bluuebunny/crossref_metadata_2025 huggingface dataset:
Siamese‐Twin Porphyrin: A Pyrazole‐Based Expanded Porphyrin of Persistent Helical Conformation
Authors: Blusch Lina K. , Hemberger Yasmin , Pröpper Kevin , Dittrich Birger , Witterauf Franziska , John Michael , Bringmann Gerhard , Brückner Christian , Meyer Franc
Published: April 2013

The 3+3‐type synthesis of a pyrazole‐based expanded porphyrin 22 H4, a hexaphyrin analogue named Siamese‐twin porphyrin, and its homobimetallic diamagnetic nickel(II) and paramagnetic copper(II) complexes, 22 Ni2 and 22 Cu2, are described. The structure of the macrocycle composed of four pyrroles and two pyrazoles all linked by single carbon atoms, can be interpreted as two conjoined porphyrin‐like subunits, with the two opposing pyrazoles acting as the fusion points. Variable‐temperature 1D and 2D NMR spectroscopic analyses suggested a conformationally flexible structure for 22 H4. NMR and UV/Vis spectroscopic evidence as well as structural parameters proved the macrocycle to be non‐aromatic, though each half of the molecule is fully conjugated. UV/Vis and NMR spectroscopic titrations of the free base macrocycle with acid showed it to be dibasic. In the complexes, each metal ion is coordinated in a square‐planar fashion by a dianionic, porphyrin‐like {N4} binding pocket. The solid‐state structures of the dication and both metal complexes were elucidated by single‐crystal diffractometry. The conformations of the three structures are all similar to each other and strongly twisted, rendering the molecules chiral. The persistent helical twist in the protonated form of the free base and in both metal complexes permitted resolution of these enantiomeric helimers by HPLC on a chiral phase. The absolute stereostructures of 22 H62+, 22 Ni2, and 22 Cu2 were assigned by a combination of experimental electronic circular dichroism (ECD) investigations and quantum‐chemical ECD calculations. The synthesis of the first member of this long‐sought class of expanded porphyrin‐like macrocycles lays the foundation for the study of the interactions of the metal centers within their bimetallic complexes.
Asymmetric Synthesis of trans‐β‐Lactams by a Kinugasa Reaction on Water
Authors: Chen Zhenling , Lin Lili , Wang Min , Liu Xiaohua , Feng Xiaoming
Published: April 2013

The asymmetric Kinugasa reaction was performed on pure water for the first time without the need for any organic co‐solvents. In contrast to most asymmetric Kinugasa reactions, trans‐β‐lactams were obtained as the major products in good yields, enantioselectivities, and diastereoselectivities (up to 90 % yield, 98 % ee, and >99:1 d.r.). This reaction is atom‐economical, environmentally friendly, and affords synthetically useful but challenging products.
Conformation and Atropisomeric Properties of Indometacin Derivatives
Authors: Wakamatsu Shintaro , Takahashi Yuka , Tabata Hidetsugu , Oshitari Tetsuta , Tani Norihiko , Azumaya Isao , Katsumoto Yukiteru , Tanaka Takeyuki , Hosoi Shinzo , Natsugari Hideaki , Takahashi Hideyo
Published: April 2013

The stereochemistry around the N‐benzoylated indole moiety of indometacin was studied by restricting the rotation about the NC7′ and/or C7′C1′ bond. In the 2′,6′‐disubstituted ones, an atropisomeric property was found and the atropoisomers were separated and isolated as stable forms. Their biological abilities to inhibit cyclooxygenase‐1 (COX‐1) and cyclooxygenase‐2 (COX‐2) were examined. Only the aR‐isomer showed specific inhibition of COX‐1, and COX‐2 was not inhibited by either atropisomer. Conformational analysis in NMR studies and X‐ray crystallography, and CD spectra in combination with calculations were utilized to elucidate the bioactive conformations.
Facile Fabrication of Nanoparticles Confined in Graphene Films and Their Electrochemical Properties
Authors: Chen Sheng , Zhu Junwu , Qiu Ling , Li Dan , Wang Xin
Published: April 2013

The development of novel nanostructured electrode materials with high performance and based on abundant elements is a key element in the societal pursuit of sustainable energy. Graphene‐based structures with rich macroporosity and high conductive networks are promising components to develop novel electrode materials. Herein, we described a facile procedure to confine Ni(OH)2 particles in a graphene film, leading to a new sandwich‐like hybrid structure. The hybrid film offers simultaneously ordered ion diffusion channels and high electrical conductivity, which facilitate the improvement of both electrode kinetics and electrochemical stability, thus leading to high capacitance, fast rate capability, and stable cycle life as supercapacitor materials. This work provides a facile pathway for optimized structures for electrode materials, and represents a benefit for the global issues of energy shortage and environmental pollution.
Bonding in Diborane–Metal Complexes: A Quantum‐Chemical and Experimental Study of Complexes Featuring Early and Late Transition Metals
Authors: Wagner Arne , Kaifer Elisabeth , Himmel Hans‐Jörg
Published: April 2013

