bluuebunny/crossref_metadata_2025 huggingface dataset:
Parameters for Inherently Homogeneous Sintering Processes
Authors: Raether Friedrich
Published: March 2015

Thermodynamic criteria are introduced to calculate the driving force for the formation of heterogeneous metastable states during sintering. As already shown for one special case of liquid phase sintering, these metastable states significantly affect the reliability of sintered ceramics. Inherently safe sintering processes are proposed, providing a homogeneous evolution of microstructure. A desintering parameter is defined which can be used for a quantitative evaluation of different sintering processes in terms of their tendency for formation of heterogeneity. The desintering parameter has been calculated using sintering simulations in 3D representative volume elements. For that, a deterministic model has been developed. It considers interface energy minimization and grain growth for random arrangements of particles. Computational effort could be significantly reduced by periodic continuation of the microstructure at the sides of the RVE. Basic parameters controlling inherently homogeneous sintering are presented. Surface diffusion is positive at large dihedral angles. Unexpectedly, grain growth can be advantageous as well, provided that it acts continuously during the entire sintering cycle.
Macroscopic Bifurcation and Fracture Mechanism of Polymethyl Methacrylate
Authors: Jiao Da , Qu Rui Tao , Zhang Zhe Feng
Published: March 2015

Polymethyl methacrylate (PMMA) is one of important engineering materials and has been widely applied in various fields. Owing to the catastrophically brittle fracture nature, exploring the fracture mechanism of PMMA is of crucial significance to guide its engineering application. In this work, tensile tests with several kinds of sample geometries including unnotched samples and notch samples with different widths were designed to systematically investigate the macroscopic bifurcation of PMMA. Based on the sufficient experimental evidences, the traditional critical stress intensity criterion was found inappropriate for predicting the macroscopic bifurcation of PMMA. Finally, the fracture features were explicitly clarified based on the detailed experimental observations, and a new explanation to elucidate the fracture mechanism of PMMA was proposed.
Associations between workplace factors and carpal tunnel syndrome: A multi‐site cross sectional study
Authors: Fan Z. Joyce , Harris‐Adamson Carisa , Gerr Fred , Eisen Ellen A. , Hegmann Kurt T. , Bao Stephen , Silverstein Barbara , Evanoff Bradley , Dale Ann Marie , Thiese Matthew S. , Garg Arun , Kapellusch Jay , Burt Susan , Merlino Linda , Rempel David
Published: March 2015

Background

Few large epidemiologic studies have used rigorous case criteria, individual‐level exposure measurements, and appropriate control for confounders to examine associations between workplace psychosocial and biomechanical factors and carpal tunnel syndrome (CTS).

Methods

Pooling data from five independent research studies, we assessed associations between prevalent CTS and personal, work psychosocial, and biomechanical factors while adjusting for confounders using multivariable logistic regression.

Results

Prevalent CTS was associated with personal factors of older age, obesity, female sex, medical conditions, previous distal upper extremity disorders, workplace measures of peak forceful hand activity, a composite measure of force and repetition (ACGIH Threshold Limit Value for Hand Activity Level), and hand vibration.

Conclusions

In this cross‐sectional analysis of production and service workers, CTS prevalence was associated with workplace and biomechanical factors. The findings were similar to those from a prospective analysis of the same cohort with differences that may be due to recall bias and other factors. Am. J. Ind. Med. 58:509–518, 2015. © 2015 Wiley Periodicals, Inc.
Enzymatically Active Ultrathin Pepsin Membranes
Authors: Raaijmakers Michiel J. T. , Schmidt Thomas , Barth Monika , Tutus Murat , Benes Nieck E. , Wessling Matthias
Published: March 2015

