bluuebunny/crossref_metadata_2025_split huggingface dataset:
National proficiency-gain curves for minimally invasive gastrointestinal cancer surgery
Authors: Mackenzie H , Markar S R , Askari A , Ni M , Faiz O , Hanna G B 
Published: November 2015

Abstract

Background
Minimal access surgery for gastrointestinal cancer has short-term benefits but is associated with a proficiency-gain curve. The aim of this study was to define national proficiency-gain curves for minimal access colorectal and oesophagogastric surgery, and to determine the impact on clinical outcomes.

Methods
All adult patients undergoing minimal access oesophageal, colonic and rectal surgery between 2002 and 2012 were identified from the Hospital Episode Statistics database. Proficiency-gain curves were created using risk-adjusted cumulative sum analysis. Change points were identified, and bootstrapping was performed with 1000 iterations to identify a confidence level. The primary outcome was 30-day mortality; secondary outcomes were 90-day mortality, reintervention, conversion and length of hospital stay.

Results
Some 1696, 15 008 and 16 701 minimal access oesophageal, rectal and colonic cancer resections were performed during the study period. The change point in the proficiency-gain curve for 30-day mortality for oesophageal, rectal and colonic surgery was 19 (confidence level 98·4 per cent), 20 (99·2 per cent) and three (99·5 per cent) procedures; the mortality rate fell from 4·0 to 2·0 per cent (relative risk reduction (RRR) 0·50, P = 0·033), from 2·1 to 1·2 per cent (RRR 0·43, P &lt; 0·001) and from 2·4 to 1·8 per cent (RRR 0·25, P = 0·058) respectively. The change point in the proficiency-gain curve for reintervention in oesophageal, rectal and colonic resection was 19 (98·1 per cent), 32 (99·5 per cent) and 26 (99·2 per cent) procedures respectively. There were also significant proficiency-gain curves for 90-day mortality, conversion and length of stay.

Conclusion
The introduction of minimal access gastrointestinal cancer surgery has been associated with a proficiency-gain curve for mortality and major morbidity at a national level. Unnecessary patient harm should be avoided by appropriate training and monitoring of new surgical techniques.
HPLC Determination of Fexofenadine in Human Plasma For Therapeutic Drug Monitoring and Pharmacokinetic Studies
Authors: Helmy S. A. , El Bedaiwy H. M. 
Published: November 2015

AbstractA simple and sensitive method was developed for fexofenadine determination in human plasma by liquid chromatography with ultraviolet detection. Satisfactory separation was achieved on a Hypersil® BDS C18 column (250 × 4.6 mm, 5μm) using a mobile phase comprising 20 mm sodium dihydrogen phosphate‐2 hydrate (pH adjusted to 3 with phosphoric acid)–acetonitrile at a ratio of 52:48, v/v. The elution was isocratic at ambient temperature with a flow rate of 1.0 mL/min. The UV detector was set at 215 nm for the drug and 330 nm for the internal standared (tinidazole). The total time for a chromatographic separation was ~6.5 min. Linearity was demonstrated over the concentration range 0.01–4 μg/mL. The observed within‐ and between‐day assay precision ranged from 0.346 to 13.6%; accuracy varied between 100.4 and 111.2%. This method was successfully applied for therapeutic drug monitoring in patients treated with clinical doses of fexofenadine and for pharmacokinetic studies. Copyright © 2015 John Wiley & Sons, Ltd.
An HPLC method with diode array detector for the simultaneous quantification of chloroquine and desethylchloroquine in plasma and whole blood samples from Plasmodium vivax patients in Vietnam, using quinine as an internal standard
Authors: Van Pham Toi , Pham Nguyen Phuong , Nguyen Duc Khanh Tho , Nguyen Thanh Thuy Nhien , Nguyen Thuy Nha Ca , Pouplin Thomas , Farrar Jeremy , Thwaites Guy E. , Tran Tinh Hien 
Published: November 2015

