bluuebunny/crossref_metadata_2025 huggingface dataset:
The Role of the Interface in Thin Film and Droplet Accelerated Reactions Studied by Competitive Substituent Effects
Authors: Li Yafeng , Yan Xin , Cooks R. Graham
Published: February 2016

Based on a study of competitive substituent effects in a Claisen–Schmidt reaction, interfacial effects have been shown to play an important role in accelerated reactions that occur in thin films and droplets. A role for the interface in an accelerated C−C bond‐formation reaction between 6hydroxy‐1‐indanone and aromatic aldehydes is indicated by cooperative interactions between p‐methylbenzaldehyde and p‐nitrobenzaldehyde. Additional acceleration over that occurring in bulk reactions is seen for p‐methylbenzaldehyde, but only in the presence of p‐nitrobenzaldehyde. A decrease in the degree of acceleration is detected when the reaction is forced electrostatically to occur inside the thin film, and the interface is shown to participate in the accelerated reactions. This experimental evidence for interfacial thin film and droplet acceleration supports a recent model and builds on earlier work which locates molecules within evaporating droplets in electrosprays.
New Isolated‐Pentagon‐Rule and Skeletally Transformed Isomers of C100 Fullerene Identified by Structure Elucidation of their Chloro Derivatives
Authors: Wang Song , Yang Shangfeng , Kemnitz Erhard , Troyanov Sergey I.
Published: February 2016

High‐temperature chlorination of C100 fullerene followed by X‐ray structure determination of the chloro derivatives enabled the identification of three isomers of C100 from the fullerene soot, specifically numbers 18, 425, and 417, which obey the isolated pentagon rule (IPR). Among them, isomers C1‐C100(425) and C2‐C100(18) afforded C1‐C100(425)Cl22 and C2‐C100(18)Cl28/30 compounds, respectively, which retain their IPR cage connectivities. In contrast, isomer C2v‐C100(417) gives Cs‐C100(417)Cl28 which undergoes a skeletal transformation by the loss of a C2 fragment, resulting in the formation of a nonclassical (NC) C1‐C98(NC)Cl26 with a heptagon in the carbon cage. Most probably, two nonclassical C1‐C100(NC)Cl18/22 chloro derivatives originate from the IPR isomer C1‐C100(382), although both C1‐C100(344) and even nonclassical C1‐C100(NC) can be also considered as the starting isomers.
Phase appearance during polymerization of fluorinated polyimide monomers and deposition into the microscopic‐scale trenches in supercritical carbon dioxide
Authors: Haruki Masashi , Oda Asuka , Wasada Atsuhiko , Hasegawa Yumi , Kihara Shin-ichi , Takishima Shigeki
Published: February 2016

The phase appearance during the synthesis of fluorinated polyamic acid (PAA) from 2,2‐bis(3,4‐anhydrodicarboxyphenyl)‐hexafluoropropane (6FDA) and 2,2′‐bis(trifluoromethyl)−4,4′‐diaminobiphenyl (TFDB) in supercritical carbon dioxide (scCO2) was investigated to obtain fundamental data for the deposition of fluorinate polyimides (PI) using scCO2. All polymerizations were carried out at 30 MPa for 60 min. The experimental temperatures ranged from 50 to 70 °C, and each of the monomer concentrations ranged from 0.67 × 10−5 to 3.3 × 10−5 mol cm−3. The holding time of the transparent phases, which was the time from the beginning of the polymerization to the appearance of a turbid phase, was increased with either a decrease in the polymerization temperature or a decrease in the initial monomer concentration. The holding time of the fluorinated PAA was longer than that of the monomers of Kapton‐type PAA. The deposition of PI into the microscopic‐scale trenches that had formed on the silicon wafer was successful in scCO2. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43334.
On the inhomogeneous hydration kinetics and stiffness evolution of HNBR‐MgO reactive elastomer composites
Authors: Qu Meng , Lou Yucun , Han Dingzhi , Gewily Ahmed Amr , Robisson Agathe
Published: February 2016

Swellable elastomers are widely used in oilfield industry for sealing and zonal isolation applications. These materials need to sustain a large amount of external load after swelling. A newly developed reactive hydrogenated nitrile butadiene rubber (HNBR) based elastomer composite with magnesium oxide (MgO) as filler can swell and stiffen when exposed to water, which makes it ideal for oil field applications. However, both the filler hydration and the stiffness evolution inside this composite material are observed to be highly inhomogeneous even for samples on the length scale of millimeters. To understand this coupled diffusion‐hydration process is critical for applications of these materials with larger length scales. In this work, the hydration kinetics and stiffness evolution of the HNBR‐MgO composite are quantitatively studied on microscopic level. The extent of MgO hydration along the thickness of the sample are measured at the different stage of swelling. These results are used to determine the diffusion coefficient of water inside the composite. The diffusivity increases orders of magnitude after the filler hydration. In addition, the modulus change is non‐proportional to the degree of filler hydration as demonstrated by instrumented grid indentation on the hydrated composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43420.
Practicing handoffs early: Applying a clinical framework in the anatomy laboratory
Authors: Lazarus Michelle D. , Dos Santos Jason A. , Haidet Paul M. , Whitcomb Tiffany L.
Published: February 2016

