scanning speed, and laser energy density.

The effect of dietary protein and phosphorus on ammonia concentration and litter composition in broilers.

PubMed

Ferguson, N S; Gates, R S; Taraba, J L; Cantor, A H; Pescatore, A J; Straw, M L; Ford, M J; Burnham, D J

1998-08-01

An experiment was conducted to determine whether broiler litter concentration of N and P and equilibrium NH3 gas concentration can be reduced by reducing dietary CP and P levels and supplementing with amino acids and phytase, respectively, without adversely affecting bird performance. Equilibrium NH3 gas concentration above the litter was measured. The experiment was divided into a starter period (1 to 21 d) and grower period (22 to 42 d), each having two different CP and P levels in a 2 x 2 factorial arrangement. The CP treatments consisted of a control with a mean CP of 204 and 202 g/kg for starter and grower periods, respectively, and a low CP diet with means of 188 and 183 g/kg, respectively, but with similar amino acid levels as the control. The P treatments comprised starter and grower control diets containing means of 6.7 and 6.3 g/kg P, respectively, and low P treatment means of 5.8 and 5.4 g/kg P supplemented with 1.0 g/kg phytase. Reducing starter diet CP by 16 g/kg reduced weight gain by 3.5% and, hence, body weight at 21 d of age, but did not affect feed intake or feed efficiency. Reducing P did not affect feed intake and weight gain, but improved feed efficiency by 2.0%. Responses in feed intake and efficiency to CP depended on the level of dietary P. For the grower period there were no significant differences in feed intake, weight gain, and feed efficiency, nor in body weight at 42 d of age, after correcting for 21-d body weight, between CP and P treatments. There were significant (P < 0.001) reductions in litter N and P concentrations, but not equilibrium NH3 gas concentration, moisture content, or pH, for low CP and P diets. Mean equilibrium NH3 gas concentration was 63 ppm. Litter N concentration was reduced 16.3% with the low CP diets, and litter P by 23.2% in low P treatments. The results suggest that dietary manipulation shows merit for reducing litter N and P concentrations while maintaining acceptable production performance from broilers.

Reducing crude protein and rumen degradable protein with a constant concentration of rumen undegradable protein in the diet of dairy cows: Production performance, nutrient digestibility, nitrogen efficiency, and blood metabolites.

PubMed

Bahrami-Yekdangi, M; Ghorbani, G R; Khorvash, M; Khan, M A; Ghaffari, M H

2016-02-01

The goals of ruminant protein nutrition are to provide adequate amounts of RDP for optimal ruminal efficiency and to obtain the desired animal productivity with a minimum amount of dietary CP. The aim of the present study was to examine effects of decreasing dietary protein by decreasing RDP with the optimum concentration of RUP on production performance, nutrient digestibility, N retention, rumen fermentation parameters, and blood metabolites in high-producing Holstein cows in early lactation. Nine multiparous lactating cows (second parities, averaging 50 ± 12 d in milk and milk yield of 48 ± 5 kg/d) were used in a triplicate 3 × 3 Latin square design with 3 rations: 1) a total mixed ration (TMR) containing 16.4% CP (10.9% RDP based on DM), 2) a TMR containing 15.6% CP (10% RDP), and 3) a TMR containing 14.8% CP (9.3% RDP). The level of RUP was constant at 5.5% DM across the treatments. All diets were calculated to supply a postruminal lysine to methionine ratio of about 3:1. Dry matter intake, milk yield and composition, 4% fat-corrected milk, and energy-corrected milk were not significantly affected by decreasing dietary CP and RDP levels. Cows fed 16.4% CP diets had greater ( < 0.01) CP and RDP intakes, which resulted in a trend toward greater concentrations of plasma urea N compared with other treatments. Daily N intake linearly decreased ( < 0.01) with decreasing dietary CP and RDP levels, whereas the intake of RUP and fecal N excretion (g/d) did not change. Apparent digestibility of nutrients, ruminal pH, and NH-N concentration were not affected with decreasing dietary CP and RDP levels. Apparent N efficiency increased, and RDP N intake and predicted urine N output decreased with decreased concentration of dietary CP and RDP in the diets ( < 0.01). Blood metabolites were not affected by treatments. In conclusion, to improve the efficiency of N utilization by early-lactation dairy cows, 9.3% RDP in rations provides adequate protein to optimize milk production while minimizing N excretion in urine when the amounts of lysine and methionine and the lysine to methionine ratio are balanced with sufficient dietary RUP.

The C2HDM revisited

NASA Astrophysics Data System (ADS)

Fontes, Duarte; Mühlleitner, Margarete; Romão, Jorge C.; Santos, Rui; Silva, João P.; Wittbrodt, Jonas

2018-02-01

The complex two-Higgs doublet model is one of the simplest ways to extend the scalar sector of the Standard Model to include a new source of CP-violation. The model has been used as a benchmark model to search for CP-violation at the LHC and as a possible explanation for the matter-antimatter asymmetry of the Universe. In this work, we re-analyse in full detail the softly broken ℤ 2 symmetric complex two-Higgs doublet model (C2HDM). We provide the code C2HDM_HDECAY implementing the C2HDM in the well-known HDECAY program which calculates the decay widths including the state-of-the-art higher order QCD corrections and the relevant off-shell decays. Using C2HDM_HDECAY together with the most relevant theoretical and experimental constraints, including electric dipole moments (EDMs), we review the parameter space of the model and discuss its phenomenology. In particular, we find cases where large CP-odd couplings to fermions are still allowed and provide benchmark points for these scenarios. We examine the prospects of discovering CP-violation at the LHC and show how theoretically motivated measures of CP-violation correlate with observables.

Measurement of D0-D0 mixing parameters in D0 --> Ks pi+ pi- decays.

PubMed

Zhang, L M; Zhang, Z P; Adachi, I; Aihara, H; Aulchenko, V; Aushev, T; Bakich, A M; Balagura, V; Barberio, E; Bay, A; Belous, K; Bitenc, U; Bondar, A; Bozek, A; Bracko, M; Brodzicka, J; Browder, T E; Chang, P; Chao, Y; Chen, A; Chen, K-F; Chen, W T; Cheon, B G; Chiang, C-C; Cho, I-S; Choi, Y; Choi, Y K; Dalseno, J; Danilov, M; Dash, M; Drutskoy, A; Eidelman, S; Epifanov, D; Fratina, S; Gabyshev, N; Gokhroo, G; Golob, B; Ha, H; Haba, J; Hara, T; Hastings, N C; Hayasaka, K; Hayashii, H; Hazumi, M; Heffernan, D; Hokuue, T; Hoshi, Y; Hou, W-S; Hsiung, Y B; Hyun, H J; Iijima, T; Ikado, K; Inami, K; Ishikawa, A; Ishino, H; Itoh, R; Iwasaki, M; Iwasaki, Y; Joshi, N J; Kah, D H; Kaji, H; Kajiwara, S; Kang, J H; Kawai, H; Kawasaki, T; Kichimi, H; Kim, H J; Kim, H O; Kim, S K; Kim, Y J; Kinoshita, K; Korpar, S; Krizan, P; Krokovny, P; Kumar, R; Kuo, C C; Kuzmin, A; Kwon, Y-J; Lee, J S; Lee, M J; Lee, S E; Lesiak, T; Li, J; Limosani, A; Lin, S-W; Liu, Y; Liventsev, D; Matsumoto, T; Matyja, A; McOnie, S; Medvedeva, T; Mitaroff, W; Miyake, H; Miyata, H; Miyazaki, Y; Mizuk, R; Nagasaka, Y; Nakamura, I; Nakano, E; Nakao, M; Natkaniec, Z; Nishida, S; Nitoh, O; Ogawa, S; Ohshima, T; Okuno, S; Olsen, S L; Onuki, Y; Ostrowicz, W; Ozaki, H; Pakhlov, P; Pakhlova, G; Park, C W; Park, H; Peak, L S; Pestotnik, R; Piilonen, L E; Poluektov, A; Sahoo, H; Sakai, Y; Schneider, O; Schümann, J; Schwanda, C; Schwartz, A J; Seidl, R; Senyo, K; Sevior, M E; Shapkin, M; Shibuya, H; Shinomiya, S; Shiu, J-G; Shwartz, B; Singh, J B; Sokolov, A; Somov, A; Soni, N; Stanic, S; Staric, M; Stoeck, H; Sumisawa, K; Sumiyoshi, T; Suzuki, S; Tajima, O; Takasaki, F; Tamai, K; Tamura, N; Tanaka, M; Taylor, G N; Teramoto, Y; Tian, X C; Tikhomirov, I; Tsuboyama, T; Uehara, S; Ueno, K; Uglov, T; Unno, Y; Uno, S; Urquijo, P; Usov, Y; Varner, G; Vervink, K; Villa, S; Vinokurova, A; Wang, C H; Wang, M-Z; Wang, P; Watanabe, Y; Won, E; Yabsley, B D; Yamaguchi, A; Yamashita, Y; Yamauchi, M; Yuan, C Z; Zhang, C C; Zhilich, V; Zupanc, A

2007-09-28

We report a measurement of D0-D(0) mixing parameters in D(0) --> K(s)(0) pi(+) pi(-) decays using a time-dependent Dalitz-plot analysis. We first assume CP conservation and subsequently allow for CP violation. The results are based on 540 fb(-1) of data accumulated with the Belle detector at the KEKB e(+)e(-) collider. Assuming negligible CP violation, we measure the mixing parameters x = (0.80 +/- 0.29(-0.07-0.14)(+0.09+0.10))% and y = (0.33+/-0.24(-0.12-0.08)(+0.08+0.06))%, where the errors are statistical, experimental systematic, and systematic due to the Dalitz decay model, respectively. Allowing for CP violation, we obtain the CP-violating parameters |q / p| = 0.86(-0.29-0.03)(+0.30+0.06) +/- 0.08 and arg(q/p) = (-14(-18-3-4)(+16+5+2)) degrees .

T-state inhibitors of E. coli aspartate transcarbamoylase that prevent the allosteric transition.

PubMed

Heng, Sabrina; Stieglitz, Kimberly A; Eldo, Joby; Xia, Jiarong; Cardia, James P; Kantrowitz, Evan R

2006-08-22

Escherichia coli aspartate transcarbamoylase (ATCase) catalyzes the committed step in pyrimidine nucleotide biosynthesis, the reaction between carbamoyl phosphate (CP) and l-aspartate to form N-carbamoyl-l-aspartate and inorganic phosphate. The enzyme exhibits homotropic cooperativity and is allosterically regulated. Upon binding l-aspartate in the presence of a saturating concentration of CP, the enzyme is converted from the low-activity low-affinity T state to the high-activity high-affinity R state. The potent inhibitor N-phosphonacetyl-l-aspartate (PALA), which combines the binding features of Asp and CP into one molecule, has been shown to induce the allosteric transition to the R state. In the presence of only CP, the enzyme is the T structure with the active site primed for the binding of aspartate. In a structure of the enzyme-CP complex (T(CP)), two CP molecules were observed in the active site approximately 7A apart, one with high occupancy and one with low occupancy. The high occupancy site corresponds to the position for CP observed in the structure of the enzyme with CP and the aspartate analogue succinate bound. The position of the second CP is in a unique site and does not overlap with the aspartate binding site. As a means to generate a new class of inhibitors for ATCase, the domain-open T state of the enzyme was targeted. We designed, synthesized, and characterized three inhibitors that were composed of two phosphonacetamide groups linked together. These two phosphonacetamide groups mimic the positions of the two CP molecules in the T(CP) structure. X-ray crystal structures of ATCase-inhibitor complexes revealed that each of these inhibitors bind to the T state of the enzyme and occupy the active site area. As opposed to the binding of Asp in the presence of CP or PALA, these inhibitors are unable to initiate the global T to R conformational change. Although the best of these T-state inhibitors only has a K(i) value in the micromolar range, the structural information with respect to their mode of binding provides important information for the design of second generation inhibitors that will have even higher affinity for the active site of the T state of the enzyme.

Effects of low-protein diets and rumen-protected conjugated linoleic acid on production and carcass traits of growing double-muscled Piemontese bulls.

PubMed

Schiavon, S; Tagliapietra, F; Dal Maso, M; Bailoni, L; Bittante, G

2010-10-01

The effects of low-protein (LP) diets and rumen-protected CLA on DMI, ADG, carcass traits, and health status of double-muscled Piemontese young bulls were investigated. Forty-eight bull calves (BW = 237 ± 24 kg) were divided in 4 groups and housed in 12 fully slatted pens. Bulls were fed 2 diets differing in CP density [high-protein (HP) diet: CP = 145 g/kg of DM; LP diet: CP = 108 g/kg of DM] and top-dressed with 80 g/d of rumen-protected CLA or 65 g/d of hydrogenated soybean oil. Orts were collected weekly and feed intake was estimated on a pen basis, with 3 replicated pens for each treatment. Each bull was weighed monthly and examined for alterations of the locomotion system by using the locomotion score as an index of lameness and by counting the number of swollen joints. Carcass quality traits were measured at slaughter, after a feeding period of 332 d. Compared with HP, LP reduced ADG only during the first 4 mo of the trial (1.30 vs. 1.53 kg/d, P = 0.003). However, because of compensatory growth, over the whole trial, no significant effects attributable to CP or to additive were found on final BW (668 kg), ADG (1.19 kg/d), DMI (8.50 or 86 g/d per kg of BW(0.75)), dressing percentage (67.3%), carcass conformation (5.2 points), and carcass fat covering (1.87 points). Feed efficiency was affected by a CP × additive interaction (P = 0.030), with CLA improving feed efficiency when added to the LP diets, whereas feed efficiency was reduced with the HP diets. The addition of both LP and CLA reduced the number of bulls presenting swollen joints (P = 0.001), and LP improved the locomotion score (P = 0.021) compared with HP. It was concluded that 10.8 g/kg of CP density in the diet is sufficient for double-muscled Piemontese bulls. The reduction in CP density from 145 to 108 g/kg of DM, in addition to reducing the feeding cost, allows a strong reduction in N consumption without negative consequences on growth performance and carcass traits.

Land use change influences soil C, N, and P stoichiometry under ‘Grain-to-Green Program’ in China

PubMed Central

Fazhu, Zhao; Jiao, Sun; Chengjie, Ren; Di, Kang; Jian, Deng; Xinhui, Han; Gaihe, Yang; Yongzhong, Feng; Guangxin, Ren

2015-01-01

Changes in land use might affect the combined C, N and P stoichiometry in soil. The Grain-to-Green Program (GTGP), which converts low-yield croplands or abandoned lands into forest, shrub, and/or grassland, was the largest land reforestation project in China. This study collected the reported C, N and P contents of soil in GTGP zones to achieve the factors driving the changes in the C:N, C:P, and N:P values. The results showed that the annual average precipitation exerted significant effects on the C:P value, and on the N:P value became significant 20 years after the change in land use. The annual average temperature was the main factor affecting the C:N value during the first 10 years, while the annual average precipitation strongly affected this value afterwards. In addition, “Redfield-like” interactions between C, N, and P in the soil may exist. A linear regression revealed significant positive correlations between the C:N, C:P, and N:P values and the restoration age, temperature, and precipitation after a change in land use. Therefore large-scale changes in land use under the ‘GTGP’ program might significantly affect the C:N, C:P and N:P ratios in soil. PMID:25988714

Chemistry of the oxophosphinidene ligand. 2. Reactivity of the anionic complexes [MCp{P(O)R*}(CO)(2)](-) (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3)) toward electrophiles based on elements different from carbon.

PubMed

Alonso, María; Alvarez, M Angeles; García, M Esther; Ruiz, Miguel A; Hamidov, Hayrullo; Jeffery, John C

2010-12-20

The anionic oxophosphinidene complexes (H-DBU)[MCp{P(O)R*}(CO)(2)] (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5), DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene) displayed multisite reactivity when faced with different electrophilic reagents. The reactions with the group 14 organochloride compounds ER(4-x)Cl(x) (E = Si, Ge, Sn, Pb) led to either phosphide-like, oxophosphinidene-bridged derivatives [MCp{P(OE')R*}(CO)(2)] (E' = SiMe(3), SiPh(3), GePh(3), GeMe(2)Cl) or to terminal oxophosphinidene complexes [MCp{P(O)R*}(CO)(2)(E')] (E' = SnPh(3), SnPh(2)Cl, PbPh(3); Mo-Pb = 2.8845(4) Å for the MoPb compound). A particular situation was found in the reaction with SnMe(3)Cl, this giving a product existing in both tautomeric forms, with the phosphide-like complex [MCp{P(OSnMe(3))R*}(CO)(2)] prevailing at room temperature and the tautomer [MCp{P(O)R*}(CO)(2)(SnMe(3))] being the unique species present below 203 K in dichloromethane solution. The title anions also showed a multisite behavior when reacting with transition-metal based electrophiles. Thus, the reactions with the complexes [M'Cp(2)Cl(2)] (M' = Ti, Zr) gave phosphide-like derivatives [MCp{P(OM')R*}(CO)(2)] (M = Mo, M' = TiCp(2)Cl, ZrCp(2)Cl; M = W, M' = ZrCp(2)Cl), displaying a bridging κ(1),κ(1)-P,O- oxophosphinidene ligand connecting MCp(CO)(2) and M'Cp(2)Cl metal fragments (W-P = 2.233(1) Å, O-Zr = 2.016(4) Å for the WZr compound]. In contrast, the reactions with the complex [AuCl{P(p-tol)(3)}] gave the metal-metal bonded derivatives trans-[MCp{P(O)R*}(CO)(2){AuP(p-tol)(3)}] (M = Mo, W; Mo-Au = 2.7071(7) Å). From all the above results it was concluded that the terminal oxophosphinidene complexes are preferentially formed under conditions of orbital control, while charge-controlled reactions tend to give derivatives with the electrophilic fragment bound to the oxygen atom of the oxophosphinidene ligand (phosphide-like, oxophosphinidene-bridged derivatives).

Stress-induced gene expression and behavior are controlled by DNA methylation and methyl donor availability in the dentate gyrus

PubMed Central

Saunderson, Emily A.; Spiers, Helen; Gutierrez-Mecinas, Maria; Trollope, Alexandra F.; Shaikh, Abeera; Mill, Jonathan; Reul, Johannes M. H. M.

2016-01-01

Stressful events evoke long-term changes in behavioral responses; however, the underlying mechanisms in the brain are not well understood. Previous work has shown that epigenetic changes and immediate-early gene (IEG) induction in stress-activated dentate gyrus (DG) granule neurons play a crucial role in these behavioral responses. Here, we show that an acute stressful challenge [i.e., forced swimming (FS)] results in DNA demethylation at specific CpG (5′-cytosine–phosphate–guanine-3′) sites close to the c-Fos (FBJ murine osteosarcoma viral oncogene homolog) transcriptional start site and within the gene promoter region of Egr-1 (early growth response protein 1) specifically in the DG. Administration of the (endogenous) methyl donor S-adenosyl methionine (SAM) did not affect CpG methylation and IEG gene expression at baseline. However, administration of SAM before the FS challenge resulted in an enhanced CpG methylation at the IEG loci and suppression of IEG induction specifically in the DG and an impaired behavioral immobility response 24 h later. The stressor also specifically increased the expression of the de novo DNA methyltransferase Dnmt3a [DNA (cytosine-5-)-methyltransferase 3 alpha] in this hippocampus region. Moreover, stress resulted in an increased association of Dnmt3a enzyme with the affected CpG loci within the IEG genes. No effects of SAM were observed on stress-evoked histone modifications, including H3S10p-K14ac (histone H3, phosphorylated serine 10 and acetylated lysine-14), H3K4me3 (histone H3, trimethylated lysine-4), H3K9me3 (histone H3, trimethylated lysine-9), and H3K27me3 (histone H3, trimethylated lysine-27). We conclude that the DNA methylation status of IEGs plays a crucial role in FS-induced IEG induction in DG granule neurons and associated behavioral responses. In addition, the concentration of available methyl donor, possibly in conjunction with Dnmt3a, is critical for the responsiveness of dentate neurons to environmental stimuli in terms of gene expression and behavior. PMID:27078100

A halogenophilic pathway in the reactions of transition metal carbonyl anions with [(η⁶-iodobenzene)Cr(CO)₃].

PubMed

Sazonov, Petr K; Ivushkin, Vasiliy A; Khrustalev, Victor N; Kolotyrkina, Natal'ya G; Beletskaya, Irina P

2014-09-21

The paper provides the first example of formal nucleophilic substitution by the halogenophilic pathway in Cr(CO)3 complexes of haloarenes with metal carbonyl anions. All metal carbonyl anions examined attack [(η(6)-iodobenzene)Cr(CO)3] at halogen, which is shown by aryl carbanion scavenging with t-BuOH. The reaction with K[CpFe(CO)2] gives only the dehalogenated arene, but the reaction with K[Cp*Fe(CO)2] (Cp* = η(5)-C5Me5) results in nucleophilic substitution to give [(η(6)-C6H5FeCp*(CO)2)Cr(CO)3]. Reaction with Na[Re(CO)5] quantitatively gives the iodo(acyl)rhenate anion Na[(η(6)-C6H5C(O)ReI(CO)4)Cr(CO)3] and in the case of K[Mn(CO)5] a mixture of σ-aryl complexes [(η(6)-C6H5Mn(CO)5)Cr(CO)3] and K[(η(6)-C6H5Mn(CO)4I)Cr(CO)3]. An analogous rhenium complex Na[(η(6)-C6H5Re(CO)4I)Cr(CO)3] is formed from the initial iodo(acyl)rhenate upon prolonged standing at 20 °C, and its structure (in the form of [NEt4](+) salt) is established by X-ray diffraction analysis. The reaction of [(η(6)-chlorobenzene)Cr(CO)3] with K[CpFe(CO)2], in contrast, proceeds by the common S(N)2Ar mechanism.