AbstractA sensitive, simple method for quantification of chloroquine (CQ) and desethylchloroquine (MCQ) in whole blood and plasma from Plasmodium vivax patients has been developed using HPLC with diode array detection (DAD). Solid‐phase extraction on Isolute‐96‐CBA was employed to process 100 μL of plasma/whole blood samples. CQ, MCQ and quinine were separated using a mobile phase of phosphate buffer 25 mm, pH 2.60–acetonitrile (88:12, v/v) with 2 mm sodium perchlorate on a Zorbax SB‐CN 150 × 4.6 mm, 5 μm column at a flow rate of 1.2 mL/min, at ambient temperature in 10 min, with the DAD wavelength of 343 nm. The method was linear over the range of 10–5000 ng/mL for both CQ and MCQ in plasma and whole blood. The limit of detection was 4 ng/mL and limit of quantification was 10 ng/mL in both plasma and blood for CQ and MCQ. The intra‐, inter‐ and total assay precision were <10% for CQ and MCQ in plasma and whole blood. In plasma, the accuracies varied between 101 and 103%, whereas in whole blood, the accuracies ranged from 97.0 to 102% for CQ and MCQ. The method is an ideal technique with simple facilities and instruments, bringing about good separation in comparison with previous methods. © 2016 The Authors Biomedical Chromatography Published by John Wiley & Sons Ltd
Highly Selective Cycloalkane Oxidation in Water with Ruthenium Nanoparticles
Authors: Denicourt‐Nowicki Audrey , Lebedeva Anastasia , Bellini Clément , Roucoux Alain 
Published: November 2015

AbstractRuthenium(0) nanospecies, with small sizes of approximately 1.75 nm, proved to be active, selective, and retrievable nanocatalysts for the oxidation of various cycloalkanes in neat water, using tert‐butylhydroperoxide as an oxidant and at room temperature. Relevant conversions and selectivities (up to 97 %) were achieved towards the major formation of the ketone product, which constitutes a high‐value‐added intermediate for polymer or fine chemistry. The lifetime of the catalyst has been checked over several runs, with no significant loss of activity and selectivity. Kinetic and mechanistic investigations proved that radical species are involved in the oxidation process. A literature comparison showed the relevance and the usefulness of the present ruthenium nanocatalytic system in a benign reaction context.
Band Gap Energies and Photocatalytic Properties of CdS and Ag/CdS Nanoparticles for Azo Dye Degradation
Authors: Fard Narges Elmi , Fazaeli Reza , Ghiasi Reza 
Published: November 2015

AbstractCdS nanoparticles were synthesized by the ultrasonic‐assisted sol‐gel method and characterized by X‐ray diffraction (XRD). The Ag‐doped CdS (Ag/CdS) nanoparticles were also synthesized by the ultrasonic‐assisted sol‐gel method and characterized by XRD, X‐ray fluorescence spectrometry, scanning electron microscopy, and energy‐dispersive X‐ray analysis. The calculated sizes and experimental results are in good agreement. The calculated band‐gaps of CdS and Ag/CdS were found to be 2.62 and 2.46 eV, respectively. Photocatalytic degradation of Direct Red 264 azo dye was investigated with CdS and Ag/CdS under UV‐C and visible light irradiation. Experimental results indicate that the degradation rate of DR 264 follows pseudo second‐order kinetics. Also, the intraparticle diffusion coefficients of CdS and Ag/CdS were determined.
Dioxygen Binding in the Active Site of Histone Demethylase JMJD2A and the Role of the Protein Environment
Authors: Cortopassi Wilian A. , Simion Robert , Honsby Charles E. , França Tanos C. C. , Paton Robert S. 
Published: November 2015