The anatomy laboratory provides an ideal environment for the integration of clinical contexts as the willed‐donor is often regarded as a student's “first patient.” This study evaluated an innovative approach to peer teaching in the anatomy laboratory using a clinical handoff context. The authors introduced the “Situation, Background, Assessment, Recommendation” (SBAR) handoff framework within the anatomy laboratory. Study participants included 147 second‐year medical students completing the head and neck portion of an anatomy course. The authors used mixed methods to evaluate the impact of the anatomic SBAR on the student anatomy laboratory experience. Qualitative analysis of student evaluations revealed three themes which emerged from students' summaries of their anatomic handoff experiences: Learning‐by‐teaching; Acquiescing to doing more with less; and Distrust of the peer handoff process. All the themes demonstrated that the anatomic handoff encouraged students' focus on the knowledge preparation and reflection. Closed question analysis suggested that that students' perceptions of handoff usefulness were tied to deeper learning strategies. The handoff provided a mechanism for promoting students' focus on anatomical relationships and facilitated students' learning of transferable clinical skills. Together, these results suggest that the introduction of a handoff process in anatomy education provided both a mechanism for learning anatomy and a unique opportunity for early exposure to an essential clinical skill. This clinical and basic science integration may serve as a vertical integration thread which can be woven throughout undergraduate medical education. Future study will focus on exploring the long‐term impacts and learning outcomes of this integration. Anat Sci Educ 9: 476–487. © 2016 American Association of Anatomists.
Robust Repetitive Control and Disturbance Rejection Based on Two‐Dimensional Model and Equivalent‐Input‐Disturbance Approach
Authors: Yu Pan , Wu Min , She Jinhua , Lei Qi
Published: February 2016

A new configuration of a modified repetitive‐control system has been devised for a class of strictly proper plants that suppresses exogenous disturbances and uncertainties in the dynamics of the plant. It extends the applicability of the control system. The system consists of four parts: a two‐dimensional augmented model of the plant, which takes into account the difference in characteristics between continuous control and discrete learning in repetitive control; an equivalent‐input‐disturbance estimator; a state observer; and a state‐feedback controller. A robust‐stability condition expressed in terms of a linear matrix equality is used to determine the gains of the observer and the controller. Finally, a comparison of our method with repetitive control based on linear active disturbance rejection control (LADRC) shows how effective our method is and that it is superior to LADRC‐based repetitive control.
Fahrdynamische Verträglichkeit
Authors: Franz Stefan
Published: February 2016

Ein Brückenstatiker gerät leicht unter Druck, wenn der Bauherr die nach ZTV‐ING geforderte Bewertung der “fahrdynamischen Verträglichkeit” der gewählten Ausgleichsgradiente einfordert. In dem schmalen Korridor einer zulässigen Mindest‐ bzw. Maximaldicke der Schutzschicht müssen herstellungsbedingte Bauungenauigkeiten der Fahrbahnplatte ausgeglichen werden. Das Bestreben seitens der ausführenden Baufirma ist, dass möglichst keine zeit‐ und kostenintensiven Fräs‐ bzw. Spachtelarbeiten mit Betonersatzsystemen erforderlich werden. Nicht selten wird dann die für das Ergebnis so bedeutende Forderung nach fahrdynamischer Verträglichkeit aus den Augen verloren, zumal hierfür keine Grenzwerte oder Kriterien angegeben sind.

In diesem Beitrag wird ein einfaches Berechnungsverfahren vorgestellt, das eine objektive Bewertung der fahrdynamischen Qualität der gewählten Ausgleichsgradiente zulässt. Die hierzu erforderlichen Grenzwerte und Berechnungsparameter werden zur Verwendung empfohlen. Es sind ferner Faustformeln angegeben, die eine erste Risikobewertung ermöglichen und ggf. genauere Untersuchungen entbehrlich machen.

Driving dynamics compatibility

The evaluation of "driving dynamics compatibility” of a compensating altitude profile according to ZTV‐ING is a particular challenge with respect to the verification process. The minimum and maximum thickness of the protection layer of the pavement is strictly regulated. However, this layer must compensate production‐related construction tolerances of the deck. The construction company wants to avoid time‐ and cost‐intensive milling and filling work with concrete replacement systems. Therefore, the contractors and the clients lose sight of the required driving dynamics comparability. On the other hand, there are no limitations or criteria specified for this purpose. In this paper, a simple calculation method is presented which allows an objective evaluation of driving dynamics quality of the chosen compensating altitude profile. Demanded limits and calculation parameters are recommended for use. Furthermore, empirical formulas are specified which allow an initial risk assessment and more detailed investigations can possibly be avoided.
Design‐und‐Build‐Projekt: Planung und Bau einer Messwarte mit Laborgebäude
Authors: Dürr André , Brendel Christiane , Borsutzky Robert , Giesa Ingo
Published: February 2016

Design und Build‐Vergaben sind für Bauherren insbesondere dann interessant, wenn kurze Ausführungsfristen für die Fertigstellung und Inbetriebnahme von Gebäuden realisiert werden müssen und die Bauvorhaben einen erhöhten Komplexitätsgrad aufweisen. Unter diesen Voraussetzungen entscheiden sich Bauherren des Öfteren dafür, getrennte Planungs‐, Vergabe‐ und Ausführungsabläufe mit den erforderlichen Schnittstellenkoordinationen aus Effizienzgründen in einem Paket zu vergeben. Beim Neubau einer dreistöckigen Messwarte mit angeschlossenen Laborgebäude für eine neue Produktionsanlage von Toluoldiisocyanat (TDI) am Standort Ludwigshafen hat die BASF SE daher die HOCHTIEF Building GmbH mit einem Design und Build‐Projekt beauftragt. Die Planung wurde dabei federführend durch die Abteilung Consult IKS Energy der HOCHTIEF Engineering GmbH am Standort Frankfurt durchgeführt. Die Planung umfasste dabei teilweise die Entwurfs‐ und Genehmigungsplanung sowie die vollständige Ausführungsplanung für alle bautechnisch erforderlichen Planungsgewerke, angefangen von der Objektplanung über die Tragwerksplanung und Fassadenplanung bis hin zu bauphysikalischen Nachweisen und der TGA‐ und Laborplanung. Darüber hinaus musste der auf einer Pfahlgründung in Massivbauweise errichtete Gebäudekomplex druckwellenfest ausgelegt werden. Bei der Gebäudeauslegung und Planung waren für den Notfall zusätzlich Anforderungen zur Gasdichtheit inklusive einer gebäudeinternen Atemluftversorgung zu berücksichtigen.