The coordination chemistry of the doubly base‐stabilised diborane(4), [HB(hpp)]2(hpp=1,3,4,6,7,8‐hexahydro‐2H‐pyrimido‐[1,2‐a]pyrimidinate), was extended by the synthesis of new late transition‐metal complexes containing CuIand RhIfragments. A detailed experimental study was conducted and quantum‐chemical calculations on the metal–ligand bonding interactions for [HB(hpp)]2complexes of Group 6, 9, 11 and 12 metals revealed the dominant BHM interactions in the case of early transition‐metal fragments, whereas the BBM bonding prevails in the case of the late d‐block compounds. These findings support the experimental results as reflected by the IR and NMR spectroscopic parameters of the investigated compounds. DFT calculations on [MeB(hpp)]2and model reactions between [B2H4⋅2NMe3] and [Rh(μ‐Cl)(C2H4)2] showed that the bicyclic guanidinate allows in principle for an oxidative addition of the BB bond. However, the formation of σ‐complexes is thermodynamically favoured. The results point to the selective BH or BB bond‐activation of diborane compounds by complexation, depending on the chosen transition‐metal fragment.
Highly Selective Copper‐Catalyzed Hydroboration of Allenes and 1,3‐Dienes
Authors: Semba Kazuhiko , Shinomiya Masataka , Fujihara Tetsuaki , Terao Jun , Tsuji Yasushi
Published: April 2013

The highly selective copper‐catalyzed hydroboration of allenes has been developed. Allylboranes and alkenylboranes were selectively prepared by the judicious choice of catalytic species (copper hydride and boryl copper). Furthermore, two types of alkenylboranes could be selectively synthesized by the choice of an appropriate ligand. Mechanistic studies confirmed that the protonation of a (Z)‐σ‐allyl copper species, which was isolated and structurally characterized by single‐crystal X‐ray diffraction, was a key step in these reactions. Besides allenes, this method is also applicable to the selective hydroboration of 1,3‐diene derivatives to afford allylboranes and homoallylboranes.
Eine Unterrichtsreihe zur experimentgestützten Erarbeitung der Molekülformel des Wassers in der Sekundarstufe I des Gymnasiums
Authors: Pfangert‐Becker Ursula
Published: April 2013

Auch wenn die Molekülformel des Wassers den meisten Schülern bekannt ist, so lässt dieses Unterrichtsbeispiel die Schüler erfahren, dass die chemische Formel einer Verbindung sukzessive aus experimentellen Ergebnissen hergeleitet werden kann.

Though the molecular formula of water is usually known to most school students, the example lessons presented here allow the students to experience for themselves that the formulaic abstraction of a substance can be successively generated from experimental results.
Mechanism and Nature of the Different Viscosity Sensitivities of Hemicyanine Dyes with Various Heterocycles
Authors: Cao Jianfang , Hu Chong , Liu Fei , Sun Wen , Fan Jiangli , Song Fengling , Sun Shiguo , Peng Xiaojun
Published: April 2013

A series of hemicyanine derivatives are excellent fluorescent viscosity sensors in live cells and in imaging of living tissues due to their low quantum yields in solution but large fluorescence enhancements in viscous environments. Herein, three carbazole‐based hemicyanine dyes with different heterocycles are studied. They have different background quantum yields, and hence different sensitivities to viscosity detection, large Stokes shifts, and high sensitivity. Better understanding of the structure–property relationships for viscosity sensitivity could benefit the design of improved dyes. Computational studies on these dyes reveal the mechanism of viscosity sensitivity of fluorescent molecular rotors and the nature of the difference in viscosity sensitivity of the three dyes. The results show that the greatly raised HOMO and greatly lowered LUMO in the S1 state compared with the S0 state are responsible for the large Stokes shift of the three dyes. The heterocyclic moieties have the primary influence on the LUMO levels of the three hemicyanine dyes. Rotation about the CC bond adjacent to the carbazole moiety of the three dyes drives the molecule toward a small energy gap between the ground state and the first excited state, which causes mainly nonradiative deactivation. The oscillator strengths in the lowest singlet excited state drop rapidly with increasing rotation between 0 and 95°, which leads to a dark state for these dyes when fully twisted at 95°. We draw a mechanistic picture at the molecular level to illustrate how these dyes work as viscosity‐sensitive fluorescent probes. The activation barriers and energy gaps of CC bond rotation strongly depend on the choice of heterocycle, which plays a major role in reducing fluorescence quantum yield in the free state and provides high sensitivity to viscosity detection in viscous environments for the carbazole‐based hemicyanine dyes.
Bragg Stack‐Functionalized Counter Electrode for Solid‐State Dye‐Sensitized Solar Cells
Authors: Park Jung Tae , Prosser Jacob H. , Kim Dong Jun , Kim Jong Hak , Lee Daeyeon
Published: April 2013

A highly reflective counter electrode is prepared through the deposition of alternating layers of organized mesoporous TiO2 (om‐TiO2) and colloidal SiO2 (col‐SiO2) nanoparticles. We present the effects of introducing this counter electrode into dye‐sensitized solar cells (DSSCs) for maximizing light harvesting properties. The om‐TiO2 layers with a high refractive index are prepared by using an atomic transfer radical polymerization and a sol–gel process, in which a polyvinyl chloride‐g‐poly(oxyethylene) methacrylate graft copolymer is used as a structure‐directing agent. The col‐SiO2 layers with a low refractive index are prepared by spin‐coating commercially available silica nanoparticles. The properties of the Bragg stack (BS)‐functionalized counter electrode in DSSCs are analyzed by using a variety of techniques, including spectroscopic ellipsometry, SEM, UV/Vis spectroscopy, incident photon‐to‐electron conversion efficiency, electrochemical impedance spectroscopy, and intensity modulated photocurrent/voltage spectroscopy measurements, to understand the critical factors contributing to the cell performance. When incorporated into DSSCs that are used in conjunction with a polymerized ionic liquid as the solid electrolyte, the energy conversion efficiency of this solid‐state DSSC (ssDSSC) approaches 6.6 %, which is one of the highest of the reported N719 dye‐based ssDSSCs. Detailed optical and electrochemical analyses of the device performance show that this assembly yields enhanced light harvesting without the negative effects of charge recombination or electrolyte penetration, which thus, presents new possibilities for effective light management.
The metabolic responses induced by acute dexamethasone predict glucose tolerance and insulin secretion over 10 years in relatives of type 2 diabetic subjects
Authors: Durck Tina Trier , Henriksen Jan Erik , Egede Mette Brogaard , Levin Klaus , Rantzau Christian , Ward Glenn , Beck‐Nielsen Henning , Alford Frank P.
Published: April 2013