AbstractJMJD2A catalyses the demethylation of di‐ and trimethylated lysine residues in histone tails and is a target for the development of new anticancer medicines. Mechanistic details of demethylation are yet to be elucidated and are important for the understanding of epigenetic processes. We have evaluated the initial step of histone demethylation by JMJD2A and demonstrate the dramatic effect of the protein environment upon oxygen binding using quantum mechanics/molecular mechanics (QM/MM) calculations. The changes in electronic structure have been studied for possible spin states and different conformations of O2, using a combination of quantum and classical simulations. O2 binding to this histone demethylase is computed to occur preferentially as an end‐on superoxo radical bound to a high‐spin ferric centre, yielding an overall quintet ground state. The favourability of binding is strongly influenced by the surrounding protein: we have quantified this effect using an energy decomposition scheme into electrostatic and dispersion contributions. His182 and the methylated lysine assist while Glu184 and the oxoglutarate cofactor are deleterious for O2 binding. Charge separation in the superoxo‐intermediate benefits from the electrostatic stabilization provided by the surrounding residues, stabilizing the binding process significantly. This work demonstrates the importance of the extended protein environment in oxygen binding, and the role of energy decomposition in understanding the physical origin of binding/recognition.
Stabilization of the Low‐Spin State in a Mononuclear Iron(II) Complex and High‐Temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding
Authors: Zheng Sipeng , Reintjens Niels R. M. , Siegler Maxime A. , Roubeau Olivier , Bouwman Elisabeth , Rudavskyi Andrii , Havenith Remco W. A. , Bonnet Sylvestre 
Published: November 2015

AbstractThe tetrapyridyl ligand bbpya (bbpya=N,N‐bis(2,2′‐bipyrid‐6‐yl)amine) and its mononuclear coordination compound [Fe(bbpya)(NCS)2] (1) were prepared. According to magnetic susceptibility, differential scanning calorimetry fitted to Sorai’s domain model, and powder X‐ray diffraction measurements, 1 is low‐spin at room temperature, and it exhibits spin crossover (SCO) at an exceptionally high transition temperature of T1/2=418 K. Although the SCO of compound 1 spans a temperature range of more than 150 K, it is characterized by a wide (21 K) and dissymmetric hysteresis cycle, which suggests cooperativity. The crystal structure of the LS phase of compound 1 shows strong NH⋅⋅⋅S intermolecular H‐bonding interactions that explain, at least in part, the cooperative SCO behavior observed for complex 1. DFT and CASPT2 calculations under vacuum demonstrate that the bbpya ligand generates a stronger ligand field around the iron(II) core than its analogue bapbpy (N,N′‐di(pyrid‐2‐yl)‐2,2′‐bipyridine‐6,6′‐diamine); this stabilizes the LS state and destabilizes the HS state in 1 compared with [Fe(bapbpy)(NCS)2] (2). Periodic DFT calculations suggest that crystal‐packing effects are significant for compound 2, in which they destabilize the HS state by about 1500 cm−1. The much lower transition temperature found for the SCO of 2 compared to 1 appears to be due to the combined effects of the different ligand field strengths and crystal packing.
Oxygen‐Assisted Synthesis of Mesoporous Palladium Nanoparticles as Highly Active Electrocatalysts
Authors: Li Cuiling , Jiang Bo , Imura Masataka , Umezawa Naoto , Malgras Victor , Yamauchi Yusuke 
Published: November 2015

AbstractMesoporous Pd nanoparticles (MPNs) enclosed by high‐index facets have been successfully prepared by taking advantage of successive oxygen adsorption and desorption caused by the oxidative etching effect. The as‐prepared MPNs exhibit excellent performance toward formic acid electro‐oxidation, which is due to the synergetic effect between the diffusion‐feasible tubular mesochannels and the high index facets.
Addressing the Glycine‐Rich Loop of Protein Kinases by a Multi‐Facetted Interaction Network: Inhibition of PKA and a PKB Mimic
Authors: Lauber Birgit S. , Hardegger Leo A. , Asraful Alam K. , Lund Bjarte A. , Dumele Oliver , Harder Michael , Kuhn Bernd , Engh Richard A. , Diederich François 
Published: November 2015

