bluuebunny/crossref_metadata_2025 huggingface dataset:
Enhancing Activity for the Oxygen Evolution Reaction: The Beneficial Interaction of Gold with Manganese and Cobalt Oxides
Authors: Frydendal Rasmus , Busch Michael , Halck Niels B. , Paoli Elisa A. , Krtil Petr , Chorkendorff Ib , Rossmeisl Jan
Published: November 2014

Electrochemical production of hydrogen, facilitated in electrolyzers, holds great promise for energy storage and solar fuel production. A bottleneck in the process is the catalysis of the oxygen evolution reaction, involving the transfer of four electrons. The challenge is that the binding energies of all reaction intermediates cannot be optimized individually. However, experimental investigations have shown that drastic improvements can be realized for manganese and cobalt‐based oxides if gold is added to the surface or used as substrate. We propose an explanation for these enhancements based on a hydrogen acceptor concept. This concept comprises a stabilization of an *OOH intermediate, which effectively lowers the potential needed for breaking bonds to the surface. On this basis, we investigate the interactions between the oxides and gold by using DFT calculations. The results suggest that the oxygen evolution reaction overpotential decreases by 100–300 mV for manganese oxides and 100 mV for cobalt oxides.
Functional Binding Surface of a β‐Hairpin VEGF Receptor Targeting Peptide Determined by NMR Spectroscopy in Living Cells
Authors: Diana Donatella , Russomanno Anna , De Rosa Lucia , Di Stasi Rossella , Capasso Domenica , Di Gaetano Sonia , Romanelli Alessandra , Russo Luigi , D'Andrea Luca D. , Fattorusso Roberto
Published: November 2014

In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast 15N‐edited NMR spectroscopic experiments. To this aim, 15N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including 15N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2.
ChemInform Abstract: Baker′s‐Yeast‐Mediated Reduction of Sulfur‐Containing Compounds
Authors: Deasy Rebecca E. , Maguire Anita R.
Published: November 2014

Review: 149 refs.
Increased thyroid cancer incidence corresponds to increased use of thyroid ultrasound and fine‐needle aspiration: A study of the Veterans Affairs health care system
Authors: Zevallos Jose P. , Hartman Christine M. , Kramer Jennifer R. , Sturgis Erich M. , Chiao Elizabeth Y.
Published: November 2014

BACKGROUND

Thyroid cancer incidence has increased in the last several decades and may represent either a true increase in the number of cases or increased screening. The objective of this study was to examine thyroid cancer incidence and the use of thyroid ultrasound and fine‐needle aspiration (FNA) screening in the Veterans Affairs (VA) health care system. The authors hypothesized that the incidence of thyroid cancer would correspond to increases in the use of these diagnostic modalities.

METHODS

This was a multiyear, cross‐sectional study using VA administrative data from 2000 to 2012. Joinpoint regression analysis was used to identify trends in thyroid cancer incidence and the use of thyroid ultrasound and FNA.

RESULTS

An increase in thyroid cancer incidence occurred from 10.3 per 100,000 individuals in 2000 to 21.5 per 100,000 individuals in 2012. The rate of thyroid ultrasound use increased from 125.6 per 100,000 individuals in 2001 to 572.1 per 100,000 individuals in 2012, and the rate of thyroid FNA use increased from 7.0 per 100,000 individuals in 2000 to 46.2 per 100,000 individuals in 2012. A statistically significant increase in thyroid cancer incidence between 2000 and 2008 (annual percent change [APC], 3.81; P < .05) was followed by a more pronounced increase between 2008 and 2012 (APC, 10.32; P < .05). A simultaneous increase in the use of thyroid ultrasound occurred between 2002 and 2012 (APC, 15.48; P < .05) and the use of thyroid FNA between 2000 and 2012 (APC, 18.36; P < .05).

CONCLUSIONS

Although the incidence of thyroid cancer doubled, a nearly 5‐fold increase in the use of thyroid ultrasound and a nearly 7‐fold increase in the use of thyroid FNA occurred between 2000 and 2012. These findings suggest that the increase in thyroid cancer incidence may be related to increases in the use of thyroid ultrasound and FNA. Cancer 2015;121:741–746. © 2014 American Cancer Society.
Critical evaluation of the scientific content in clinical practice guidelines
Authors: Abdelsattar Zaid M. , Reames Bradley N. , Regenbogen Scott E. , Hendren Samantha , Wong Sandra L.
Published: November 2014

BACKGROUND

Increasing pressures to provide high‐quality evidence‐based cancer care have driven the rapid proliferation of clinical practice guidelines (CPGs). The quality and validity of CPGs have been questioned, and adherence to guidelines is relatively low. The purpose of this study was to critically evaluate the development process and scientific content of CPGs.

METHODS

CPGs addressing management of rectal cancer were evaluated. We quantitatively assessed guideline quality with the validated Appraisal of Guidelines Research & Evaluation (AGREE II) instrument. We identified 21 independent processes of care using the nominal group technique. We then compared the evidence base and scientific agreement for the management recommendations for these processes of care.

RESULTS

The quality and content of rectal cancer CPGs varied widely. Mean overall AGREE II scores ranged from 27% to 90%. Across the 5 CPGs, average scores were highest for the clarity of presentation domain (85%; range, 58% to 99%) and lowest for the applicability domain (21%; range, 8% to 56%). Randomized controlled trials represented a small proportion of citations (median, 18%; range, 13%‐35%), 78% of the recommendations were based on low‐ or moderate‐quality evidence, and the CPGs only had 11 references in common with the highest‐rated CPG. There were conflicting recommendations for 13 of the 21 care processes assessed (62%).