Enzymatically active proteins enable efficient and specific cleavage reactions of peptide bonds. Covalent coupling of the enzymes permits immobilization, which in turn reduces autolysis‐induced deactivation. Ultrathin pepsin membranes were prepared by facile interfacial polycondensation of pepsin and trimesoyl chloride. The pepsin membrane allows for simultaneous enzymatic conversion and selective removal of digestion products. The large water fluxes through the membrane expedite the transport of large molecules through the pepsin layers. The presented method enables the large‐scale production of ultrathin, cross‐linked, enzymatically active membranes.
Sekundärionen‐Massenspektrometrie von genetisch kodierten Zielproteinen
Authors: Vreja Ingrid C. , Kabatas Selda , Saka Sinem K. , Kröhnert Katharina , Höschen Carmen , Opazo Felipe , Diederichsen Ulf , Rizzoli Silvio O.
Published: March 2015

Sekundärionen‐Massenspektrometrie (SIMS) wird üblicherweise für die Analyse der Isotopenzusammensetzung verschiedener Materialen eingesetzt. In der Biologie findet sie immer häufiger Anwendung, vor allem um den Stoffwechsel in Zellen zu untersuchen. Einzelne Zielproteine sind mit SIMS jedoch schwer zu identifizieren, wodurch diese Methode in ihren Anwendungsmöglichkeiten bezüglich Studien bestimmter Kompartimente oder Proteinkomplexe eingeschränkt wird. Wir stellen hier eine Methode vor, mit der spezifische Proteine durch eine Klick‐Reaktion mit Isotopen‐ und Fluoreszenzmarkierungen versehen werden (specific protein isotopic and fluorescence labeling, SPILL). Wir haben mit dieser Methode verschiedene Proteine mit 19F markiert und mit NanoSIMS und Fluoreszenzmikroskopie abgebildet. Anhand des 19F‐Signals (mit minimalem Hintergrund) konnten Zielproteine präzise lokalisiert werden, wodurch korrelative Studien der Proteinverteilung und des Zellstoffwechsels oder der Zellzusammensetzung ermöglicht wurden. SPILL kann in allen biologischen Proben angewendet werden, in denen Klick‐Reaktionen durchführbar sind, welche die meisten Zellkultursysteme und kleine Modellorganismen umfassen.
Heterogen katalysierte direkte C‐H‐Thiolierung von Heteroarenen
Authors: Vásquez‐Céspedes Suhelen , Ferry Angélique , Candish Lisa , Glorius Frank
Published: March 2015

Die erste generelle Methode zur direkten Thiolierung elektronenreicher Heteroarene wird vorgestellt. Sie nutzt den kommerziell erhältlichen Heterogenkatalysator Pd/Al2O3 und CuCl2. Die Methode eröffnet einen einfachen Zugang zu solchen wertvollen Verbindungen. Mechanistische Experimente deuten auf ein heterogenkatalytisches System hin, in dem beide Metalle eine komplementäre Rolle bei der Bildung der thiolierten Produkte spielen.
Fabrication of b‐Oriented MFI Zeolite Films under Neutral Conditions without the Use of Hydrogen Fluoride
Authors: Peng Yong , Lu Xiaofei , Wang Zhengbao , Yan Yushan
Published: March 2015

The fabrication of MFI zeolite films with particular b‐axis orientation is especially fascinating. Unlike the conventional alkaline or hydrofluoric acid (HF) assisted neutral synthesis route, here we develop a novel neutral synthesis solution system of TPABr/fumed silica/H2O without the use of HF and successfully synthesize highly b‐oriented MFI zeolite films on glass‐plate substrates by secondary growth. The localized weak alkaline environment created by the dissolved Na2O species from the substrate is identified as the key factor for the depolymerization of fumed silica and subsequently the in‐plane growth of zeolite seed layers. Continuous b‐oriented MFI films can also be synthesized on other substrates in the presence of a glass plate or a trace amount of NaOH, which making our neutral synthesis route promising for the direct synthesis of MFI zeolite films and membranes on various substrates.
Glycopeptide Mimetics Recapitulate High‐Mannose‐Type Oligosaccharide Binding and Function
Authors: Lusvarghi Sabrina , Ghirlando Rodolfo , Wong Chi‐Huey , Bewley Carole A.
Published: March 2015