Background

This study aimed to compare the metabolic and insulin secretory responses to dexamethasone with the metabolic responses observed at 10 years in normoglycaemic relatives of type 2 diabetic and healthy control subjects.

Methods

Twenty relatives and 20 matched control subjects were studied twice at 0 year (pre‐ and post‐dexamethasone) and at 10 years, employing a 75‐g oral glucose tolerance test (OGTT), with serial measurements of glucose and insulin, for determination of glucose tolerance and calculations of acute insulin release (ΔI30/ΔG30; insulinogenic index) and insulin sensitivity (SIHOMA).

Results

Following dexamethasone, the relatives group developed varying degrees of glucose intolerance, associated with reduced insulin sensitivity and insulinogenic index. By 10 years, fasting glucose and 2‐h OGTT glucose were raised in the relatives group, especially in the relatives most metabolically affected by dexamethasone, including a reduced insulinogenic index. Multiple regression analysis of the data in relatives demonstrated that the 2‐h OGTT glucose and fasting glucose values at 10 years depended on the 0‐year post‐dexamethasone 2‐h OGTT glucose, post‐dexamethasone fasting glucose and post‐dexamethasone insulin sensitivity, r2adj = 56% (p < 0.001) and r2adj = 60% (p < 0.0001), respectively. No pre‐dexamethasone metabolic or insulin secretory responses entered these models.

Conclusions

In relatives, fasting and 2‐h OGTT glucose concentrations and β‐cell responses to acute dexamethasone‐induced insulin resistance are similar to those observed at 10 years, especially in relatives who develop the most disturbed dexamethasone‐induced glucose intolerance and impaired acute insulin secretion. The combined 0‐year, post‐dexamethasone fasting and 2‐h OGTT glucose concentrations and insulin resistance, measured as SIHOMA, are the best predictors in relatives of future dysglycaemia. Copyright © 2013 John Wiley & Sons, Ltd.
Influence of river channel geometry in stream flow modelling and guidelines for field investigation
Authors: Zhang Hongbo , Zhang Fan , Shi Xiaonan , Zeng Chen , Shih Dong‐Sin , Yeh Gour‐Tsyh , Joswiak Daniel R.
Published: April 2013

Fully physics‐based, process‐level, distributed fluid flow and reactive transport hydrological models are rarely used in practice until recent years. These models are useful tools to help understand the fundamental physical, chemical, and biological processes that take place in nature. In this study, sensitivity analyses based on a mountain area river basin modelling study are performed to investigate the effect of river channel geometric characteristics on downstream water flow. Numerical experiments show that reduction in the river channel geometric measurement interval may not significantly affect the downstream water stage simulation as long as measurement accuracy at special nodes is guaranteed. The special upstream nodes include but are not limited to 1) nodes located close to the observation station, 2) nodes near the borders of different land covers with considerable riverbed roughness changes, 3) nodes at entering points of tributaries causing discharge jump and 4) nodes with a narrow cross‐section width that may control the flow conditions. This information provides guidelines for field investigation to efficiently obtain necessary geometric data for physics‐based hydrological modelling. It is especially useful in alpine areas such as the Tibetan Plateau where field investigation capability is limited under severe topography and climate condition. Copyright © 2013 John Wiley & Sons, Ltd.
Delayed efficient anticoagulation with heparin in patients with a weight of 110 kg and more treated for acute coronary syndrome
Authors: Joncas Sebastien X. , Poirier Paul , Ardilouze Jean‐Luc , Carrier Nathalie , Fayad Tania , Farand Paul
Published: April 2013

Objective

The use of a weight‐based nomogram is considered as standard care for prescribing appropriate doses of unfractionated heparin (UFH). Because of the need for multiple other medications that may affect bleeding and that clinical data have relied on similar dosing algorithms, maximum initial bolus and infusion rates have been suggested (capped initial dose). Whether these weight‐based heparin nomograms properly address therapeutic dosing in obese patients remains questionable.

Design and Methods

Thirty patients treated for acute coronary syndrome and weighing ≥110 kg were retrospectively compared with 90 controls (three groups of 30 patients, weighting 50‐69.9, 70‐89.9, or 90‐109.9 kg), all treated with UFH, July 2008 to April 2009. The primary end point was the time required to obtain a threshold activated partial thromboplastin time (aPTT).

Results

Mean time to achieve threshold aPTT was longer for obese patients weighing ≥110 kg than for controls (31.47 vs. 12.89 hours; P < 0.0001). At 24 hours, 63% of obese patients weighing ≥110 kg had not reached threshold aPTT vs. 7% of controls (P < 0.0001). However, threshold infusion rate did not differ between weight categories (13.0 vs. 13.1 U/kg/h; P = NS) and approximated the initial infusion rate recommended by nomograms without applying the dose cap (12 U/kg/h).