CONCLUSIONS

There is significant variation in CPG development processes and scientific content. With conflicting recommendations between CPGs, there is no reliable resource to guide high‐quality evidence‐based cancer care. The quality and consistency of CPGs are in need of improvement. Cancer 2015;121:783–789. © 2014 American Cancer Society.
The rise in metastasectomy across cancer types over the past decade
Authors: Bartlett Edmund K. , Simmons Kristina D. , Wachtel Heather , Roses Robert E. , Fraker Douglas L. , Kelz Rachel R. , Karakousis Giorgos C.
Published: November 2014

BACKGROUND

Although studies of metastasectomy have been limited primarily to institutional experiences, reports of favorable long‐term outcomes have generated increasing interest. In the current study, the authors attempted to define the national practice patterns in metastasectomy for 4 common malignancies with varying responsiveness to systemic therapy.

METHODS

The National (Nationwide) Inpatient Sample was used to estimate the national incidence of metastasectomy for colorectal cancer, lung cancer, breast cancer, and melanoma from 2000 through 2011. Incidence‐adjusted rates were determined for liver, lung, brain, small bowel, and adrenal metastasectomies. The average annual percentage change (AAPC) in metastasectomy by cancer type was calculated using joinpoint regression.

RESULTS

Colorectal cancer was the most common indication for metastasectomy (87,407 cases; 95% confidence interval [95% CI], 86,307‐88,507 cases) followed by lung cancer (58,245 cases; 95% CI, 57,453‐59,036 cases), breast cancer (26,271 cases; 95% CI, 25,672‐26,870 cases), and melanoma (20,298 cases; 95% CI, 19,897‐20,699 cases). Metastasectomy increased significantly for all cancer types over the study period: colorectal cancer (AAPC, 6.83; 95% CI, 5.7‐7.9), lung cancer (AAPC, 5.8; 95% CI, 5.1‐6.4), breast cancer (AAPC, 5.5; 95% CI, 3.7‐7.3), and melanoma (AAPC, 4.03; 95% CI, 2.1‐6.0). Despite an increasing number of comorbidities in patients undergoing metastasectomy (P<.05 for each cancer type), inpatient mortality rates after metastasectomy fell for all cancer types, most significantly for colorectal (AAPC, −5.49; 95% CI, −8.2 to −2.7) and lung (AAPC, −6.2; 95% CI, −11.7 to −0.3) cancers. The increasing performance of metastasectomy was largely driven by high‐volume institutions, in which patients had a lower mean number of comorbidities (P<.01 for all cancer types) and lower inpatient mortality (P<.01 for all cancers except melanoma).

CONCLUSIONS

From 2000 through 2011, the performance of metastasectomy increased substantially across common cancer types, notwithstanding various advances in systemic therapies. Metastasectomy was performed more safely, despite increasing patient comorbidity. High‐volume institutions appeared to drive practice patterns. Cancer 2015;121:747–757. © 2014 American Cancer Society.
Conformational Transformations of Sulfur‐Containing Rings: 2‐Methyltetrahydrothiophene Gas‐Phase Structures
Authors: Van Vinh , Dindic Christina , Nguyen Ha Vinh Lam , Stahl Wolfgang
Published: November 2014

Stable conformations of five‐member rings with the prototype cyclopentane are well‐known to exist as twist or envelope structures and are of general interest in chemistry. Here, we report on the conformational analysis of the sulfur‐containing ring 2‐methyltetrahydrothiophene studied by a combination of molecular beam Fourier transform microwave (MB‐FTMW) spectroscopy and quantum chemistry. Two twist conformers were observed, whereby highly accurate molecular parameters could be determined. In addition, the 34S‐isotopologue of the most stable conformer was assigned in natural abundances. Geometry optimizations were performed at different levels of theory and the calculated rotational constants were compared with experimental values. Two transition states optimized at the MP2/6‐311++G(d,p) level using the Berny algorithm could illustrate the intramolecular conversion between both conformers.
Differential space–time network coding in MIMO two‐way relay channel network
Authors: Jin Xiaoping , Han Xinqiang , Jin Ning , Li Youming , Li Zhengquan , Wang Xiuming
Published: November 2014

This paper focuses on noncoherent detection scheme for multiple‐input multiple‐output two‐way relay channel network with two two‐antennas source nodes and one single‐antenna relay node. An orthogonal differential space–time network coding (ODSTNC) scheme based on relay detection and forward protocol is proposed. The proposed scheme combines space–time coding with network coding, and the differential modulation and detection are used in both multiple access stage and broadcast stage. The multiple‐symbol differential detection is employed at the relay. The maximum likelihood decision and its low‐complexity sphere decoding decision are given. The upper and lower bounds on the average symbol error probability for this system under differential binary phase shift keying (DBPSK) are derived, and a diversity order of 2 is confirmed to be achieved. The simulation results show that the ODSTNC scheme has good performance, and it is available for the applications of far distance signal transmission between two terminals where channel state information is unknown. Copyright © 2014 John Wiley & Sons, Ltd.
Insulin‐like genes in ascidians: Findings in Ciona and hypotheses on the evolutionary origins of the pancreas
Authors: Thompson Jordan M. , Di Gregorio Anna
Published: November 2014