High‐mannose‐type glycans (HMTGs) decorating viral spike proteins are targets for virus neutralization. For carbohydrate‐binding proteins, multivalency is important for high avidity binding and potent inhibition. To define the chemical determinants controlling multivalent interactions we designed glycopeptide HMTG mimetics with systematically varied mannose valency and spacing. Using the potent antiviral lectin griffithsin (GRFT) as a model, we identified by NMR spectroscopy, SPR, analytical ultracentrifugation, and microcalorimetry glycopeptides that fully recapitulate the specificity and kinetics of binding to Man9GlcNAc2Asn and a synthetic nonamannoside. We find that mannose spacing and valency dictate whether glycopeptides engage GRFT in a face‐to‐face or an intermolecular binding mode. Surprisingly, although face‐to‐face interactions are of higher affinity, intermolecular interactions are longer lived. These findings yield key insights into mechanisms involved in glycan‐mediated viral inhibition.
Makromolekulare Oberflächen: Photomusterung mit funktionellen stabilen Nitriloxiden
Authors: Altintas Ozcan , Glassner Mathias , Rodriguez‐Emmenegger Cesar , Welle Alexander , Trouillet Vanessa , Barner‐Kowollik Christopher
Published: March 2015

Das effiziente Abfangen photogenerierter Thioaldehyde durch funktionelle stabile Nitriloxide in einer 1,3‐dipolaren Cycloaddition ist eine neue und vielseitige photochemische Strategie zur Funktionalisierung von Polymeren und zur Oberflächenmodifikation unter milden und äquimolaren Bedingungen. Die modulare Ligation in Lösung wird im Detail durch ESI‐MS verfolgt. XPS wird zur Analyse der funktionalisierten Oberflächen verwendet, während ToF‐SIMS die durch Anwendung einer Schattenmaske erreichte räumliche Kontrolle der Oberflächenfunktionalisierung belegt. Polymerbürsten wurden in einem räumlich begrenzten Bereich durch SI‐ATRP von der Oberfläche aus wachsen gelassen, was mithilfe von ToF‐SIMS, XPS sowie Ellipsometrie belegt wird.
A Single‐Chain Magnet Tape Based on Hexacyanomanganate(III)
Authors: Zhang Yuan‐Zhu , Zhao Han‐Hua , Funck Edward , Dunbar Kim R.
Published: March 2015

The tape‐like chain {[(tptz)MnII(H2O)MnIII(CN)6]2MnII(H2O)2}n⋅4n MeOH⋅2n H2O based on the anisotropic building block hexacyanomanganate(III) exhibits long‐range magnetic ordering below 5.1 K as well as single‐chain magnetic behavior at lower temperatures with an effective energy barrier of 40.5(7) K.
Secondary‐Ion Mass Spectrometry of Genetically Encoded Targets
Authors: Vreja Ingrid C. , Kabatas Selda , Saka Sinem K. , Kröhnert Katharina , Höschen Carmen , Opazo Felipe , Diederichsen Ulf , Rizzoli Silvio O.
Published: March 2015

Secondary ion mass spectrometry (SIMS) is generally used in imaging the isotopic composition of various materials. It is becoming increasingly popular in biology, especially for investigations of cellular metabolism. However, individual proteins are difficult to identify in SIMS, which limits the ability of this technology to study individual compartments or protein complexes. We present a method for specific protein isotopic and fluorescence labeling (SPILL), based on a novel click reaction with isotopic probes. Using this method, we added 19F‐enriched labels to different proteins, and visualized them by NanoSIMS and fluorescence microscopy. The 19F signal allowed the precise visualization of the protein of interest, with minimal background, and enabled correlative studies of protein distribution and cellular metabolism or composition. SPILL can be applied to biological systems suitable for click chemistry, which include most cell‐culture systems, as well as small model organisms.
Enantioselective Intramolecular Hydroacylation of Unactivated Alkenes: An NHC‐Catalyzed Robust and Versatile Formation of Cyclic Chiral Ketones
Authors: Janssen‐Müller Daniel , Schedler Michael , Fleige Mirco , Daniliuc Constantin G. , Glorius Frank
Published: March 2015