Conclusions

Adequate anticoagulation time doubled in patients weighing ≥110 kg, suggesting that these patients were not receiving appropriate heparin doses initially to achieve threshold aPTT rapidly. Using initial infusion rate recommended by a nomogram without capping for total body weight is suggested as acceptable in this study. This approach should be further evaluated in a prospective study.
Longitudinal study shows increasing obesity and hyperglycemia in micronesia
Authors: Murdock David , Salit Jacqueline , Stoffel Markus , Friedman Jeffrey M. , Pe'er Itsik , Breslow Jan L. , Bonnen Penelope E.
Published: April 2013

Objective

Obesity and diabetes are particularly high in indigenous populations exposed to a Western diet and lifestyle. The prevalence of obesity, diabetes, hyperglycemia, dyslipidemia, and hypertension in one such population, the Micronesian island of Kosrae was described.

Design and Methods

Longitudinal screenings for metabolic traits were conducted on adult Kosraens ≥ 20 years of age in 1994 and again in 2001. Data was obtained on 3,106 Kosraens, comprising ∼80% of the adult population. Diabetes was diagnosed using World Health Organization guidelines. Prevalences of obesity, hyperglycemia, dyslipidemia, and hypertension were assessed.

Results

The overall age‐adjusted prevalence of diabetes increased from 14 to 21%. The most significant change observed in the population was increases in obesity and hyperglycemia, especially among young Kosraens and women. Obesity age‐adjusted prevalence increased from 45 to 62%, and hyperglycemia age‐adjusted prevalence increased from 19 to 44%. Of note, Kosraens as a group had unusually low high density lipoprotein (HDL) levels with 80% classified as low HDL by NCEP‐ATPIII criteria, despite lacking the usually accompanying increase in triglycerides. Comparison to reports from other populations shows that Kosrae experiences one of the highest rates of obesity, hyperglycemia, and low HDL globally while maintaining relatively healthy levels of triglycerides.

Conclusion

Our study shows a dramatic increase in obesity and hyperglycemia in Kosrae in just 7 years and forebodes significantly increased health risks for this part of the world.
Cell proliferation monitoring by multiplexed electrochemical impedance spectroscopy on microwell assays
Authors: Duchateau Stijn , Broeders Jeroen , Croux Dieter , Janssen Daniel , Rigo Jean‐Michel , Wagner Patrick , Thoelen Ronald , De Ceuninck Ward
Published: April 2013

Cell proliferation can be monitored by a wide range of well‐established techniques. Most of the principles used rely on optical, single end‐point methods, often involving the use of absorbent, fluorescent or luminescent compounds. These additives can interfere with the cell growth, thus producing distorted results. Electrochemical impedance spectroscopy provides a solution for this problem and enables continuous monitoring without interference. However equipment for this measurement technique is often bulky, highly expensive and lacks multichannel features. This paper presents a low‐cost, compact hardware platform optimized for proliferation measurements, together with custom software to ease interpretation and physical modelling of data. Performance is demonstrated and measurement parameters are fine‐tuned for three commonly used cell types in proliferation measurements. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
The impact of offshore financial centers on international financial markets
Authors: Dufey Gunter , Bartram Söhnke M.
Published: April 2013

Offshore centers have come to play an important role in the institutional structure of international financial markets. The article identifies two dimensions of dynamic competition that are relevant for an analysis of the offshore center phenomenon. First, there is competition between the offshore centers and one or more domestic financial markets. Second, there is dynamic competition among the offshore centers. The system of offshore centers generates a three‐tier structure of international financial markets: domestic, foreign traditional, and offshore markets, both with respect to financial intermediaries as well as securities markets. This structure constitutes the institutional base for trends in the international financial markets which result in a process of increasing globalization.
Internationalization of currencies: The case of the US dollar and its challenger euro
Authors: Tavlas George S.
Published: April 2013

This article examines the benefits and costs to the United States of having the US dollar used as an international currency and explains the factors underlying the dollar's use internationally. The main benefit for the United States is that it derives seigniorage from the dollar's international use while the main cost is that there is less scope for controlling domestic monetary conditions. There are three prerequisites for the international use of a currency: (1) confidence in the political stability of the issuing country; (2) deep, broad, and open financial markets in the issuing country; and (3) a large share of world exports on the part of the issuing country. The implications of the euro for the dollar's leading international position are discussed. Data are presented showing that the dollar is the world's leading international currency.
Toward global regulatory harmonization in banking
Authors: Kim Taeho
Published: April 2013

Several principles of international bank regulatory jurisdictions have emerged since the mid‐1970s. Each principle has advantages and disadvantages in promoting cross‐border competition, ensuring prudent banking practice, and maintaining worldwide financial stability. At the same time, simultaneous application of different principles by different countries has caused overlapping, underlapping, or sheer avoidance of bank regulations, resulting in less transparency and an uneven playing field for internationally competing banks. To level the playing field, bank regulatory harmonization has been advocated, particularly under the auspices of the Basle Committee on Banking Supervision. However, as demonstrated in the case of setting minimum capital standards for market risks, a successive harmonization approach may not be the panacea. There is a need for rethinking of efficiency in regulation, including incentive‐compatible approaches.
A time diversification approach to the emerging stock markets of Latin America: Argentina, Brazil, Chile, and Mexico
Authors: Ratner Mitchell , Arbeláez Harvey , Leal Ricardo
Published: April 2013