Design‐and‐Build Project: Design and construction of a control room with laboratory

Design and build contracts are of particular interest for clients if tight schedule requirements for the completion and commissioning of buildings have to be considered and the projects have a high level of complexity. With these preconditions clients rather decide to award separate planning, procurement and construction processes with all necessary interface coordination to one contractor for reasons of efficiency. BASF SE has awarded a design and build contract to HOCHTIEF Building GmbH for a three‐storey control room building with laboratory for a new production plant of toluoldiisocyanat (TDI) at the main BASF site in Ludwighafen, Germany. The planning was performed by the department Consult IKS Energy of the HOCHTIEF Engineering GmbH in Frankfurt. The scope of planning included partially the design engineering and the approval planning as well as the full detail planning for all disciplines (architectural planning, structural and façade engineering, building physics, HVAC engineering and laboratory planning). Furthermore, the reinforced concrete structure built on a pile foundation had to be designed blast wave resistant. In addition the requirement for gas tightness had to be considered in the building design, including the execution of an internal air supply in the case of emergency.
A rapid and sensitive LC–MS/MS method for quantification of quercetin‐3‐O‐β‐d‐glucopyranosyl‐7‐O‐β‐d‐gentiobioside in plasma and its application to a pharmacokinetic study
Authors: He Xin , Tao Guizhou , Gao Hang , Li Keyan , Zhang Yazhuo , Sun Limin , Zhang Yingjie
Published: February 2016

A rapid and sensitive LC–MS/MS method with good accuracy and precision was developed and validated for the pharmacokinetic study of quercetin‐3‐O‐β‐d‐glucopyranosyl‐7‐O‐β‐d‐gentiobioside (QGG) in Sprague–Dawley rats. Plasma samples were simply precipitated by methanol and then analyzed by LC–MS/MS. A Venusil® ASB C18 column (2.1 × 50 mm, i.d. 5 μm) was used for separation, with methanol–water (50:50, v/v) as the mobile phase at a flow rate of 300 μL/min. The optimized mass transition ion‐pairs (m/z) for quantitation were 787.3/301.3 for QGG, and 725.3/293.3 for internal standard. The linear range was 7.32–1830 ng/mL with an average correlation coefficient of 0.9992, and the limit of quantification was 7.32 ng/mL. The intra‐ and inter‐day precision and accuracy were less than ±15%. At low, medium and high quality control concentrations, the recovery and matrix effect of the analyte and IS were in the range of 89.06–92.43 and 88.58–97.62%, respectively. The method was applied for the pharmacokinetic study of QGG in Sprague–Dawley rats. Copyright © 2016 John Wiley & Sons, Ltd.
Porphyrin/Platinum(II) C^N^N Acetylide Complexes: Synthesis, Photophysical Properties, and Singlet Oxygen Generation
Authors: Jana Atanu , McKenzie Luke , Wragg Ashley B. , Ishida Masatoshi , Hill Jonathan P. , Weinstein Julia A. , Baggaley Elizabeth , Ward Michael D.
Published: February 2016

A new class of substituted porphyrins has been developed in which a different number of cyclometalated PtII C^N^N acetylides and polyethylene glycol (PEG) chains are attached to the meso positions of the porphyrin core, which are meant for photophysical, electrochemical, and in vitro light‐induced singlet oxygen (1O2) generation studies. All of these ZnII porphyrin–PtII C^N^N acetylide conjugates show moderate to high (ΦΔ=0.55 to 0.63) singlet oxygen generation efficiency. The complexes are soluble in organic solvents but, despite the PEG substituents, slowly aggregate in aqueous solvent systems. These conjugates also exhibit interesting photophysical properties, including near‐complete photoinduced energy transfer (PEnT) through the rigid acetylenic bond(s) from the PtII C^N^N antenna units to the ZnII porphyrin core, which shows sensitized luminescence, as shown by quenching of PtII C^N^N‐based luminescence. Electrochemical measurements show a set of redox processes that are approximately the sum of what is observed for the PtII C^N^N acetylide and ZnII porphyrin units. UV/Vis spectroscopic properties are supported by DFT calculations.
Lewis Acid Catalyzed Synthesis of Cyanidophosphates
Authors: Bläsing Kevin , Ellinger Stefan , Harloff Jörg , Schulz Axel , Sievert Katharina , Täschler Christoph , Villinger Alexander , Zur Täschler Cornelia
Published: February 2016

Salts containing new cyanido(fluorido)phosphate anions of the general formula [PF6−n(CN)n]− (n=1–4) were synthesized by a very mild Lewis‐acid‐catalyzed synthetic protocol and fully characterized. All [PF6−n(CN)n]− (n=1–4) salts could be isolated on a preparative scale. It was also possible to detect the [PF(CN)5]− but not the [P(CN)6]− anion. The best results with respect to purity, yield, and low cost were obtained when the F−/CN− substitution reactions were carried out in ionic liquids.
Lipid Nanotube Tailored Fabrication of Uniquely Shaped Polydopamine Nanofibers as Photothermal Converters
Authors: Ding Wuxiao , Chechetka Svetlana A. , Masuda Mitsutoshi , Shimizu Toshimi , Aoyagi Masaru , Minamikawa Hiroyuki , Miyako Eijiro
Published: February 2016