Insulin plays an extensively characterized role in the control of sugar metabolism, growth and homeostasis in a wide range of organisms. In vertebrate chordates, insulin is mainly produced by the beta cells of the endocrine pancreas, while in non‐chordate animals insulin‐producing cells are mainly found in the nervous system and/or scattered along the digestive tract. However, recent studies have indicated the notochord, the defining feature of the chordate phylum, as an additional site of expression of insulin‐like peptides. Here we show that two of the three insulin‐like genes identified in Ciona intestinalis, an invertebrate chordate with a dual life cycle, are first expressed in the developing notochord during embryogenesis and transition to distinct areas of the adult digestive tract after metamorphosis. In addition, we present data suggesting that the transcription factor Ciona Brachyury is involved in the control of notochord expression of at least one of these genes, Ciona insulin‐like 2. Finally, we review the information currently available on insulin‐producing cells in ascidians and on pancreas‐related transcription factors that might control their expression. genesis 53:82–104, 2015. © 2014 Wiley Periodicals, Inc.
Off‐target assessment of CRISPR‐Cas9 guiding RNAs in human iPS and mouse ES cells
Authors: Tan E‐Pien , Li Yilong , Del Castillo Velasco‐Herrera Martin , Yusa Kosuke , Bradley Allan
Published: November 2014

The CRISPR‐Cas9 system consists of a site‐specific, targetable DNA nuclease that holds great potential in gene editing and genome‐wide screening applications. To apply the CRISPR‐Cas9 system to these assays successfully, the rate at which Cas9 induces DNA breaks at undesired loci must be understood. We characterized the rate of Cas9 off‐target activity in typical Cas9 experiments in two human and one mouse cell lines. We analyzed the Cas9 cutting activity of 12 gRNAs in both their targeted sites and ∼90 predicted off‐target sites per gRNA. In a Cas9‐based knockout experiment, gRNAs induced detectable Cas9 cutting activity in all on‐target sites and in only a few off‐target sites genome‐wide in human 293FT, human‐induced pluripotent stem (hiPS) cells, and mouse embryonic stem (ES) cells. Both the cutting rates and DNA repair patterns were highly correlated between the two human cell lines in both on‐target and off‐target sites. In clonal Cas9 cutting analysis in mouse ES cells, biallelic Cas9 cutting was observed with low off‐target activity. Our results show that off‐target activity of Cas9 is low and predictable by the degree of sequence identity between the gRNA and a potential off‐target site. Off‐target Cas9 activity can be minimized by selecting gRNAs with few off‐target sites of near complementarity. genesis 53:225–236, 2015. © 2014 The Authors. Genesis Published by Wiley Periodicals, Inc.
Control of tissue‐localized immune responses by human regulatory T cells
Authors: Pesenacker Anne M. , Broady Raewyn , Levings Megan K.
Published: November 2014

Treg cells control immune responses to self and nonharmful foreign antigens. Emerging data from animal models indicate that Treg cells function in both secondary lymphoid organs and tissues, and that these different microenvironments may contain specialized subsets of Treg cells with distinct mechanisms of action. The design of therapies for the restoration of tissue‐localized immune homeostasis is dependent upon understanding how local immune responses are influenced by Treg cells in health versus disease. Here we review the current state of knowledge about human Treg cells in four locations: the skin, lung, intestine, and joint. Despite the distinct biology of these tissues, there are commonalities in the biology of their resident Treg cells, including phenotypic and functional differences from circulating Treg cells, and the presence of cytokine‐producing (e.g. IL‐17+) FOXP3+ cells. We also highlight the challenges to studying tissue Treg cells in humans, and opportunities to use new technologies for the detailed analysis of Treg cells at the single‐cell level. As emerging biological therapies are increasingly targeted toward tissue‐specific effects, it is critical to understand their potential impact on local immune regulation.
Redirecting soluble antigen for MHC class I cross‐presentation during phagocytosis
Authors: Hari Aswin , Ganguly Anutosh , Mu Libing , Davis Shevaun P. , Stenner Melanie D. , Lam Raymond , Munro Fay , Namet Inana , Alghamdi Enaam , Fürstenhaupt Tobias , Dong Wei , Detampel Pascal , Shen Lian Jun , Amrein Matthias W. , Yates Robin M. , Shi Yan
Published: November 2014

Peptides presented by MHC class I molecules are mostly derived from proteins synthesized by the antigen‐presenting cell itself, while peptides presented by MHC class II molecules are predominantly from materials acquired by endocytosis. External antigens can also be presented by MHC class I molecules in a process referred to as cross‐presentation. Here, we report that mouse dendritic cell (DC) engagement to a phagocytic target alters endocytic processing and inhibits the proteolytic activities. During phagocytosis, endosome maturation is delayed, shows less progression toward the lysosome, and the endocytosed soluble antigen is targeted for MHC class I cross‐presentation. The antigen processing in these arrested endosomes is under the control of NAPDH oxidase associated ROS. We also show that cathepsin S is responsible for the generation of the MHC class I epitope. Taken together, our results suggest that in addition to solid structure uptake, DC phagocytosis simultaneously modifies the kinetics of endosomal trafficking and maturation. As a consequence, external soluble antigens are targeted into the MHC class I cross‐presentation pathway.
Nitrogen‐Rich Energetic Salts of Bis‐Heterocycle‐Substituted 1,2,3‐Triazole (HTANFT)
Authors: Bian Chengming , Wang Kai , Liang Lixuan , Zhang Man , Li Chuan , Zhou Zhiming
Published: November 2014