Base-CP proteasome can serve as a platform for stepwise lid formation

PubMed Central

Yu, Zanlin; Livnat-Levanon, Nurit; Kleifeld, Oded; Mansour, Wissam; Nakasone, Mark A.; Castaneda, Carlos A.; Dixon, Emma K.; Fushman, David; Reis, Noa; Pick, Elah; Glickman, Michael H.

2015-01-01

26S proteasome, a major regulatory protease in eukaryotes, consists of a 20S proteolytic core particle (CP) capped by a 19S regulatory particle (RP). The 19S RP is divisible into base and lid sub-complexes. Even within the lid, subunits have been demarcated into two modules: module 1 (Rpn5, Rpn6, Rpn8, Rpn9 and Rpn11), which interacts with both CP and base sub-complexes and module 2 (Rpn3, Rpn7, Rpn12 and Rpn15) that is attached mainly to module 1. We now show that suppression of RPN11 expression halted lid assembly yet enabled the base and 20S CP to pre-assemble and form a base-CP. A key role for Regulatory particle non-ATPase 11 (Rpn11) in bridging lid module 1 and module 2 subunits together is inferred from observing defective proteasomes in rpn11–m1, a mutant expressing a truncated form of Rpn11 and displaying mitochondrial phenotypes. An incomplete lid made up of five module 1 subunits attached to base-CP was identified in proteasomes isolated from this mutant. Re-introducing the C-terminal portion of Rpn11 enabled recruitment of missing module 2 subunits. In vitro, module 1 was reconstituted stepwise, initiated by Rpn11–Rpn8 heterodimerization. Upon recruitment of Rpn6, the module 1 intermediate was competent to lock into base-CP and reconstitute an incomplete 26S proteasome. Thus, base-CP can serve as a platform for gradual incorporation of lid, along a proteasome assembly pathway. Identification of proteasome intermediates and reconstitution of minimal functional units should clarify aspects of the inner workings of this machine and how multiple catalytic processes are synchronized within the 26S proteasome holoenzymes. PMID:26182356

The Relationship between Motor Abilities and Early Social Development in a Preschool Cohort of Children with Cerebral Palsy

ERIC Educational Resources Information Center

Whittingham, Koa; Fahey, Michael; Rawicki, Barry; Boyd, Roslyn

2010-01-01

Aim: To investigate the relationship between motor ability and early social development in a cohort of preschool children with cerebral palsy (CP). Design: Population-based cohort study. Methods: Participants were 122 children with CP assessed at 18, 24 and 30 months, corrected age (ca). Motor ability was measured by the Gross Motor Function…

Hand Function in Relation to Brain Lesions and Corticomotor-Projection Pattern in Children with Unilateral Cerebral Palsy

ERIC Educational Resources Information Center

Holmstrom, Linda; Vollmer, Brigitte; Tedroff, Kristina; Islam, Mominul; Persson, Jonas Ke; Kits, Annika; Forssberg, Hans; Eliasson, Ann-Christin

2010-01-01

Aim: To investigate relationships between hand function, brain lesions, and corticomotor projections in children with unilateral cerebral palsy (CP). Method: The study included 17 children (nine males, eight females; mean age 11.4 [SD 2.4] range 7-16y), with unilateral CP at Gross Motor Function Classification System level I and Manual Ability…

Being in Pain: A Phenomenological Study of Young People with Cerebral Palsy

ERIC Educational Resources Information Center

Castle, Kirstyn; Imms, Christine; Howie, Linsey

2007-01-01

This study explored the experience and impact of chronic pain on the lives of adolescents and young adults with cerebral palsy (CP). Six participants with CP (four males, two females; age range 14-24y) who were known to experience chronic pain participated in individual in-depth interviews. Five participants had quadriplegia and used wheelchairs;…

Typical and Atypical (Cerebral Palsy) Development of Unimanual and Bimanual Grasp Planning

ERIC Educational Resources Information Center

Janssen, Loes; Steenbergen, Bert

2011-01-01

In the present study we tested 13 children with cerebral palsy (CP) and 24 typically developing children (7-12 years old) in a unimanual and bimanual motor planning task. We focused on two research questions: (1) How does motor planning develop in children with and without CP? and (2) Is motor planning facilitated when the task is performed with…

Electronic Structure and Multisite Basicity of the Pyramidal Phosphinidene-Bridged Dimolybdenum Complex [Mo2(η(5)-C5H5)(μ-κ(1):κ(1),η(5)-PC5H4)(η(6)-C6H3(t)Bu3)(CO)2(PMe3)].

PubMed

Albuerne, Isabel G; Alvarez, M Angeles; García, M Esther; García-Vivó, Daniel; Ruiz, Miguel A

2015-10-19

The title phosphinidene complex could be sequentially protonated with HBF4·OEt2 or [H(OEt2)2](BAr'4) to give the phosphido-bridged derivatives [Mo2Cp(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X and then the hydrides [Mo2Cp(H)(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X2 (X = BF4, BAr'4; Ar' = 3,5-C6H3(CF3)2; Mes* = 2,4,6-C6H2(t)Bu3). Density functional theory (DFT) calculations revealed that the most favored site for initial electrophilic attack is the metallocene Mo atom, but attachment of the electrophile to the phosphinidene P atom gives more stable products. This was in agreement with all other reactions investigated, which invariably involved the attachment of the added electrophile at the P site. Thus, the title compound reacted with S8 at 223 K to give the thiophosphinidene-bridged complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(S)C5H4}(η(6)-HMes*)(CO)2(PMe3)], a poorly stable molecule which reacted with MeI at room temperature to give the corresponding thiolatophosphido derivative, isolated as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(SMe)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4) (P-S = 2.128(4) Å) after anion exchange with Na(BAr'4). Reaction of the title compound with MeI proceeded smoothly to give the corresponding methylphosphido derivative, isolated analogously as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4). The related complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe2Ph)](BAr'4) (P-C(Me) = 1.841(5) Å) could be prepared analogously from the neutral precursor [Mo2Cp{μ-κ(1):κ(1),η(5)-PC5H4}(η(6)-HMes*)(CO)2(PMe2Ph)]. In contrast, reaction of the title complex with ethylene sulfide involved opening of the C2S ring and formation of new P-C and Mo-S bonds (1.886(7) and 2.493(2) Å, respectively), with displacement of the PMe3 ligand, to give the phosphido-thiolato complex [Mo2Cp{μ-κ(2)(P,S):κ(1)P,η(5)-P(C2H4S)C5H4}(η(6)-HMes*)(CO)2]. All these derivatives of the title complex displayed an unusual trigonal pyramidal-like environment around the bridging P atom, with the added electrophile placed in the Mo2P plane as a result of the directionality of the relevant frontier orbital of the phosphinidene complex, according to DFT calculations.

Enhanced sensitivity of CpG island search and primer design based on predicted CpG island position.

PubMed

Park, Hyun-Chul; Ahn, Eu-Ree; Jung, Ju Yeon; Park, Ji-Hye; Lee, Jee Won; Lim, Si-Keun; Kim, Won

2018-05-01

DNA methylation has important biological roles, such as gene expression regulation, as well as practical applications in forensics, such as in body fluid identification and age estimation. DNA methylation often occurs in the CpG site, and methylation within the CpG islands affects various cellular functions and is related to tissue-specific identification. Several programs have been developed to identify CpG islands; however, the size, location, and number of predicted CpG islands are not identical due to different search algorithms. In addition, they only provide structural information for predicted CpG islands without experimental information, such as primer design. We developed an analysis pipeline package, CpGPNP, to integrate CpG island prediction and primer design. CpGPNP predicts CpG islands more accurately and sensitively than other programs, and designs primers easily based on the predicted CpG island locations. The primer design function included standard, bisulfite, and methylation-specific PCR to identify the methylation of particular CpG sites. In this study, we performed CpG island prediction on all chromosomes and compared CpG island search performance of CpGPNP with other CpG island prediction programs. In addition, we compared the position of primers designed for a specific region within the predicted CpG island using other bisulfite PCR primer programs. The primers designed by CpGPNP were used to experimentally verify the amplification of the target region of markers for body fluid identification and age estimation. CpGPNP is freely available at http://forensicdna.kr/cpgpnp/. Copyright © 2018 Elsevier B.V. All rights reserved.

Ruthenium chalcogenonitrosyl and bridged nitrido complexes containing chelating sulfur and oxygen ligands.

PubMed

Ng, Ho-Yuen; Cheung, Wai-Man; Kwan Huang, Enrique; Wong, Kang-Long; Sung, Herman H-Y; Williams, Ian D; Leung, Wa-Hung

2015-11-14

Ruthenium thio- and seleno-nitrosyl complexes containing chelating sulfur and oxygen ligands have been synthesised and their de-chalcogenation reactions have been studied. The reaction of mer-[Ru(N)Cl3(AsPh3)2] with elemental sulfur and selenium in tetrahydrofuran at reflux afforded the chalcogenonitrosyl complexes mer-[Ru(NX)Cl3(AsPh3)2] [X = S (1), Se (2)]. Treatment of 1 with KN(R2PS)2 afforded trans-[Ru(NS)Cl{N(R2PS)2}2] [R = Ph (3), Pr(i) (4), Bu(t) (5)]. Alternatively, the thionitrosyl complex 5 was obtained from [Bu(n)4N][Ru(N)Cl4] and KN(Bu(t)2PS)2, presumably via sulfur atom transfer from [N(Bu(t)2PS)2](-) to the nitride. Reactions of 1 and 2 with NaLOEt (LOEt(-) = [Co(η(5)-C5H5){P(O)(LOEt)2}3](-)) gave [Ru(NX)LOEtCl2] (X = S (8), Se (9)). Treatment of [Bu(n)4N][Ru(N)Cl4] with KN(R2PS)2 produced Ru(IV)-Ru(IV)μ-nitrido complexes [Ru2(μ-N){N(R2PS)2}4Cl] [R = Ph (6), Pr(i) (7)]. Reactions of 3 and 9 with PPh3 afforded 6 and [Ru(NPPh3)LOEtCl2], respectively. The desulfurisation of 5 with [Ni(cod)2] (cod = 1,5-cyclooctadiene) gave the mixed valance Ru(III)-Ru(IV)μ-nitrido complex [Ru2(μ-N){N(Bu(t)2PS)2}4] (10) that was oxidised by [Cp2Fe](PF6) to give the Ru(IV)-Ru(IV) complex [Ru2(μ-N){N(Bu(t)2PS)2}4](PF6) ([10]PF6). The crystal structures of 1, 2, 3, 7, 9 and 10 have been determined.

Combination of bioaugmentation and biostimulation for remediation of paddy soil contaminated with 2,4-dichlorophenoxyacetic acid.

PubMed

Yang, Zhiman; Xu, Xiaohui; Dai, Meng; Wang, Lin; Shi, Xiaoshuang; Guo, Rongbo

2018-04-22

The batch and fed-batch tests were performed to evaluate the efficiency of bioaugmentation in combination with biostimulation for remediation of paddy soil contaminated with 2,4-dichlorophenoxyacetic acid (2,4-D). 2,4-D degrading enrichments were used for bioaugmentation, and effluents prepared through biological hydrogen production process were used as substrate for biostimulation. The batch tests indicated that 2,4-D degradation depended on the enrichment/substrate ratio (E/S), where E/S of 0.03 showed an excellent performance. The fed-batch tests showed that biostimulation only led to an improvement in 2,4-D degradation, while the pattern of repeated augmentation of enrichments (FRA) together with biostimulation obviously improved degradation of 2,4-D, 2-chlorophenol (2-CP) and phenol. DNA-sequencing approach showed that the FRA pattern altered the bacterial community composition, and high removal of 2,4-D, 2-CP and phenol may be attributed to the acclimation and persistence of Thauera. The findings demonstrated the importance of the FRA pattern on remediation of paddy soil contaminated with 2,4-D. Copyright © 2018 Elsevier B.V. All rights reserved.

Association of β-catenin with P-Smad3 but not LEF-1 dissociates in vitro profibrotic from anti-inflammatory effects of TGF-β1.

PubMed

Tian, Xinrui; Zhang, Jianlin; Tan, Thian Kui; Lyons, J Guy; Zhao, Hong; Niu, Bo; Lee, So Ra; Tsatralis, Tania; Zhao, Ye; Wang, Ya; Cao, Qi; Wang, Changqi; Wang, Yiping; Lee, Vincent W S; Kahn, Michael; Zheng, Guoping; Harris, David C H

2013-01-01

Transforming growth factor β1 (TGF-β1) is known to be both anti-inflammatory and profibrotic. Cross-talk between TGF-β/Smad and Wnt/β-catenin pathways in epithelial-mesenchymal transition (EMT) suggests a specific role for β-catenin in profibrotic effects of TGF-β1. However, no such mechanistic role has been demonstrated for β-catenin in the anti-inflammatory effects of TGF-β1. In the present study, we explored the role of β-catenin in the profibrotic and anti-inflammatory effects of TGF-β1 by using a cytosolic, but not membrane, β-catenin knockdown chimera (F-TrCP-Ecad) and the β-catenin/CBP inhibitor ICG-001. TGF-β1 induced nuclear Smad3/β-catenin complex, but not β-catenin/LEF-1 complex or TOP-flash activity, during EMT of C1.1 (renal tubular epithelial) cells. F-TrCP-Ecad selectively degraded TGF-β1-induced cytoplasmic β-catenin and blocked EMT of C1.1 cells. Both F-TrCP-Ecad and ICG-001 blocked TGF-β1-induced Smad3/β-catenin and Smad reporter activity in C1.1 cells, suggesting that TGF-β1-induced EMT depends on β-catenin binding to Smad3, but not LEF-1 downstream of Smad3, through canonical Wnt. In contrast, in J774 macrophages, the β-catenin level was low and was not changed by interferon-γ (IFN-γ) or lipopolysaccharide (LPS) with or without TGF-β1. TGF-β1 inhibition of LPS-induced TNF-α and IFN-γ-stimulated inducible NO synthase (iNOS) expression was not affected by F-TrCP-Ecad, ICG-001 or by overexpression of wild-type β-catenin in J774 cells. Inhibition of β-catenin by either F-TrCP-Ecad or ICG-001 abolished LiCl-induced TOP-flash, but not TGF-β1-induced Smad reporter, activity in J774 cells. These results demonstrate for the first time that β-catenin is required as a co-factor of Smad in TGF-β1-induced EMT of C1.1 epithelial cells, but not in TGF-β1 inhibition of macrophage activation. Targeting β-catenin may dissociate the TGF-β1 profibrotic and anti-inflammatory effects.

Age, task complexity, and sex as potential moderators of attentional focus effects.

PubMed

Becker, Kevin; Smith, Peter J K

2013-08-01

The study tested whether age, sex, or task complexity moderate the effect of attentional focus on motor learning. Children (24 boys, 24 girls) and adults (24 men, 24 women) were assigned to an internal or external attentional focus, and were timed while riding either a Double Pedalo with handles (simple task) or without handles (complex task) over a distance of 7 meters. A Double Pedalo is a four-wheeled device that involves standing on two connected platforms, and alternately pushing them forward to make it move. Participants completed 20 acquisition trials, followed by a 24-hour retention test. For the simpler task, no time differences due to attentional focus emerged. With the complex task, an external focus resulted in faster times in retention than an internal focus, but only for males. These findings suggest that attentional focus affects children and adults similarly, but task complexity and sex moderate these effects.

Quality of life in Chronic Pancreatitis is determined by constant pain, disability/unemployment, current smoking and associated co-morbidities

PubMed Central

Machicado, Jorge D.; Amann, Stephen T; Anderson, Michelle A.; Abberbock, Judah; Sherman, Stuart; Conwell, Darwin; Cote, Gregory A.; Singh, Vikesh K.; Lewis, Michele; Alkaade, Samer; Sandhu, Bimaljit S.; Guda, Nalini M.; Muniraj, Thiruvengadam; Tang, Gong; Baillie, John; Brand, Randall; Gardner, Timothy B.; Gelrud, Andres; Forsmark, Christopher E.; Banks, Peter A.; Slivka, Adam; Wilcox, C. Mel; Whitcomb, David C.; Yadav, Dhiraj

2018-01-01

Background Chronic pancreatitis (CP) has a profound independent effect on quality of life (QOL). Our aim was to identify factors that impact the QOL in CP patients. Methods We used data on 1,024 CP patients enrolled in the three NAPS2 studies. Information on demographics, risk factors, co-morbidities, disease phenotype and treatments was obtained from responses to structured questionnaires. Physical (PCS) and mental (MCS) component summary scores generated using responses to the Short Form-12 (SF-12) survey were used to assess QOL at enrollment. Multivariable linear regression models determined independent predictors of QOL. Results Mean PCS and MCS scores were 36.7±11.7 and 42.4±12.2, respectively. Significant (p<0.05) negative impact on PCS scores in multivariable analyses was noted due to constant mild-moderate pain with episodes of severe pain or constant severe pain (10 points), constant mild-moderate pain (5.2), pain-related disability/unemployment (5.1), current smoking (2.9 points) and medical co-morbidities. Significant (p<0.05) negative impact on MCS scores was related to constant pain irrespective of severity (6.8-6.9 points), current smoking (3.9 points) and pain-related disability/unemployment (2.4 points). In women, disability/unemployment resulted in an additional reduction 3.7 point reduction in MCS score. Final multivariable models explained 27% and 18% of the variance in PCS and MCS scores, respectively. Etiology, disease duration, pancreatic morphology, diabetes, exocrine insufficiency and prior endotherapy/pancreatic surgery had no significant independent effect on QOL. Conclusion Constant pain, pain-related disability/unemployment, current smoking, and concurrent co-morbidities significantly affect the QOL in CP. Further research is needed to identify factors impacting QOL not explained by our analyses. PMID:28244497

Effect of mechanical processing and fat removal on the nutritive value of cottonseed for lactating dairy cows.

PubMed

Meyer, M J; Shirley, J E; Titgemeyer, E C; Park, A F; VanBaale, M J

2001-11-01

In experiment 1, 24 midlactation, multiparous Holstein cows were used in six 4 x 4 Latin squares to evaluate extruded-expelled cottonseed (EEC) as a source of ruminally undegradable protein (RUP). Diets were formulated to contain: 16% crude protein (CP), 35% RUP (SBM16); 18% CP, 35% RUP (SBM18); 16% CP, 40% RUP using EEC (EC16); and 16% CP, 40% RUP using a fishmeal-blood meal blend (FBM16). Milk yields (37.2 kg/d) and percentages of milk fat, protein, casein, and SNF were similar across diets. Cows fed FBM16 consumed less dry matter (DM) (28.0 kg/d) than those consuming other diets (29.4 kg/d). In experiment 2, 18 midlactation, multiparous Holstein cows were used in six 3 x 3 Latin squares to determine the value of EEC as a replacement for whole cottonseed in lactating cow diets. Diets contained whole cottonseed (CS), EEC plus tallow (ECT), or EEC (EC). Diets were formulated to be similar in energy, N, and RUP. Milk yields (35.5 kg/d), DM intake (27.0 kg/d), and milk fat percent were similar across diets. Percentages of milk protein and SNF were higher for EC than CS or ECT. These production data suggest that EEC can replace whole cottonseed in isocaloric diets and can be partially substituted for soybean meal or a fishmeal-blood meal blend without affecting lactational performance. In situ ruminal degradation and in vitro ammonia N release indicate that processing of EEC was inadequate to protect the protein from ruminal degradation and EEC would not be a source of RUP.

Quality of Life in Chronic Pancreatitis is Determined by Constant Pain, Disability/Unemployment, Current Smoking, and Associated Co-Morbidities.

PubMed

Machicado, Jorge D; Amann, Stephen T; Anderson, Michelle A; Abberbock, Judah; Sherman, Stuart; Conwell, Darwin L; Cote, Gregory A; Singh, Vikesh K; Lewis, Michele D; Alkaade, Samer; Sandhu, Bimaljit S; Guda, Nalini M; Muniraj, Thiruvengadam; Tang, Gong; Baillie, John; Brand, Randall E; Gardner, Timothy B; Gelrud, Andres; Forsmark, Christopher E; Banks, Peter A; Slivka, Adam; Wilcox, C Mel; Whitcomb, David C; Yadav, Dhiraj

2017-04-01

Chronic pancreatitis (CP) has a profound independent effect on quality of life (QOL). Our aim was to identify factors that impact the QOL in CP patients. We used data on 1,024 CP patients enrolled in the three NAPS2 studies. Information on demographics, risk factors, co-morbidities, disease phenotype, and treatments was obtained from responses to structured questionnaires. Physical and mental component summary (PCS and MCS, respectively) scores generated using responses to the Short Form-12 (SF-12) survey were used to assess QOL at enrollment. Multivariable linear regression models determined independent predictors of QOL. Mean PCS and MCS scores were 36.7±11.7 and 42.4±12.2, respectively. Significant (P<0.05) negative impact on PCS scores in multivariable analyses was noted owing to constant mild-moderate pain with episodes of severe pain or constant severe pain (10 points), constant mild-moderate pain (5.2), pain-related disability/unemployment (5.1), current smoking (2.9 points), and medical co-morbidities. Significant (P<0.05) negative impact on MCS scores was related to constant pain irrespective of severity (6.8-6.9 points), current smoking (3.9 points), and pain-related disability/unemployment (2.4 points). In women, disability/unemployment resulted in an additional 3.7 point reduction in MCS score. Final multivariable models explained 27% and 18% of the variance in PCS and MCS scores, respectively. Etiology, disease duration, pancreatic morphology, diabetes, exocrine insufficiency, and prior endotherapy/pancreatic surgery had no significant independent effect on QOL. Constant pain, pain-related disability/unemployment, current smoking, and concurrent co-morbidities significantly affect the QOL in CP. Further research is needed to identify factors impacting QOL not explained by our analyses.

