bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hemilabile BINAP(O) as a Chiral Ligand in Desymmetrizing Mizoroki–Heck Cyclizations
Authors: Wöste Thorsten H. , Oestreich Martin 
Published: August 2012

AbstractBINAP(O), rarely used as a chiral ligand, was found to induce significantly higher levels of enantioselection in representative desymmetrizing Mizoroki–Heck cyclizations where conventional BINAP produces essentially racemic material. BINAP(O) is a ligand with a stronger and weaker donor atom, and that hemilabile nature lends itself the ability to act as either a bi‐ or monodentate ligand. On that basis, we introduce mechanistic models where the weak donor, in one case, mediates the equilibration of diastereomeric alkene–palladium(II) complexes and, in another case, dissociates from the palladium(II) atom, thereby rendering BINAP(O) as a monodentate ligand. These new findings, along with the recently reported effects in intermolecular Mizoroki–Heck reactions, suggest that BINAP(O) ought to be included into ligand screenings.
Polymeric Adsorption of Methylene Blue in TiO2 Colloids—Highly Sensitive Thermochromism and Selective Photocatalysis
Authors: Liu Baoshun , Wen Liping , Nakata Kazuya , Zhao Xiujian , Liu Shanhu , Ochiai Tsuyoshi , Murakami Taketoshi , Fujishima Akira 
Published: August 2012

AbstractThe polymeric adsorption of methylene blue (MB) on a TiO2 surface is reported. The MB molecule on the TiO2 surface mainly exists as the H‐trimeric adsorption state, which results in the MB@TiO2 polymeric sol. The trimeric adsorption leads to a remarkable “blueshift” of visible‐light adsorption of MB. Electrostatic attraction is important for trimeric adsorption of MB on TiO2 surfaces. The trimer–monomer equilibrium is highly sensitive on temperature changes, showing an interesting reversible thermochromism. The MB@TiO2 polymeric sol can be photodegraded under UV illumination without destroying the equilibrium of trimer–monomer. Compared with anionic methyl orange, the TiO2 colloid hydrosol shows highly selective photocatalysis of MB and other cationic dyes, including crystal violet, methylene green, and victoria blue B. The MB@TiO2 polymeric sol is stable under visible‐light illumination because interfacial transfer of electrons does not exist between MB and TiO2.
Molecular Propellers that Consist of Dehydrobenzo[14]annulene Blades
Authors: Nobusue Shunpei , Mukai Yuichi , Fukumoto Yo , Umeda Rui , Tahara Kazukuni , Sonoda Motohiro , Tobe Yoshito 
Published: August 2012

AbstractA new class of propel‐ ler‐shaped compound (4), which consisted of dehydrobenzo[14]annulene ([14]DBA) blades, as well as its naphtho homologues (5 and 6), have been prepared. Although NMR studies of compound 4 did not provide useful information regarding its conformation in solution, DFT calculations with different functionals and the 6‐31G* basis set all indicated that the D3‐symmetric structure was energetically more favorable than the C2 conformer. From X‐ray crystallographic analysis, it appeared that compound 4 adopted a propeller‐shaped‐, approximately D3‐symmetric structure in the solid state, in which the [14]DBA blades were twisted substantially owing to steric repulsion between the neighboring benzene rings. On the contrary, in the case of compound 6, although the DFT calculations with the B3LYP functional predicted that the D3‐symmetric conformation was more stable, calculations with the M05 and M05‐2X functionals indicated that the C2 conformer was more favorable because of π–π interactions between the naphthalene units of a pair of neighboring blades. Indeed, X‐ray analysis of compound 6 showed that it adopted an approximately C2‐symmetric conformation. Moreover, on the basis of variable‐temperature 1H NMR measurements, we found that compound 6 adopted a C2 conformation and the barrier for interconversion between the C2–C2 conformers was estimated to be 16.2 kcal mol−1; however, no indication of the presence of the D3 isomer was obtained. The relatively small energy barriers to interconversion, despite the large overlapping of neighboring blades, was ascribed to the flexibility of the acetylene linkages, which could be deformed substantially in the transition state of the ring‐flip.
Water Oxidation with Molecularly Defined Iridium Complexes: Insights into Homogeneous versus Heterogeneous Catalysis
Authors: Junge Henrik , Marquet Nicolas , Kammer Anja , Denurra Stefania , Bauer Matthias , Wohlrab Sebastian , Gärtner Felix , Pohl Marga‐Martina , Spannenberg Anke , Gladiali Serafino , Beller Matthias 
Published: August 2012