This article provides the analytical basis for the adoption of a longer view to portfolio diversification in Latin America. The benefits to be gained through time diversification are studied in the context of four countries: Argentina, Brazil, Chile, and Mexico. The empirical evidence of actual annualized returns indicates that risk in investment in Latin American equity returns tends to diminish over longer term investment horizons.
Electronic Origin of the Structural Anomalies of Zinc and Cadmium
Authors: Wedig Ulrich , Nuss Hanne , Nuss Jürgen , Jansen Martin , Andrae Dirk , Paulus Beate , Kirfel Armin , Weyrich Wolf
Published: April 2013

The electron distributions in position and in momentum space of thehcpmetals magnesium and zinc are investigated experimentally and compared to results of quantum‐chemical calculations. Furthermore, a survey is given on recent analyses of the bonding properties of zinc and cadmium, using the method of increments. The experimental deformation densities were obtained by refining multipole models to X‐ray diffraction data sets measured at 100 K with either Mo‐Kα(Mg) or Ag‐Kα(Zn) radiation. The finalRFvalues (Valray/Jana2006) are 0.0028/0.0034 (Mg) and 0.0068/0.0068 (Zn). The differences to deformation densities obtained from periodic density functional calculations are discussed. The effect of dynamical electron correlation on the electron density was analyzed, using cluster models. Compton profiles were measured with 88.67 keV synchrotron radiation at beamline ID15B at the ESRF in Grenoble. Varied orientations of the samples allowed for probing the projected momentum distribution along the [100], [423] and [001] directions. Fourier transforms of the computed reciprocal form factorB(r) resulted in the corresponding theoretical Compton profiles. It is suggested that the anomaloushcpstructure of zinc is favored by a kinetic balancing of the valence electrons, i.e. correlation mediated 4s‐3dinteractions.
Video‐assisted Thoracoscopic Surgery Sleeve Lobectomy with Bronchoplasty
Authors: Li Yun , Wang Jun
Published: April 2013

Background

We review our experiences with video‐assisted thoracoscopic surgery (VATS) sleeve lobectomy with bronchoplasty for NSCLC. The safety, effectiveness, indications, and operation precautions of this approach were examined.

Methods

From September 2011 to September 2012, 11 patients underwent VATS sleeve lobectomy with bronchoplasty in our hospital (right upper lobe = 8, left lower lobe = 2, left upper lobe = 1). The operation consisted of VATS anatomic sleeve lobectomy with bronchoplasty combined with systematic lymph node dissection. Three incisions were made. Bronchial anastomosis was combined with simple continuous suture anastomosis of the membranous part of the bronchus and simple interrupted suture anastomosis of the cartilaginous part of the bronchus.

Results

All procedures went uneventfully. Median operative time was 178 min; median bronchial anastomosis time was 42 min; median blood loss was 180 ml. There was no case of conversion to thoracotomy. Pathological examination showed 10 squamous cell carcinomas and 1 adenocarcinoma. All patients recovered well, except one who suffered minor complications. Median postoperative chest tube drainage duration was 6.8 days, and median hospital stay was 8.9 days. All patients were followed up for 2–13 months without recurrence.

Conclusions

Video‐assisted thoracoscopic surgery sleeve lobectomy with bronchoplasty is a safe and effective surgical approach in the treatment of non‐small cell lung cancer. The operating incision placed at the 4th intercostal space on the anterior axillary line is convenient for anastomosis our experience shows that anastomosis combining simple continuous suture of the membranous part of bronchus and simple interrupted suture anastomosis of the cartilaginous part of the bronchus is fast and secure. Moreover, preserving the azygos vein does not affect the anastomosis.
Outcome of routine use of microsurgical biliary reconstruction in pediatric living donor liver transplantation
Authors: Chen Chao‐Long , Concejero Allan M. , Lin Tsan‐Shiun , Lin Yu‐Hung , Chiang Yuan‐Cheng , Wang Chih‐Chi , Wang Shih‐Ho , Lin Chih‐Che , Liu Yueh‐Wei , Yong Chee‐Chien
Published: April 2013

Objective

Microsurgical techniques, initially used for hepatic artery reconstruction, have been extended to biliary reconstruction to decrease biliary complications. The routine use of microsurgical biliary reconstruction in pediatric living donor liver transplantation (LDLT) has not been elucidated.

Methods

Sixty‐seven pediatric patients underwent primary LDLT. All biliary reconstructions were performed by a single microsurgeon using microsurgical techniques. A biliary stent was not used. The minimum follow‐up was 12 months. Thirty‐four patients had a minimum follow‐up of 36 months. The outcomes of those who underwent microsurgical biliary reconstruction were compared with the outcomes of a cohort of 67 patients who underwent conventional biliary reconstruction.

Results

The demographical and clinical profiles of the two groups were not significantly different. There were 5 anastomotic complications in the conventional and 2 anastomotic complications in the microsurgical reconstruction groups. All complications developed within 90 days after transplant. There were no late biliary complications. Further analysis showed that conventional reconstruction increased the risk of biliary complications by 2.4 times (relative risk: 2.42; attributable risk: 4.5).