Energetic salts based on bis‐heterocycle‐substituted 1,2,3‐triazole (HTANFT) were synthesized and characterized by 1H and 13C NMR spectroscopy, infrared spectroscopy, and elemental analysis. The crystal structure of neutral HTANFT (4) was confirmed through single‐crystal X‐ray diffraction. The density of 4 and its salts ranged from 1.60 to 1.83 g cm–3, their nitrogen contents ranged from 56.4 to 65.2 % and their decomposition temperatures ranged between 187 and 236 °C. The determined sensitivities towards impact, friction and electrostatic discharge suggest that all salts are much less sensitive than 1,3,5‐trinitro‐1,3,5‐triazinane (RDX). Moreover, the detonation pressures and velocities were calculated to be 24.6 to 32.9 GPa and 7956 to 8757 m s–1, respectively. Therefore salts 9, 11 and 12 are potential alternatives to RDX in explosive applications.
Na2(smbipy) – A Bipyridine‐Derived Ligand with Chelating Sulfonate Tags and Its 3d Metal Complexes
Authors: Oelkers Benjamin
Published: November 2014

The sulfonated bipyridine derivative disodium 6,6′‐bis(sulfonatomethyl)‐2,2′‐bipyridine [Na2(smbipy)] was synthesized, and its complexation behaviour towards divalent 3d metals in aqueous solution was explored. The complexes of late 3d metals [M(smbipy)(H2O)2]·H2O (M = Co, Ni, Zn) and [Cu(smbipy)(H2O)] are sparingly soluble in water, and their crystal structures show fourfold equatorial coordination (κ4N,N′,O,O′) of the smbipy ligand. Ammonia‐rich solutions of the NiII and CuII aqua complexes yield the decomplexation products [Ni(NH3)6](smbipy), [Ni(NH3)5(H2O)](smbipy) and [Cu(NH3)4](smbipy)·2H2O. Buffered solutions with a reduced ammonia content lead to [Ni(smbipy)(NH3)2] and [Cu(smbipy)(NH3)3]·2H2O, and the latter shows twofold coordination of the smbipy ligand through the nitrogen atoms only (κ2N,N′). When nearly quantitative amounts of ammonia are applied, two closely related complexes with the core motif [(smbipy)Cu(μ‐OH)2Cu] form. Crystal structures of all complexes were obtained, and their features are discussed.
Coordination Behavior and Reactivity of α‐Heterosubstituted Trimethylsilylalkynes at Titano‐ and Zirconocene
Authors: Altenburger Kai , Baumann Wolfgang , Spannenberg Anke , Arndt Perdita , Rosenthal Uwe
Published: November 2014

The coordination behavior of the α‐donor‐atom‐substituted (trimethylsilyl)alkynes OC4H8N–C≡C–SiMe3 (2), EtO–C≡C–SiMe3 (3), and Me2P–C≡C–SiMe3 (4) towards group 4 metallocene generators [Cp2Ti(η2‐btmsa)] (1a), [Cp2Zr(py)(η2‐btmsa)] (1b), and [Cp*2Ti(η2‐btmsa)] (1c) [Cp = η5‐cyclopentadienyl; btmsa = bis(trimethylsilyl)acetylene; py = pyridine; Cp* = η5‐pentamethylcyclopentadienyl] was investigated. By using 1a and 1b, metallacyclopropenes were obtained for alkyne 2, a titanacyclopentadiene for alkyne 3, and dimeric‐stabilized metallacyclopropenes for alkyne 4. Employing the sterically demanding metallocene 1c resulted in monomeric metallacyclopropenes for alkynes 3 and 4. The reactivity of the obtained complexes towards CO2 and acetone was explored as well, thus leading to regioselective formation of metallafuranones and metalladihydrofurans.
Stereoselective Synthesis of C‐2‐Methylene and C‐2‐Methyl α‐ and β‐C‐Glycosides from 2‐C‐Branched Glycals: Formal Total Synthesis of (–)‐Brevisamide
Authors: Sudharani Chalapala , Venukumar Patteti , Sridhar Perali Ramu
Published: November 2014

The stereoselective synthesis of deoxy C‐glycoside derivatives that have a methylene or methyl group at C‐2 position was investigated by employing the Claisen rearrangement of 2‐vinyloxy methyldeoxy‐glycals as the synthetic precursors. The method proceeded with high diastereoselectivity to afford C‐2‐methylene α‐C‐glycosides. Complementary to this protocol, a ZnII‐mediated anomerization of the α‐C‐glycosides to give the corresponding β‐C‐glycosides was also used to obtain diastereomerically pure C‐2‐methylene β‐C‐glycosides. The generality of the reaction was fully evaluated, and the developed method was successfully applied to the formal stereoselective total synthesis of (–)‐brevisamide, a monocyclic ether alkaloid that was isolated from Karenia brevis (red tide dinoflagellate).
Electrodeposition of Cobalt Oxide Nanostructure on the Glassy Carbon Electrode for Electrocatalytic Determination of para‐Nitrophenol
Authors: Noorbakhsh Abdollah , Mirkalaei Mohsen Mosavi , Yousefi Mohammad H. , Manochehri Sohrab
Published: November 2014

Cobalt oxide nanostructure (CoOxNS) deposited on the glassy carbon (GC) electrode surface is proposed as a novel electrocatalytic system for the reduction of para‐Nitrophenol. Cyclic voltammetry, electrochemical impedance spectroscopy, atomic force microscopy and scanning electron microscopy were used for characterization of deposited CoOxNS. CoOxNS deposited by cycling at positive potentials (0 to +1.3 V) show less charge‐transfer resistance (Rct) and more catalytic activity for the electroreduction of p‐nitrophenol compared to those CoOxNS obtained by scanning the applied potential throughout a negative V range. The GC/CoOxNS electrode showed good electrocatalytic activity toward the reduction of p‐nitrophenol at different pH values.
Single‐breath analysis using a novel simple sampler and capillary electrophoresis with contactless conductometric detection
Authors: Greguš Michal , Foret František , Kubáň Petr
Published: November 2014