A highly enantioselective intramolecular N‐heterocyclic carbene (NHC)‐catalyzed hydroacylation reaction gives access to a range of cyclic ketones from unactivated olefin‐substituted aldehydes (up to 99 % ee). Remarkably, aliphatic aldehydes were also transformed efficiently in an NHC‐catalyzed hydroacylation reaction for the first time.
Bioorthogonal Deprotection on the Dendritic Cell Surface for Chemical Control of Antigen Cross‐Presentation
Authors: Pawlak Joanna B. , Gential Geoffroy P. P. , Ruckwardt Tracy J. , Bremmers Jessica S. , Meeuwenoord Nico J. , Ossendorp Ferry A. , Overkleeft Herman S. , Filippov Dmitri V. , van Kasteren Sander I.
Published: March 2015

The activation of CD8+ T‐cells requires the uptake of exogenous polypeptide antigens and proteolytic processing of these antigens to octamer or nonamer peptides, which are loaded on MHC‐I complexes and presented to the T‐cell. By using an azide as a bioorthogonal protecting group rather than as a ligation handle, masked antigens were generated—antigens that are not recognized by their cognate T‐cell unless they are deprotected on the cell using a Staudinger reduction.
Macromolecular Surface Design: Photopatterning of Functional Stable Nitrile Oxides
Authors: Altintas Ozcan , Glassner Mathias , Rodriguez‐Emmenegger Cesar , Welle Alexander , Trouillet Vanessa , Barner‐Kowollik Christopher
Published: March 2015

The efficient trapping of photogenerated thioaldehydes with functional shelf‐stable nitrile oxides in a 1,3‐dipolar cycloaddition is a novel and versatile photochemical strategy for polymer end‐group functionalization and surface modification under mild and equimolar conditions. The modular ligation in solution was followed in detail by electrospray ionization mass spectrometry (ESI‐MS). X‐ray photoelectron spectroscopy (XPS) was employed to analyze the functionalized surfaces, whereas time‐of‐flight secondary‐ion mass spectrometry (ToF‐SIMS) confirmed the spatial control of the surface functionalization using a micropatterned shadow mask. Polymer brushes were grown from the surface in a spatially confined regime by surface‐initiated atom transfer radical polymerization (SI‐ATRP) as confirmed by TOF‐SIMS, XPS as well as ellipsometry.
Synthesis of Ultrathin Face‐Centered‐Cubic Au@Pt and Au@Pd Core–Shell Nanoplates from Hexagonal‐Close‐Packed Au Square Sheets
Authors: Fan Zhanxi , Zhu Yihan , Huang Xiao , Han Yu , Wang Qingxiao , Liu Qing , Huang Ying , Gan Chee Lip , Zhang Hua
Published: March 2015

The synthesis of ultrathin face‐centered‐cubic (fcc) Au@Pt rhombic nanoplates is reported through the epitaxial growth of Pt on hexagonal‐close‐packed (hcp) Au square sheets (AuSSs). The Pt‐layer growth results in a hcp‐to‐fcc phase transformation of the AuSSs under ambient conditions. Interestingly, the obtained fcc Au@Pt rhombic nanoplates demonstrate a unique (101)f orientation with the same atomic arrangement extending from the Au core to the Pt shell. Importantly, this method can be extended to the epitaxial growth of Pd on hcp AuSSs, resulting in the unprecedented formation of fcc Au@Pd rhombic nanoplates with (101)f orientation. Additionally, a small amount of fcc (100)f‐oriented Au@Pt and Au@Pd square nanoplates are obtained with the Au@Pt and Au@Pd rhombic nanoplates, respectively. We believe that these findings will shed new light on the synthesis of novel noble bimetallic nanostructures.
Improving the Electrochemical Performance of the Li4Ti5O12 Electrode in a Rechargeable Magnesium Battery by Lithium–Magnesium Co‐Intercalation
Authors: Wu Na , Yang Zhen‐Zhong , Yao Hu‐Rong , Yin Ya‐Xia , Gu Lin , Guo Yu‐Guo
Published: March 2015