Structural Analysis of the Bacterial Proteasome Activator Bpa in Complex with the 20S Proteasome.

PubMed

Bolten, Marcel; Delley, Cyrille L; Leibundgut, Marc; Boehringer, Daniel; Ban, Nenad; Weber-Ban, Eilika

2016-12-06

Mycobacterium tuberculosis harbors proteasomes that recruit substrates for degradation through an ubiquitin-like modification pathway. Recently, a non-ATPase activator termed Bpa (bacterial proteasome activator) was shown to support an alternate proteasomal degradation pathway. Here, we present the cryo-electron microscopy (cryo-EM) structure of Bpa in complex with the 20S core particle (CP). For docking into the cryo-EM density, we solved the X-ray structure of Bpa, showing that it forms tight four-helix bundles arranged into a 12-membered ring with a 40 Å wide central pore and the C-terminal helix of each protomer protruding from the ring. The Bpa model was fitted into the cryo-EM map of the Bpa-CP complex, revealing its architecture and striking symmetry mismatch. The Bpa-CP interface was resolved to 3.5 Å, showing the interactions between the C-terminal GQYL motif of Bpa and the proteasome α-rings. This docking mode is related to the one observed for eukaryotic activators with features specific to the bacterial complex. Copyright © 2016 Elsevier Ltd. All rights reserved.

Photodissociation dynamics of gaseous CpCo(CO)2 and ligand exchange reactions of CpCoH2 with C3H4, C3H6, and NH3.

PubMed

Oana, Melania; Nakatsuka, Yumiko; Albert, Daniel R; Davis, H Floyd

2012-05-31

The photodissociation dynamics of CpCo(CO)(2) was studied in a molecular beam using photofragment translational energy spectroscopy with 157 nm photoionization detection of the metallic products. At 532 and 355 nm excitation, the dominant one-photon channel involved loss of a single CO ligand producing CpCoCO. The product angular distributions were isotropic, and a large fraction of excess energy appeared as product vibrational excitation. Production of CpCO + 2CO resulted from two-photon absorption processes. The two-photon dissociation of mixtures containing CpCo(CO)(2) and H(2) at the orifice of a pulsed nozzle was used to produce a novel 16-electron unsaturated species, CpCoH(2). Transition metal ligand exchange reactions, CpCoH(2) + L → CpCoL + H(2) (L = propyne, propene, or ammonia), were studied under single-collision conditions for the first time. In all cases, ligand exchange occurred via 18-electron association complexes with lifetimes comparable to their rotational periods. Although ligand exchange reactions were not detected from CpCoH(2) collisions with methane or propane (L = CH(4) or C(3)H(8)), a molecular beam containing CpCoCH(4) was produced by photolysis of mixtures containing CpCo(CO)(2) and CH(4).

Functional sub-division of the Drosophila genome via chromatin looping: the emerging importance of CP190.

PubMed

Ahanger, Sajad H; Shouche, Yogesh S; Mishra, Rakesh K

2013-01-01

Insulators help in organizing the eukaryotic genomes into physically and functionally autonomous regions through the formation of chromatin loops. Recent findings in Drosophila and vertebrates suggest that insulators anchor multiple loci through long-distance interactions which may be mechanistically linked to insulator function. Important to such processes in Drosophila is CP190, a common co-factor of insulator complexes. CP190 is also known to associate with the nuclear matrix, components of the RNAi machinery, active promoters and borders of the repressive chromatin domains. Although CP190 plays a pivotal role in insulator function in Drosophila, vertebrates lack a probable functional equivalent of CP190 and employ CTCF as the major factor to carry out insulator function/chromatin looping. In this review, we discuss the emerging role of CP190 in tethering genome, specifically in the perspective of insulator function in Drosophila. Future studies aiming genome-wide role of CP190 in chromatin looping is likely to give important insights into the mechanism of genome organization.

Genome-Wide Associations between Genetic and Epigenetic Variation Influence mRNA Expression and Insulin Secretion in Human Pancreatic Islets

PubMed Central

Olsson, Anders H.; Volkov, Petr; Bacos, Karl; Dayeh, Tasnim; Hall, Elin; Nilsson, Emma A.; Ladenvall, Claes; Rönn, Tina; Ling, Charlotte

2014-01-01

Genetic and epigenetic mechanisms may interact and together affect biological processes and disease development. However, most previous studies have investigated genetic and epigenetic mechanisms independently, and studies examining their interactions throughout the human genome are lacking. To identify genetic loci that interact with the epigenome, we performed the first genome-wide DNA methylation quantitative trait locus (mQTL) analysis in human pancreatic islets. We related 574,553 single nucleotide polymorphisms (SNPs) with genome-wide DNA methylation data of 468,787 CpG sites targeting 99% of RefSeq genes in islets from 89 donors. We identified 67,438 SNP-CpG pairs in cis, corresponding to 36,783 SNPs (6.4% of tested SNPs) and 11,735 CpG sites (2.5% of tested CpGs), and 2,562 significant SNP-CpG pairs in trans, corresponding to 1,465 SNPs (0.3% of tested SNPs) and 383 CpG sites (0.08% of tested CpGs), showing significant associations after correction for multiple testing. These include reported diabetes loci, e.g. ADCY5, KCNJ11, HLA-DQA1, INS, PDX1 and GRB10. CpGs of significant cis-mQTLs were overrepresented in the gene body and outside of CpG islands. Follow-up analyses further identified mQTLs associated with gene expression and insulin secretion in human islets. Causal inference test (CIT) identified SNP-CpG pairs where DNA methylation in human islets is the potential mediator of the genetic association with gene expression or insulin secretion. Functional analyses further demonstrated that identified candidate genes (GPX7, GSTT1 and SNX19) directly affect key biological processes such as proliferation and apoptosis in pancreatic β-cells. Finally, we found direct correlations between DNA methylation of 22,773 (4.9%) CpGs with mRNA expression of 4,876 genes, where 90% of the correlations were negative when CpGs were located in the region surrounding transcription start site. Our study demonstrates for the first time how genome-wide genetic and epigenetic variation interacts to influence gene expression, islet function and potential diabetes risk in humans. PMID:25375650

Diverse Reactivity of ECp* (E = Al, Ga) toward Low-Coordinate Transition Metal Amides [TM(N(SiMe3)2)2] (TM = Fe, Co, Zn): Insertion, Cp* Transfer, and Orthometalation.

PubMed

Weßing, Jana; Göbel, Christoph; Weber, Birgit; Gemel, Christian; Fischer, Roland A

2017-03-20

The reactivity of the carbenoid group 13 metal ligands ECp* (E = Al, Ga) toward low valent transition metal complexes [TM(btsa) 2 ] (TM = Fe, Co, Zn; btsa = bis(trimethylsilyl)amide) was investigated, revealing entirely different reaction patterns for E = Al and Ga. Treatment of [Co(btsa) 2 ] with AlCp* yields [Cp*Co(μ-H)(Al(κ 2 -(CH 2 SiMe 2 )NSiMe 3 )(btsa))] (1) featuring an unusual heterometallic bicyclic structure that results from the insertion of AlCp* into the TM-N bond with concomitant ligand rearrangement including C-H activation at one amide ligand. For [Fe(btsa) 2 ], complete ligand exchange gives FeCp* 2 , irrespective of the employed stoichiometric ratio of the reactants. In contrast, treatment of [TM(btsa) 2 ] (TM = Fe, Co) with GaCp* forms the 1:1 and 1:2 adducts [(GaCp*)Co(btsa) 2 ] (2) and [(GaCp*) 2 Fe(btsa) 2 ] (3), respectively. The tendency of AlCp* to undergo Cp* transfer to the TM center appears to be dependent on the nature of the TM center: For [Zn(btsa) 2 ], no Cp* transfer is observed on reaction with AlCp*; instead, the insertion product [Zn(Al(η 2 -Cp*)(btsa)) 2 ] (4) is formed. In the reaction of [Co(btsa) 2 ] with the trivalent [Cp*AlH 2 ], transfer of the amide ligands without further ligand rearrangement is observed, leading to [Co(μ-H) 4 (Al(η 2 -Cp*)(btsa)) 2 ] (5).

Observation of Excited Quadrupole-Bound States in Cold Anions

NASA Astrophysics Data System (ADS)

Zhu, Guo-Zhu; Liu, Yuan; Wang, Lai-Sheng

2017-07-01

We report the first observation of an excited quadrupole-bound state (QBS) in an anion. High-resolution photoelectron imaging of cryogenically cooled 4-cyanophenoxide (4 CP- ) anions yields an electron detachment threshold of 24 927 cm-1 . The photodetachment spectrum reveals a resonant transition 20 cm-1 below the detachment threshold, which is attributed to an excited QBS of 4 CP- because neutral 4CP has a large quadrupole moment with a negligible dipole moment. The QBS is confirmed by observation of seventeen above-threshold resonances due to autodetachment from vibrational levels of the QBS.

MeCP2 regulates ethanol sensitivity and intake.

PubMed

Repunte-Canonigo, Vez; Chen, Jihuan; Lefebvre, Celine; Kawamura, Tomoya; Kreifeldt, Max; Basson, Oan; Roberts, Amanda J; Sanna, Pietro Paolo

2014-09-01

We have investigated the expression of chromatin-regulating genes in the prefrontal cortex and in the shell subdivision of the nucleus accumbens during protracted withdrawal in mice with increased ethanol drinking after chronic intermittent ethanol (CIE) vapor exposure and in mice with a history of non-dependent drinking. We observed that the methyl-CpG binding protein 2 (MeCP2) was one of the few chromatin-regulating genes to be differentially regulated by a history of dependence. As MeCP2 has the potential of acting as a broad gene regulator, we investigated sensitivity to ethanol and ethanol drinking in MeCP2(308/) (Y) mice, which harbor a truncated MeCP2 allele but have a milder phenotype than MeCP2 null mice. We observed that MeCP2(308/) (Y) mice were more sensitive to ethanol's stimulatory and sedative effects than wild-type (WT) mice, drank less ethanol in a limited access 2 bottle choice paradigm and did not show increased drinking after induction of dependence with exposure to CIE vapors. Alcohol metabolism did not differ in MeCP2(308/) (Y) and WT mice. Additionally, MeCP2(308/) (Y) mice did not differ from WT mice in ethanol preference in a 24-hour paradigm nor in their intake of graded solutions of saccharin or quinine, suggesting that the MeCP2(308/) (Y) mutation did not alter taste function. Lastly, using the Gene Set Enrichment Analysis algorithm, we found a significant overlap in the genes regulated by alcohol and by MeCP2. Together, these results suggest that MeCP2 contributes to the regulation of ethanol sensitivity and drinking. © 2013 The Authors, Addiction Biology © 2013 Society for the Study of Addiction.

FBXL19 recruits CDK-Mediator to CpG islands of developmental genes priming them for activation during lineage commitment

PubMed Central

Dimitrova, Emilia; Nakayama, Manabu; Koseki, Yoko; Konietzny, Rebecca; Kessler, Benedikt M; Koseki, Haruhiko

2018-01-01

CpG islands are gene regulatory elements associated with the majority of mammalian promoters, yet how they regulate gene expression remains poorly understood. Here, we identify FBXL19 as a CpG island-binding protein in mouse embryonic stem (ES) cells and show that it associates with the CDK-Mediator complex. We discover that FBXL19 recruits CDK-Mediator to CpG island-associated promoters of non-transcribed developmental genes to prime these genes for activation during cell lineage commitment. We further show that recognition of CpG islands by FBXL19 is essential for mouse development. Together this reveals a new CpG island-centric mechanism for CDK-Mediator recruitment to developmental gene promoters in ES cells and a requirement for CDK-Mediator in priming these developmental genes for activation during cell lineage commitment. PMID:29809150

μ3-η(2):η(2):η(2)-Coordination of Primary Silane on a Triruthenium Plane.

PubMed

Nagaoka, Masahiro; Tsuruda, Hiroyuki; Amako, Masa-aki; Suzuki, Hiroharu; Takao, Toshiro

2015-12-01

A μ3-η(2):η(2):η(2)-silane complex, [(Cp*Ru)3(μ3-η(2):η(2):η(2)-H3SitBu)(μ-H)3] (2 a; Cp* = η(5)-C5Me5), was synthesized from the reaction of [{Cp*Ru(μ-H)}3(μ3-H)2] (1) with tBuSiH3. Complex 2 a is the first example of a silane ligand adopting a μ3-η(2):η(2):η(2) coordination mode. This unprecedented coordination mode was established by NMR and IR spectroscopy as well as X-ray diffraction analysis and supported by a density functional study. Variable-temperature NMR analysis implied that 2 a equilibrates with a tautomeric μ3-silyl complex (3 a). Although 3 a was not isolated, the corresponding μ3-silyl complex, [(Cp*Ru)3(μ3-η(2):η(2)-H2SiPh)(H)(μ-H)3] (3 b), was obtained from the reaction of 1 with PhSiH3. Treatment of 2 a with PhSiH3 resulted in a silane exchange reaction, leading to the formation of 3 b accompanied by the elimination of tBuSiH3. This result indicates that the μ3-silane complex can be regarded as an "arrested" intermediate for the oxidative addition/reductive elimination of a primary silane to a trinuclear site. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New simple A{sub 4} neutrino model for nonzero {theta}{sub 13} and large {delta}{sub CP}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ishimori, Hajime

In a new simple application of the non-Abelian discrete symmetry A{sub 4} to charged-lepton and neutrino mass matrices, we show that for the current experimental central value of sin{sup 2} 2{theta}{sub 13} Asymptotically-Equal-To 0.1, leptonic CP violation is necessarily large, i.e. Double-Vertical-Line tan{delta}{sub CP} Double-Vertical-Line > 1.3. We also consider T{sub 7} model with one parameter to be complex, thus allowing for one Dirac CP phase {delta}{sub CP} and two Majorana CP phases {alpha}{sub 1,2}. We find a slight modification to this correlation as a function of {delta}{sub CP}. For a given set of input values of {Delta}m{sup 2}{sub 21},more » {Delta}m{sup 2}{sub 32}, {theta}{sub 12}, and {theta}{sub 13}, we obtain sin{sup 2} 2{theta}{sub 23} and m{sub ee} (the effective Majorana neutrino mass in neutrinoless double beta decay) as functions of tan {delta}{sub CP}. We find that the structure of this model always yields small Double-Vertical-Line tan {delta}{sub CP} Double-Vertical-Line .« less

Extreme heterogeneity of polyadenylation sites in mRNAs encoding chloroplast RNA-binding proteins in Nicotiana plumbaginifolia.

PubMed

Klahre, U; Hemmings-Mieszczak, M; Filipowicz, W

1995-06-01

We have previously characterized nuclear cDNA clones encoding two RNA binding proteins, CP-RBP30 and CP-RBP-31, which are targeted to chloroplasts in Nicotiana plumbaginifolia. In this report we describe the analysis of the 3'-untranslated regions (3'-UTRs) in 22 CP-RBP30 and 8 CP-RBP31 clones which reveals that mRNAs encoding both proteins have a very complex polyadenylation pattern. Fourteen distinct poly(A) sites were identified among CP-RBP30 clones and four sites among the CP-RBP31 clones. The authenticity of the sites was confirmed by RNase A/T1 mapping of N. plumbaginifolia RNA. CP-RBP30 provides an extreme example of the heterogeneity known to be a feature of mRNA polyadenylation in higher plants. Using PCR we have demonstrated that CP-RBP genes in N. plumbaginifolia and N. sylvestris, in addition to the previously described introns interrupting the coding region, contain an intron located in the 3' non-coding part of the gene. In the case of the CP-RBP31, we have identified one polyadenylation event occurring in this intron.

1-(Diphenyl-phosphinothio-yl)-2-[(4-methyl-phen-yl)meth-oxy-meth-yl]ferrocene.

PubMed

Daran, Jean-Claude; Audin, Catherine; Deydier, Eric; Manoury, Eric; Poli, Rinaldo

2010-10-20

Following our continuing inter-est in developing new chiral phosphine-containing ferrocenyl ligands, we synthesized the title compound, [Fe(C(5)H(5))(C(26)H(24)OPS)], in which there are two nearly identical mol-ecules in the asymmetric unit. The conformation of the cyclo-penta-dienyl (Cp) rings in each ferrocenyl group are inter-mediate between eclipsed and staggered, with twist angles of 16.6 (2) and 8.9 (2)°. The protecting S atom is located endo with respect to the substituted Cp ring. In the crystal, mol-ecules are connected through inter-molecular C-H⋯π inter-actions.

Bis(μ2-iso-propyl-imido-κ(2) N:N)bis-[(η(5)-cyclo-penta-dien-yl)(ethenolato-κO)titanium(IV)].

PubMed

Haehnel, Martin; Spannenberg, Anke; Rosenthal, Uwe

2014-01-01

The title dinuclear half-sandwich complex, [CpTi(OCH=CH2)(μ2-N-iPr)]2 (Cp = cyclo-penta-dien-yl; iPr = isopropyl), was ob-tained from the reaction of Cp2TiCl2, n-butyl-lithium and iso-propyl-amine in tetra-hydro-furan. Each Ti(IV) atom is coordinated by one Cp ligand, one vin-yloxy unit and two bridging imido groups in a strongly distorted tetra-hedral geometry. There are two half mol-ecules in the asymmetric unit, such that whole mol-ecules being generated by inversion symmetry.

Sociometric status and the attribution of intentions in a sample of adolescents with cerebral palsy.

PubMed

Voyer, Anne-Pier; Tessier, Réjean; Nadeau, Line

2017-03-01

Purpose To examine how cerebral palsy (CP) and sociometric status at age 10 explain the development of a cognitive bias across two groups of adolescents aged 15. Method Children with CP (N = 60) and without CP (N = 57) are part of a follow-up study. Three categories of sociometric status (popular, average, rejected) were obtained by conducting a class-wide interview in the class of the target children at age 10. At 15 years old, the same children (CP and non-CP) were asked to complete the Home Interview With Child questionnaire measuring a cognitive bias (hostile attribution of intentions (AI)). Results Children with CP, especially girls, were significantly more rejected and less popular than controls at age 10. At age 15, among all participants, sociometric rejected and popular children tended to have a higher percentage of hostile AI than sociometric average children. Conclusions There were no significant results for the combined effect of CP and sociometric status on the development of hostile AI at age 15. However, knowing the risk incurred by children with CP of being socially rejected, attention should be paid in the rehabilitation process to opportunities for social participation to facilitate the development of social competence. Implications for Rehabilitation Level I or II cerebral palsy (CP) is a condition that affects not only motor abilities but also social competence in children. Sociometric status in a group tends to affect the development of the ability to interprete intentions of others during adolescence. Sociometric measures in the class of children with CP could be a useful tool in the rehabilitation process in order to better define social participation opportunities. To improve social participation attempts, rehabilitation interventions should target social initiating skills, flexibility in interpreting peers' behaviours, and ability to react effectively to negative peer treatment.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Shaoguang; Appel, Aaron M.; Bullock, R. Morris

Controlling the heterolytic cleavage of the H-H bond of dihydrogen is critically important in catalytic hydrogenations and in the catalytic oxidation of H2. We show how the rate of reversible heterolytic cleavage of H2 can be controlled over nearly four orders of magnitude at 25 °C, from 2.1 × 103 s-1 to ≥107 s-1. Bifunctional Mo complexes, [CpMo(CO)(κ3-P2N2)]+ (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane with alkyl/aryl groups on N and P), have been developed for heterolytic cleavage of H2 into a proton and a hydride, akin to Frustrated Lewis Pairs. The H-H bond cleavage is enabled by the basic amine in the secondmore » coordination sphere. The products of heterolytic cleavage of H2, Mo hydride complexes bearing protonated amines, [CpMo(H)(CO)(P2N2H)]+, were characterized by spectroscopic studies and by X-ray crystallography. Variable temperature 1H, 15N and 2-D 1H-1H ROESY NMR spectra indicated rapid exchange of the proton and hydride. The exchange rates are in the order [CpMo(H)(CO)(PPh2NPh2H)]+ > [CpMo(H)(CO)(PtBu2NPh2H)]+ > [CpMo(H)(CO)(PPh2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NBn2H)]+ > [CpMo(H)(CO)(PtBu2NtBu2H)]+. The pKa values determined in acetonitrile range from 9.3 to 17.7, and show a linear correlation with the logarithm of the exchange rates. Thus the exchange dynamics are controlled through the relative acidity of the [CpMo(H)(CO)(P2N2H)]+ and [CpMo(H2)(CO)(P2N2)]+ isomers, providing a design principle for controlling heterolytic cleavage of H2.« less

Differential Expression and Regulation of Brain-Derived Neurotrophic Factor (BDNF) mRNA Isoforms in Brain Cells from Mecp2(308/y) Mouse Model.