Helically coiled and linear polydopamine (PDA) nanofibers were selectively fabricated with two different types of lipid nanotubes (LNTs) that acted as templates. The obtained coiled PDA‐LNT hybrid showed morphological advantages such as higher light absorbance and photothermal conversion effect compared to a linear counterpart. Laser irradiation of the coiled PDA‐LNT hybrid induced a morphological change and subsequent release of the encapsulated guest molecule. In cellular experiments, the coiled PDA‐LNT efficiently eliminated HeLa cells because of its strong affinity with the tumor cells. This work illustrates the first approach to construct characteristic morphologies of PDA nanofibers using LNTs as simple templates, and the coiled PDA‐LNT hybrid exhibits attractive photothermal features derived from its unique coiled shape.
Messung und thermodynamische Bewertung von VOC‐ und Wasser‐Adsorptionsisothermen an granulierten Aktivkohlen
Authors: Fickinger Daniel , Zellner Stefan , Kimmerle Klaus , Schippert Egbert
Published: February 2016

Mit einer Versuchsanlage wurden Adsorptionsisothermen auf granulierten Aktivkohlen bei Temperauren zwischen 50 °C und 130 °C gemessen. Trotz der kinetischen Überlegenheit von Aktivkohlefasergewebe, das ursprünglich ausschließlich vermessen wurde, konnte mittels einer neuen Probenaufnahme für granulierte Aktivkohle gezeigt werden, dass mit der Versuchsanlage auch Adsorptionsisothermen an diesen Materialien schnell, kostengünstig und in einem großen Messbereich bestimmt werden können. Adsorptionsisothermen wurden mit dem ALIc‐Modell sowie den Modellen von Dubinin‐Asthakov, Toth und Do&Do angepasst und die Modelle bzgl. Anpassungsgüte und anderer Kriterien verglichen und bewertet.
Predictors of Medical Management in Patients Undergoing Elective Cardiac Catheterization for Chronic Ischemic Heart Disease
Authors: Atreya Auras R. , Sivalingam Senthil K. , Arora Sonali , Kashef Mohammad Amin , Fitzgerald Janice , Visintainer Paul , Lotfi Amir , Rothberg Michael B.
Published: February 2016

Background

Compared with medical therapy, percutaneous coronary intervention (PCI) does not reduce mortality or myocardial infarction in patients with stable angina. Therefore, PCI should be guided by refractory anginal symptoms and not just lesion characteristics.

Hypothesis

We hypothesized that angiographic lesion characteristics and stress test results would have a greater role in the decision to proceed with PCI than would symptom severity.

Methods

We performed a retrospective cohort study of patients undergoing elective cardiac catheterization and possible PCI at an academic medical center. Anginal symptoms, optimal medical therapy, antianginal therapy, stress test results, and angiographic lesions (including American College of Cardiology/American Heart Association [ACC/AHA] lesion type) were analyzed. Logistic regression was used to determine predictors of medical management among patients not referred for coronary artery bypass surgery.

Results

Of the 207 patients with obstructive lesions amenable to PCI, 163 underwent PCI and 44 were referred to medical therapy. In the multivariable logistic model, the following variables were associated with medical management: advancing age (odds ratio [OR] per 1 year: 0.94, 95% confidence interval [CI]: 0.91‐0.98), chronic kidney disease (OR: 0.23, 95% CI: 0.06‐0.95), distal location (OR: 0.21, 95% CI: 0.09‐0.48), and ACC/AHA type C lesion (OR: 0.08, 95% CI: 0.03‐0.22). There was no association with sex, race, symptoms, optimal medical therapy, maximal antianginal therapy, referral status, or type of interventional cardiologist (academic vs private practice).

Conclusions

For patients undergoing cardiac catheterization for stable angina, the decision to proceed to PCI vs medical management appears to depend largely on patient and angiographic characteristics, but not on symptoms or ischemia. Distal and high‐risk lesions (ACC/AHA type C) are more often referred for medical therapy.
Implications of the New US Cholesterol Guidelines in the Brazilian Longitudinal Study of Adult Health (ELSA‐Brasil)
Authors: Bittencourt Marcio Sommer , Staniak Henrique Lane , Pereira Alexandre Costa , Santos Itamar S. , Duncan Bruce B. , Santos Raul D. , Blaha Michael J. , Jones Steve R. , Toth Peter P. , Bensenor Isabela M. , Lotufo Paulo A.
Published: February 2016

Background

The new US guidelines for the primary prevention of cardiovascular disease have substantially changed the approach to hyperlipidemia treatment. However, the impact of those recommendations in other populations is limited. In the present study, we evaluated the potential implications of those recommendations in the Brazilian population.

Hypothesis

The new U.S. recommendations may increase the proportion of individuals who are candidates for statin therapy.

Methods

We included all participants of the Brazilian Longitudinal Study of Adult Health (ELSA‐Brasil) without known cardiovascular disease. We calculated the indication for statin therapy according to the current Brazilian recommendations and the new US guidelines, using both the 5.0% and the 7.5% risk cutoffs to recommend treatment, and compared their impact in the Brazilian population stratified by age, sex, and race.

Results

Although the current guidelines would recommend treatment for 5499 (39.1%) individuals, the number of individuals eligible for statin therapy increased to 6014 (42.7%) and to 7130 (50.7%) using the 7.5% and 5% cutoffs, respectively (P < 0.001). This difference is more pronounced for older individuals, and virtually all individuals age >70 years would be eligible for statins, whereas the new guidelines would reduce the number of candidates for statin therapy in individuals age <45 years.