Conclusion

The routine use of microsurgical biliary reconstruction in pediatric LDLT is a technical innovation that led to decreased anastomotic biliary complications.
IS THE EU SEAL PRODUCTS REGULATION A SEALED DEAL? EU AND WTO CHALLENGES
Authors: Perišin Tamara
Published: April 2013

In both the EU and the WTO there are currently pending cases on the legality of EU Regulation 1007/2009 on trade in seal products and its Implementing Regulation 737/2010. While seals seem to be very attractive to the public so that raising arguments against these EU measures are not popular, the Regulations do raise concerns about competences, subsidiarity and proportionality which are relevant for compliance with EU primary law. They also raise concerns about possible protectionism, the use of public morals, coherence and necessity with regard to compatibility with WTO law. This paper seeks to examine all these issues.
THE APPLICATION OF CONSTITUTIONAL PREAMBLES AND THE CONSTITUTIONAL RECOGNITION OF INDIGENOUS AUSTRALIANS
Authors: Twomey Anne
Published: April 2013

The debate on the recognition of Indigenous Australians in the Australian Constitution is more about how, than whether, this should occur. The two main proposals involve the use of a preamble. One proposes symbolic recognition in a new constitutional preamble with a clause prohibiting use of the preamble in constitutional interpretation. The other would give Parliament power to make laws with respect to Indigenous Australians, but qualify it in a preamble so that it could only be exercised for their ‘advancement’. This article draws on comparative experience of the use of preambles in other common law countries to challenge the assumptions underlying each proposal.
The Philosopher Doth Protest Too Much: Rousseauian Enlightenment and the Rhetoric of Despair
Authors: Field Laura K.
Published: April 2013

The most striking feature of Rousseau's self-presentation in the Confessions is his pathos-filled anticipation of future adversity. Never quite arriving at the depths of despair he foresees, however, Rousseau instead offers the reader glimpses of a surprisingly robust happiness. In this article I present a new political reading of the Confessions that is attentive both to the rhetorical surface of the work and to its charming subplot. Guided by Rousseau's humorous understanding of truth telling, I argue that the Confessions is shaped by a complex literary ruse that colors much of what Rousseau has to say about frankness, happiness, and his own idiosyncrasy. Far from being undone by his shadow-dappled imaginings, Rousseau's conscious dissimulations reflect his concerns about the public value of enlightenment and his commitment to authorial responsibility.
Iron Age Enclosed Settlements in West Wales
Authors: Murphy K. , Mytum H. , Austin L. , Caseldine A.E. , Griffiths C.J. , Gwilt A. , Webster P. , Young T.P.
Published: April 2013

This paper presents the results of several years' research on late Iron Age enclosed settlements in west Wales. Geophysical survey was conducted on 21 sites and three of these, Troedyrhiw, Ffynnonwen, and Berry Hill, were part-excavated. Most sites examined were heavily plough-damaged, but results of the surveys and excavations demonstrated that substantial archaeological remains survive. Approximately 60 enclosed settlements lay in the core study area of southern Ceredigion (Cardiganshire), half of which were oval in shape and half rectangular. Both types contain suites of buildings seen in much of the British Iron Age – round-houses and 4-/6-post structures. Evidence from the excavations supports data from elsewhere in the region indicating that small oval enclosures appear in the landscape in the 2nd–1st centuriesbc, with rectangular enclosures constructed right at the end of the Iron Age. Dating is based almost entirely on radiocarbon determinations as, in common with other similar-aged sites in west Wales, artefacts are almost completely absent. It was not possible during excavation at Troedyrhiw to conclusively demonstrate late prehistoric use of the rectangular enclosed settlement, but a Roman pottery assemblage in the upper fills of the enclosure ditch coupled with a two phase entrance is interpreted as indicating Late Iron Age construction. More complex remains were revealed during excavations at Ffynnonwen, a circular enclosed settlement within a larger oval enclosure. Here, three round-houses, a 4- and 6-post structure and other remains were investigated and radiocarbon dated to the 8th–6th centuriesbcthrough to the early Romano-British period. Berry Hill, an inland promontory fort, appeared to be unfinished and abandoned. Radiocarbon determinations indicated a Late Bronze Age construction (10th–8th centuriesbc). The paper concludes with a consideration of a number of interpretive issues regarding settlement, enclosure, identity, and ways of living.
Pursuing ‘the Pressure of the Past’: British Prehistoric Research, 1980–2010
Authors: Cooper Anwen
Published: April 2013

This article presents a detailed analysis of developments in British prehistoric research practices from 1980–2010, traversing the period during which Planning Policy Guidance Note 16 (PPG16) was introduced and changed substantially the way that archaeology was carried out. Using evidence from Proceedings of the Prehistoric Society (PPS) itself together with key fieldwork records collated over the duration of this period, a consideration is made of changes in the character of prehistoric investigations, in the evidence base available to researchers, and in the methodologies drawn upon and interpretations put forward in significant outputs of British prehistoric research. Several major shifts in research practices are highlighted. The findings augment considerably broad claims which have been made about the changing character of British prehistoric research practices and reveal some perhaps surprising traits of the investigative process. PPS's own role within this broader research milieu is also assessed.
PERFORMING VICTORIAN WOMANHOOD: ELSIE FOGERTY STAGES TENNYSON'S PRINCESS IN GIRLS' SCHOOLS
Authors: Norcia Megan A.
Published: April 2013