PubMed

Rousseaud, Audrey; Delépine, Chloé; Nectoux, Juliette; Billuart, Pierre; Bienvenu, Thierry

2015-08-01

Rett syndrome (RTT) is a severe neurodevelopmental disease caused by mutations in methyl-CpG-binding protein 2 (MECP2), which encodes a transcriptional modulator of many genes including BDNF. BDNF comprises nine distinct promoter regions, each triggering the expression of a specific transcript. The role of this diversity of transcripts remains unknown. MeCP2 being highly expressed in neurons, RTT was initially considered as a neuronal disease. However, recent studies have shown that MeCP2 was also expressed in astrocytes. Though several studies explored Bdnf IV expression in Mecp2-deficient mice, the differential expression of Bdnf isoforms in Mecp2-deficient neurons and astrocytes was never studied. By using TaqMan technology and a mouse model expressing a truncated Mecp2 (Mecp2(308/y)), we firstly showed in neurons that Bdnf transcripts containing exon I, IIb, IIc, IV, and VI are prominently expressed, whereas in astrocytes, Bdnf transcript containing exon VI is preferentially expressed, suggesting a specific regulation of Bdnf expression at the cellular level. Secondly, we confirmed the repressive role of Mecp2 only on the expression of Bdnf VI in neurons. Our data suggested that the truncated Mecp2 protein maintains its function on Bdnf expression regulation in neurons and in astrocytes. Interestingly, we observed that Bdnf transcripts (I and IXA), regulated by neural activity induced by bicuculline in Mecp2(308/y) neurons, were not affected by histone deacetylase inhibition. In contrast, Bdnf transcripts (IIb, IIc, and VI), regulated by histone deacetylation, were not affected by bicuculline treatment in wild-type and Mecp2(308/y) neurons. All these results reflect the complexity of regulation of Bdnf gene.

Transcranial Direct Current Stimulation (tDCS) Targeting Left Dorsolateral Prefrontal Cortex Modulates Task-Induced Acute Pain in Healthy Volunteers

PubMed Central

Mariano, Timothy Y.; Wout, Mascha van't; Garnaat, Sarah L.; Rasmussen, Steven A.; Greenberg, Benjamin D.

2016-01-01

Objective Current chronic pain treatments target nociception rather than affective “suffering” and its associated functional and psychiatric comorbidities. Left dorsolateral prefrontal cortex (DLPFC) has been implicated in affective, cognitive, and attentional aspects of pain and is a primary target of neuromodulation for affective disorders. Transcranial direct current stimulation (tDCS) can noninvasively modulate cortical activity. The present study tests if anodal tDCS targeting left DLPFC will increase tolerability of acute painful stimuli versus cathodal tDCS. Methods Forty tDCS-naive healthy volunteers received anodal and cathodal stimulation targeting left DLPFC in two randomized and counterbalanced sessions. During stimulation, each participant performed cold pressor (CP) and breath holding (BH) tasks. We measured pain intensity with the Defense and Veterans Pain Rating Scale (DVPRS) before and after each task. Results Mixed ANOVA revealed no main effect of stimulation polarity for mean CP threshold, tolerance, or endurance, or mean BH time (all p > 0.27). However, DVPRS rise associated with CP was significantly smaller with anodal versus cathodal tDCS (p = 0.024). We further observed a significant tDCS polarity × stimulation order interaction (p = 0.042) on CP threshold suggesting task sensitization. Conclusions Although our results do not suggest that polarity of tDCS targeting left DLPFC differentially modulates tolerability of CP- and BH-related pain distress in healthy volunteers, there was a significant effect on DVPRS pain ratings. This contrasts with our previous findings that tDCS targeting left dorsal anterior cingulate cortex showed a trend towards higher mean CP tolerance with cathodal versus anodal stimulation. The present results may suggest tDCS-related effects on nociception or DLPFC-mediated attention, or preferential modulation of the affective valence of pain as captured by DVPRS. Sham-controlled clinical studies are needed. PMID:26814276

Transcranial Direct Current Stimulation (tDCS) Targeting Left Dorsolateral Prefrontal Cortex Modulates Task-Induced Acute Pain in Healthy Volunteers.

PubMed

Mariano, Timothy Y; Van't Wout, Mascha; Garnaat, Sarah L; Rasmussen, Steven A; Greenberg, Benjamin D

2016-04-01

Current chronic pain treatments target nociception rather than affective "suffering" and its associated functional and psychiatric comorbidities. The left dorsolateral prefrontal cortex (DLPFC) has been implicated in affective, cognitive, and attentional aspects of pain and is a primary target of neuromodulation for affective disorders. Transcranial direct current stimulation (tDCS) can non-invasively modulate cortical activity. The present study tests whether anodal tDCS targeting the left DLPFC will increase tolerability of acute painful stimuli vs cathodal tDCS. Forty tDCS-naive healthy volunteers received anodal and cathodal stimulation targeting the left DLPFC in two randomized and counterbalanced sessions. During stimulation, each participant performed cold pressor (CP) and breath holding (BH) tasks. We measured pain intensity with the Defense and Veterans Pain Rating Scale (DVPRS) before and after each task. Mixed ANOVA revealed no main effect of stimulation polarity for mean CP threshold, tolerance, or endurance, or mean BH time (allP > 0.27). However, DVPRS rise associated with CP was significantly smaller with anodal vs cathodal tDCS (P = 0.024). We further observed a significant tDCS polarity × stimulation order interaction (P = 0.042) on CP threshold, suggesting task sensitization. Although our results do not suggest that polarity of tDCS targeting the left DLPFC differentially modulates the tolerability of CP- and BH-related pain distress in healthy volunteers, there was a significant effect on DVPRS pain ratings. This contrasts with our previous findings that tDCS targeting the left dorsal anterior cingulate cortex showed a trend toward higher mean CP tolerance with cathodal vs anodal stimulation. The present results may suggest tDCS-related effects on nociception or DLPFC-mediated attention, or preferential modulation of the affective valence of pain as captured by the DVPRS. Sham-controlled clinical studies are needed. © 2015 American Academy of Pain Medicine. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Selection bias in genetic-epidemiological studies of cleft lip and palate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christensen, K.; Holm, N.V.; Kock, K.

1992-09-01

The possible impact of selection bias in genetic and epidemiological studies of cleft lip and palate was studied, using three nationwide ascertainment sources and an autopsy study in a 10% sample of the Danish population. A total of 670 cases were identified. Two national record systems, when used together, were found suitable for ascertaining facial cleft in live births. More than 95% ascertainment was obtained by means of surgical files for cleft lip (with or without cleft palate) without associated malformations/syndromes. However, surgical files could be a poor source for studying isolated cleft palate (CP) (only a 60% and biasedmore » ascertainment), and they cannot be used to study the prevalence of associated malformations or syndromes in facial cleft cases. The male:female ratio was 0.88 in surgically treated cases of CP and was 1.5 in nonoperated CP cases, making the overall sex ratio for CP 1.1 (95% confidence limits 0.86-1.4) The sex ratio for CP without associated malformation was 1.1 (95% confidence limits 0.84-1.6). One of the major test criteria in CP multifactorial threshold models (higher CP liability among male CP relatives) must be reconsidered, if other investigations confirm that a CP sex-ratio reversal to male predominance occurs when high ascertainment is achieved. 24 refs., 1 fig., 4 tabs.« less

Early alterations in glycemic control and pancreatic endocrine function in non-diabetic patients with chronic pancreatitis

PubMed Central

Lundberg, Rachel; Beilman, Gregory J.; Dunn, Ty B.; Pruett, Tim L.; Freeman, Martin L.; Ptacek, Peggy E.; Berry, K. Louise; Robertson, R. Paul; Moran, Antoinette; Bellin, Melena D.

2015-01-01

Objectives Diabetes mellitus (DM) is a frequent consequence of chronic pancreatitis (CP). Little is known about pancreatic endocrine function before the development of DM in CP, particularly in females, or those without calcific and/or alcoholic pancreatitis. Methods Twenty-five non-diabetic adult CP patients (19 female, age 34.2 ± 2.4 yrs) were compared to 25 healthy controls matched for age, gender, and BMI. Subjects underwent frequent sample intravenous glucose tolerance testing (FSIVGTT) and mixed meal tolerance testing (MMTT). Results Mean fasting glucose was higher in CP patients (89.5 ±2.3 mg/dL) than in controls (84.4 ±1.2 mg/dL, p=0.04). On MMTT, CP patients had a higher area under the curve (AUC) glucose and AUC glucagon compared to controls (p≤0.01). AUC C-peptide was equivalent (p=0.6) but stimulated C-peptide at 30 minutes was lower in CP patients (p=0.04). Mean insulin sensitivity index calculated from the FSIVGTT was lower in CP group, indicating reduced insulin sensitivity (p≤0.01). Disposition index (insulin secretion adjusted for insulin sensitivity on FSIVGTT) was lower in CP patients (p=0.01). Conclusions CP patients had higher fasting and MMTT glucose levels, without a compensatory increase in insulin secretion suggesting subtle early islet dysfunction. Our cohort had relative hyperglucagonemia and were less insulin sensitive than controls. PMID:26918872

Molecular structures and metabolic characteristics of protein in brown and yellow flaxseed with altered nutrient traits.

PubMed

Khan, Nazir Ahmad; Booker, Helen; Yu, Peiqiang

2014-07-16

The objectives of this study were to investigate the chemical profiles; crude protein (CP) subfractions; ruminal CP degradation characteristics and intestinal digestibility of rumen undegraded protein (RUP); and protein molecular structures using molecular spectroscopy of newly developed yellow-seeded flax (Linum usitatissimum L.). Seeds from two yellow flaxseed breeding lines and two brown flaxseed varieties were evaluated. The yellow-seeded lines had higher (P < 0.001) contents of oil (44.54 vs 41.42% dry matter (DM)) and CP (24.94 vs 20.91% DM) compared to those of the brown-seeded varieties. The CP in yellow seeds contained lower (P < 0.01) contents of true protein subfraction (81.31 vs 92.71% CP) and more (P < 0.001) extensively degraded (70.8 vs 64.9% CP) in rumen resulting in lower (P < 0.001) content of RUP (29.2 vs 35.1% CP) than that in the brown-seeded varieties. However, the total supply of digestible RUP was not significantly different between the two seed types. Regression equations based on protein molecular structural features gave relatively good estimation for the contents of CP (R(2) = 0.87), soluble CP (R(2) = 0.92), RUP (R(2) = 0.97), and intestinal digestibility of RUP (R(2) = 0.71). In conclusion, molecular spectroscopy can be used to rapidly characterize feed protein molecular structures and predict their nutritive value.

The ventilatory anaerobic threshold is related to, but is lower than, the critical power, but does not explain exercise tolerance at this workrate.

PubMed

Okudan, N; Gökbel, H

2006-03-01

The aim of the present study was to investigate the relationships between critical power (CP), maximal aerobic power and the anaerobic threshold and whether exercise time to exhaustion and work at the CP can be used as an index in the determination of endurance. An incremental maximal cycle exercise test was performed on 30 untrained males aged 18-22 years. Lactate analysis was carried out on capillary blood samples at every 2 minutes. From gas exchange parameters and heart rate and lactate values, ventilatory anaerobic thresholds, heart rate deflection point and the onset of blood lactate accumulation were calculated. CP was determined with linear work-time method using 3 loads. The subjects exercised until they could no longer maintain a cadence above 24 rpm at their CP and exercise time to exhaustion was determined. CP was lower than the power output corresponding to VO2max, higher than the power outputs corresponding to anaerobic threshold. CP was correlated with VO2max and anaerobic threshold. Exercise time to exhaustion and work at CP were not correlated with VO2max and anaerobic threshold. Because of the correlations of the CP with VO2max and anaerobic threshold and no correlation of exercise time to exhaustion and work at the CP with these parameters, we conclude that exercise time to exhaustion and work at the CP cannot be used as an index in the determination of endurance.

Synthesis of Pt-Ni-Fe/CNT/CP nanocomposite as an electrocatalytic electrode for PEM fuel cell cathode

NASA Astrophysics Data System (ADS)

Litkohi, Hajar Rajaei; Bahari, Ali; Ojani, Reza

2017-08-01

In order to use carbon nanotube (CNT)-supported catalyst as fuel cell electrodes, Pt-Ni-Fe/CNT/carbon paper (CP) electrode was prepared using an ethylene glycol reduction method. CNTs were directly synthesized on Ni-impregnated carbon paper, plain carbon cloth, and Teflonized carbon cloth using chemical vapor deposition. FESEM and TEM images and thermogravimetric analysis indicated that in situ CNT on carbon paper (ICNT/CP) possesses more appropriate structural quality and stronger adhesion to the substrate than other substrates. The contact angle analysis demonstrated that the degree of ICNT/CP surface hydrophobicity encountered a 24% increase in comparison to CP and promoted to superhydrophobicity from hydrophobicity. The polarization curves and electrochemical impedance spectroscopy results of the loaded Pt-Ni-Fe on in situ and ex situ CNT/CP illustrated that the power density increased and charge transfer resistance reduced compared to commercial Pt/C loaded on CP. The results can be attributed to the outstanding properties of CNTs and high catalytic activity of triple catalysts causing alloying of Pt with Ni and Fe, which makes them a proper candidate to be used as cathode electrodes in proton exchange membrane fuel cells.

Assessment of directionality performances: comparison between Freedom and CP810 sound processors.

PubMed

Razza, Sergio; Albanese, Greta; Ermoli, Lucilla; Zaccone, Monica; Cristofari, Eliana

2013-10-01

To compare speech recognition in noise for the Nucleus Freedom and CP810 sound processors using different directional settings among those available in the SmartSound portfolio. Single-subject, repeated measures study. Tertiary care referral center. Thirty-one monoaurally and binaurally implanted subjects (24 children and 7 adults) were enrolled. They were all experienced Nucleus Freedom sound processor users and achieved a 100% open set word recognition score in quiet listening conditions. Each patient was fitted with the Freedom and the CP810 processor. The program setting incorporated Adaptive Dynamic Range Optimization (ADRO) and adopted the directional algorithm BEAM (both devices) and ZOOM (only on CP810). Speech reception threshold (SRT) was assessed in a free-field layout, with disyllabic word list and interfering multilevel babble noise in the 3 different pre-processing configurations. On average, CP810 improved significantly patients' SRTs as compared to Freedom SP after 1 hour of use. Instead, no significant difference was observed in patients' SRT between the BEAM and the ZOOM algorithm fitted in the CP810 processor. The results suggest that hardware developments achieved in the design of CP810 allow an immediate and relevant directional advantage as compared to the previous-generation Freedom device.

Mono- and dinuclear tetraphosphabutadiene ferrate anions.

PubMed

Chakraborty, Uttam; Leitl, Julia; Mühldorf, Bernd; Bodensteiner, Michael; Pelties, Stefan; Wolf, Robert

2018-03-12

Reduction of [Cp Ar Fe(μ-Br)] 2 (1, Cp Ar = C 5 (C 6 H 4 -4-Et) 5 ) by potassium napthalenide, followed by the addition of white phosphorus, affords [K(18-c-6){Cp Ar Fe(η 4 -P 4 )}] (2, 18-c-6 = [18]crown-6), which features a planar cyclo-P 4 2- ligand. The related diiron complex [Na 2 (THF) 5 (Cp Ar Fe) 2 (μ,η 4:4 -P 4 )] (3) was obtained by reducing 1 with sodium amalgam in the presence of P 4 . Protonation of 3 affords [Na(THF) 3 ][(Cp Ar Fe) 2 (μ,η 4:4 -P 4 )(H)] (4), while the reaction of 3 with trimethylchlorosilane gives the nortricyclane compound P 7 (SiMe 3 ) 3 as the main product.

Methylation changes and pathways affected in preterm birth: a role for SLC6A3 in neurodevelopment.

PubMed

Arpón, Ana; Milagro, Fermín I; Laja, Ana; Segura, Víctor; de Pipaón, Miguel Sáenz; Riezu-Boj, José-Ignacio; Alfredo Martínez, J

2018-01-01

To analyze whether preterm newborns show differences in methylation patterns in comparison to full-term newborns in white blood cells. Anthropometrical, biochemical features and methylation levels of preterm newborns (n = 24) and full-term newborns (n = 22) recruited in La Paz University Hospital (Spain) were assessed at 12 months of gestational age, whereas Bayley Scale of Infant Development was evaluated at 24/36 months. From all the statistically significant CpGs, methylation levels of cg00997378 (SLC6A3 gene) showed the highest differences (p < 0.0001), being associated with prematurity risk factors.  SLC6A3 methylation, previously related to attention-deficit/hyperactivity disorder, neuronal function and behavior, might be a potential epigenetic biomarker with value in the early diagnosis and management of neurodevelopmental diseases in newborns.

Effect of field pea-based creep feed on intake, digestibility, ruminal fermentation, and performance by nursing calves grazing native range in western North Dakota.

PubMed

Gelvin, A A; Lardy, G P; Soto-Navarro, S A; Landblom, D G; Caton, J S

2004-12-01

Two experiments evaluated digestive and performance effects of field pea-based creep feed in nursing calf diets. In Exp.1, eight nursing steer calves (145 +/- 27 kg initial BW) with ruminal cannulas were used to evaluate effects of supplementation and advancing season on dietary composition, intake, digestion, and ruminal fermentation characteristics. Treatments were unsupplemented control (CON) and field pea-based creep (SUP; 19.1% CP, DM basis) fed at 0.45% BW (DM basis) daily. Calves grazed native range with their dams from early July through early November. Periods were 24 d long and occurred in July (JUL), August (AUG), September (SEP), and October (OCT). Experiment 2 used 80 crossbred nursing calves, 48 calves in yr 1 and 32 calves in yr 2 (yr 1 = 144 +/- 24 kg; yr 2 = 121 +/- 20 kg initial BW), to evaluate effects of field pea-based creep on calf performance. Treatments included unsupplemented control (CON); field pea-based creep feeds containing either 8% (LS); or 16% (HS) salt; and soybean meal/field pea-based creep containing (as-fed basis) 16% salt (HIPRO). Masticate samples from SUP calves in Exp.1 had greater CP (P = 0.05) than those from CON calves. Forage CP and ADIN decreased linearly with advancing season (P = 0.01 and 0.03, respectively). In vitro OM digestibility of diet masticate decreased from JUL to OCT (P < 0.01; 58.5 to 41.3%). Forage intake did not differ (P = 0.33) between treatments but increased linearly with advancing season (1.67, 1.90, 3.12, 3.38 kg/d for JUL, AUG, SEP, and OCT, respectively; P < 0.01). Milk intake (percentage of BW) did not differ (P = 0.56) between CON and SUP calves but decreased linearly (P < 0.01) with advancing season. Supplemented calves had greater (P = 0.03) total intake (g/kg of BW; forage + milk + creep) compared with CON calves. Treatment did not affect (P < 0.30) rate of in situ disappearance of forage or creep. Forage DM, CP, and creep DM disappearance rate decreased linearly (P < or = 0.02) with advancing season. Supplementation decreased (P = 0.05) ruminal pH, whereas ruminal ammonia and VFA concentrations were greater (P < or = 0.02) in SUP calves. In Exp. 2, creep-fed calves had greater ADG and final BW than CON calves (P < 0.01). Calves offered HS tended (P = 0.07) to have increased gain efficiency above CON than LS calves. Field peas can be used as an ingredient in creep feed to increase calf weight gain without negatively affecting ruminal fermentation and digestion.

Registration of ‘CP 09-1822’ Sugarcane

USDA-ARS?s Scientific Manuscript database

‘CP 09-1822’ (Reg. No. __; PI 686942 sugarcane (a complex hybrid of Saccharum spp.) was released in June 2016 for commercial cultivation on sand (mineral) soils in Florida. This cultivar was developed through a collaborative sugarcane cultivar development program of the USDA-ARS, the University of F...

Registration of ‘CP 06-2400’ Sugarcane

USDA-ARS?s Scientific Manuscript database

‘CP 06-2400’ (Reg. No. ; PI ____) sugarcane (a complex hybrid of Saccharum spp.) was developed through cooperative research conducted by the USDA-ARS, the University of Florida, and the Florida Sugar Cane League, Inc. and released to growers for organic (muck) soils in Florida in October 2013. ...

Registration of ‘CP 06-2400’ Sugarcane

USDA-ARS?s Scientific Manuscript database

Technical Abstract: ‘CP 06-2400’ (Reg. No. ; PI 670018) sugarcane (a complex hybrid of Saccharum spp.) was developed through cooperative research conducted by the USDA-ARS, the University of Florida, and the Florida Sugar Cane League, Inc. and released to growers for organic (muck) soils in Fl...