AbstractMolecularly defined Ir complexes and different samples of supported IrO2 nanoparticles have been tested and compared in the catalytic water oxidation with cerium ammonium nitrate (CAN) as the oxidant. By comparing the activity of nano‐scaled supported IrO2 particles to the one of organometallic complexes it is shown that the overall activity of the homogeneous Ir precursors is defined by both the formation of the homogeneous active species and its conversion to IrIV‐oxo nanoparticles. In the first phase of the reaction the activity is dominated by the homogeneous active species. With increasing reaction time, the influence of nano‐sized Ir‐oxo particles becomes more evident. Notably, the different conversion rates of the homogeneous precursor into the active species as well as the conversion into Ir‐oxo nanoparticles and the different particle sizes have a significant influence on the overall activity. In addition to the homogeneous systems, IrO2@MCM‐41 has also been synthesized, which contains stabilized nanoparticles of between 1 and 3 nm in size. This latter system shows a similar activity to IrCl3⋅xH2O and complexes 4 and 5. Mechanistic insights were obtained by in situ X‐ray absorption spectroscopy and scanning transmission electron microscopy.
Psychological Woundedness and its Evaluation in Applications for Clinical Psychology Training
Authors: Ivey Gavin , Partington Theresa 
Published: August 2012

This paper reports on a qualitative study investigating clinical psychology programme selectors' perceptions of psychological ‘woundedness’ in the autobiographical narratives of applicants for clinical psychology training. Woundedness was here defined in terms of the ongoing or residual psychological impact of adverse experiences and psychic conflicts. Ten selectors were presented with a sample of applicants' written autobiographical narratives, differentiated by the conspicuous presence or absence of psychological woundedness. The selectors, who were not informed of the specific aims of the study, ranked applicant protocols and were interviewed individually about their impressions of the protocols and the criteria that they used to rank them. Most selectors were positively biased toward ‘wounded’ narratives and suspicious of those in which woundedness was manifestly absent. Although generally disposed to favour wounded applicants, how woundedness was presented, rather than the mere presence of it, was a discriminating feature in selectors' appraisal of wounded narratives. Selectors were concerned that unresolved woundedness may compromise applicants' professional boundaries, impair self‐reflective capacity and lead to damaging countertransference enactments. The relative extent to which applicant woundedness appeared to be resolved was significant in selectors' assessment of applicants' clinical training potential. A distinction is thus proposed between obstructive and facilitative woundedness in clinical psychology applicants. Copyright © 2012 John Wiley & Sons, Ltd.Key Practitioner Message

A sample of clinical psychology programme selectors identified psychological woundedness as a significant feature in applicant autobiographies.
Selectors favoured applicant autobiographies showing evidence of woundedness.
The distinction between obstructive and facilitative woundedness is important in how the selector sample evaluated woundedness.
Less bluster ahead? Ecohydrological implications of global trends of terrestrial near‐surface wind speeds
Authors: McVicar Tim R. , Roderick Michael L. , Donohue Randall J. , Van Niel Thomas G. 
Published: August 2012

ABSTRACTWhy, in a globally warming climate, have observed rates of atmospheric evaporative demand (AED) declined at many sites over recent decades? The answer is that the evaporative process is primarily driven by radiative and aerodynamic components (the latter mainly influenced by wind speed and atmospheric humidity). So, although increases in air temperatures in isolation would result in increases of both pan evaporation (Epan) observations, and fully physically based model estimates of potential evapotranspiration (ETp), results show that changes in the other meteorological variables governing AED are currently exerting a greater opposing influence. Widespread declines in wind speed (denoted ‘stilling’) of ~−0.014 m s−1 a−1 have recently been reported. In studies assessing the relative contribution of the four primary meteorological variables on AED dynamics, wind speed trends are often indentified as being important. Stilling reduces AED, but its impact on actual evapotranspiration and streamflow is situation dependant. For wet catchments under steady state conditions, stilling‐induced declines in actual evapotranspiration will result in an approximate complementary increase in streamflow. In contrast, for dry catchments, actual evapotranspiration dynamics more closely follow precipitation dynamics so stilling has negligible impact on streamflow. In ‘equitant’ catchments (i.e. those that straddle the energy–water limitation divide), the likely impact of stilling on the catchment water balance depends on sub‐annual processes and requires that new approaches (either top–down or bottom–up) be developed to allow better predictions to be made. Copyright © 2012 Commonwealth of Australia
Correlations of CSF tau and amyloid levels with Alzheimer pathology in neuropathologically verified dementia with Lewy bodies
Authors: Brunnström Hans , Hansson Oskar , Zetterberg Henrik , Londos Elisabet , Englund Elisabet 
Published: August 2012