Tennyson's poem The Princess (1847) has long intrigued readers with its polarizing gender politics and playful, lilting verses recounting the grim bloodshed that results when an ambitious Princess establishes a women's college. The frame narrative focuses on a group of friends at a summer party who are inspired by a tale of an ancient warrior queen, who “sallying thro’ the gate, / Had beat her foes with slaughter from her walls” (Prologue 30–34). At some moments jocular and at others acerbic, the men spin the Princess's story, with the women of the gathering providing interludes of music between the tales. In the narrative that unfolds, the Princess establishes a separatist women's college deep in the country, but counter to her plans, a neighboring prince has determined to make her his wife. Along with two friends, the Prince sneaks into the school disguised as a woman. Comedy and romance ensue, leading to the Prince's eventual unmasking and a deadly serious battle between his father and the Princess's father over how her body will be disposed in marriage. The Prince is wounded in the battle and the Princess is smitten with remorse. While nursing him back to health she is “ultimately transformed from a fierce feminist into a broken nurse” (Buchanan 573) as she anticipates the possibilities of agency through marriage and motherhood. The poem ends with the disbanding of the Princess's school and the reinstallation of its female leaders under patriarchal control.
Household-level dietary quality indicator for countries in nutritional transition: application to vulnerable communities in El Salvador
Authors: Fuster Melissa , Houser Robert F , Messer Ellen , de Fulladolsa Patricia Palma , Deman Hedi , Bermudez Odilia I
Published: April 2013

Objective

To develop a household-level diet quality indicator (HDQI) using the Salvadorian dietary guidelines to assess the dietary quality of households in vulnerable communities in El Salvador.

Design

The Salvadorian dietary guidelines were reviewed and eighteen HDQI components were identified (nine foods and nine nutrients). The components were evaluated using a proportional scoring system from 0 to 1, penalizing over- and under-consumption, where appropriate. The HDQI was validated in consultations with experts in El Salvador and by statistical analyses of the study sample data. Dietary variety and energy, nutrient and food intakes were compared among households above and below the median HDQI score using Student's t test.

Setting

Vulnerable, border communities in El Salvador.

Subjects

Households (n 140) provided food consumption information using an FFQ and sociodemographic data.

Results

The mean HDQI score was 63·5, ranging from 43·6 to 90·0. The indicator showed a positive, significant association with the dietary variety components. The statistical associations of the indicator with the energy and nutrient components were as expected.

Conclusions

Based on the indicator's demonstrated face validity and the results of the expert consultations, the indicator is suggested as a good measure of diet quality for households in El Salvador.
The Empirical Versus DSM-Oriented Approach of the Child Behavior Checklist
Authors: de Wolff Marianne S. , Vogels Anton G. C. , Reijneveld Sijmen A.
Published: April 2013

The DSM-oriented approach of the Child Behavior Checklist (CBCL) is a relatively new classification of problem behavior in children and adolescents. Given the clinical and scientific relevance of the CBCL, this study examines similarities and dissimilarities between the empirical and the DSM-oriented approach of the CBCL. We used data from 7,852 children aged 5 and 6 years, whose parents completed the Dutch version of the CBCL/4–18. Spearman rank order correlations, kappas, and logistical regressions were used to examine the similarities and dissimilarities between empirical and DSM-oriented scales of the CBCL. For Total Problems, Internalizing Problems, and Externalizing Problems, we found a substantial agreement between the two approaches of the CBCL. The DSM-oriented syndromes showed a slight overlap with the empirical syndrome scales. With regard to Total Problems, Internalizing Problems, and Externalizing Problems, the same child and family characteristics were associated with elevated scores in both approaches: sex, ethnicity, parental educational level, family composition, and the physician’s identification of the child’s psychosocial problems. Our study shows that both approaches of the CBCL are meaningfully related, but do not identify exactly the same groups of children as deviant. Future studies should explore the differences between the two approaches by examining the correlates and predictive power of both types of scales.
Dietary arginine from 15 to 35 days of age affects feed intake and carcass yield in White Pekin ducks
Authors: Wang Chao , Xie Ming , Huang Wei , Yu Jun-Ying , Feng Yu-Long , Hou Shui-Sheng
Published: April 2013

An experiment was conducted to investigate the effect of dietary arginine (ARG) provided from 15 to 35 days of age on the feed intake and carcass yield of White Pekin ducks. Sixty 14-day-old White Pekin ducks were allotted to one of three dietary treatments, with 10 males and 10 females per treatment. Birds were kept individually and fed diets containing 0.60, 0.85 or 1.70% ARG for 3 weeks. Ducks that were fed the diet containing 1.70% ARG had greater bodyweight gain (P < 0.05), higher feed intake (P < 0.05), and a lower feed conversion ratio (P < 0.05) than those fed the diet containing 0.60% ARG. The hypothalamic contents of neuropeptide Y and leptin at 35 days of age were not affected by dietary ARG levels. Breast muscle yield increased with each increment of dietary ARG content (P < 0.05), and birds fed the diet containing 1.70% ARG had highest leg muscle yield (P < 0.05) and total muscle yield (P < 0.05); in contrast, the abdominal fat yield was not affected (P > 0.05) by dietary ARG. No interaction between dietary ARG level and sex was observed for the above mentioned indices (P > 0.05). In conclusion, dietary ARG supplementation promoted appetite without changing the concentrations of neuropeptide Y or leptin in hypothalamus, and ARG supplementation stimulated muscle growth, especially breast muscle growth, in growing White Pekin ducks of both sexes.
The kinetics of starch and nitrogen digestion regulate growth performance and nutrient utilisation of broilers fed coarsely ground, sorghum-based diets
Authors: Liu S. Y. , Selle P. H. , Cowieson A. J.
Published: April 2013