Registration of ‘CP 09-1430’ Sugarcane

USDA-ARS?s Scientific Manuscript database

‘CP 09-1430’ (Reg. No. ; PI 686940 sugarcane (a complex hybrid of Saccharum spp.) was developed and released (6 Jun. 2016) through cooperative research conducted by the USDA-ARS Sugarcane Field Station , Canal Point, the University of Florida, and the Florida Sugar Cane League, Inc. for use on ...

Affinity purification of the Arabidopsis 26 S proteasome reveals a diverse array of plant proteolytic complexes.

PubMed

Book, Adam J; Gladman, Nicholas P; Lee, Sang-Sook; Scalf, Mark; Smith, Lloyd M; Vierstra, Richard D

2010-08-13

Selective proteolysis in plants is largely mediated by the ubiquitin (Ub)/proteasome system in which substrates, marked by the covalent attachment of Ub, are degraded by the 26 S proteasome. The 26 S proteasome is composed of two subparticles, the 20 S core protease (CP) that compartmentalizes the protease active sites and the 19 S regulatory particle that recognizes and translocates appropriate substrates into the CP lumen for breakdown. Here, we describe an affinity method to rapidly purify epitope-tagged 26 S proteasomes intact from Arabidopsis thaliana. In-depth mass spectrometric analyses of preparations generated from young seedlings confirmed that the 2.5-MDa CP-regulatory particle complex is actually a heterogeneous set of particles assembled with paralogous pairs for most subunits. A number of these subunits are modified post-translationally by proteolytic processing, acetylation, and/or ubiquitylation. Several proteasome-associated proteins were also identified that likely assist in complex assembly and regulation. In addition, we detected a particle consisting of the CP capped by the single subunit PA200 activator that may be involved in Ub-independent protein breakdown. Taken together, it appears that a diverse and highly dynamic population of proteasomes is assembled in plants, which may expand the target specificity and functions of intracellular proteolysis.

Affinity Purification of the Arabidopsis 26 S Proteasome Reveals a Diverse Array of Plant Proteolytic Complexes*

PubMed Central

Book, Adam J.; Gladman, Nicholas P.; Lee, Sang-Sook; Scalf, Mark; Smith, Lloyd M.; Vierstra, Richard D.

2010-01-01

Selective proteolysis in plants is largely mediated by the ubiquitin (Ub)/proteasome system in which substrates, marked by the covalent attachment of Ub, are degraded by the 26 S proteasome. The 26 S proteasome is composed of two subparticles, the 20 S core protease (CP) that compartmentalizes the protease active sites and the 19 S regulatory particle that recognizes and translocates appropriate substrates into the CP lumen for breakdown. Here, we describe an affinity method to rapidly purify epitope-tagged 26 S proteasomes intact from Arabidopsis thaliana. In-depth mass spectrometric analyses of preparations generated from young seedlings confirmed that the 2.5-MDa CP-regulatory particle complex is actually a heterogeneous set of particles assembled with paralogous pairs for most subunits. A number of these subunits are modified post-translationally by proteolytic processing, acetylation, and/or ubiquitylation. Several proteasome-associated proteins were also identified that likely assist in complex assembly and regulation. In addition, we detected a particle consisting of the CP capped by the single subunit PA200 activator that may be involved in Ub-independent protein breakdown. Taken together, it appears that a diverse and highly dynamic population of proteasomes is assembled in plants, which may expand the target specificity and functions of intracellular proteolysis. PMID:20516081

Differential global structural changes in the core particle of yeast and mouse proteasome induced by ligand binding

PubMed Central

Arciniega, Marcelino; Beck, Philipp; Lange, Oliver F.; Groll, Michael; Huber, Robert

2014-01-01

Two clusters of configurations of the main proteolytic subunit β5 were identified by principal component analysis of crystal structures of the yeast proteasome core particle (yCP). The apo-cluster encompasses unliganded species and complexes with nonpeptidic ligands, and the pep-cluster comprises complexes with peptidic ligands. The murine constitutive CP structures conform to the yeast system, with the apo-form settled in the apo-cluster and the PR-957 (a peptidic ligand) complex in the pep-cluster. In striking contrast, the murine immune CP classifies into the pep-cluster in both the apo and the PR-957–liganded species. The two clusters differ essentially by multiple small structural changes and a domain motion enabling enclosure of the peptidic ligand and formation of specific hydrogen bonds in the pep-cluster. The immune CP species is in optimal peptide binding configuration also in its apo form. This favors productive ligand binding and may help to explain the generally increased functional activity of the immunoproteasome. Molecular dynamics simulations of the representative murine species are consistent with the experimentally observed configurations. A comparison of all 28 subunits of the unliganded species with the peptidic liganded forms demonstrates a greatly enhanced plasticity of β5 and suggests specific signaling pathways to other subunits. PMID:24979800

The Use of Contact Mode Atomic Force Microscopy in Aqueous Medium for Structural Analysis of Spinach Photosynthetic Complexes

DOE PAGES

Phuthong, Witchukorn; Huang, Zubin; Wittkopp, Tyler M.; ...

2015-07-28

To investigate the dynamics of photosynthetic pigment-protein complexes in vascular plants at high resolution in an aqueous environment, membrane-protruding oxygen-evolving complexes (OECs) associated with photosystem II (PSII) on spinach ( Spinacia oleracea) grana membranes were examined using contact mode atomic force microscopy. This study represents, to our knowledge, the first use of atomic force microscopy to distinguish the putative large extrinsic loop of Photosystem II CP47 reaction center protein (CP47) from the putative oxygen-evolving enhancer proteins 1, 2, and 3 (PsbO, PsbP, and PsbQ) and large extrinsic loop of Photosystem II CP43 reaction center protein (CP43) in the PSII-OEC extrinsicmore » domains of grana membranes under conditions resulting in the disordered arrangement of PSII-OEC particles. Moreover, we observed uncharacterized membrane particles that, based on their physical characteristics and electrophoretic analysis of the polypeptides associated with the grana samples, are hypothesized to be a domain of photosystem I that protrudes from the stromal face of single thylakoid bilayers. Furthermore, our results are interpreted in the context of the results of others that were obtained using cryo-electron microscopy (and single particle analysis), negative staining and freeze-fracture electron microscopy, as well as previous atomic force microscopy studies.« less

Hydration of nucleic acid fragments: comparison of theory and experiment for high-resolution crystal structures of RNA, DNA, and DNA-drug complexes.

PubMed Central

Hummer, G; García, A E; Soumpasis, D M

1995-01-01

A computationally efficient method to describe the organization of water around solvated biomolecules is presented. It is based on a statistical mechanical expression for the water-density distribution in terms of particle correlation functions. The method is applied to analyze the hydration of small nucleic acid molecules in the crystal environment, for which high-resolution x-ray crystal structures have been reported. Results for RNA [r(ApU).r(ApU)] and DNA [d(CpG).d(CpG) in Z form and with parallel strand orientation] and for DNA-drug complexes [d(CpG).d(CpG) with the drug proflavine intercalated] are described. A detailed comparison of theoretical and experimental data shows positional agreement for the experimentally observed water sites. The presented method can be used for refinement of the water structure in x-ray crystallography, hydration analysis of nuclear magnetic resonance structures, and theoretical modeling of biological macromolecules such as molecular docking studies. The speed of the computations allows hydration analyses of molecules of almost arbitrary size (tRNA, protein-nucleic acid complexes, etc.) in the crystal environment and in aqueous solution. Images FIGURE 1 FIGURE 2 FIGURE 5 FIGURE 6 FIGURE 9 FIGURE 12 FIGURE 13 PMID:7542034

Passive Range of Motion in a Population-Based Sample of Children with Spastic Cerebral Palsy Who Walk

ERIC Educational Resources Information Center

McDowell, Brona C.; Salazar-Torres, Jose J.; Kerr, Claire; Cosgrove, Aidan P.

2012-01-01

-While passive range of motion (PROM) is commonly used to inform decisions on therapeutic management, knowledge of PROM of children with spastic cerebral palsy (CP) is limited. A population-based sample of 178 children with spastic CP (110 male; unilateral, n = 94; bilateral, n = 84; age range 4-17 years) and 68 typically developing children (24…

7 CFR 944.31 - Avocado import maturity regulation.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 10-10 22 311/16 10-24 18 37/16 11-07 Herman 10-03 16 3 9/16 10-17 14 3 6/16 10-31 Pinkerton (CP) 10... (P) 12-12 13 3 2/16 12-26 11 3 0/16 1-09 Reed (CP) 12-12 12 3 4/16 12-26 10 3 3/16 1-09 9 3 0/16 1-23...

7 CFR 944.31 - Avocado import maturity regulation.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10-10 22 311/16 10-24 18 37/16 11-07 Herman 10-03 16 3 9/16 10-17 14 3 6/16 10-31 Pinkerton (CP) 10... (P) 12-12 13 3 2/16 12-26 11 3 0/16 1-09 Reed (CP) 12-12 12 3 4/16 12-26 10 3 3/16 1-09 9 3 0/16 1-23...

7 CFR 944.31 - Avocado import maturity regulation.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 10-10 22 311/16 10-24 18 37/16 11-07 Herman 10-03 16 3 9/16 10-17 14 3 6/16 10-31 Pinkerton (CP) 10...) 12-12 13 3 2/16 12-26 11 3 0/16 1-09 Reed (CP) 12-12 12 3 4/16 12-26 10 3 3/16 1-09 9 3 0/16 1-23 1...

7 CFR 944.31 - Avocado import maturity regulation.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 10-10 22 311/16 10-24 18 37/16 11-07 Herman 10-03 16 3 9/16 10-17 14 3 6/16 10-31 Pinkerton (CP) 10...) 12-12 13 3 2/16 12-26 11 3 0/16 1-09 Reed (CP) 12-12 12 3 4/16 12-26 10 3 3/16 1-09 9 3 0/16 1-23 1...

Self-Concept of Children with Cerebral Palsy Compared with that of Children without Impairment

ERIC Educational Resources Information Center

Shields, Nora; Loy, Yijun; Murdoch, Alison; Taylor, Nicholas F.; Dodd, Karen J

2007-01-01

This study examined whether the self-concept of children with cerebral palsy (CP) differed from that of children without impairment. Forty-seven children (24 males, 23 females; mean age 11y 8mo [SD 2y 6mo]) with spastic diplegia or hemiplegia were matched with children without impairment. The level of disability of the children with CP was…

Weight-for-height values and limb anthropometric composition of tube-fed children with quadriplegic cerebral palsy.

PubMed

Kong, Chi-Keung; Wong, Heung-Sang Stephen

2005-12-01

Research has shown that growth retardation among children with quadriplegic cerebral palsy (CP) is often attributed to feeding dysfunction and malnutrition. The study compared weight-for-height values and limb anthropometric composition of nasogastric and gastrostomy tube-fed children with quadriplegic CP with those of orally fed children with quadriplegic CP and normal children, to examine the plausible effects of tube feeding on weight-for-height, fat, and muscle values for children with quadriplegic CP. Triceps, anterior mid-thigh, and medial calf skinfold thicknesses and the corresponding circumferences of the right or less affected side were measured. The subjects consisted of 119 normal children and 62 orally fed and 48 tube-fed children with quadriplegic CP. Body weight and height were recorded. For children with CP whose height could not be measured, height was estimated from the ulna length. Weight-for-height z scores, limb skinfold thicknesses, fat areas, skinfold-corrected muscle girths, and muscle areas of the children were compared. Tube-fed children with CP had normal mean weight-for-height z scores. Weight-for-height z scores of the orally fed children with CP were significantly below those of normal children and tube-fed children with CP. For children with CP, whereas triceps skinfold thickness seemed to predict the mid-upper arm fat area correctly, leg skinfold thicknesses seemed to overestimate the corresponding fat areas. Stepwise multiple regression analysis showed that triceps skinfold thicknesses had good correlation (r = 0.86) and the presence of CP had nonsignificant correlation with mid-upper arm fat areas. Multiple regression analysis of fat areas with skinfold thicknesses and the presence of CP, however, showed that CP was correlated negatively (partial correlation of CP: thigh, -0.45; calf, -0.53) with thigh and calf fat areas. Although skinfold-corrected mid-upper arm muscle girths of children with CP were quite similar to those of normal children, leg muscle girths were much reduced for both orally fed and tube-fed children with CP. The apparent thickening of leg skinfold thicknesses among children with CP probably was attributable to disproportional leg muscle wasting, with resulting reduced internal circumference of the subcutaneous fat layer. For tube-fed children with CP, skinfold thicknesses and fat areas were increased significantly, although their leg skinfold-corrected muscle girths and areas remained reduced. Skinfold thickness may overestimate the fat area in the affected limb with significant muscle wasting for children with CP. The condition was particularly obvious in the leg, where muscle wasting was prominent. Because leg muscles represent approximately one quarter of the normal body weight, low weight-for-height values among children with CP can be caused by leg muscle wasting attributable to disuse atrophy, which is unlikely to be correctable with tube feeding. Tube feeding may improve body weight mainly through fat deposition.

Unusual Characteristics of the DNA Binding Domain of Epigenetic Regulatory Protein MeCP2 Determine Its Binding Specificity

PubMed Central

2015-01-01

The protein MeCP2 mediates epigenetic regulation by binding methyl-CpG (mCpG) sites on chromatin. MeCP2 consists of six domains of which one, the methyl binding domain (MBD), binds mCpG sites in duplex DNA. We show that solution conditions with physiological or greater salt concentrations or the presence of nonspecific competitor DNA is necessary for the MBD to discriminate mCpG from CpG with high specificity. The specificity for mCpG over CpG is >100-fold under these solution conditions. In contrast, the MBD does not discriminate hydroxymethyl-CpG from CpG. The MBD is unusual among site-specific DNA binding proteins in that (i) specificity is not conferred by the enhanced affinity for the specific site but rather by suppression of its affinity for generic DNA, (ii) its specific binding to mCpG is highly electrostatic, and (iii) it takes up as well as displaces monovalent cations upon DNA binding. The MBD displays an unusually high affinity for single-stranded DNA independent of modification or sequence. In addition, the MBD forms a discrete dimer on DNA via a noncooperative binding pathway. Because the affinity of the second monomer is 1 order of magnitude greater than that of nonspecific binding, the MBD dimer is a unique molecular complex. The significance of these results in the context of neuronal function and development and MeCP2-related developmental disorders such as Rett syndrome is discussed. PMID:24828757

Monometallic Ni(0) and Heterobimetallic Ni(0) /Au(I) Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis.

PubMed

Cluff, Kyle J; Bhuvanesh, Nattamai; Blümel, Janet

2015-07-06

The tridentate chelate nickel complexes [(CO)Ni{(PPh2 CH2 )3 CMe}] (2), [(CO)Ni{(PPh2 CH2 CH2 )3 SiMe}] (6), and [Ph3 PNi{(PPh2 CH2 CH2 )3 SiMe}] (7), as well as the bidentate complex [(CO)2 Ni{(PPh2 CH2 )2 CMeCH2 PPh2 }] (3) and the heterobimetallic complex [(CO)2 Ni{(PPh2 CH2 )2 CMeCH2 Ph2 PAuCl}] (4), have been synthesized and fully characterized in solution. All (1) H and (13) C NMR signal assignments are based on 2D-NMR methods. Single crystal X-ray structures have been obtained for all complexes. Their (31) P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2-4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Feasibility of trialling cord blood stem cell treatments for cerebral palsy in Australia.

PubMed

Crompton, Kylie E; Elwood, Ngaire; Kirkland, Mark; Clark, Pamela; Novak, Iona; Reddihough, Dinah

2014-07-01

Umbilical cord blood may have therapeutic benefit in children with cerebral palsy (CP), but further studies are required. On first appearance it seems that Australia is well placed for such a trial because we have excellence in CP research backed by extensive CP registers, and both public and private cord blood banks. We aimed to examine the possibilities of conducting a trial of autologous umbilical cord blood cells (UCBCs) as a treatment for children with CP in Australia. Data linkages between CP registers and cord blood banks were used to estimate potential participant numbers for a trial of autologous UCBCs for children with CP. As of early 2013, one Victorian child with CP had cord blood stored in the public bank, and between 1 and 3 children had their cord blood stored at Cell Care Australia (private cord blood bank). In New South Wales, we counted two children on the CP register who had their stored cord blood available in early 2013. We estimate that there are between 10 and 24 children with CP of any type who have autologous cord blood available across Australia. In nations with small populations like Australia, combined with Australia's relatively low per capita cord blood storage to date, it is not currently feasible to conduct trials of autologous UCBCs for children with CP. Other options must be explored, such as allogeneic UCBCs or prospective trials for neonates at risk of CP. © 2014 The Authors. Journal of Paediatrics and Child Health © 2014 Paediatrics and Child Health Division (Royal Australasian College of Physicians).

Clinical characteristics and functional status of children with different subtypes of dyskinetic cerebral palsy.

PubMed

Sun, Dianrong; Wang, Qiang; Hou, Mei; Li, Yutang; Yu, Rong; Zhao, Jianhui; Wang, Ke

2018-05-01

Dyskinetic cerebral palsy (CP) is the second major subtype of CP. Dyskinetic CP can be classified into different subtypes, but the exact clinical characteristics of these subtypes have been poorly studied. To investigate the clinical characteristics and functional classification of dyskinetic CP from the perspective of neurologic subtypes in a hospital-based follow-up study.This was an observational study of consecutive children with dyskinetic CP treated at The Affiliated Women & Children Hospital of Qingdao University (China) from October 2005 to February 2015. The children were stratified according to their neurologic subtype and assessed with the Gross Motor Function Classification System (GMFCS), Manual Ability Classification System (MACS), and Communication Function Classification System (CFCS). MRI scanning was conducted at 1 year of age for most children.Twenty-six participants (28.0%) had dystonic CP, 26 (28.0%) had choreoathetotic CP, and 41 (44.1%) had mixed CP. Auditory impairment and basal ganglion lesions occurred more frequently in the dystonia group (n = 8, 31%; and n = 16, 67%), while seizures, microcephaly, white matter lesions, and mixed lesions were more frequent in the mixed type (n = 14, 34%; n = 10, 24%; n = 15, 41%; n = 12, 32%). Functional classification levels were distributed unequally among the 3 subgroups (P < .01). No significant difference between GMFCS and MACS was found among the 3 subgroups (P > .05).Different subtypes of dyskinetic CP have specific comorbidities, radiological characteristics, and functional attributes according to their etiological factors and brain lesions. Children with dystonic CP have more limited functional status than children with choreoathetotic CP.

Affective dysfunction in a mouse model of Rett syndrome: Therapeutic effects of environmental stimulation and physical activity.

PubMed

Kondo, Mari A; Gray, Laura J; Pelka, Gregory J; Leang, Sook-Kwan; Christodoulou, John; Tam, Patrick P L; Hannan, Anthony J

2016-02-01

Rett syndrome (RTT) is a neurodevelopmental disorder associated with mutations in the X-linked gene encoding methyl-CpG-binding protein 2 (MeCP2) and consequent dysregulation of brain maturation. Patients suffer from a range of debilitating physical symptoms, however, behavioral and emotional symptoms also severely affect their quality of life. Here, we present previously unreported and clinically relevant affective dysfunction in the female heterozygous Mecp2(tm1Tam) mouse model of RTT (129sv and C57BL6 mixed background). The affective dysfunction and aberrant anxiety-related behavior of the Mecp2(+/-) mice were found to be reversible with environmental enrichment (EE) from 4 weeks of age. The effect of exercise alone (via wheel running) was also explored, providing the first evidence that increased voluntary physical activity in an animal model of RTT is beneficial for some phenotypes. Mecp2(+/-) mutants displayed elevated corticosterone despite decreased Crh expression, demonstrating hypothalamic-pituitary-adrenal axis dysregulation. EE of Mecp2(+/-) mice normalized basal serum corticosterone and hippocampal BDNF protein levels. The enrichment-induced rescue appears independent of the transcriptional regulation of the MeCP2 targets Bdnf exon 4 and Crh. These findings provide new insight into the neurodevelopmental role of MeCP2 and pathogenesis of RTT, in particular the affective dysfunction. The positive outcomes of environmental stimulation and physical exercise have implications for the development of therapies targeting the affective symptoms, as well as behavioral and cognitive dimensions, of this devastating neurodevelopmental disorder. © 2015 Wiley Periodicals, Inc.

In vitro ruminal fermentation characteristics and utilisable CP supply of sainfoin and birdsfoot trefoil silages and their mixtures with other legumes.