Rechargeable magnesium batteries have attracted recent research attention because of abundant raw materials and their relatively low‐price and high‐safety characteristics. However, the sluggish kinetics of the intercalated Mg2+ ions in the electrode materials originates from the high polarizing ability of the Mg2+ ion and hinders its electrochemical properties. Here we report a facile approach to improve the electrochemical energy storage capability of the Li4Ti5O12 electrode in a Mg battery system by the synergy between Mg2+ and Li+ ions. By tuning the hybrid electrolyte of Mg2+ and Li+ ions, both the reversible capacity and the kinetic properties of large Li4Ti5O12 nanoparticles attain remarkable improvement.
New di‐ and triorganotin(IV) carboxylates derived from a Schiff base: synthesis, characterization and in vitro antimicrobial activities
Authors: Dias Letícia C. , de Lima Geraldo M. , Takahashi Jacqueline A. , Ardisson José D.
Published: March 2015

A new carboxylic acid, 2‐{[5‐(2‐nitrophenyl)furan‐2‐yl]methyleneamino}benzoic acid (HOBZ), has been produced by reacting 5‐(2‐nitrophenyl)furfural with 2‐aminobenzoic acid. Reactions of NaOBZ with organotin chlorides led to formation of [Me3Sn(OBZ)] (1), [Bu3Sn(OBZ)] (2), [Me2Sn(OBZ)2] (3) and [Bu2Sn(OBZ)2] (4). Complexes 1, 2, 3, 4 have been characterized using elemental analyses and infrared, 1H NMR, 13C NMR, 119Sn NMR and 119Sn Mössbauer spectroscopies. In the solid state, the OBZ ligands might coordinate to tin in an anisobidentate fashion via the carboxylate group. The in vitro antimicrobial activity of all compounds has been screened against the following fungi: Aspergillus niger, A. flavus, A. parasiticus, Penicillium citrinum, Candida dubliniensis, C. lusitaniae, C. albicans, C. tropicalis, C. parapsilosis and C. glabrata; and against the following bacteria: Staphylococcus aureus, Listeria monocytogenes, Bacillus cereus, Streptococcus sanguinis, Escherichia coli, Citrobacter frendii, Salmonella typhimurium and Pseudomonas aeruginosa. Complexes 2 and 4 exhibited higher biocide activity in comparison to 1 and 3 and to the control drugs nystatin and miconazole nitrate for the yeasts, and chloramphenicol and ampicillin for the bacteria. The biological activity of 2 was superior to that of 4. In addition, the toxicity of HOBZ, NaOBz and 1, 2, 3, 4 were determined using Chlorella vulgaris, revealing low toxicity of the complexes at MIC50 concentrations. We also performed cell viability studies, using XTT assay, displaying no change in the mitochondrial function after 2–4 h of exposure of the microorganism to the complexes at MIC50 concentrations. The butyl‐containing complexes 2 and 4 display greater lipophilicities than do the methyl analogues 1 and 3, thereby endowing 2 and 4 with superior abilities to cross the microbe cell membrane, the possible mechanism of action. Copyright © 2015 John Wiley & Sons, Ltd.
Microwave‐assisted copper powder‐catalyzed coupling and cyclization of β‐bromo‐α,β‐unsaturated amides with amidine hydrochlorides leading to pyrimidinones
Authors: Jiao Yang , Cho Chan Sik
Published: March 2015