A study was conducted to examine the effect of starch and nitrogen digestion kinetics on broiler performance using sorghum-based diets as a model. Three sorghum varieties with red, white and yellow pericarps and three feed forms, mash, intact pellets and reground pellets, constituted a 3 × 3 factorial array of dietary treatments. Starch and nitrogen digestion kinetics were determined using an exponential mathematical model to relate digestion coefficients in the proximal jejunum, proximal ileum and distal ileum with mean retention times in each segment. There were interactions between sorghum variety and feed form for starch and nitrogen digestion kinetics. Steam-pelleting at a conditioning temperature of 90°C (unprocessed mash versus reground pellets) substantially influenced starch digestion rate in red and yellow sorghum-based diets, but not in white sorghum-based diets. Alternatively, with nitrogen digestion rate, there were no significant differences in yellow sorghum-based diets between feed forms but there were in red and white sorghum-based diets. The digestion rate of starch was more rapid than nitrogen, especially in the proximal jejunum. Starch digestion rates were significantly correlated with nitrogen retention but this was not the case with nitrogen digestion rates. The rate of glucose absorption from predicted glycaemic indices was highly correlated with enhanced feed efficiency. Thus this study demonstrates that even under ad libitum feeding regimes, kinetics of starch and protein digestion regulated feed efficiency and nitrogen retention in broiler chickens. The dynamics of starch and protein digestion were more accurate indicators of feed efficiency and nitrogen retention than apparent ileal starch and nitrogen digestibility.
Effects of high hydrostatic pressure on genomic expression profiling of porcine parthenogenetic activated and cloned embryos
Authors: Lin Lin , Luo Yonglun , Sørensen Peter , Prætorius Helle , Vajta Gabor , Callesen Henrik , Pribenszky Csaba , Bolund Lars , Kristensen Torsten Nygård
Published: April 2013

Handmade cloning (HMC) has been used to generate transgenic pigs for biomedical research. Recently, we found that parthenogenetic activation (PA) of porcine oocytes and improved HMC efficiency could be achieved by treatment with sublethal high hydrostatic pressure (HHP). However, the molecular mechanism underlying the effects of HHP treatment on embryonic development is poorly understood and so was investigated in the present study. Thus, in the present study, we undertook genome-wide gene expression analysis in HHP-treated and untreated oocytes, as well as in 4-cell and blastocyst stage embryos derived by PA or HMC. Hierarchical clustering depicted stage-specific genomic expression profiling. At the 4-cell and blastocyst stages, 103 and 163 transcripts were differentially expressed between the HMC and PA embryos, respectively (P < 0.05). These transcripts are predominantly involved in regulating cellular differentiation, gene expression and cell-to-cell signalling. We found that 44 transcripts were altered by HHP treatment, with most exhibiting lower expression in HHP-treated oocytes. Genes involved in embryonic development were prominent among the transcripts affected by HHP. Two of these genes (INHBB and ME3) were further validated by quantitative reverse transcription–polymerase chain reaction. We also observed that HHP treatment activated expression of the imprinting gene DLX5 in 4-cell PA embryos. In conclusion, our genomic expression profiling data suggest that HHP alters the RNA constitution in porcine oocytes and affects the expression of imprinting genes during embryonic development.
Turbulent convection in liquid metal with and without rotation
Authors: King Eric M. , Aurnou Jonathan M.
Published: April 2013

The magnetic fields of Earth and other planets are generated by turbulent, rotating convection in liquid metal. Liquid metals are peculiar in that they diffuse heat more readily than momentum, quantified by their small Prandtl numbers,

. Most analog models of planetary dynamos, however, use moderate

fluids, and the systematic influence of reducing

is not well understood. We perform rotating Rayleigh–Bénard convection experiments in the liquid metal gallium

over a range of nondimensional buoyancy forcing

and rotation periods (
E
). Our primary diagnostic is the efficiency of convective heat transfer

. In general, we find that the convective behavior of liquid metal differs substantially from that of moderate

fluids, such as water. In particular, a transition between rotationally constrained and weakly rotating turbulent states is identified, and this transition differs substantially from that observed in moderate

fluids. This difference, we hypothesize, may explain the different classes of magnetic fields observed on the Gas and Ice Giant planets, whose dynamo regions consist of

and

fluids, respectively.
Evolution of modular intraflagellar transport from a coatomer-like progenitor
Authors: van Dam Teunis J. P. , Townsend Matthew J. , Turk Martin , Schlessinger Avner , Sali Andrej , Field Mark C. , Huynen Martijn A.
Published: April 2013

The intraflagellar transport (IFT) complex is an integral component of the cilium, a quintessential organelle of the eukaryotic cell. The IFT system consists of three subcomplexes [i.e., intraflagellar transport (IFT)-A, IFT-B, and the BBSome], which together transport proteins and other molecules along the cilium. IFT dysfunction results in diseases collectively called ciliopathies. It has been proposed that the IFT complexes originated from vesicle coats similar to coat protein complex (COP) I, COPII, and clathrin. Here we provide phylogenetic evidence for common ancestry of IFT subunits and α, β′, and ε subunits of COPI, and trace the origins of the IFT-A, IFT-B, and the BBSome subcomplexes. We find that IFT-A and the BBSome likely arose from an IFT-B–like complex by intracomplex subunit duplication. The distribution of IFT proteins across eukaryotes identifies the BBSome as a frequently lost, modular component of the IFT. Significantly, loss of the BBSome from a taxon is a frequent precursor to complete cilium loss in related taxa. Given the inferred late origin of the BBSome in cilium evolution and its frequent loss, the IFT complex behaves as a “last-in, first-out” system. The protocoatomer origin of the IFT complex corroborates involvement of IFT components in vesicle transport. Expansion of IFT subunits by duplication and their subsequent independent loss supports the idea of modularity and structural independence of the IFT subcomplexes.