PubMed

Grosse Brinkhaus, A; Wyss, U; Arrigo, Y; Girard, M; Bee, G; Zeitz, J O; Kreuzer, M; Dohme-Meier, F

2017-04-01

The extensive protein degradation occurring during ensiling decreases the nutritive value of silages, but this might be counteracted by tannins. Therefore, silages from two legume species containing condensed tannins (CT) - sainfoin (SF) and birdsfoot trefoil (two cultivars: birdsfoot trefoil, cv. Bull (BTB) and birdsfoot trefoil, cv. Polom) - were compared for their in vitro ruminal fermentation characteristics. The effect of combining them with two CT-free legume silages (lucerne (LU) and red clover (RC)) was also determined. The supply of duodenally utilisable CP (uCP) in the forages was emphasised. The legumes were each harvested from three field sites. After 24 h of wilting on the field, the legumes were ensiled in laboratory silos for 86 days. Proximate constituents, silage fermentation characteristics, CT content and CP fractions were determined. Subsequently, silage samples and 1 : 1 mixtures of the CT-containing and CT-free silages were incubated for 24 h in batch cultures using ruminal fluid and buffer (1 : 2, v/v). Each treatment was replicated six times in six runs. The effects on pH, ammonia and volatile fatty acid concentrations, protozoal counts, and total gas and methane production were determined. uCP content was calculated by considering the CP in the silage and the ammonia in the incubation fluid from treatments and blanks. Statistical evaluation compared data from single plants alone and together with that from the mixtures. Among treatments, SF silage contained the least CP and the most CT. The non-protein nitrogen content was lower, favouring neutral detergent soluble and insoluble protein fractions, in the SF and RC silages. Absolute uCP content was lowest in SF and SF mixtures, although the ratio to total CP was the highest. In comparison with LU, the ammonia concentration of the incubation fluid was lower for SF, RC and BTB and for the mixture of SF with LU. The total gas and methane production was similar among the treatments, and the total volatile fatty acid production was decreased with the CT-containing legumes. Protozoal count was increased with the mixtures containing LU and either SF or BTB compared with single LU. In conclusion, compared with the other legumes, SF and RC have similar advantages as they show limited proteolysis during ensiling. In addition, SF supplies more uCP relative to total CP. The CT-containing legumes also differed in their effect on ruminal fermentation and ammonia formation, probably because of their different CT contents. Thus, SF and its mixtures appear promising for improving the protein utilisation of ruminants.

Mechanism of Mitochondrial Transcription Factor A Attenuation of CpG-Induced Antibody Production

PubMed Central

Saifee, Jessica F.; Torres, Raul M.; Janoff, Edward N.

2016-01-01

Mitochondrial transcription factor A (TFAM) had previously been shown to act as a damage associated molecular pattern with the ability to enhance CpG-A phosphorothioate oligodeoxynucleotide (ODN)-mediated stimulation of IFNα production from human plasmacytoid dendritic cells. Examination of the mechanism by which TFAM might influence CpG ODN mediated innate immune responses revealed that TFAM binds directly, tightly and selectively to the structurally related CpG-A, -B, and -C ODN. TFAM also modulated the ability of the CpG-B or -C to stimulate the production of antibodies from human B cells. TFAM showed a dose-dependent modulation of CpG-B, and -C -induced antibody production from human B cells in vitro, with enhancement of high dose and inhibition of low doses of CpG stimulation. This effect was linked to the ability of TFAM to directly inhibit the binding of CpG ODNs to B cells, in a manner consistent with the relative binding affinities of TFAM for the ODNs. These data suggest that TFAM alters the free concentration of the CpG available to stimulate B cells by sequestering this ODN in a TFAM-CpG complex. Thus, TFAM has the potential to decrease the pathogenic consequences of exposure to natural CpG-like hypomethylated DNA in vivo, as well as such as that found in traumatic injury, infection, autoimmune disease and during pregnancy. PMID:27280778

Regulation of mitosis-meiosis transition by the ubiquitin ligase β-TrCP in male germ cells.

PubMed

Nakagawa, Tadashi; Zhang, Teng; Kushi, Ryo; Nakano, Seiji; Endo, Takahiro; Nakagawa, Makiko; Yanagihara, Noriko; Zarkower, David; Nakayama, Keiko

2017-11-15

The mitosis-meiosis transition is essential for spermatogenesis. Specific and timely downregulation of the transcription factor DMRT1, and consequent induction of Stra8 expression, is required for this process in mammals, but the molecular mechanism has remained unclear. Here, we show that β-TrCP, the substrate recognition component of an E3 ubiquitin ligase complex, targets DMRT1 for degradation and thereby controls the mitosis-meiosis transition in mouse male germ cells. Conditional inactivation of β-TrCP2 in male germ cells of β-TrCP1 knockout mice resulted in sterility due to a lack of mature sperm. The β-TrCP-deficient male germ cells did not enter meiosis, but instead underwent apoptosis. The induction of Stra8 expression was also attenuated in association with the accumulation of DMRT1 at the Stra8 promoter in β-TrCP-deficient testes. DMRT1 contains a consensus β-TrCP degron sequence that was found to bind β-TrCP. Overexpression of β-TrCP induced the ubiquitylation and degradation of DMRT1. Heterozygous deletion of Dmrt1 in β-TrCP-deficient spermatogonia increased meiotic cells with a concomitant reduction of apoptosis. Collectively, our data indicate that β-TrCP regulates the transition from mitosis to meiosis in male germ cells by targeting DMRT1 for degradation. © 2017. Published by The Company of Biologists Ltd.

Cartilage preservation by inhibition of Janus kinase 3 in two rodent models of rheumatoid arthritis

PubMed Central

Milici, Anthony J; Kudlacz, Elizabeth M; Audoly, Laurent; Zwillich, Samuel; Changelian, Paul

2008-01-01

Introduction CP-690550 is a small molecule inhibitor of Janus kinase 3 (JAK3), a critical enzyme in the signaling pathway of multiple cytokines (interleukin (IL)-2, -7, -15 and -21) that are important in various T cell functions including development, activation and homeostasis. The purpose of this study was to evaluate CP-690550 in murine collagen-induced (CIA) and rat adjuvant-induced (AA) models of rheumatoid arthritis (RA). Methods CIA and AA were induced using standard protocols and animals received the JAK3 inhibitor via osmotic mini-pump infusion at doses ranging from 1.5–15 mg/kg/day following disease induction. Arthritis was assessed by clinical scores in the CIA models and paw swelling monitored using a plethysmometer in the AA model until study conclusion, at which time animals were killed and evaluated histologically. Results CP-690550 dose-dependently decreased endpoints of disease in both RA models with greater than 90% reduction observed at the highest administered dose. An approximate ED50 of approximately 1.5 mg/kg/day was determined for the compound based upon disease endpoints in both RA models examined and corresponds to CP-690550 serum levels of 5.8 ng/ml in mice (day 28) and 24 ng/ml in rats (day 24). The compound also reduced inflammatory cell influx and joint damage as measured histologically. Animals receiving a CP-690550 dose of 15 mg/k/d showed no histological evidence of disease. Conclusion The efficacy observed with CP-690550 in CIA and AA suggests JAK3 inhibition may represent a novel therapeutic target for the treatment of RA. PMID:18234077

Relationship between communication skills and gross motor function in preschool-aged children with cerebral palsy.

PubMed

Coleman, Andrea; Weir, Kelly A; Ware, Robert S; Boyd, Roslyn N

2013-11-01

To explore the communication skills of children with cerebral palsy (CP) at 24 months' corrected age with reference to typically developing children, and to determine the relationship between communication ability, gross motor function, and other comorbidities associated with CP. Prospective, cross-sectional, population-based cohort study. General community. Children with CP (N=124; mean age, 24mo; functional severity on Gross Motor Function Classification System [GMFCS]: I=47, II=14, III=22, IV=19, V=22). Not applicable. Parents reported communication skills on the Communication and Symbolic Behavior Scales Developmental Profile (CSBS-DP) Infant-Toddler Checklist. Two independent physiotherapists classified motor type, distribution, and GMFCS. Data on comorbidities were obtained from parent interviews and medical records. Children with mild CP (GMFCS I/II) had mean CSBS-DP scores that were 0.5 to 0.6 SD below the mean for typically developing peers, while those with moderate-severe impairment (GMFCS III-V) were 1.4 to 2.6 SD below the mean. GMFCS was significantly associated with performance on the CSBS-DP (F=18.55, P<.001), with gross motor ability accounting for 38% of the variation in communication. Poorer communication was strongly associated with gross motor function and full-term birth. Preschool-aged children with CP, with more severe gross motor impairment, showed delayed communication, while children with mild motor impairment were less vulnerable. Term-born children had significantly poorer communication than those born prematurely. Because a portion of each gross motor functional severity level is at risk, this study reinforces the need for early monitoring of communication development for all children with CP. Copyright © 2013 American Congress of Rehabilitation Medicine. Published by Elsevier Inc. All rights reserved.

[Degradation of 4-chlorophenol in aqueous solution by high-voltage pulsed discharge-ozone technology].

PubMed

Wen, Yuezhong; Jiang, Xuanzhen; Liu, Weiping

2002-03-01

The combination of high voltage pulse discharge and ozonation as an advanced oxidation technology was used to investigate the degradation of 4-chlorophenol (4-CP) in water. The factors that affect the rate of degradation were discussed. The 1.95 x 10(-3) mol/L solutions of 4-CP were almost completely (96%) degraded after the discharge treatment of 30 min. The degradation of 4-CP was investigated as a function of the ozone concentration, radical scavenger and electrode distance. The rate of 4-CP degradation increases with an increase in ozone concentration and a decrease in the electrode distance from 20 mm to 10 mm. The presence of radical scavenger decreased the rate of 4-CP degradation.

Conciliatory Inductive Model Explaining the Origin of Changes in the η(2)-SiH Bond Length Caused by Presence of Strongly Electronegative Atoms X (X = F, Cl) in Cp(OC)2Mn[η(2)-H(SiH3-nXn)] (n = 0-3) Complexes.

PubMed

Jabłoński, Mirosław

2016-06-23

Using three theoretical methods, QTAIM, IQA, and NCI, we analyze an influence of halogen atoms X (X = F, Cl) substituted at various positions in the -SiH3-nXn group on the charge density distribution within the η(2)-SiH bond and on the SiH bond energies in Cp(OC)2Mn[η(2)-H(SiH3-nXn)] complexes and isolated HSiH3-nXn molecules. It is shown that shortening of the η(2)-SiH bond in Cp(OC)2Mn[η(2)-H(SiH3-nXn)] complexes should be considered as a normal inductive result of halogenation. This η(2)-SiH bond's compression may, however, be overcome by a predominant elongation resulting from a contingent presence of a halogen atom at position trans to the η(2)-SiH bond. This trans effect is particularly large for bulky and highly polarizable chlorine. Moreover, peculiar properties of the trans chlorine atom are manifested in several ways. To explain the origin of all the observed changes in both the length and the electron charge distribution of the η(2)-SiH bond in investigated Cp(OC)2Mn[η(2)-H(SiH3-nXn)] complexes a new model, called the Conciliatory Inductive Model, is being proposed.

Effects of dietary protein levels and 2-methylbutyrate on ruminal fermentation, nutrient degradability, bacterial populations and urinary purine derivatives in Simmental steers.

PubMed

Wang, C; Liu, Q; Guo, G; Huo, W J; Pei, C X; Zhang, S L; Yang, W Z

2018-06-01

The objective of this study was to evaluate the effects of dietary crude protein (CP) levels and 2-methylbutyrate (MB) supplementation on ruminal fermentation, bacterial populations, microbial enzyme activity and urinary excretion of purine derivatives (PD) in Simmental steers. Eight ruminally cannulated Simmental steers, averaging 18 months of age and 465 ± 8.6 kg of body weight (BW), were used in a replicated 4 × 4 Latin square design by a 2 × 2 factorial arrangement. Low protein (98.5 g CP/kg dry matter [LP] or high protein (128.7 g CP/kg dry matter [HP]) diets were fed with MB supplementation (0 g [MB-] or 16.8 g steer -1  day -1 [MB+]). Steers were fed a total mixed ration with dietary corn straw to concentrate ratio of 50:50 (dry matter [DM] basis). The CP × MB interaction was observed for ruminal total VFA, molar proportions of acetate and propionate, acetate to propionate ratio, ammonia-N, effective degradability of neutral detergent fibre (NDF) and CP, microbial enzyme activity, bacterial populations and total PD excretion (p < .05). Ruminal pH decreased (p < .05), but ruminal total VFA concentration increased (p < .05) with increasing dietary CP level or MB supplementation. Acetate molar proportion increased (p = .043) with MB supplementation, but was not affected by dietary CP level. Propionate molar proportion decreased (p < .05) with increasing dietary CP level or MB supplementation. Consequently, acetate-to-propionate ratio increased (p = .001) with MB supplementation, but was not affected by dietary CP level. Ruminal ammonia-N content increased (p = .034) with increasing dietary CP level, but decreased (p = .012) with MB supplementation. The effective degradability of NDF and CP increased (p < .05) with increasing dietary CP level or MB supplementation. Microbial enzyme activity, bacterial populations and total PD excretion also increased (p < .05) with increasing dietary CP level or MB supplementation. The results indicated that ruminal fermentation, nutrient degradability, microbial enzyme activity, ruminal bacterial populations and microbial protein synthesis improved with increasing dietary CP level or MB supplementation in steers. © 2017 Blackwell Verlag GmbH.

Validity and reliability of the VOAA-DDD to assess spontaneous hand use with a video observation tool in children with spastic unilateral cerebral palsy.

PubMed

Aarts, Pauline B M; Jongerius, Peter H; Geerdink, Yvonne A; Geurts, Alexander C

2009-11-25

In 2003 new computer software, the VOAA (Video Observations Aarts and Aarts), was designed to score and evaluate two important aspects of spontaneous upper limb use, i.e. overall duration and frequency of specific behaviours. The aim of this study was to investigate the test-retest, interrater and intrarater reliability and the construct validity of a new module, the VOAA-DDD, to determine developmental disregard in children with spastic unilateral cerebral palsy (CP). A test-retest design with three raters for reliability and a two-group design for construct validity were used. Subjects were a total of 20 children with spastic unilateral CP equally divided in two age groups (2.5-5 and 5-8 years), and 56 healthy children of the same age groups. Overall duration and frequency of specific behaviours of the affected arm and hand were assessed during a task demanding ('stringing beads') and a task stimulating ('decorating a muffin') the use of both hands. Reliability was estimated by intraclass correlation coefficients (ICCs). Construct validity was assessed by comparing children with CP to healthy children. All ICCs exceeded 0.87. In contrast with healthy children, children with CP used their affected hand less during the 'muffin' task compared to the 'beads' task. Of the children with CP, 90% in the age group of 2.5-5 years and 50% in the age group of 5-8 years showed values exceeding the extreme values of healthy controls, respectively, indicating developmental disregard. The VOAA-DDD is a reliable and valid instrument to assess spontaneous use of the affected arm and hand in order to determine developmental disregard in children with spastic unilateral CP.

Hypothermia and cerebral protection strategies in aortic arch surgery: a comparative effectiveness analysis from the STS Adult Cardiac Surgery Database.

PubMed

Englum, Brian R; He, Xia; Gulack, Brian C; Ganapathi, Asvin M; Mathew, Joseph P; Brennan, J Matthew; Reece, T Brett; Keeling, W Brent; Leshnower, Bradley G; Chen, Edward P; Jacobs, Jeffrey P; Thourani, Vinod H; Hughes, G Chad

2017-09-01

Hypothermic circulatory arrest is essential to aortic arch surgery, although consensus regarding optimal cerebral protection strategy remains lacking. We evaluated the current use and comparative effectiveness of hypothermia/cerebral perfusion (CP) strategies in aortic arch surgery. Using the Society of Thoracic Surgeons Database, cases of aortic arch surgery with hypothermic circulatory arrest from 2011 to 2014 were categorized by hypothermia strategy-deep/profound (D/P; ≤20°C), low-moderate (L-M; 20.1-24°C), and high-moderate (H-M; 24.1-28°C)-and CP strategy-no CP, antegrade (ACP), retrograde (RCP) or both ACP/RCP. After adjusting for potential confounders, strategies were compared by composite end-point (operative mortality or neurologic complication). Of the 12 521 aortic arch repairs with hypothermic circulatory arrest, the most common combined strategies were straight D/P without CP (25%), D/P + RCP (16%) and D/P + ACP (14%). Overall rates of the primary end-point, operative mortality and stroke were 23%, 12% and 8%, respectively. Among the 7 most common strategies, the 2 not utilizing CP (straight D/P and straight L-M) appeared inferior, associated with significantly higher risk of the composite end-point (odds ratio: 1.6; P < 0.01); there was no significant difference in composite outcome between the remaining strategies (D/P + ACP, D/P + RCP, L-M + ACP, L-M + RCP and H-M + ACP). In a comparative effectiveness study of cerebral protection strategies for aortic arch repair, strategies without adjunctive CP, including the most commonly utilized strategy of straight D/P hypothermia, appeared inferior to those utilizing CP. There was no clearly superior strategy among remaining techniques, and randomized trials are needed to define best practice. © The Author 2017. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.

Efficient interfacial charge transfer through plasmon sensitized Ag@Bi2O3 hierarchical photoanodes for photoelectrocatalytic degradation of chlorinated phenols.

PubMed

Eswar, Neerugatti KrishnaRao; Adhikari, Sangeeta; Ramamurthy, Praveen C; Madras, Giridhar

2018-01-31

The present work demonstrates an extremely proficient and robust study of efficient interfacial charge transfer through plasmonic Ag decorated Bi 2 O 3 hierarchical photoanodes for the photoelectrochemical treatment of chlorinated phenols. Unique 2D flake-like Bi 2 O 3 hierarchical nanostructures were grown onto a fluorine-doped tin oxide (FTO) substrate by a simple chemical bath deposition method using triethanolamine as complexing agent. The formation of Bi 2 O 3 on FTO was governed by the decomposition of a nucleated bismuth-hydroxyl complex (Bi 2 O 1-x (OH) x ) and modification to the electrode was carried out by the deposition of Ag via a chemical reduction method using hydrazine hydrate. Both the fabricated electrodes were well characterized for their photo- and electro-optical properties. Efficient charge separation was observed due to the surface plasmon resonance phenomenon of silver nanoparticles with the favorable intrinsic properties of Bi 2 O 3 under application of a small electric bias of 1 V preventing the recombination of charge carriers and thereby increasing the rate of photoelectrocatalytic degradation of the chlorinated phenols. PEC degradation using the Ag@Bi 2 O 3 photoelectrode followed the trend 4-CP < 2,4-DCP < 2,4,6-TCP < P-CP due to efficient attack at the chlorinated positions by reactive oxygen species with increasing chlorine substitution and also due to the absence of an expected chain reaction of the generated chlorine radicals (Cl˙) during the PEC reaction. The PEC activity of Ag@Bi 2 O 3 was 1.5 times higher than a Bi 2 O 3 nanoflake electrode for 4-CP over 2 h. The fabricated Ag@Bi 2 O 3 proved to be an efficient photoelectrode with synergistic solar-induced photoactivity. A detailed mechanistic study in the presence of scavengers suggests degradation by produced hydroxyl radical species. Thus, physical insights into the degradation of chlorinated phenols were obtained.

Comparative analysis of immune effects in mice model: Clonorchis sinensis cysteine protease generated from recombinant Escherichia coli and Bacillus subtilis spores.

PubMed

Wu, Zhanshuai; Tang, Zeli; Shang, Mei; Zhao, Lu; Zhou, Lina; Kong, Xiangzhan; Lin, Zhipeng; Sun, Hengchang; Chen, Tingjin; Xu, Jin; Li, Xuerong; Huang, Yan; Yu, Xinbing

2017-07-01

Clonorchiasis remains a nonnegligible public health problem in endemic areas. Cysteine protease of Clonorchis sinensis (CsCP) plays indispensable roles in the parasitic physiology and pathology, and has been exploited as a promising drug and vaccine candidate. In recent years, development of spore-based vaccines against multiple pathogens has attracted many investigators' interest. In previous studies, the recombinant Escherichia coli (BL21) and Bacillus subtilis spores expressing CsCP have been successfully constructed, respectively. In this study, the immune effects of CsCP protein purified from recombinant BL21 (rCsCP) and B. subtilis spores presenting CsCP (B.s-CsCP) in Balb/c mice model were conducted with comparative analysis. Levels of specific IgG, IgG1 and IgG2a were significantly increased in sera from both rCsCP and B.s-CsCP intraperitoneally immunized mice. Additionally, recombinant spores expressing abundant fusion CsCP (0.03125 pg/spore) could strongly enhance the immunogenicity of CsCP with significantly higher levels of IgG and isotypes. Compared with rCsCP alone, intraperitoneal administration of mice with spores expressing CsCP achieved a better effect of fighting against C. sinensis infection by slowing down the process of fibrosis. Our results demonstrated that a combination of Th1/Th2 immune responses could be elicited by rCsCP, while spores displaying CsCP prominently induced Th1-biased specific immune responses, and the complex cytokine network maybe mediates protective immune responses against C. sinensis. This work further confirmed that the usage of B. subtilis spores displaying CsCP is an effective way to against C. sinensis.

Phosphorylation coexists with O-GlcNAcylation in a plant virus protein and influences viral infection.