The analysis of ionic content of exhaled breath condensate (EBC) from one single breath by CE with C4D is demonstrated for the first time. A miniature sampler made from a 2‐mL syringe and an aluminum cooling cylinder for collection of EBC was developed. Various parameters of the sampler that influence its collection efficiency, repeatability, and effect of respiratory patterns were studied in detail. Efficient procedures for the cleanup of the miniature sampler were also developed and resulted in significant improvement of sampling repeatability. Analysis of EBC was performed by CE‐C4D in a 60 mM MES/l‐histidine BGE with 30 μM CTAB and 2 mM 18‐crown‐6 at pH 6 and excellent repeatability of migration times (RSD < 1.3% (n = 7)) and peak areas (RSD < 7% (n = 7)) of 12 inorganic anions, cations, and organic acids was obtained. It has been shown that the breathing pattern has a significant impact on the concentration of the analytes in the collected EBC. As the ventilatory pattern can be easily controlled during single exhalation, the developed collection system and method provides a highly reproducible and fast way of collecting EBC with applicability in point‐of‐care diagnostics.
Temperament‐based Treatment for Anorexia Nervosa
Authors: Kaye Walter H. , Wierenga Christina E. , Knatz Stephanie , Liang June , Boutelle Kerri , Hill Laura , Eisler Ivan
Published: November 2014

Anorexia nervosa (AN) tends to be a chronic and deadly disorder with no proven treatments that reverse core symptoms in adults. New insight into neurobiological mechanisms that contribute to symptoms may support development of more effective interventions. We describe the development of a temperament‐based treatment for AN on the basis of empirically supported models. It uses a systemized approach and takes into consideration an understanding of how neurobiological mechanisms are expressed through behaviour and personality and contribute to specific AN symptomatology. This model integrates the development of AN‐focused constructive coping strategies with carer‐focused strategies to manage temperament traits that contribute to AN symptomatology. This intervention is consistent with the recent Novel Interventions for Mental Disorders initiative mandating that treatment trials follow an experimental medicine approach by identifying underlying mechanisms that are directly targeted by the intervention to influence symptoms. Copyright © 2014 John Wiley & Sons, Ltd and Eating Disorders Association.
Transplanted glial restricted precursor cells improve neurobehavioral and neuropathological outcomes in a mouse model of neonatal white matter injury despite limited cell survival
Authors: Porambo Michael , Phillips Andre W. , Marx Joel , Ternes Kylie , Arauz Edwin , Pletnikov Mikhail , Wilson Mary Ann , Rothstein Jeffery D. , Johnston Michael V. , Fatemi Ali
Published: November 2014

Objective

Neonatal white matter injury (NWMI) is the leading cause of cerebral palsy and other neurocognitive deficits in prematurely‐born children, and no restorative therapies exist. Our objective was to determine the fate and effect of glial restricted precursor cell (GRP) transplantation in an ischemic mouse model of NWMI.

Methods

Neonatal CD‐1 mice underwent unilateral carotid artery ligation on postnatal‐Day 5 (P5). At P22, intracallosal injections of either enhanced green fluorescent protein (eGFP) + GRPs or saline were performed in control and ligated mice. Neurobehavioral and postmortem studies were performed at 4 and 8 weeks post‐transplantation.

Results

GRP survival was comparable at 1 month but significantly lower at 2 months post‐transplantation in NWMI mice compared with unligated controls. Surviving cells showed better migration capability in controls; however, the differentiation capacity of transplanted cells was similar in control and NWMI. Saline‐treated NWMI mice showed significantly altered response in startle amplitude and prepulse inhibition (PPI) paradigms compared with unligated controls, while these behavioral tests were completely normal in GRP‐transplanted animals. Similarly, there was significant increase in hemispheric myelin basic protein density, along with significant decrease in pathologic axonal staining in cell‐treated NWMI mice compared with saline‐treated NWMI animals.

Interpretation

The reduced long‐term survival and migration of transplanted GRPs in an ischemia‐induced NWMI model suggests that neonatal ischemia leads to long‐lasting detrimental effects on oligodendroglia even months after the initial insult. Despite limited GRP‐survival, behavioral, and neuropathological outcomes were improved after GRP‐transplantation. Our results suggest that exogenous GRPs improve myelination through trophic effects in addition to differentiation into mature oligodendrocytes. GLIA 2015;63:452–465
tBu3P/ZnR2 (R=Et, I) Frustrated Lewis Pair Catalysts for Functionalization and Reduction of CO2
Authors: Dobrovetsky Roman , Stephan Douglas W.
Published: November 2014

The functionalization and reduction of CO2 are important targets not only because of concerns about its accumulation or the impact of this greenhouse gas on Earth’s climate, but also because of its potential as a C‐1 feedstock. In this work, both functionalization and reduction of CO2 were performed using tBu3P/ZnR2 (R=Et, I) “frustrated Lewis pairs” (FLPs). Phosphine‐catalyzed carboxylation of alkyl‐Zn bonds and catalytic reduction of CO2 using silanes as hydride sources and tBu3P/ ZnR2 (R=Et, I) FLPs as catalysts are reported. This is also the first time Zn‐based FLP chemistry in functionalization of CO2 is reported.
Shock from Graying: Is the Demographic Shift Weakening Monetary Policy Effectiveness
Authors: Imam Patrick A.
Published: November 2014