AbstractProtein kinases continue to be hot targets in drug discovery research, as they are involved in many essential cellular processes and their deregulation can lead to a variety of diseases. A series of 32 enantiomerically pure inhibitors was synthesized and tested towards protein kinase A (PKA) and protein kinase B mimic PKAB3 (PKA triple mutant). The ligands bind to the hinge region, ribose pocket, and glycine‐rich loop at the ATP site. Biological assays showed high potency against PKA, with Ki values in the low nanomolar range. The investigation demonstrates the significance of targeting the often neglected glycine‐rich loop for gaining high binding potency. X‐ray co‐crystal structures revealed a multi‐facetted network of ligand–loop interactions for the tightest binders, involving orthogonal dipolar contacts, sulfur and other dispersive contacts, amide–π stacking, and H‐bonding to organofluorine, besides efficient water replacement. The network was analyzed in a computational approach.
Calibration of interphase fluorescence in situ hybridization cutoff by mathematical models
Authors: Du Qinghua , Li Qingshan , Sun Daochun , Chen Xiaoyan , Yu Bizhen , Ying Yi 
Published: November 2015

AbstractFluorescence in situ hybridization (FISH) continues to play an important role in clinical investigations. Laboratories may create their own cutoff, a percentage of positive nuclei to determine whether a specimen is positive or negative, to eliminate false positives that are created by signal overlap in most cases. In some cases, it is difficult to determine the cutoff value because of differences in both the area of nuclei and the number of signals. To address these problems, we established two mathematical models using probability theory. To verify these two models, normal disomy cells from healthy individuals were used to simulate cells with different numbers of signals by hybridization with different probes. We used an X/Y probe to obtain the average distance between two signals and the probability of signal overlap in different nuclei area. Frequencies of all signal patterns were scored and compared with theoretical frequencies, and models were assessed using a goodness of fit test. We used five BCR/ABL1‐positive samples, 20 BCR/ABL1‐negative samples and two samples with ambiguous results to verify the cutoff calibrated by these two models. The models were in agreement with experimental results. The dynamic cutoff can classify cases in routine analysis correctly, and it can also correct for influences from nuclei area and the number of signals in some ambiguous cases. The probability models can be used to assess the effect of signal overlap and calibrate the cutoff. © 2015 International Society for Advancement of Cytometry
More rain, less soil: long‐term changes in rainfall intensity with climate change
Authors: Burt Tim , Boardman John , Foster Ian , Howden Nicholas 
Published: November 2015

AbstractThis commentary discusses the role of long‐term climate change in driving increases in soil erosion. Assuming that land use and management remain effectively constant, we discuss changes in the ability of rainfall to cause erosion (erosivity), using long daily rainfall data sets from southeast England. An upward trend in mean rainfall per rain day is detected at the century‐plus timescale. Implications for soil erosion and sediment delivery are discussed and evidence from other regions reviewed. We conclude that rates of soil erosion may well increase in a warmer, wetter world. Copyright © 2015 John Wiley & Sons, Ltd.
Some Remarks on Rainbow Connectivity
Authors: Kamčev Nina , Krivelevich Michael , Sudakov Benny 
Published: November 2015

AbstractAn edge (vertex) colored graph is rainbow‐connected if there is a rainbow path between any two vertices, i.e. a path all of whose edges (internal vertices) carry distinct colors. Rainbow edge (vertex) connectivity of a graph G is the smallest number of colors needed for a rainbow edge (vertex) coloring of G. In this article, we propose a very simple approach to studying rainbow connectivity in graphs. Using this idea, we give a unified proof of several known results, as well as some new ones.
Functional outcomes after different types of transoral supraglottic laryngectomy
Authors: Piazza Cesare , Barbieri Diego , Del Bon Francesca , Grazioli Paola , Perotti Pietro , Paderno Alberto , Frittoli Barbara , Mazza Giancarlo , Penco Sara , Gaggero Giovanna , Nicolai Piero , Peretti Giorgio 
Published: November 2015