PubMed

Martínez-Turiño, Sandra; Pérez, José De Jesús; Hervás, Marta; Navajas, Rosana; Ciordia, Sergio; Udeshi, Namrata D; Shabanowitz, Jeffrey; Hunt, Donald F; García, Juan Antonio

2018-06-01

Phosphorylation and O-GlcNAcylation are two widespread post-translational modifications (PTMs), often affecting the same eukaryotic target protein. Plum pox virus (PPV) is a member of the genus Potyvirus which infects a wide range of plant species. O-GlcNAcylation of the capsid protein (CP) of PPV has been studied extensively, and some evidence of CP phosphorylation has also been reported. Here, we use proteomics analyses to demonstrate that PPV CP is phosphorylated in vivo at the N-terminus and the beginning of the core region. In contrast with the 'yin-yang' mechanism that applies to some mammalian proteins, PPV CP phosphorylation affects residues different from those that are O-GlcNAcylated (serines Ser-25, Ser-81, Ser-101 and Ser-118). Our findings show that PPV CP can be concurrently phosphorylated and O-GlcNAcylated at nearby residues. However, an analysis using a differential proteomics strategy based on iTRAQ (isobaric tags for relative and absolute quantitation) showed a significant enhancement of phosphorylation at Ser-25 in virions recovered from O-GlcNAcylation-deficient plants, suggesting that crosstalk between O-GlcNAcylation and phosphorylation in PPV CP takes place. Although the preclusion of phosphorylation at the four identified phosphotarget sites only had a limited impact on viral infection, the mimicking of phosphorylation prevents PPV infection in Prunus persica and weakens infection in Nicotiana benthamiana and other herbaceous hosts, prompting the emergence of potentially compensatory second mutations. We postulate that the joint action of phosphorylation and O-GlcNAcylation in the N-proximal segment of CP allows a fine-tuning of protein stability, providing the amount of CP required in each step of viral infection. © 2017 BSPP AND JOHN WILEY & SONS LTD.

Combined study of genetic and epigenetic biomarker risperidone treatment efficacy in Chinese Han schizophrenia patients

PubMed Central

Shi, Y; Li, M; Song, C; Xu, Q; Huo, R; Shen, L; Xing, Q; Cui, D; Li, W; Zhao, J; He, L; Qin, S

2017-01-01

Nowadays, risperidone is an atypical antipsychotic drug that has been increasingly used for treatment and maintenance therapy in schizophrenia. However, partially affected by genetic or environmental factors, there is significant difference in treatment outcomes among patients. In this study, we aimed to interpret the difference between good and poor responders treated with risperidone in both genetic and epigenetic levels in 288 mainland Chinese patients. We recruited a Henan cohort including 98 patients as initial discovery group and then confirmed our results in Shanghai cohort. In genetic studies, we found 10 candidate single-nucleotide polymorphisms (SNPs) and 2 rare variants in Henan cohort by next-generation sequencing of 100 risperidone-response-related genes. After replication in Shanghai cohort by massarray platform, ultimately, rs6706232 and rs4818 were significantly associated with risperidone response in the two cohort meta-analysis (P=0.024 and 0.04, respectively). Besides, we also selected another reported 17 candidate SNPs associated with risperidone drug response to replicate in our mainland Chinese samples, while, we found no significant SNPs after Bonferroni correction. In epigenetic studies, we investigated the methylation status in promoters or gene-coding region of risperidone drug response-related genes including CYP3A4, CYP2D6, ABCB1, HTR2A, DRD2. Totally we found seven significant CpG sites in the meta-analysis with Bonferroni-corrected PCYP3A4_CpG_-36=0.0014, PCYP3A4_CpG_-258=0.0013, PCYP3A4_CpG_-296=0.0014, PCYP3A4_CpG_-367:-372:-374=0.028, PCYP2D6_CpG_193=0.012, PCYP2D6_CpG_242:244:250=0.00076 and PCYP2D6_CpG_284=0.034, respectively. As genetic and epigenetic factors may interactively affect drug response, we finally carried out a multivariant interaction analysis with multifactor dimensionality reduction and discovered a significant four-locus model (CYP3A4_CpG_-82:-86 +rs6280+rs1800497+rs6265, P=0.038) affecting drug response. These findings could partially explain different risperidone response outcome in Chinese population in a systematic level. PMID:28696411

Adjuvant-Loaded Spiky Gold Nanoparticles for Activation of Innate Immune Cells.

PubMed

Nam, Jutaek; Son, Sejin; Moon, James J

2017-10-01

Gold nanoparticles are versatile carriers for delivery of biomacromolecules. Here, we have developed spiky gold nanoparticles (SGNPs) that can efficiently deliver immunostimulatory agents. Our goal was to develop a platform technology for co-delivery of multiple adjuvant molecules for synergistic stimulation and maturation of innate immune cells. SGNPs were synthesized by a seed-mediated, surfactant-free synthesis method and incorporated with polyinosinic-polycytidylic acid (pIC) and DNA oligonucleotide containing unmethylated CpG motif (CpG) by an electrostatic layer-by-layer approach. Adjuvant-loaded SGNP nano-complexes were examined for their biophysical and biochemical properties and studied for immune activation using bone marrow-derived dendritic cells (BMDCs). We have synthesized SGNPs with branched nano-spikes layered with pIC and/or CpG. Adjuvant-loaded SGNP nano-complexes promoted cellular uptake of the adjuvants. Importantly, we achieved spatio-temporal control over co-delivery of pIC and CpG via SGNPs, which produced synergistic enhancement in cytokine release (IL-6, TNF-α) and upregulation of co-stimulatory markers (CD40, CD80, CD86) in BMDCs, compared with pIC, CpG, or their admixtures. SGNPs serve as a versatile delivery platform that allows flexible and on-demand cargo fabrication for strong activation of innate immune cells.

Frustrated Lewis pairs beyond the main group: cationic zirconocene-phosphinoaryloxide complexes and their application in catalytic dehydrogenation of amine boranes.

PubMed

Chapman, Andy M; Haddow, Mairi F; Wass, Duncan F

2011-06-15

The cationic zirconocene-phosphinoaryloxide complexes [Cp(2)ZrOC(6)H(4)P(t-Bu)(2)][B(C(6)F(5))(4)] (3) and [Cp*(2)ZrOC(6)H(4)P(t-Bu)(2)][B(C(6)F(5))(4)] (4) were synthesized by the reaction of Cp(2)ZrMe(2) or Cp*(2)ZrMe(2) with 2-(diphenylphosphino)phenol followed by protonation with [2,6-di-tert-butylpyridinium][B(C(6)F(5))(4)]. Compound 3 exhibits a Zr-P bond, whereas the bulkier Cp* derivative 4 was isolated as a chlorobenzene adduct without this Zr-P interaction. These compounds can be described as transition-metal-containing versions of linked frustrated Lewis pairs (FLPs), and treatment of 4 with H(2) under mild conditions cleaved H(2) in a fashion analogous to that for main-group FLPs. Their reactivity in amine borane dehydrogenation also mimics that of main-group FLPs, and they dehydrogenate a range of amine borane adducts. However, in contrast to main-group FLPs, 3 and 4 achieve this transformation in a catalytic rather than stoichiometric sense, with rates superior to those for previous high-valent catalysts. © 2011 American Chemical Society

Cancer immunotherapeutic effects of novel CpG ODN in murine tumor model.

PubMed

Cho, Hyeon Cheol; Kim, Bo Hwan; Kim, Kyunghoon; Park, Ju Youn; Chang, Jae-Ho; Kim, Soo-Ki

2008-10-01

While CpG oligodeoxynucleotides (ODN) are excellent candidates for cancer immunotherapeutics, the numbers of usable CpG ODNs are limited in current clinical settings. To resolve this, we investigated whether novel CpG ODN (KSK-CpG) would be an effective immunotherapeutic in a murine tumor model by affecting in vivo and in vitro parameters, such as survival span, the number of tumor nodules, natural killer (NK) cell and cytotoxic T lymphocyte (CTL) activity and interleukin (IL)-6 or IL-12 cytokine release in splenocytes. We found that KSK-CpG was effective in the murine cancer model by way of prolonging survival span, reducing the number of tumor nodules, augmenting NK cell and CTL cytotoxicity, as well as evoking IL-6 and IL-12 cytokine release in splenocytes. Collectively, these data demonstrate that KSK-CpG is active against the highly malignant B16BL6 and EL4 tumor mouse model via innate immune augmentation.

Allosteric Coupling of CARMIL and V-1 Binding to Capping Protein Revealed by Hydrogen-Deuterium Exchange.

PubMed

Johnson, Britney; McConnell, Patrick; Kozlov, Alex G; Mekel, Marlene; Lohman, Timothy M; Gross, Michael L; Amarasinghe, Gaya K; Cooper, John A

2018-05-29

Actin assembly is important for cell motility. The ability of actin subunits to join or leave filaments via the barbed end is critical to actin dynamics. Capping protein (CP) binds to barbed ends to prevent subunit gain and loss and is regulated by proteins that include V-1 and CARMIL. V-1 inhibits CP by sterically blocking one binding site for actin. CARMILs bind at a distal site and decrease the affinity of CP for actin, suggested to be caused by conformational changes. We used hydrogen-deuterium exchange with mass spectrometry (HDX-MS) to probe changes in structural dynamics induced by V-1 and CARMIL binding to CP. V-1 and CARMIL induce changes in both proteins' binding sites on the surface of CP, along with a set of internal residues. Both also affect the conformation of CP's ββ subunit "tentacle," a second distal actin-binding site. Concerted regulation of actin assembly by CP occurs through allosteric couplings between CP modulator and actin binding sites. Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.

The Physiological Functions and Structural Determinants of Catalytic Bias in the [FeFe]-Hydrogenases CpI and CpII of Clostridium pasteurianum Strain W5.

PubMed

Therien, Jesse B; Artz, Jacob H; Poudel, Saroj; Hamilton, Trinity L; Liu, Zhenfeng; Noone, Seth M; Adams, Michael W W; King, Paul W; Bryant, Donald A; Boyd, Eric S; Peters, John W

2017-01-01

The first generation of biochemical studies of complex, iron-sulfur-cluster-containing [FeFe]-hydrogenases and Mo-nitrogenase were carried out on enzymes purified from Clostridium pasteurianum (strain W5). Previous studies suggested that two distinct [FeFe]-hydrogenases are expressed differentially under nitrogen-fixing and non-nitrogen-fixing conditions. As a result, the first characterized [FeFe]-hydrogenase (CpI) is presumed to have a primary role in central metabolism, recycling reduced electron carriers that accumulate during fermentation via proton reduction. A role for capturing reducing equivalents released as hydrogen during nitrogen fixation has been proposed for the second hydrogenase, CpII. Biochemical characterization of CpI and CpII indicated CpI has extremely high hydrogen production activity in comparison to CpII, while CpII has elevated hydrogen oxidation activity in comparison to CpI when assayed under the same conditions. This suggests that these enzymes have evolved a catalytic bias to support their respective physiological functions. Using the published genome of C. pasteurianum (strain W5) hydrogenase sequences were identified, including the already known [NiFe]-hydrogenase, CpI, and CpII sequences, and a third hydrogenase, CpIII was identified in the genome as well. Quantitative real-time PCR experiments were performed in order to analyze transcript abundance of the hydrogenases under diazotrophic and non-diazotrophic growth conditions. There is a markedly reduced level of CpI gene expression together with concomitant increases in CpII gene expression under nitrogen-fixing conditions. Structure-based analyses of the CpI and CpII sequences reveal variations in their catalytic sites that may contribute to their alternative physiological roles. This work demonstrates that the physiological roles of CpI and CpII are to evolve and to consume hydrogen, respectively, in concurrence with their catalytic activities in vitro , with CpII capturing excess reducing equivalents under nitrogen fixation conditions. Comparison of the primary sequences of CpI and CpII and their homologs provides an initial basis for identifying key structural determinants that modulate hydrogen production and hydrogen oxidation activities.

The Physiological Functions and Structural Determinants of Catalytic Bias in the [FeFe]-Hydrogenases CpI and CpII of Clostridium pasteurianum Strain W5

DOE PAGES

Therien, Jesse B.; Artz, Jacob H.; Poudel, Saroj; ...

2017-07-12

Here, the first generation of biochemical studies of complex, iron-sulfur-cluster-containing [FeFe]-hydrogenases and Mo-nitrogenase were carried out on enzymes purified from Clostridium pasteurianum (strain W5). Previous studies suggested that two distinct [FeFe]-hydrogenases are expressed differentially under nitrogen-fixing and non-nitrogen-fixing conditions. As a result, the first characterized [FeFe]-hydrogenase (CpI) is presumed to have a primary role in central metabolism, recycling reduced electron carriers that accumulate during fermentation via proton reduction. A role for capturing reducing equivalents released as hydrogen during nitrogen fixation has been proposed for the second hydrogenase, CpII. Biochemical characterization of CpI and CpII indicated CpI has extremely high hydrogenmore » production activity in comparison to CpII, while CpII has elevated hydrogen oxidation activity in comparison to CpI when assayed under the same conditions. This suggests that these enzymes have evolved a catalytic bias to support their respective physiological functions. Using the published genome of C. pasteurianum (strain W5) hydrogenase sequences were identified, including the already known [NiFe]-hydrogenase, CpI, and CpII sequences, and a third hydrogenase, CpIII was identified in the genome as well. Quantitative real-time PCR experiments were performed in order to analyze transcript abundance of the hydrogenases under diazotrophic and non-diazotrophic growth conditions. There is a markedly reduced level of CpI gene expression together with concomitant increases in CpII gene expression under nitrogen-fixing conditions. Structure-based analyses of the CpI and CpII sequences reveal variations in their catalytic sites that may contribute to their alternative physiological roles. This work demonstrates that the physiological roles of CpI and CpII are to evolve and to consume hydrogen, respectively, in concurrence with their catalytic activities in vitro, with CpII capturing excess reducing equivalents under nitrogen fixation conditions. Comparison of the primary sequences of CpI and CpII and their homologs provides an initial basis for identifying key structural determinants that modulate hydrogen production and hydrogen oxidation activities.« less

The Physiological Functions and Structural Determinants of Catalytic Bias in the [FeFe]-Hydrogenases CpI and CpII of Clostridium pasteurianum Strain W5

PubMed Central

Therien, Jesse B.; Artz, Jacob H.; Poudel, Saroj; Hamilton, Trinity L.; Liu, Zhenfeng; Noone, Seth M.; Adams, Michael W. W.; King, Paul W.; Bryant, Donald A.; Boyd, Eric S.; Peters, John W.

2017-01-01

The first generation of biochemical studies of complex, iron-sulfur-cluster-containing [FeFe]-hydrogenases and Mo-nitrogenase were carried out on enzymes purified from Clostridium pasteurianum (strain W5). Previous studies suggested that two distinct [FeFe]-hydrogenases are expressed differentially under nitrogen-fixing and non-nitrogen-fixing conditions. As a result, the first characterized [FeFe]-hydrogenase (CpI) is presumed to have a primary role in central metabolism, recycling reduced electron carriers that accumulate during fermentation via proton reduction. A role for capturing reducing equivalents released as hydrogen during nitrogen fixation has been proposed for the second hydrogenase, CpII. Biochemical characterization of CpI and CpII indicated CpI has extremely high hydrogen production activity in comparison to CpII, while CpII has elevated hydrogen oxidation activity in comparison to CpI when assayed under the same conditions. This suggests that these enzymes have evolved a catalytic bias to support their respective physiological functions. Using the published genome of C. pasteurianum (strain W5) hydrogenase sequences were identified, including the already known [NiFe]-hydrogenase, CpI, and CpII sequences, and a third hydrogenase, CpIII was identified in the genome as well. Quantitative real-time PCR experiments were performed in order to analyze transcript abundance of the hydrogenases under diazotrophic and non-diazotrophic growth conditions. There is a markedly reduced level of CpI gene expression together with concomitant increases in CpII gene expression under nitrogen-fixing conditions. Structure-based analyses of the CpI and CpII sequences reveal variations in their catalytic sites that may contribute to their alternative physiological roles. This work demonstrates that the physiological roles of CpI and CpII are to evolve and to consume hydrogen, respectively, in concurrence with their catalytic activities in vitro, with CpII capturing excess reducing equivalents under nitrogen fixation conditions. Comparison of the primary sequences of CpI and CpII and their homologs provides an initial basis for identifying key structural determinants that modulate hydrogen production and hydrogen oxidation activities. PMID:28747909

Three-dimensional lumbar segment movement characteristics during paediatric cerebral palsy gait.

PubMed

Kiernan, D; Malone, A; O'Brien, T; Simms, C K

2017-03-01

Kinematic analysis of the trunk during cerebral palsy (CP) gait has been well described. In contrast, movement of the lumbar spine is generally ignored. This is most likely due to the complex nature of the spine. As an alternative to using complex sensor protocols, this study modelled the lumbar region as a single segment and investigated characteristic patterns of movement during CP gait. In addition, the impact of functional level of impairment and the relationship with lower lumbar spinal loading were examined. Fifty-two children with CP (26 GMFCS I and 26 GMFCS II) and 26 controls were recruited. A full barefoot 3-dimensional kinematic and kinetic analysis were conducted. Lumbar segment movement demonstrated increased forward flexion for CP children. This movement became more pronounced according to GMFCS level with GMFCS II children demonstrating increases of up to 8°. In addition, a moderate correlation was present between lumbar flexion/extension and L5/S1 sagittal moments (r=0.427 in the global frame and r=0.448 with respect to the pelvis, p<0.01). Children with CP demonstrated increased movement of the lumbar region compared to TD, with movement becoming more excessive as GMFCS level increased. Excessive forward flexion and loading at the lumbar spine were linked. However, the moderate correlation suggests other contributors to increased loading were present. In conclusion, this study is a first step at identifying how lumbar segment movement is altered during CP gait. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of nutrition level of concentrate-based diets on growth performance and carcass characteristics of Hainan black goats.

PubMed

Wang, Dingfa; Zhou, Luli; Zhou, Hanlin; Hou, Guanyu; Li, Mao; Shi, Liguang; Huang, Xianzhou; Guan, Song

2014-06-01

This study assessed the effects of different nutrition levels of diets on growth performance and carcass characteristics of Hainan black goat. Twenty-four goats were divided into six diet treatments, which consisted of two levels of crude protein (CP; 15 and 17 %) and three levels of digestive energy (DE; 11.72, 12.55, and 13.39 MJ/kg). The results revealed that 17 % CP significantly (P < 0.05) increased ADG and improved FCR compared with 15 % CP. Therefore, the CP levels of diet affected growth performance. CP and DE levels in the diet had no significant effects (P > 0.05) on carcass characteristics of the goats. The mRNA expression levels of insulin-like growth factor 1 in muscle tissues increased with increasing CP and DE levels (P < 0.05).

Measurement of CP observables in B{sup {+-}{yields}D}{sub CP}K{sup {+-}}decays and constraints on the CKM angle {gamma}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amo Sanchez, P. del; Lees, J. P.; Poireau, V.

Using the entire sample of 467x10{sup 6} {Upsilon}(4S){yields}BB decays collected with the BABAR detector at the PEP-II asymmetric-energy B factory at the SLAC National Accelerator Laboratory, we perform an analysis of B{sup {+-}}{yields}DK{sup {+-}}decays, using decay modes in which the neutral D meson decays to either CP-eigenstates or non-CP-eigenstates. We measure the partial decay rate charge asymmetries for CP-even and CP-odd D final states to be A{sub CP+}=0.25{+-}0.06{+-}0.02 and A{sub CP-}=-0.09{+-}0.07{+-}0.02, respectively, where the first error is the statistical and the second is the systematic uncertainty. The parameter A{sub CP+} is different from zero with a significance of 3.6 standardmore » deviations, constituting evidence for direct CP violation. We also measure the ratios of the charged-averaged B partial decay rates in CP and non-CP decays, R{sub CP+}=1.18{+-}0.09{+-}0.05 and R{sub CP-}=1.07{+-}0.08{+-}0.04. We infer frequentist confidence intervals for the angle {gamma} of the unitarity triangle, for the strong phase difference {delta}{sub B}, and for the amplitude ratio r{sub B}, which are related to the B{sup -}{yields}DK{sup -} decay amplitude by r{sub B}e{sup i({delta}{sub B}-{gamma})}=A(B{sup -}{yields}D{sup 0}K{sup -})/A(B{sup -}{yields}D{sup 0}K{sup -}). Including statistical and systematic uncertainties, we obtain 0.24

Influence of corrosion on lipopolysaccharide affinity for two different titanium materials.

PubMed

Barão, Valentim Adelino Ricardo; Mathew, Mathew T; Yuan, Judy Chia-Chun; Knoernschild, Kent L; Assunção, Wirley Gonçalves; Wimmer, Markus A; Sukotjo, Cortino

2013-12-01

Titanium is subject to corrosion in the oral cavity, which could contribute to periimplantitis. However, the effect of corrosion on the lipopolysaccharide affinity for titanium remains unknown. This study evaluated the role of corrosion (in artificial saliva at pHs 3, 6.5, and 9) on the lipopolysaccharide (LPS) affinity for commercially pure titanium (cp-Ti) and Ti-6Al-4V alloy. Seventy-two titanium disks were anodically polarized in a controlled environment (n=9). Control specimens were not corroded. Deionized water with different concentrations of LPS (1.5, 15, and 150 μg/mL) were used to treat the disks for 24 hours to investigate LPS adherence (n=3). Then specimens were immersed in LPS-free water to evaluate LPS elution at 24, 48, and 72 hours. Data were analyzed by the 2-way, 3-way, and 3-way repeated measures ANOVA, t tests, and the Tukey honestly significant difference (HSD) tests (α=.05). A greater corrosion rate of cp-Ti and Ti-6Al-4V alloy and a higher LPS adherence to titanium surfaces (P<.05) were noted at acidic pH. The LPS affinity was higher for the Ti-6Al-4V alloy than for cp-Ti (P<.05). More LPS was eluted from titanium surfaces after a 24-hour interval. Lipopolysaccharide affinity for cp-Ti and Ti-6Al-4V alloy is influenced by the corrosion process. Copyright © 2013 Editorial Council for the Journal of Prosthetic Dentistry. Published by Mosby, Inc. All rights reserved.