ObjectiveThe presence of concomitant Alzheimer pathology has been linked to earlier death in cases with dementia with Lewy bodies (DLB). Recently, elevated cerebrospinal fluid (CSF) tau protein levels have been reported to be associated with shorter survival in clinically diagnosed DLB. Correlations between CSF biomarkers and neuropathological findings in DLB are missing. The aim of this study was to investigate correlations between CSF biomarker levels and histopathological findings, with a focus on concomitant Alzheimer pathology, in neuropathologically verified DLB cases.MethodsThe extent of neurofibrillary pathology (Braak stage), neuritic plaques (CERAD stage), Alzheimer pathology (PPAD9 stage) and cerebral amyloid angiopathy was assessed in 16 cases with DLB in whom total tau (T‐tau), hyperphosphorylated tau and amyloid beta 1–42 (Aβ42) protein levels in CSF had been analyzed in vivo. Demographic and clinical data were collected.ResultsBoth Braak and PPAD9 stages were inversely correlated with Aβ42 levels, whereas CERAD stage showed no significant correlations. Cerebral amyloid angiopathy correlated positively with T‐tau and T‐tau/Aβ42 ratio, and inversely with Aβ42 levels, but the group showed a very heterogeneous extent of cerebral amyloid angiopathy.ConclusionsThe burden of concomitant Alzheimer pathology correlates with CSF Aβ42 but not with T‐tau levels in cases with neuropathologically defined DLB. Copyright © 2012 John Wiley & Sons, Ltd.
Activated tumor-infiltrating CD4+ regulatory T cells restrain antitumor immunity in patients with primary or metastatic liver cancer
Authors: Pedroza-Gonzalez Alexander , Verhoef Cornelis , Ijzermans Jan N. M. , Peppelenbosch Maikel P. , Kwekkeboom Jaap , Verheij Joanne , Janssen Harry L. A. , Sprengers Dave 
Published: August 2012

Abstract
The mechanisms that enable liver cancer to escape elimination by the immune system remain unclear, but their elucidation may provide novel therapeutic interventions. We investigated the influence of tumor-infiltrating regulatory T cells on tumor-specific T cell responses in patients with liver cancer, using ex vivo isolated cells from individuals with hepatocellular carcinoma (HCC) or liver metastases from colorectal cancer (LM-CRC). Here we report that in both HCC and LM-CRC, CD4+CD25+Foxp3+ regulatory T cells (Tregs) accumulate in the tumor milieu and are potent suppressors of autologous tumor-specific T cell responses. Especially in LM-CRC, where Treg accumulation is more prominent, there is good evidence for local proliferation of Tregs at the cancer site. We show that tumor Tregs up-regulate the expression of glucocorticoid-induced tumor necrosis factor receptor (GITR) compared with Tregs in tumor-free liver tissue and blood. Importantly, treatment with soluble GITR ligand (GITRL) induces a decrease in the suppression mediated by the activated tumor-infiltrating Tregs and restores the proliferative capacity and cytokine production of CD4+CD25− T cells. Conclusion: Our results show that tumor-associated Tregs are critical for immune evasion in liver cancer, and we propose that GITRL constitutes a rational treatment for this disease. (Hepatology 2013)
Monocyte subsets in human liver disease show distinct phenotypic and functional characteristics
Authors: Liaskou Evaggelia , Zimmermann Henning W. , Li Ka-Kit , Oo Ye H. , Suresh Shankar , Stamataki Zania , Qureshi Omar , Lalor Patricia F. , Shaw Jean , Syn Wing-kin , Curbishley Stuart M. , Adams David H. 
Published: August 2012