There is mounting evidence that in advanced economies, changes in monetary policy have a more benign impact on the economy—given better anchored inflation expectations and inflation being less responsive to variation in unemployment—compared with the past. We examine another aspect that could explain this empirical finding, namely the demographic shift to an older society. The paper first clarifies potential transmission channels that could explain why monetary policy effectiveness may moderate in graying societies. Then, using Bayesian estimation techniques for the USA, Canada, Japan, the UK and Germany, a weakening of monetary policy effectiveness over time with regard to unemployment and inflation is confirmed. After proving the existence of a panel co‐integration relationship between ageing and a weakening of monetary policy, the study uses dynamic panel ordinary least squares techniques to attribute this weakening of monetary policy effectiveness to demographic changes. The paper concludes with policy implications. Copyright © 2014 John Wiley & Sons, Ltd.
Incorporating additional targets into learning trials for individuals with autism spectrum disorder
Authors: Nottingham Casey L. , Vladescu Jason C. , Kodak Tiffany M.
Published: November 2014

Recently, researchers have investigated the effectiveness and efficiency of presenting secondary targets during learning trials for individuals with autism spectrum disorder (ASD). This instructional method may be more efficient than typical methods used with learners with ASD, because learners may acquire secondary targets without additional instruction. This review will discuss the recent literature on providing secondary targets during teaching trials for individuals with ASD, identify common aspects and results among these studies, and identify areas for future research.
Variability of tornado climatology across the continental United States
Authors: Farney Tory J. , Dixon P. Grady
Published: November 2014

Previous tornado climatology research has relied primarily upon a mean value of tornadoes or tornado days fixed on one period to define regions of elevated tornado risk. However, a more comprehensive understanding of the climatological distribution of tornadoes is achieved by analysing the spatial and temporal variability of tornado days. Two methods of analysing tornado days for predefined areas across the continental United States using a refined version of the Storm Prediction Center's tornado data set for 1950–2011 are considered in this study. Statistical analyses of averages and return periods reveal the variability in the record, while consecutive tornado days present an alternative method to assess the seasonal repeatability and risk for historic, multi‐day tornado outbreaks. The results of this research better define the climatological variability of tornado events in addition to offering insight regarding the spatial patterns of locations with the greatest tornado risks, especially those with higher interannual variability.
Development of a silica monolith modified with Fe3O4 nano‐particles in centrifugal spin column format for the extraction of phosphorylated compounds
Authors: Alwy Ali , Clarke Sarah P. , Brougham Dermot F. , Twamley Brendan , Paull Brett , White Blánaid , Connolly Damian
Published: November 2014

In this study, citrate‐stabilised iron oxide nano‐particles (∼16 nm) have been immobilised on commercial silica monolithic centrifugal spin columns (MonoSpin) for the extraction of phosphorylated compounds. Two alternative strategies were adopted involving either direct electrostatic attachment to an aminated MonoSpin (single‐layer method) in the first instance, or the use of a layer‐by‐layer method with poly(diallyldimethylammonium) chloride. Field‐emission scanning electron spectroscopy and energy‐dispersive X‐ray spectroscopy was used for confirming notably higher coverage of nano‐particles using the layer‐by‐layer method (2.49 ± 0.53 wt%) compared with the single‐layer method (0.43 ± 0.30 wt%). The modified monolith was used for the selective separation/extraction of adenosine monophosphate, adenosine diphosphate and adenosine triphosphate with elution using a phosphate buffer. A reversed‐phase liquid chromatographic assay was used for confirming that adenosine, as a non‐phosphorylated control was not retained on the modified MonoSpin devices, whereas recovery of 80% for adenosine monophosphate, 86% for adenosine diphosphate and 82% for adenosine triphosphate was achieved.
In‐office biopsy of upper airway lesions: Safety, tolerance, and effect on time to treatment
Authors: Lippert Dylan , Hoffman Matthew R. , Dang Phat , McCulloch Timothy M. , Hartig Gregory K. , Dailey Seth H.
Published: November 2014

Objectives/Hypothesis

Definitive tissue diagnosis for lesions warranting biopsy is shifting from the operating room to the office. Safety, tolerance, factors related to successful biopsy, and time to treatment are not well‐defined.

Methods

Retrospective review of 116 patients undergoing in‐office biopsy of oropharynx, larynx, or hypopharynx were included. Logistic regression determined if demographics, site, T‐stage, or approach (transoral/transnasal) were related to success. Time to definitive treatment was also analyzed.

Results

Ninety‐two transnasal and 24 transoral biopsies were performed on 73 laryngeal, 35 oropharyngeal, and 8 hypopharyngeal lesions. Of those, 97 of 116 diagnoses were made in‐office. There were no complications; two patients did not tolerate the procedure. Success was not related to age (P = 0.374), site (P = 0.527), T‐stage (P = 0.587), or approach (P = 0.566). Time to treatment was 24.2 ± 13.9 days with successful office biopsy and 48.8 ± 49.4 days without.

Conclusions

High procedural completion rate was observed across patients, sites, and approaches. All patients should be considered for in‐office biopsy, a more time‐ and cost‐effective option leading to earlier treatment.