Angiotensin II type 2 receptor stimulation improves fatty acid ovarian uptake and hyperandrogenemia in an obese rat model of polycystic ovary syndrome.

PubMed

Leblanc, Samuel; Battista, Marie-Claude; Noll, Christophe; Hallberg, Anders; Gallo-Payet, Nicole; Carpentier, André C; Vine, Donna F; Baillargeon, Jean-Patrice

2014-09-01

Polycystic ovary syndrome (PCOS) is mainly defined by hyperandrogenism but is also characterized by insulin resistance (IR). Studies showed that overexposure of nonadipose tissues to nonesterified fatty acids (NEFA) may explain both IR and hyperandrogenism. Recent studies indicate that treatment with an angiotensin II type 2 receptor (AT2R)-selective agonist improves diet-induced IR. We thus hypothesized that PCOS hyperandrogenism is triggered by ovarian NEFA overexposure and is improved after treatment with an AT2R agonist. Experiments were conducted in 12-week-old female JCR:LA-cp/cp rats, which are characterized by visceral obesity, IR, hyperandrogenism, and polycystic ovaries. Control JCR:LA +/? rats have a normal phenotype. Rats were treated for 8 days with saline or the selective AT2R agonist C21/M24 and then assessed for: 1) fasting testosterone, NEFA, and insulin levels; and 2) an iv 14(R,S)-[(18)F]fluoro-6-thia-heptadecanoic acid test to determine NEFA ovarian tissue uptake (Km). Compared with controls, saline-treated PCOS/cp rats displayed higher insulin (100 vs 5.6 μU/mL), testosterone (0.12 vs 0.04 nmol/L), NEFA (0.98 vs 0.48 mmol/L), and Km (20.7 vs 12.9 nmol/g·min) (all P < .0001). In PCOS/cp rats, C21/M24 did not significantly improve insulin or NEFA but normalized testosterone (P = .004) and Km (P = .009), which were strongly correlated together in all PCOS/cp rats (ρ = 0.74, P = .009). In conclusion, in an obese PCOS rat model, ovarian NEFA uptake and testosterone levels are strongly associated and are both significantly reduced after short-term C21/M24 therapy. These findings provide new information on the role of NEFA in PCOS hyperandrogenemia and suggest a potential role for AT2R agonists in the treatment of PCOS.

Non-neural Muscle Weakness Has Limited Influence on Complexity of Motor Control during Gait

PubMed Central

Goudriaan, Marije; Shuman, Benjamin R.; Steele, Katherine M.; Van den Hauwe, Marleen; Goemans, Nathalie; Molenaers, Guy; Desloovere, Kaat

2018-01-01

Cerebral palsy (CP) and Duchenne muscular dystrophy (DMD) are neuromuscular disorders characterized by muscle weakness. Weakness in CP has neural and non-neural components, whereas in DMD, weakness can be considered as a predominantly non-neural problem. Despite the different underlying causes, weakness is a constraint for the central nervous system when controlling gait. CP demonstrates decreased complexity of motor control during gait from muscle synergy analysis, which is reflected by a higher total variance accounted for by one synergy (tVAF1). However, it remains unclear if weakness directly contributes to higher tVAF1 in CP, or whether altered tVAF1 reflects mainly neural impairments. If muscle weakness directly contributes to higher tVAF1, then tVAF1 should also be increased in DMD. To examine the etiology of increased tVAF1, muscle activity data of gluteus medius, rectus femoris, medial hamstrings, medial gastrocnemius, and tibialis anterior were measured at self-selected walking speed, and strength data from knee extensors, knee flexors, dorsiflexors and plantar flexors, were analyzed in 15 children with CP [median (IQR) age: 8.9 (2.2)], 15 boys with DMD [8.7 (3.1)], and 15 typical developing (TD) children [8.6 (2.7)]. We computed tVAF1 from 10 concatenated steps with non-negative matrix factorization, and compared tVAF1 between the three groups with a Mann-Whiney U-test. Spearman's rank correlation coefficients were used to determine if weakness in specific muscle groups contributed to altered tVAF1. No significant differences in tVAF1 were found between DMD [tVAF1: 0.60 (0.07)] and TD children [0.65 (0.07)], while tVAF1 was significantly higher in CP [(0.74 (0.09)] than in the other groups (both p < 0.005). In CP, weakness in the plantar flexors was related to higher tVAF1 (r = −0.72). In DMD, knee extensor weakness related to increased tVAF1 (r = −0.50). These results suggest that the non-neural weakness in DMD had limited influence on complexity of motor control during gait and that the higher tVAF1 in children with CP is mainly related to neural impairments caused by the brain lesion. PMID:29445330

Phylogeographic Structure of a Tethyan Relict Capparis spinosa (Capparaceae) Traces Pleistocene Geologic and Climatic Changes in the Western Himalayas, Tianshan Mountains, and Adjacent Desert Regions.

PubMed

Wang, Qian; Zhang, Ming-Li; Yin, Lin-Ke

2016-01-01

Complex geological movements more or less affected or changed floristic structures, while the alternation of glacials and interglacials is presumed to have further shaped the present discontinuous genetic pattern of temperate plants. Here we consider Capparis spinosa, a xeromorphic Tethyan relict, to discuss its divergence pattern and explore how it responded in a stepwise fashion to Pleistocene geologic and climatic changes. 267 individuals from 31 populations were sampled and 24 haplotypes were identified, based on three cpDNA fragments (trnL-trnF, rps12-rpl20, and ndhF). SAMOVA clustered the 31 populations into 5 major clades. AMOVA suggests that gene flow between them might be restricted by vicariance. Molecular clock dating indicates that intraspecific divergence began in early Pleistocene, consistent with a time of intense uplift of the Himalaya and Tianshan Mountains, and intensified in mid-Pleistocene. Species distribution modeling suggests range reduction in the high mountains during the Last Glacial Maximum (LGM) as a result of cold climates when glacier advanced, while gorges at midelevations in Tianshan appear to have served as refugia. Populations of low-altitude desert regions, on the other hand, probably experienced only marginal impacts from glaciation, according to the high levels of genetic diversity.

Phylogeographic Structure of a Tethyan Relict Capparis spinosa (Capparaceae) Traces Pleistocene Geologic and Climatic Changes in the Western Himalayas, Tianshan Mountains, and Adjacent Desert Regions

PubMed Central

Wang, Qian; Zhang, Ming-Li; Yin, Lin-Ke

2016-01-01

Complex geological movements more or less affected or changed floristic structures, while the alternation of glacials and interglacials is presumed to have further shaped the present discontinuous genetic pattern of temperate plants. Here we consider Capparis spinosa, a xeromorphic Tethyan relict, to discuss its divergence pattern and explore how it responded in a stepwise fashion to Pleistocene geologic and climatic changes. 267 individuals from 31 populations were sampled and 24 haplotypes were identified, based on three cpDNA fragments (trnL-trnF, rps12-rpl20, and ndhF). SAMOVA clustered the 31 populations into 5 major clades. AMOVA suggests that gene flow between them might be restricted by vicariance. Molecular clock dating indicates that intraspecific divergence began in early Pleistocene, consistent with a time of intense uplift of the Himalaya and Tianshan Mountains, and intensified in mid-Pleistocene. Species distribution modeling suggests range reduction in the high mountains during the Last Glacial Maximum (LGM) as a result of cold climates when glacier advanced, while gorges at midelevations in Tianshan appear to have served as refugia. Populations of low-altitude desert regions, on the other hand, probably experienced only marginal impacts from glaciation, according to the high levels of genetic diversity. PMID:27314028

Registration of ‘CP 08-1110’ Sugarcane

USDA-ARS?s Scientific Manuscript database

‘CP 08-1110’ (Reg. No.CV-171; PI 678579) sugarcane (a complex hybrid of Saccharum spp.) was developed through cooperative research conducted by the USDA-ARS, the University of Florida, and the Florida Sugar Cane League, Inc. and released to growers for mineral (sand) soils in Florida in October 2014...

Registration of ‘CP 06-2042’ Sugarcane

USDA-ARS?s Scientific Manuscript database

‘CP 06-2042’ (Reg. No.CV-169; PI 675156) sugarcane (a complex hybrid of Saccharum spp.) was developed through cooperative research conducted by the USDA-ARS, the University of Florida, and the Florida Sugar Cane League, Inc., and released to growers for organic (muck) and mineral (sand) soils in Fl...

Impact of CP-violating interference effects on MSSM Higgs searches

NASA Astrophysics Data System (ADS)

Fuchs, Elina; Weiglein, Georg

2018-02-01

Interference and mixing effects between neutral Higgs bosons in the MSSM with complex parameters are shown to have a significant impact on the interpretation of LHC searches for additional Higgs bosons. Complex MSSM parameters introduce mixing between the CP-even and CP-odd Higgs states h, H, A into the mass eigenstates h_1, h_2, h_3 and generate CP-violating interference terms. Both effects are enhanced in the case of almost degenerate states. Employing as an example an extension of a frequently used benchmark scenario by a non-zero phase φ _{A_t}, the interference contributions are obtained for the production of neutral Higgs bosons in gluon-fusion and in association with b-quarks followed by the decay into a pair of τ -leptons. While the resonant mixing increases the individual cross sections for the two heavy Higgs bosons h_2 and h_3, strongly destructive interference effects between the contributions involving h_2 and h_3 leave a considerable parameter region unexcluded that would appear to be ruled out if the interference effects were neglected.

Ameliorative efficacy of quercetin against cisplatin‑induced mitochondrial dysfunction: Study on isolated rat liver mitochondria.

PubMed

Waseem, Mohammad; Tabassum, Heena; Bhardwaj, Monica; Parvez, Suhel

2017-09-01

The present study aimed to investigate the hepatoprotective effects of the bioflavonoid quercetin (QR) on cisplatin (CP)‑induced mitochondrial oxidative stress in the livers of rats, to elucidate the role of mitochondria in CP‑induced hepatotoxicity, and its underlying mechanism. Isolated liver mitochondria were incubated with 100 µg/ml CP and/or 50 µM QR in vitro. CP treatment triggered a significant increase in membrane lipid peroxidation (LPO) levels, protein carbonyl (PC) contents, and a decrease in reduced glutathione (GSH) and non‑protein thiol (NP‑SH) levels. In addition, CP caused a marked decline in the activities of enzymatic antioxidants and mitochondrial complexes (I, II, III and V) in liver mitochondria. QR pre‑treatment significantly modulated the activities of enzymatic antioxidants and mitochondrial complex enzymes. Furthermore, QR reversed the alterations in LPO and PC levels, and GSH and NP‑SH contents in liver mitochondria. The results of the present study suggested that QR supplementation may suppress CP‑induced mitochondrial toxicity during chemotherapy, and provides a potential prophylactic and defensive candidate for anticancer agent‑induced oxidative stress.

Reliability of the Quality of Upper Extremity Skills Test for Children with Cerebral Palsy Aged 2 to 12 Years

ERIC Educational Resources Information Center

Thorley, Megan; Lannin, Natasha; Cusick, Anne; Novak, Iona; Boyd, Roslyn

2012-01-01

Aim: To investigate reliability of the Quality of Upper Extremity Skills Test (QUEST) scores for children with cerebral palsy (CP) aged 2-12 years. Method: Thirty-one QUESTs from 24 children with CP were rated once by two raters and twice by one rater. Internal consistency of total scores, inter- and intra-rater reliability findings for total,…

Parameters and Measures in Assessment of Motor Learning in Neurorehabilitation; A Systematic Review of the Literature

PubMed Central

Shishov, Nataliya; Melzer, Itshak; Bar-Haim, Simona

2017-01-01

Upper limb function, essential for daily life, is often impaired in individuals after stroke and cerebral palsy (CP). For an improved upper limb function, learning should occur, and therefore training with motor learning principles is included in many rehabilitation interventions. Despite accurate measurement being an important aspect for examination and optimization of treatment outcomes, there are no standard algorithms for outcome measures selection. Moreover, the ability of the chosen measures to identify learning is not well established. We aimed to review and categorize the parameters and measures utilized for identification of motor learning in stroke and CP populations. PubMed, Pedro, and Web of Science databases were systematically searched between January 2000 and March 2016 for studies assessing a form of motor learning following upper extremity training using motor control measures. Thirty-two studies in persons after stroke and 10 studies in CP of any methodological quality were included. Identified outcome measures were sorted into two categories, “parameters,” defined as identifying a form of learning, and “measures,” as tools measuring the parameter. Review's results were organized as a narrative synthesis focusing on the outcome measures. The included studies were heterogeneous in their study designs, parameters and measures. Parameters included adaptation (n = 6), anticipatory control (n = 2), after-effects (n = 3), de-adaptation (n = 4), performance (n = 24), acquisition (n = 8), retention (n = 8), and transfer (n = 14). Despite motor learning theory's emphasis on long-lasting changes and generalization, the majority of studies did not assess the retention and transfer parameters. Underlying measures included kinematic analyses in terms of speed, geometry or both (n = 39), dynamic metrics, measures of accuracy, consistency, and coordination. There is no exclusivity of measures to a specific parameter. Many factors affect task performance and the ability to measure it—necessitating the use of several metrics to examine different features of movement and learning. Motor learning measures' applicability to clinical setting can benefit from a treatment-focused approach, currently lacking. The complexity of motor learning results in various metrics, utilized to assess its occurrence, making it difficult to synthesize findings across studies. Further research is desirable for development of an outcome measures selection algorithm, while considering the quality of such measurements. PMID:28286474

Detection of core-periphery structure in networks based on 3-tuple motifs

NASA Astrophysics Data System (ADS)

Ma, Chuang; Xiang, Bing-Bing; Chen, Han-Shuang; Small, Michael; Zhang, Hai-Feng

2018-05-01

Detecting mesoscale structure, such as community structure, is of vital importance for analyzing complex networks. Recently, a new mesoscale structure, core-periphery (CP) structure, has been identified in many real-world systems. In this paper, we propose an effective algorithm for detecting CP structure based on a 3-tuple motif. In this algorithm, we first define a 3-tuple motif in terms of the patterns of edges as well as the property of nodes, and then a motif adjacency matrix is constructed based on the 3-tuple motif. Finally, the problem is converted to find a cluster that minimizes the smallest motif conductance. Our algorithm works well in different CP structures: including single or multiple CP structure, and local or global CP structures. Results on the synthetic and the empirical networks validate the high performance of our method.

Bioinspired Design and Computational Prediction of Iron Complexes with Pendant Amines for the Production of Methanol from CO2 and H2.

PubMed

Chen, Xiangyang; Yang, Xinzheng

2016-03-17

Inspired by the active site structure of [FeFe]-hydrogenase, we built a series of iron dicarbonyl diphosphine complexes with pendant amines and predicted their potentials to catalyze the hydrogenation of CO2 to methanol using density functional theory. Among the proposed iron complexes, [(P(tBu)2N(tBu)2H)FeH(CO)2(COOH)](+) (5COOH) is the most active one with a total free energy barrier of 23.7 kcal/mol. Such a low barrier indicates that 5COOH is a very promising low-cost catalyst for high-efficiency conversion of CO2 and H2 to methanol under mild conditions. For comparison, we also examined Bullock's Cp iron diphosphine complex with pendant amines, [(P(tBu)2N(tBu)2H)FeHCp(C5F4N)](+) (5Cp-C5F4N), as a catalyst for hydrogenation of CO2 to methanol and obtained a total free energy barrier of 27.6 kcal/mol, which indicates that 5Cp-C5F4N could also catalyze the conversion of CO2 and H2 to methanol but has a much lower efficiency than our newly designed iron complexes.

Intramolecular Hydrogen Transfer Reactions Catalyzed by Pentamethylcyclopentadienyl Rhodium and Cobalt Olefin Complexes: Mechanistic Studies.

PubMed

Bolig, Andrew D; Lyons, Thomas W; DiSalvo, Darren T; Brookhart, Maurice

2016-01-08

The mechanism of intramolecular transfer dehydrogenation catalyzed by [Cp * M(VTMS) 2 ] ( 1 , M=Rh, 2 , M=Co, Cp* = C 5 Me 5 , VTMS = vinyltrimethylsilane) complexes has been studied using vinyl silane protected alcohols as substrates. Deuterium-labeled substrates have been synthesized and the regioselectivity of H/D transfers investigated using 1 H and 2 H NMR spectroscopy. The labeling studies establish a regioselective pathway consisting of alkene directed α C-H activation, 2,1 alkene insertion, and finally β-hydride elimination to give silyl enol ether products.

An "intermediate spin" nickel hydride complex stemming from delocalized Ni2(μ-H)2 bonding.

PubMed

Yao, Shu A; Corcos, Amanda R; Infante, Ivan; Hillard, Elizabeth A; Clérac, Rodolphe; Berry, John F

2014-10-01

The nickel hydride complex [Cp'Ni(μ-H)]2 (1, Cp' = 1,2,3,4-tetraisopropylcyclopentadienyl) is found to have a strikingly short Ni-Ni distance of 2.28638(3) Å. Variable temperature and field magnetic measurements indicate an unexpected triplet ground state for 1 with a large zero-field splitting of +90 K (63 cm(-1)). Electronic structure calculations (DFT and CASSCF/CASPT2) explain this ground state as arising from half occupation of two nearly degenerate Ni-Ni π* orbitals.

Synthesis, structure and DFT study of cymantrenyl Fischer carbene complexes of group VI and VII transition metals

NASA Astrophysics Data System (ADS)

Fraser, Roan; van Rooyen, Petrus H.; Landman, Marilé

2016-02-01

Bi- and trimetallic carbene complexes of group VI and VII transition metals (Cr, Mo, W, Mn and Re), with CpMn(CO)3 as the initial synthon, have been synthesised according to the classical Fischer methodology. Crystal structures of the novel carbene complexes with general formula [Mx(CO)y-1{C(OEt)(MnCp(CO)3)}], where x = 1 then y = 3 or 6; x = 2 then y = 10, of the complexes are reported. A density functional theory (DFT) study was undertaken to determine natural bonding orbitals (NBOs) and conformational as well as isomeric aspects of the polymetallic complexes. Application of the second-order perturbation theory (SOPT) of the natural bond orbital (NBO) method revealed stabilizing interactions between the methylene C-H bonds and the carbonyl ligands of the carbene metal moiety. These stabilization interactions show a linear decrease for the group VI metal carbene complexes down the group.

Coat protein expression strategy of oat blue dwarf virus.

PubMed

Edwards, Michael C; Weiland, John J

2014-02-01

Oat blue dwarf virus (OBDV) is a member of the genus Marafivirus whose genome encodes a 227 kDa polyprotein (p227) ostensibly processed post-translationally into its functional components. Encoded near the 3' terminus and coterminal with the p227 ORF are ORFs specifying major and minor capsid proteins (CP). Since the CP expression strategy of marafiviruses has not been thoroughly investigated, we produced a series of point mutants in the OBDV CP encoding gene and examined expression in protoplasts. Results support a model in which the 21 kDa major CP is the product of direct translation of a sgRNA, while the 24 kDa minor CP is a cleavage product derived from both the polyprotein and a larger ~26 kDa precursor translated directly from the sgRNA. Cleavage occurs at an LXG[G/A] motif conserved in many viruses that use papain-like proteases for polyprotein processing and protection against degradation via the ubiquitin-proteasome system. Published by Elsevier Inc.

Dendritic Arborization and Spine Dynamics Are Abnormal in the Mouse Model of MECP2 Duplication Syndrome

PubMed Central

Jiang, Minghui; Ash, Ryan T.; Baker, Steven A.; Suter, Bernhard; Ferguson, Andrew; Park, Jiyoung; Rudy, Jessica; Torsky, Sergey P.; Chao, Hsiao-Tuan; Zoghbi, Huda Y.

2013-01-01

MECP2 duplication syndrome is a childhood neurological disorder characterized by intellectual disability, autism, motor abnormalities, and epilepsy. The disorder is caused by duplications spanning the gene encoding methyl-CpG-binding protein-2 (MeCP2), a protein involved in the modulation of chromatin and gene expression. MeCP2 is thought to play a role in maintaining the structural integrity of neuronal circuits. Loss of MeCP2 function causes Rett syndrome and results in abnormal dendritic spine morphology and decreased pyramidal dendritic arbor complexity and spine density. The consequences of MeCP2 overexpression on dendritic pathophysiology remain unclear. We used in vivo two-photon microscopy to characterize layer 5 pyramidal neuron spine turnover and dendritic arborization as a function of age in transgenic mice expressing the human MECP2 gene at twice the normal levels of MeCP2 (Tg1; Collins et al., 2004). We found that spine density in terminal dendritic branches is initially higher in young Tg1 mice but falls below control levels after postnatal week 12, approximately correlating with the onset of behavioral symptoms. Spontaneous spine turnover rates remain high in older Tg1 animals compared with controls, reflecting the persistence of an immature state. Both spine gain and loss rates are higher, with a net bias in favor of spine elimination. Apical dendritic arbors in both simple- and complex-tufted layer 5 Tg1 pyramidal neurons have more branches of higher order, indicating that MeCP2 overexpression induces dendritic overgrowth. P70S6K was hyperphosphorylated in Tg1 somatosensory cortex, suggesting that elevated mTOR signaling may underlie the observed increase in spine turnover and dendritic growth. PMID:24336718