Abstract
Liver fibrosis is a wound healing response to chronic liver injury and inflammation in which macrophages and infiltrating monocytes participate in both the development and resolution phase. In humans, three monocyte subsets have been identified: the classical CD14++CD16−, intermediate CD14++CD16+, and nonclassical CD14+CD16++ monocytes. We studied the phenotype and function of these monocyte subsets in peripheral blood and liver tissue from patients with chronic inflammatory and fibrotic liver diseases. The frequency of intrahepatic monocytes increased in disease compared with control liver tissue, and in both nondiseased and diseased livers there was a higher frequency of CD14++CD16+ cells with blood. Our data suggest two nonexclusive mechanisms of CD14++CD16+ accumulation in the inflamed liver: (1) recruitment from blood, because more than twice as many CD14++CD16+ monocytes underwent transendothelial migration through hepatic endothelial cells compared with CD14++CD16− cells; and (2) local differentiation from CD14++CD16− classical monocytes in response to transforming growth factor β and interleukin (IL)-10. Intrahepatic CD14++CD16+ cells expressed both macrophage and dendritic cell markers but showed high levels of phagocytic activity, antigen presentation, and T cell proliferation and secreted proinflammatory (tumor necrosis factor α, IL-6, IL-8, IL-1β) and profibrogenic cytokines (IL-13), chemokines (CCL1, CCL2, CCL3, CCL5), and growth factors (granulocyte colony-stimulating factor and granulocyte-macrophage colony-stimulating factor), consistent with a role in the wound healing response. Conclusion: Intermediate CD14++CD16+ monocytes preferentially accumulate in chronically inflamed human liver as a consequence of enhanced recruitment from blood and local differentiation from classical CD14++CD16− monocytes. Their phagocytic potential and ability to secrete inflammatory and profibrogenic cytokines suggests they play an important role in hepatic fibrogenesis. (Hepatology 2013)
Hepatitis C virus NS4B protein targets STING and abrogates RIG-I–mediated type I interferon-dependent innate immunity
Authors: Nitta Sayuri , Sakamoto Naoya , Nakagawa Mina , Kakinuma Sei , Mishima Kako , Kusano-Kitazume Akiko , Kiyohashi Kei , Murakawa Miyako , Nishimura-Sakurai Yuki , Azuma Seishin , Tasaka-Fujita Megumi , Asahina Yasuhiro , Yoneyama Mitsutoshi , Fujita Takashi , Watanabe Mamoru 
Published: August 2012

Abstract
Hepatitis C virus (HCV) infection blocks cellular interferon (IFN)-mediated antiviral signaling through cleavage of Cardif by HCV-NS3/4A serine protease. Like NS3/4A, NS4B protein strongly blocks IFN-β production signaling mediated by retinoic acid–inducible gene I (RIG-I); however, the underlying molecular mechanisms are not well understood. Recently, the stimulator of interferon genes (STING) was identified as an activator of RIG-I signaling. STING possesses a structural homology domain with flaviviral NS4B, which suggests a direct protein-protein interaction. In the present study, we investigated the molecular mechanisms by which NS4B targets RIG-I–induced and STING-mediated IFN-β production signaling. IFN-β promoter reporter assay showed that IFN-β promoter activation induced by RIG-I or Cardif was significantly suppressed by both NS4B and NS3/4A, whereas STING-induced IFN-β activation was suppressed by NS4B but not by NS3/4A, suggesting that NS4B had a distinct point of interaction. Immunostaining showed that STING colocalized with NS4B in the endoplasmic reticulum. Immunoprecipitation and bimolecular fluorescence complementation (BiFC) assays demonstrated that NS4B specifically bound STING. Intriguingly, NS4B expression blocked the protein interaction between STING and Cardif, which is required for robust IFN-β activation. NS4B truncation assays showed that its N terminus, containing the STING homology domain, was necessary for the suppression of IFN-β promoter activation. NS4B suppressed residual IFN-β activation by an NS3/4A-cleaved Cardif (Cardif1-508), suggesting that NS3/4A and NS4B may cooperate in the blockade of IFN-β production. Conclusion: NS4B suppresses RIG-I–mediated IFN-β production signaling through a direct protein interaction with STING. Disruption of that interaction may restore cellular antiviral responses and may constitute a novel therapeutic strategy for the eradication of HCV. (Hepatology 2013)
Interferon regulatory factor 3 deficiency leads to interleukin-17-mediated liver ischemia-reperfusion injury
Authors: Loi Patrizia , Yuan Qing , Torres David , Delbauve Sandrine , Laute Marie-Aline , Lalmand Marie-Claude , Pétein Michel , Goriely Stanislas , Goldman Michel , Flamand Véronique 
Published: August 2012