Level of Evidence

4. Laryngoscope, 125:919–923, 2015
Validation of CT‐MRI fusion for intraoperative assessment of stereotactic accuracy in DBS surgery
Authors: Mirzadeh Zaman , Chapple Kristina , Lambert Meg , Dhall Rohit , Ponce Francisco A.
Published: November 2014

Deep brain stimulation is typically performed with intraoperative microelectrode recording and test stimulation for target confirmation. Recent studies have shown accurate, clinically efficacious results after lead placement without microelectrode recording or test stimulation, using interventional magnetic resonance imaging (MRI) or intraoperative computed tomography (CT; iCT) for verification of accuracy. The latter relies on CT–MRI fusion. To validate CT–MRI fusion in this setting, we compared stereotactic coordinates determined intraoperatively using CT–MRI fusion with those obtained on postoperative MRI. Deep brain stimulation electrodes were implanted with patients under general anesthesia. Direct targeting was performed on preoperative MRI, which was merged with preimplantation iCT images for stereotactic registration and postimplantation iCT images for accuracy confirmation. Magnetic resonance imaging was obtained 6 weeks postoperatively for comparison. Postoperative MRI was obtained for 48 patients, with 94 leads placed over a 1‐year period. Vector error of the targeted contact relative to the initial plan was 1.1 ± 0.7 mm on iCT and 1.6 ± 0.7 mm on postoperative MRI. Variance comparisons (F‐tests) showed that the discrepancy between iCT‐ and postoperative MRI‐determined errors was attributable to measurement error on postoperative MRI, as detected in inter‐rater reliability testing. In multivariate analysis, improved lead placement accuracy was associated with frame‐based stereotaxy with the head of the bed at 0° compared with frameless stereotaxy with the head of the bed at 30° (P = 0.037). Intraoperative CT can be used to determine lead placement accuracy in deep brain stimulation surgery. The discrepancy between coordinates determined intraoperatively by CT–MRI fusion and postoperatively by MRI can be accounted for by inherent measurement error. © 2014 International Parkinson and Movement Disorder Society
In Situ Detection and Identification of Hesperidin Crystals in Satsuma Mandarin (Citrus unshiu) Peel Cells
Authors: Inoue Tsuyoshi , Yoshinaga Arata , Takabe Keiji , Yoshioka Terutaka , Ogawa Kazunori , Sakamoto Masahiro , Azuma Jun‐ichi , Honda Yoichi
Published: November 2014

Introduction

Hesperidin, a flavonoid known to have important pharmacological effects, accumulates particularly in the peels of satsuma mandarin (Citrus unshiu). Although histochemical studies have suggested that hesperidin forms crystals in some tissues of the Rutaceae and Umbelliferae, there has been no rigorous in situ detection or identification of hesperidin crystals in C. unshiu.

Objective

To characterise the chemical component of the crystals found in C. unshiu peels using Raman microscopy.

Methods

Sections of C. unshiu peels were made. The distribution and morphology of crystals in the sections were analysed microscopically. Raman microscopy was used to detect hesperidin in the sections directly.

Results

The crystals were more abundant in immature peel and were observed particularly in areas surrounding vascular bundles, around the border between the flavedo and albedo layers and just below the epidermal cells. In the morphological analysis by scanning electron microscopy, needle‐shaped crystals aggregated and formed clusters of spherical crystals. Spectra obtained by Raman microscopy of the crystals in the peel sections were consistent with those of the hesperidin standard.

Conclusion

This study showed the detailed distribution of crystals in C. unshiu peels and their main component was identified using Raman microscopy to be hesperidin for the first time. Copyright © 2014 John Wiley & Sons, Ltd.
Characteristic differences and reference ranges for mitral, tricuspid, aortic, and pulmonary Doppler velocity waveforms during fetal life
Authors: Kurihara Yasushi , Tachibana Daisuke , Yanai Sakika , Kitada Kohei , Sano Miho , Wada Natsuko , Nakagawa Kayoko , Yamamoto Hiroko , Hamuro Akihiro , Nakano Akemi , Terada Hiroyuki , Ozaki Koji , Fukui Mitsuru , Koyama Masayasu
Published: November 2014

Objectives

We aimed to construct reference ranges for time intervals of each component of cardiac flow velocity waveforms in normal fetuses, comparing those variables between right and left ventricles.

Methods

In 359 fetuses at the gestational age of 17–38 weeks, the durations of atrioventricular (AV) valve opening (AVVO), AV valve closure (AVVC), total E‐ (total‐E) and A‐ (total‐A) waves, total ejection time (total‐ET), acceleration time (acc‐E for E‐wave, acc‐A for A‐wave, and acc‐ET for ejection time), and deceleration time (dec‐E for E‐wave, dec‐A for A‐wave, and dec‐ET for ejection time) were studied cross sectionally.

Results

Both right and left acc‐E showed the strongest correlations with gestational age (r = 0.478 and r = 0.519, respectively). Left AVVO showed a stronger correlation (r = 0.474) than right AVVO (r = 0.282) and, conversely, right AVVC showed a stronger correlation (r = 0.399) than left AVVC (r = 0.195) with gestational age. Significant differences (all P values <0.001) were observed for all right and left parameters other than total‐A and acc‐E.