Conclusions

The application of the new US guidelines for the use of lipid‐lowering medications in a large middle‐aged Brazilian cohort would result in a significant increase in the population eligible for statins. This is largely driven by males and older individuals. Additional cost‐effectiveness analyses are needed to define the appropriateness of this strategy in the Brazilian population.
Dendritic spine actin dynamics in neuronal maturation and synaptic plasticity
Authors: Hlushchenko Iryna , Koskinen Mikko , Hotulainen Pirta
Published: February 2016

The majority of the postsynaptic terminals of excitatory synapses in the central nervous system exist on small bulbous structures on dendrites known as dendritic spines. The actin cytoskeleton is a structural element underlying the proper development and morphology of dendritic spines. Synaptic activity patterns rapidly change actin dynamics, leading to morphological changes in dendritic spines. In this mini‐review, we will discuss recent findings on neuronal maturation and synaptic plasticity‐induced changes in the dendritic spine actin cytoskeleton. We propose that actin dynamics in dendritic spines decrease through actin filament crosslinking during neuronal maturation. In long‐term potentiation, we evaluate the model of fast breakdown of actin filaments through severing and rebuilding through polymerization and later stabilization through crosslinking. We will discuss the role of Ca2+ in long‐term depression, and suggest that actin filaments are dissolved through actin filament severing. © 2016 Wiley Periodicals, Inc.
Computational evaluation of aortic occlusion and the proposal of a novel, improved occluder: Constrained endo‐aortic balloon occlusion
Authors: de Vaal M. H. , Gee M. W. , Stock U. A. , Wall W. A.
Published: February 2016

Because aortic occlusion is arguably one of the most dangerous aortic manipulation maneuvers during cardiac surgery in terms of perioperative ischemic neurological injury, the purpose of this investigation is to assess the structural mechanical impact resulting from the use of existing and newly proposed occluders. Existing (clinically used) occluders considered include different cross‐clamps (CCs) and endo‐aortic balloon occlusion (EABO). A novel occluder is also introduced, namely, constrained EABO (CEABO), which consists of applying a constrainer externally around the aorta when performing EABO. Computational solid mechanics are employed to investigate each occluder according to a comprehensive list of functional requirements. The potential of a state of occlusion is also considered for the first time. Three different constrainer designs are evaluated for CEABO. Although the CCs were responsible for the highest strains, largest deformation, and most inefficient increase of the occlusion potential, it remains the most stable, simplest, and cheapest occluder. The different CC hinge geometries resulted in poorer performance of CC used for minimally invasive procedures than conventional ones. CEABO with a profiled constrainer successfully addresses the EABO shortcomings of safety, stability, and positioning accuracy, while maintaining its complexities of operation (disadvantage) and yielding additional functionalities (advantage). Moreover, CEABO is able to achieve the previously unattainable potential to provide a clinically determinable state of occlusion. CEABO offers an attractive alternative to the shortcomings of existing occluders, with its design rooted in achieving the highest patient safety. Copyright © 2016 John Wiley & Sons, Ltd.
Standardization of cryopreserved peripheral blood mononuclear cells through a resting process for clinical immunomonitoring—Development of an algorithm
Authors: Wang Lei , Hückelhoven Angela , Hong Jian , Jin Nan , Mani Jiju , Chen Bao‐an , Schmitt Michael , Schmitt Anita
Published: February 2016

Flow cytometry, as a powerful tool for immunomonitoring and quality control of peripheral blood mononuclear cells (PBMCs), is routinely used in clinical studies. However, flow cytometry based assays for cryopreserved peripheral blood mononuclear cells (cPBMCs) constitute a challenge. Down‐regulation of surface and intracellular markers, as well as impairment of cell function might result from cryopreservation. Furthermore, protocols for resting cPBMCs are available but diverse. Therefore, we performed a standardization of the resting process concerning resting position, cell concentration, resting period and material of cell culture tubes as well as culture media. We further investigated the influence of resting on the phenotype and functionality of T cells comparing fresh PBMCs as gold standard to rested and non‐rested cPBMCs. Polychromatic flow cytometry staining, peptide‐MHC class I restricted tetramer staining and intracellular cytokine staining as major methods were used. Our results revealed that a horizontal position, a cell concentration of 2 to 5 × 106 cells/ml and an overnight resting phase is beneficial to eliminate dead or dying cells in cPBMCs with a mean cell loss of 14% overall cell populations. In addition, the quality and quantity of regulatory T cells and antigen specific T cells recovered upon resting. For multifunctional T cells a decrease of activation threshold in the way of a twofold mean fluorescence intensity (MFI) and increase of degranulation marker CD107a, co‐stimulatory marker CD28, adhesion molecule CD62L as well as the ability to secrete antiviral cytokines like interferon gamma (IFN‐γ), tumor necrosis factor (TNF), and interleukin 2 (IL‐2) comparable to fresh PBMCs were observed. However, based upon our data resting is not helpful for the flow cytometric analyses of myeloid‐derived suppressor cells (MDSCs) and large/intermediate size lymphocytes which rather decreased/vanished ex vivo. Therefore, we developed an algorithm to indicate for which cell population and for which type of analyses the resting process is useful or not. © 2016 International Society for Advancement of Cytometry
A long journey coming to fruition: In sight of the preselection T‐cell repertoire
Authors: Ciucci Thomas , Bosselut Rémy
Published: February 2016