Abstract
Interferon regulatory factor 3 (IRF3) is an important transcription factor in Toll-like receptor 4 (TLR4) signaling, a pathway that is known to play a critical role in liver ischemia-reperfusion injury. In order to decipher the involvement of IRF3 in this setting, we first compared the intensity of hepatic lesions in IRF3-deficient versus wildtype mice. We found increased levels of blood transaminases, enhanced liver necrosis, and more pronounced neutrophil infiltrates in IRF3-deficient mice. Neutrophil depletion by administration of anti-Ly6G monoclonal antibody indicated that neutrophils play a dominant role in the development of severe liver necrosis in IRF3-deficient mice. Quantification of cytokine genes expression revealed increased liver expression of interleukin (IL)-12/IL-23p40, IL-23p19 messenger RNA (mRNA), and IL-17A mRNA in IRF3-deficient versus wildtype (WT) mice, whereas IL-27p28 mRNA expression was diminished in the absence of IRF3. The increased IL-17 production in IRF3-deficient mice was functionally relevant, as IL-17 neutralization prevented the enhanced hepatocellular damages and liver inflammation in these animals. Evidence for enhanced production of IL-23 and decreased accumulation of IL-27 cytokine in M1 type macrophage from IRF3-deficient mice was also observed after treatment with lipopolysaccharide, a setting in which liver gamma-delta T cells and invariant natural killer T cells were found to be involved in IL-17A hyperproduction. Conclusion: IRF3-dependent events downstream of TLR4 control the IL-23/IL-17 axis in the liver and this regulatory role of IRF3 is relevant to liver ischemia-reperfusion injury. (Hepatology 2013)
An autonomous mathematical reconstruction to effectively measure volume loss on retrieved polyethylene tibial inserts
Authors: Knowlton Christopher B. , Wimmer Markus A. 
Published: August 2012

AbstractWear of the polyethylene tibial component is a major factor in the success of total knee replacements. However, sampling resolution and the challenges of estimating original surfaces with relatively complex articulating geometries have limited the accuracy of volumetric measurements of wear on surgically retrieved inserts. A mathematical model analyzed volume error due to sampling resolution and found that 100 × 100 μm2 point spacing reduced error below 1 mm3. Small volumes of material were progressively removed from the topside of three unworn tibial inserts, after which each component was weighed and digitized with a laser coordinate measuring machine. Six inserts worn in knee simulator tests and nine surgically retrieved inserts visually scored for damage were also digitized. For these tests, the original surface of an insert was mathematically reconstructed from unworn regions of the same component, and volume loss and its spatial distribution were calculated. Volume loss estimated by autonomous reconstruction correlated strongly to mass removed manually (R2 = 0.954, slope = 1.02 ± 0.04), mass lost during simulator testing (R2 = 0.935, slope = 1.01 ± 0.07) and visual damage scores separated by size (R2large = 0.9824, R2small = 0.9728). These results suggest that an autonomous mathematical reconstruction can be used to effectively measure volume loss in retrieved tibial inserts. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 101B: 449–457, 2013.
Enhanced attachment, proliferation, and differentiation of human gingival fibroblasts on titanium surface modified with biomolecules
Authors: Jin Can , Ren Ling‐fei , Ding Hua‐zhu , Shi Geng‐sheng , Lin Hai‐sheng , Zhang Feng 
Published: August 2012

AbstractSurface modification of dental implants with biomolecules is of particularly interest recently. To mimic the structure and function of native extracellular matrix (ECM), a derivative of hyaluronic acid (HA), HA–GRGDSP, was synthesized, Arg–Gly–Asp (RGD)‐containing collagen (Col)/HA multilayer polyelectrolyte films (MPFs) coating was fabricated on titanium (Ti) through alternate deposition of Col and HA–GRGDSP with 4.5 assembly cycles; moreover, bioactive molecule, basic fibroblast growth factor (bFGF), was also incorporated into such coating. This coating was then carefully characterized using scanning electronic microscope (SEM) and scanning force microscopy (SFM); bFGF release from the coating was also evaluated. (Col + bFGF)/HA–RGD coating was successfully deposited on Ti surface, and about 300 pg of bFGF could be slowly released from this coating for a week. This coating significantly promoted the initial cell attachment of human gingival fibroblasts (HGFs) compared with other groups (p < 0.05), and HGFs adhered and spread better on this coating than other groups (p < 0.05). Regarding cell proliferation and differentiation of HGFs, they were greatly stimulated when cultured on this coating (p < 0.05). These results indicated that surface modification of Ti using biomolecules might improve the sealing between the neck section of a dental implant and the soft tissue. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2012.