Objectives/HypothesisTo seek a correlation between the four types of transoral supraglottic laryngectomies (TSLs) according to the European Laryngological Society (ELS) and postoperative morbidity.Study DesignRetrospective case series at an academic institution.MethodsChart review was done for 96 patients affected by T1–T3 supraglottic cancers (28 pT1, 46 pT2, 22 pT3) treated by TSL (29 type I, 14 type II, 35 type III, 18 type IV) with CO2 laser. Five‐year overall survival (OS), disease‐specific survival (DSS), local control with laser alone (LCL), and organ preservation (OP) were calculated by Kaplan‐Meier curves. Thirty‐six patients were submitted to swallowing evaluation by M. D. Anderson Dysphagia Inventory (MDADI), videoendoscopy of swallow (VEES), and videofluoroscopy (VFS). Hospitalization, tracheotomy, nasogastric feeding tube (NGFT), and complications were compared between type I–II versus III–IV TSLs for the entire series. MDADI and VEES/VFS scores were compared in the subgroup of 36 patients.ResultsFive‐year OS, DSS, LCL, and OP rates were 69%, 85.9%, 89.2%, and 92.6%. Mean hospitalization was 9 days, tracheotomy was required in 7% of patients, an NGFT was required in 33%, and 11% experienced complications. Type III–IV TSLs were associated with increased hospitalization (P < .001), more NGFTs (P = .001), and 90% of complications (P = .021). Aspiration was seen in 0% and 9% of type I–II TSLs, and in 7% and 43% of type III–IV TSLs by VEES and VFS, respectively.ConclusionsType III–IV TSLs present higher morbidity and complications, thus confirming the utility of the ELS classification in preoperative counseling and therapeutic planning.Level of Evidence4 Laryngoscope, 126:1131–1135, 2016
Light on a beam splitter: More randomness with single photons
Authors: Oberreiter Lukas , Gerhardt Ilja 
Published: November 2015

AbstractOne of the most fundamental quantum random number generators is implemented with light impinging onto a beam splitter, and two single photon detectors at its output. Often, this generator is described as “a photon which takes one or other path towards a detector”. The input state of light in conjunction with the detector response is relevant for the amount, the pattern, and the correlation of the generated clicks. Only a fraction of all generator outcomes, the min‐entropy, can be used as a further resource for true randomness. This paper addresses the difference in the common description with incoming single photons and the often implemented scheme with a weak coherent light source, such as an attenuated laser. For this very fundamental and widely used configuration the amount of usable entropy is compared. If single photons from an anti‐bunched light source are supplied, the amount of entropy is higher than for the case of a supplied coherent state – although the latter can be arbitrarily bright unlike the single photon source.
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On the Environmental and Electrical Bias Stability of Radical Polymer Conductors in the Solid State
Authors: Baradwaj Aditya G. , Rostro Lizbeth , Boudouris Bryan W. 
Published: November 2015

Radical polymers are emerging as a promising class of electronically active macromolecules for solid‐state organic electronic applications due to their synthetic flexibility and scalability; however, the electrical and chemical stability of radical polymer thin films has yet to be established. Here, it is demonstrated that the model radical polymer, poly(2,2,6,6‐tetramethylpiperidinyloxy methacrylate) (PTMA), shows excellent solid‐state electrochemical stability when exposed to both bias stressing and varying amounts of moisture in the environment. Specifically, PTMA thin films show consistent performance when continuously swept across a variety of voltage ranges. Furthermore, PTMA remains stable when exposed to a constantly applied bias for 20 h. These two key results demonstrate the stability of the open‐shell repeat unit and the reversibility of the chemical oxidation–reduction (redox) reaction that facilitates charge transport. Additionally, PTMA thin films that are exposed to a range of relative humidity values for 2 h retained consistent electronic performance before and after humidity exposure. This highlights that exposure to water vapor does not decrease the robustness associated with the nitroxide radical. These results establish the stoutness associated with radical polymers and highlight the potential for radical polymers to be implemented in a number of advanced organic electronic technologies.
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Reliability of eccentric position of the pedicle instead of central position in a thoracodorsal artery perforator flap
Authors: Kim Youn Hwan , Lee Han Earl , Lee Jang Hyun , Kim Jeong Tae , Kim Sang Wha 
Published: November 2015