In addition to MHC restriction and its structural correlate the recognition of an MHC‐peptide complex by the TCR, T‐cell reactivity is constrained by positive and negative selection in the thymus. While mouse genetic studies have provided compelling evidence for both processes, the actual impact of selection on the mature T‐cell repertoire has remained difficult to assess, in particular because it has so far not been possible to follow the intrathymic differentiation of antigen‐specific T cells carrying endogenous TCR specificities. In this issue of the European Journal of Immunology, Hesnard et al. [Eur. J. Immunol. 2016. 46: 560‐569] report the detection of human antigen‐specific immature thymocytes, thereby opening the way to addressing these questions. Here, we discuss the implications of this technological advance.
Photoinduced and Self‐Activated Nuclease Activity of Copper(II) Complexes with N‐(Quinolin‐8‐yl)quin­olin‐8‐sulfonamide – DNA and Bovine Serum Albumin Binding
Authors: Pascual‐Álvarez Alejandro , Topala Tamara , Estevan Francisco , Sanz Francisca , Alzuet‐Piña Gloria
Published: February 2016

Two CuII complexes with a new quinoline sulfonamide derivative and phenanthroline (phen), [Cu(QSQ)(phen)]ClO4·0.5H2O (1) and [Cu(QSQ)(phen)(H2O)]ClO4 (2) [HQSQ = N‐(quinolin‐8‐yl)quinolin‐8‐sulfonamide], have been synthesized and physicochemically characterized. Single‐crystal X‐ray diffraction studies have revealed a highly distorted trigonal‐bipyramidal structure for 1 (τ = 0.68) and an almost perfect trigonal‐bipyramidal geometry for 2 (τ = 0.92). DNA binding studies, which were performed by thermal denaturation, viscometry, fluorescence spectroscopy, and cyclic voltammetry, indicated a partial intercalation of 1 with Kapp = 2.45 × 106 M–1. The nuclease activity of 1 was investigated upon photoirradiation, with ascorbate/H2O2 as the activating agent, and also in the absence of any external reagent. In all cases, 1 was able to perform DNA cleavage, and its nuclease efficiency varied in the order ascorbate/H2O2 > photoirradiation > without external cofactors. Mechanistic investigations suggest an oxidative cleavage of DNA involving reactive oxygen species (ROS). The protein binding ability of 1 was also studied with bovine serum albumin (BSA) as a model protein.
Synthesis of DNA‐Intercalating 6H‐Benzo[c]chromen‐6‐one Derivatives through a Strategic Combination of Garratt–Braverman and Minisci Acyloxylation Reactions
Authors: Bhattacharya Prabuddha , Mandal Santi M. , Basak Amit
Published: February 2016

A new strategy for the synthesis of 6H‐benzo[c]chromen‐6‐ones through judicious use of Garratt–Braverman (GB) Cyclization and Minisci acyloxylation reactions in moderate to good yield is reported. The uniqueness of the GB reaction is exemplified in providing the required biaryl esters, which could be successfully converted into the target skeleton by means of Minisci reaction on the free carboxylates. Ethidium bromide displacement and UV‐based assay on the final molecules established them as DNA intercalators with binding constants in the range of about 104.
Sequential Synthesis of Organosilicon‐Linked 2‐Methoxypyridines by Non‐Cryogenic ortho‐Metallation Using the nBu2TMPMg·Li Reagent and Hydrosilylation
Authors: Struk Łukasz , Sośnicki Jacek G. , Idzik Tomasz J. , Maciejewska Gabriela
Published: February 2016

The non‐cryogenic synthesis of 5/6‐ and/or 3‐silyl‐functionalised 2‐methoxypyridines by a 5‐Br/Mg exchange process using nBu2iPrMg Li and LiCl and involving C‐3 metallation using a novel nBu2TMPMg Li reagent is described. Furthermore, the usefulness of nBu2TMPMg Li in the functionalisation of 2‐methoxypyridine at the 3‐position with a wide range of electrophiles was successfully tested. The above achievements have allowed the construction of organosilicon‐linked 2‐methoxypyridines composed of two, three and four rings by the hydrosilylation of 5‐ and/or 3‐SiH(or alkenyl) derivatives using the hitherto rarely applied [Pt(cod)Me2] catalyst. Additionally, the synthesis of a one‐chain oligomer consisting of eight 2‐methoxypyridines obtained by the hydrosilylation/polymerisation approach, followed by protodesilylation of the SiHMe2 group was also achieved by manipulating the amount of catalyst in the reactions.
Neonatal developmental care in infant pain management and internalizing behaviours at 18 months in prematurely born children
Authors: Montirosso R. , Casini E. , Del Prete A. , Zanini R. , Bellù R. , Borgatti R. ,   NEO‐ACQUA Study Group
Published: February 2016

Background

Very preterm infants are exposed to adverse stressful experiences, which may result in long‐term behavioural outcomes. The developmental care practices, including pain management and environmental support, can minimize the effects of stress exposure. However, developmental care quality levels may vary among Neonatal Intensive Care Units (NICUs) and little is known about how differences in developmental care quality affect long‐term behavioural outcomes. The aim of this study was to examine the relation between quality levels NICUs developmental care and behaviour problems at 18 months corrected age in preterm children.

Methods

The behaviour of 134 preterm children from 22 NICUs and 123 full‐term controls was examined using the questionnaire Child Behaviour Checklist 1½–5. We compared the behavioural profile of children by splitting NICUs into units with high‐ and low quality of developmental care according to two main care factors: (1) infant centered care (ICC) index, and (2) infant pain management (IPM) index.

Results

Preterm children from low‐care units in IPM group reported higher scores in Internalizing Problems, compared to children from high‐care units. No differences were found between preterm children from high‐care in IPM and full‐term children. No significant IPM effect was found for externalizing problems. No significant ICC effect emerged both for internalizing and externalizing problems.