Conclusions

Characteristic differences between right and left ventricles were found in the reference ranges, suggesting the developmental properties of the fetal heart. © 2014 John Wiley & Sons, Ltd.
Comparison of amorphous silicon absorber materials: Kinetics of light‐induced degradation
Authors: Stuckelberger Michael , Billet Adrian , Riesen Yannick , Boccard Mathieu , Despeisse Matthieu , Schüttauf Jan‐Willem , Haug Franz‐Josef , Ballif Christophe
Published: November 2014

We investigate the influence of the deposition parameters for intrinsic amorphous silicon absorber layers on light‐induced degradation (LID) of thin‐film silicon solar cells. The focus is on absorber layers with different bandgaps: on one side, solar cells with a wide‐bandgap absorber layer that provides open‐circuit voltages up to 1.04V; on the other, cells with short‐circuit current densities of 18.2mA/cm2 with a 300‐nm‐thick narrow‐bandgap absorber layer, and 20mA/cm2 at reverse bias for a cell with a 1000‐nm‐thick absorber layer. Between these extremes, we varied the hydrogen‐to‐silane ratio and the deposition pressure during the absorber layer deposition. The light‐induced degradation of these materials—covering the deposition regimes of low‐pressure, protocrystalline, polymorphous, and high‐pressure amorphous silicon—incorporated in single‐junction amorphous silicon solar cells is detailed here. For each pressure, we found an optimum hydrogen dilution with least LID close to the amorphous‐to‐microcrystalline transition. The relative LID is similar for all pressures at optimized hydrogen dilutions. Further, we present the influence of absorber layer thickness, p‐layer thickness, and deposition rate on the kinetics of light‐induced degradation to facilitate the choice of a material for its application in several types of multi‐junction thin‐film silicon solar cells. We show that the degradation kinetics depends, in semi‐logarithmic scale, only weakly on time but more on deposition conditions. Copyright © 2014 John Wiley & Sons, Ltd.
Role of the source of free radicals in crosslinking of polyethylene
Authors: Rado R. , Lazár M.
Published: November 2014

Crosslinked polyethylene, owing to changes in structure, is a product with technically important properties. The crosslinking may be brought about with the aid of various free radical sources, such as ultraviolet light, ionizing irradiation of high intensities, and organic peroxides. The kinetics and mechanism of the crosslinking process depend predominantly upon the free radical source employed for crosslinking of polyethylene. When peroxides are used, the kinetics and mechanism depend on both the chemical mechanism of the peroxide decomposition and the reaction of primary radicals with the polyethylene macromolecules. When radiation is used, the excited molecules dissociate after absorption of energy, hydrogen is evolved, and radicals from the polymer form crosslinks. The hydrogen atom eliminated is quite mobile and easily abstracts another hydrogen from the polymer. Hence, during a single primary reaction two polymer radicals or one crosslink and one hydrogen molecule are formed. The number of crosslinks as well as the amount of hydrogen produced are then simply proportional to the absorbed radiation dose. Crosslinking of polyethylene by the peroxide method is a more complicated process, the polymer radicals not forming directly, but by transfer to the polyethylene macromolecules of radicals produced by peroxide decomposition. In the termination reaction, in addition to crosslinkages, products of the reaction between primary and polymer radicals may form. When the peroxide decomposes by a chain mechanism the dependence of the crosslinks upon the initial peroxide concentration becomes more involved. In the induced decomposition, the free radical sources are inefficiently consumed and. owing to the difference in reaction orders of the simultaneous ineffective induced and effective self decomposition, of peroxide, the ratio between the two reactions varies in the course of the process. From a kinetic analysis of the experimental results quantitative relations between the formation of crosslinks in polyethylene and the free radicals produced from the various sources were established. Both the simplest cases of direct production of radicals capable of crosslinkage as well as the cases in which the formation of the primary radicals is determined by the initiation process and rate of radical transfer and the nature of the termination reactions are of major importance have been considered. Finally a still more complicated case, in which crosslinking of polyethylene takes place during chain decomposition of the peroxide, has been treated. With the aid of the derived equations and the experimentally determined rate constants the crosslink concentration was calculated and the results have been compared with experimental values.
Investigation of the factors causing chain structure change in ionic diene polymerization
Authors: Dolgoplosk B. A. , Belonovskaja G. P. , Boldyreva I. I. , Kropacheva E. N. , Nelson K. V. , Rosinoer Ja. M. , Chernova J. D.
Published: November 2014

Ether‐induced isomerization of crotyllithium to 3‐lithium‐butene‐1 may be regarded as a model of reactions taking place in the chain growth process during organolithium initiated diene polymerization. In this reaction, as is well known, ethers and other complexating agents considerably increase the number of 1,2‐ (and 3,4‐) links in the chain. Various ionic type catalysts (organoaluminum compounds, titanium halides, hydrogen halides) induce the cis‐trans isomerization of units of the polymer chain (natural rubber) at low temperatures. The process is accompanied by a significant fall in degree of unsaturation of the polymer. The oxidation of Ti3+ to Ti4+ under the influence of peroxides is accompanied by the formation of free radicals, initiating low temperature polymerization of monomers or structuration of rubbers. The oxidation of Ti3+ to Ti4+ effected by hydroperoxides in hydrocarbon media is also accompanied by radical reactions, leading to oxidation and degradation of the polymers. These secondary reactions are depressed by the conventional inhibitors of radical reactions. Alkylaluminumhalides formed during interaction of alkylaluminumnitrites with halides of variable valency metals are efficient cationic catalysts, inducing the polymerization of isobutylene and (3,3‐bischloromethyl)oxacyclobutane. During polymerization of butadiene and isoprene in the presence of alkylaluminumchloride, amorphous, insoluble polymers are formed with very high softening temperatures (410 and 370°C, respectively). Similar conversions are undergone by natural rubber in solution under the influence of titanium tetrachloride and alkylaluminumchloride. Under the action of alkylmagnesium halides 1,4‐polybutadiene in solution shows a considerable loss in degree of unsaturation and an elevation of the glass temperature, preserving at the same time its solubility, which evidently is due to the occurrence of intramolecular cyclization at the diallyl links. Apparently associated with such processes is the diminished unsaturation of sodium butadiene rubber (ca. 85% of the theoretical).