IntroductionTo obtain longer vascular pedicle in perforator flaps, surgeons often use eccentrically rather than centrally located perforators. The aim of this study was to compare the safety and reliability of thoracodorsal artery perforator (TDAP) flaps harvested with centrally or eccentrically located perforators.MethodsBetween January 2008 and March 2012, 100 TDAP flaps were used to reconstruct the lower extremity defects. Flaps longer than 10 cm, with a single musculocutaneous perforator, and one artery‐one vein anastomoses were included. The cases were divided into two groups according to perforator location; Central perforators in 60 cases (group 1), and peripheral perforators in 40 cases (group 2). Total pedicle length was between the points where the perforator enters the flap to the end of the pedicle. Real pedicle length was from flap margin to the end of the pedicle. The flap dimension, total pedicle length, real pedicle length, and flap related complications were measured.ResultsThe flaps were smaller in group 1 than in group 2 (159.6 ± 94.08 vs.189.95 ± 134.30 cm2, P = 0.455). Total pedicle length was almost the same (12.12 ± 1.57 vs.12.88 ± 2.10 cm, P = 0.420), but the mean real pedicle length was longer in group 2 (6.13 ± 1.33 vs.11.65 ± 2.08 cm, P < 0.05).There were 4 cases of partial loss of flap in group 1 and 3 partial loss and one total flap loss in group 2 without significant difference (P = 0.547).ConclusionsUsing eccentrically located perforators is simple method of extending real pedicle length, but there have been concerns regarding flap perfusion and distal vascularity. Our findings suggest that, in TDAP flaps, both eccentric and central perforator are safe options. © 2014 Wiley Periodicals, Inc. Microsurgery 37:44–48, 2017.
Hydroxytyrosol, a product from olive oil, reduces colon cancer growth by enhancing epidermal growth factor receptor degradation
Authors: Terzuoli Erika , Giachetti Antonio , Ziche Marina , Donnini Sandra 
Published: November 2015

ScopeWe studied the effects and mechanism of 2‐(3,4‐dihydroxyphenil)ethanol (or hydroxytyrosol, HT), a polyphenol from extra virgin olive oil, investigating the regulation of epidermal growth factor receptor (EGFR) expression in colon tumour cells.Methods and resultsWe demonstrate that HT significantly downregulates EGFR expression in human colorectal adenocarcinoma cells HT‐29, CaCo2, and WiDr, and in HT‐29 xenografts. HT accelerates EGFR degradation by reducing its half‐life. Specifically, HT induces EGFR ubiquitination that is mediated by phosphorylation at pY1045, the docking site for Cbl, thereby enabling receptor ubiquitination and degradation. Pretreatment with either the lysosomal inhibitor chloroquine, or the proteasomal inhibitor MG132 blocks HT‐induced EGFR downregulation. In colon cancer cells, EGFR downregulation by HT is associated with reduced cell proliferation. Tumour growth and EGFR expression levels are also decreased by HT treatment in HT‐29 xenograft.ConclusionWe conclude that HT downregulates EGFR expression via lysosomal and proteasomal degradation, activated by HT‐induced EGFR phosphorylation at pY1045 and increased Cbl activity. Cbl activation induces, in turn, EGFR ubiquitination. Our results reveal a new mechanism for HT's antitumour effects that may be important for colon tumour prevention and treatment.