Conclusions

Findings suggest that higher quality of developmental care related to infant pain management can mitigate behavioural problems at 18 months in children born preterm, to such an extent that preterm children exhibit a behavioural profile similar to that displayed by full‐term children.
Non‐parametric combination and related permutation tests for neuroimaging
Authors: Winkler Anderson M. , Webster Matthew A. , Brooks Jonathan C. , Tracey Irene , Smith Stephen M. , Nichols Thomas E.
Published: February 2016

In this work, we show how permutation methods can be applied to combination analyses such as those that include multiple imaging modalities, multiple data acquisitions of the same modality, or simply multiple hypotheses on the same data. Using the well‐known definition of union‐intersection tests and closed testing procedures, we use synchronized permutations to correct for such multiplicity of tests, allowing flexibility to integrate imaging data with different spatial resolutions, surface and/or volume‐based representations of the brain, including non‐imaging data. For the problem of joint inference, we propose and evaluate a modification of the recently introduced non‐parametric combination (NPC) methodology, such that instead of a two‐phase algorithm and large data storage requirements, the inference can be performed in a single phase, with reasonable computational demands. The method compares favorably to classical multivariate tests (such as MANCOVA), even when the latter is assessed using permutations. We also evaluate, in the context of permutation tests, various combining methods that have been proposed in the past decades, and identify those that provide the best control over error rate and power across a range of situations. We show that one of these, the method of Tippett, provides a link between correction for the multiplicity of tests and their combination. Finally, we discuss how the correction can solve certain problems of multiple comparisons in one‐way ANOVA designs, and how the combination is distinguished from conjunctions, even though both can be assessed using permutation tests. We also provide a common algorithm that accommodates combination and correction.Hum Brain Mapp 37:1486‐1511, 2016. © 2016 Wiley Periodicals, Inc.
Classification of vocal fold leukoplakia by clinical scoring
Authors: Fang Tuan‐Jen , Lin Wan‐Ni , Lee Li‐Yu , Young Chi‐Kuang , Lee Li‐Ang , Chang Kai‐Ping , Liao Chun‐Ta , Li Hseuh‐Yu , Yen Tzu‐Chen
Published: February 2016

Background

Vocal cord leukoplakia comprises a variety of lesions. The purpose of this study was to stratify vocal leukoplakias before surgery.

Methods

Patients with an initial diagnosis of vocal leukoplakia who underwent surgical excision at a tertiary referral center in Taiwan were recruited for this study. Their clinical records, including age, sex, preoperative laryngoscopic images in the office setting, and final pathology reports were collected and analyzed.

Results

Patient age (p= .010), nonhomogenous lesion texture (p= .001), and existence of hyperemia (p= .014) were identified as independent factors predicting malignancy. A predictive formula was established accordingly. The model showed an excellent discrimination role by receiver operating characteristic curve analysis (area under the curve = 0.86;p< .001).

Conclusion

This study confirmed the value of a scoring system based on laryngoscopic characteristics and patient age for predicting the histologic results in vocal leukoplakia. It is helpful for classifying vocal leukoplakia and pretreatment planning. © 2016 Wiley Periodicals, Inc.Head Neck38: E1998–E2003, 2016
Autophagy and 3-Phosphoinositide-Dependent Kinase 1 (PDK1)-Related Kinome in Pagetic Osteoclasts
Authors: McManus Stephen , Bisson Martine , Chamberland Richard , Roy Michèle , Nazari Shekeba , Roux Sophie
Published: February 2016

In Paget's disease of bone (PDB), a major contributory factor are osteoclasts (OCs) that are larger, more numerous, resistant to apoptosis, and hyperactive. The aim of this human in vitro study was to identify kinase cascades involved in the OC phenotype and to determine their impact on downstream processes. Basal phosphorylation levels of Akt and ERK were found to be elevated in PDB OCs. Given our previous findings that 3-phosphoinositide-dependent protein kinase 1 (PDK1) associates with the crucial adaptor p62 in OCs, we hypothesized that PDK1 may play an important role in OC-related kinome regulation. The increased phosphorylation of Akt and its substrate GSK3β observed in PDB OCs was reduced significantly upon PDK1 inhibition, as well as that of 4EBP1 and Raptor. This suggests a PDK1/Akt-dependent activation of mammalian target of rapamycin complex 1 (mTORC1) in PDB OCs. The resistance to apoptosis and the bone resorption were also overcome upon PDK1 inhibition. Studying autophagy by LC3B expression, we found a less inducible autophagy compared with control cells, which was reversed by PDK1 inhibition. In addition, PBD OCs exhibited higher LC3B-II/LC3B-I ratios and numbers of p62 and LC3B puncta per OC area, which did not further increase in the presence of lysosomal protease inhibitors, suggesting an accumulation of non-degradative autophagosomes. Together these results indicate a strong potential regulatory role for PDK1 in OC stimulatory pathways (Akt, ERK) and autophagy induction (via mTORC1), which may contribute to the OC phenotype in PDB. We also identified defects in late autophagosome maturation in these cells, the mechanism of which remains to be determined. © 2016 American Society for Bone and Mineral Research.
sDFIRE: Sequence‐specific statistical energy function for protein structure prediction by decoy selections
Authors: Hoque Md Tamjidul , Yang Yuedong , Mishra Avdesh , Zhou Yaoqi
Published: February 2016

An important unsolved problem in molecular and structural biology is the protein folding and structure prediction problem. One major bottleneck for solving this is the lack of an accurate energy to discriminate near‐native conformations against other possible conformations. Here we have developed sDFIRE energy function, which is an optimized linear combination of DFIRE (the Distance‐scaled Finite Ideal gas Reference state based Energy), the orientation dependent (polar‐polar and polar‐nonpolar) statistical potentials, and the matching scores between predicted and model structural properties including predicted main‐chain torsion angles and solvent accessible surface area. The weights for these scoring terms are optimized by three widely used decoy sets consisting of a total of 134 proteins. Independent tests on CASP8 and CASP9 decoy sets indicate that sDFIRE outperforms other state‐of‐the‐art energy functions in selecting near native structures and in the Pearson's correlation coefficient between the energy score and structural accuracy of the model (measured by TM‐score). © 2016 Wiley Periodicals, Inc.
Delaunay–Voronoi surface integration: a full‐wave electromagnetics discretization for electronic device simulation
Authors: Miller N. C. , Albrecht J. D. , Grupen M.
Published: February 2016

A promising time domain electromagnetics numerical method for treating the highly nonlinear problem of charge transport in electronic devices called Delaunay–Voronoi surface integration is presented. This method couples the rotational electric and magnetic fields governed by Ampere's and Faraday's laws with the electrostatic potential dictated by Poisson's equation in a simultaneous solution. Discretization of the governing equations using dual meshes and the relevant boundary conditions are presented. The engineering application details specific to electronic device simulation are treated, and an example calculation is shown to compare with an analytical solution for propagation in a waveguide. Benchmark results are presented for the rotational equations, Poisson's equation, and the complete set of electromagnetic equations. Copyright © 2016 John Wiley & Sons, Ltd.
Spinal metastasectomy of renal cell carcinoma: A 16‐year single center experience with a minimum 3‐year follow‐up
Authors: Kato Satoshi , Murakami Hideki , Demura Satoru , Nambu Koshi , Fujimaki Yoshiyasu , Yoshioka Katsuhito , Kawahara Norio , Tomita Katsuro , Tsuchiya Hiroyuki
Published: February 2016

Background and Objectives

Metastasectomy of spinal lesions from renal cell carcinoma (RCC) is a promising strategy. However, its clinical outcome after spinal metastasectomy is unknown owing to the difficulty of curative surgical resection. This is the first study to examine the survival rates of patients who underwent metastasectomy of solitary spinal metastases from RCC.

Methods

A retrospective cohort study of 36 consecutive patients with RCC who underwent nephrectomy and complete removal of solitary spinal lesions between 1995 and 2010 at our institution. Cancer‐specific survival (CSS) time from the spinal metastasectomy to death or last follow‐up was the main endpoint. Potential factors associated with survival were evaluated with Kaplan–Meier analysis and the long‐rank test.

Results

For all patients, the estimated median CSS time was 130 months. The 3, 5, and 10‐year CSS rates were 77.8%, 69.1%, and 58.0%, respectively, for all patients, and 72.7%, 54.5%, and 27.3%, respectively, for patients with lung metastases at the time of surgery. Only the presence of liver metastases was significantly associated with short‐term survival after spinal metastasectomy.

Conclusions

Liver metastases were associated with short‐term survival, although lung metastases were not. For selected patients, curative resection of solitary spinal metastases can potentially prolong survival. J. Surg. Oncol. 2016;113:587–592. © 2016 Wiley Periodicals, Inc.
Role of PET CT scan in redefining treatment of incidental gall bladder carcinoma
Authors: Goel Mahesh , Tamhankar Anup , Rangarajan Venkatesh , Patkar Shraddha , Ramadwar Mukta , Shrikhande Shailesh V.
Published: February 2016

Introduction

Incidental diagnosis of gall bladder cancer is increasing. The role of PET‐CT in modifying the extent of surgery and adjuvant treatment is still unclear. We have evaluated the same in this study.

Methods

This is a prospective audit of gall bladder cancer from Tata Memorial Hospital, Mumbai, India. Patients found non‐metastatic on initial imaging underwent laparotomy for revision surgery.

Results

One hundred and eight patients had a PET‐CT scan done before revision surgery. Median duration of PET‐CT from primary surgery was 42 days. PET scan of 64 (59.3%) patients had no uptake in body (N‐PET). Rest had loco‐regional uptake (L‐PET). N‐PET patients had lesser residual disease than L‐PET patients (23% vs. 52%; P = 0.004). N‐PET pT1b patients had no residual disease as compared to L‐PET patients (0% vs. 33%, P = 0.028). pT1b patients did not have residual disease in liver wedge irrespective of PET status. Majority of the recurrences were distant and happened in pT2 patients. RFS was longer in N‐PET than L‐PET patients (P = 0.09) and in pT1b patients than pT2 and pT3 (P = 0.006). OS was longer in pT1b patients than pT2 patients (P = 0.038).

Conclusions

PET‐CT scan is useful to stratify patients with incidentally diagnosed gall bladder cancer for effective treatment. Liver wedge resection may be avoided in all pT1b patients. PET negative pT1b patients may be observed as chance of relapse is low. There may be a role for giving chemotherapy to all pT2 patients as they have high chance of recurrence and nodal metastases. J. Surg. Oncol. 2016;113:652–658. © 2016 Wiley Periodicals, Inc.
Borderline Particles: Approaching the Limit between Colloidal Stability and Instability during Heterophase Polymerization
Authors: Yu Ran , Peh Eddie , Mavliutova Liliia , Weber Nancy , Tauer Klaus
Published: February 2016

Multiple suspension particles — a new morphology of polymer particles — are generated on the verge of colloidal stability in the course of redox‐initiated aqueous heterophase copolymerization. These particles consist of block copolymers which are arranged in the form of a micrometer‐sized poly(N‐isopropylacrylamide) physical network as scaffold containing nanometer‐sized particles of hydrophobic polymers covalently attached.

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