β‐Bromo‐α,β‐unsaturated amides are coupled and cyclized with amidine hydrochlorides using microwave irradiation in the presence of a catalytic amount of copper powder and a base to give the corresponding pyrimidinones in good yields. Copyright © 2015 John Wiley & Sons, Ltd.
Zn( L‐proline)2 as a powerful and reusable organometallic catalyst for the very fast synthesis of 2‐amino‐4H‐benzo[g]chromene derivatives under solvent‐free conditions
Authors: Maleki Behrooz , Babaee Saeed , Tayebee Reza
Published: March 2015

An efficient route for the synthesis of 2‐amino‐4H‐benzo[g]chromenes via a three‐component coupling reaction of aldehydes, malononitrile and 2‐hydroxy‐1,4‐naphthaquinone in the presence of Zn( L‐proline)2 is reported. High yields, short reaction times, non‐toxicity and recyclability of the catalyst, and easy work‐up are the main merits of this protocol. Copyright © 2015 John Wiley & Sons, Ltd.
Preparation of artificial wood films with controlled biodegradability
Authors: Kim Sung Hee , Kim Min Hoo , Kim Ji Hyun , Park Saerom , Kim Hyungsup , Won Keehoon , Lee Sang Hyun
Published: March 2015

Artificial wood films containing cellulose, xylan, and lignin were easily prepared by the dissolution of wood components in 1‐ethyl‐3‐methylimidazolium acetate followed by reconstitution with distilled water. The composition and characteristics of wood films were highly controllable and predictable through the variation of the concentration of each component in the wood solution. The water vapor solubility of the wood films was increased when the xylan content was increased and the content of lignin was decreased. The biodegradability of the artificial wood films was investigated with cellulase from Trichoderma viride. The relative degradability of the wood film prepared with 5% cellulose and 5% lignin was 42%, whereas that of the wood film made with 5% cellulose and 5% xylan was 189%. The biodegradability of cellulose in the wood films correlated well with the content of xylan and lignin, and it was enhanced when the xylan content was increased and the content of lignin was decreased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42109.
Photodynamic antifungal activities of nanostructured fabrics grafted with rose bengal and phloxine B against Aspergillus fumigatus
Authors: Kim Joo Ran , Michielsen Stephen
Published: March 2015

This study demonstrates that nanostructured fabrics grafted with rose bengal (RB) and phloxine B (PB) have photodynamic antifungal effects on Aspergillus fumigatus. RB and PB were attached to vinyl benzyl chloride, and, subsequently, this was polymerized with acrylic acid and styrene sulfonic acid to produce long, water‐soluble polymers to attach to the fabric surface. This gave high grafting yield and photodynamic antifungal activity against A. fumigatus. In RB and PB microdilution tests, there was no visible turbidity at 63 µmol/L. When polymerized RB and PB were incorporated into fabrics, the actions of polymerized RB and PB resulted in less hyphal growth and germination of conidia on A. fumigatus than the free RB and PB dyes. Nanostructured fabrics created by bonding RB‐ or PB‐containing polymers to electrospun nylon mats exhibited higher concentrations of the dyes, equivalent to 86 µmol/L. The microstructured fabrics created by bonding RB‐ or PB‐containing polymers to spunbonded nylon nonwoven fabrics only exhibited the equivalent of 32 µmol/L of the dyes. The nanostructured fabrics had a specific surface area of 28.1 m2/g, whereas the microfabric had 1.5 m2/g. Thus, the nanostructured fabrics increased the surface area 18.7× and the reflectance percent 16.2× when compared with the microstructured fabrics. This resulted in much higher photodynamic antifungal activity against A. fumigatus. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42114.
Colorimetric and Fluorescent Bimodal Ratiometric Probes for pH Sensing of Living Cells
Authors: Liu Yuan‐Yuan , Wu Ming , Zhu Li‐Na , Feng Xi‐Zeng , Kong De‐Ming
Published: March 2015

pH measurement is widely used in many fields. Ratiometric pH sensing is an important way to improve the detection accuracy. Herein, five water‐soluble cationic porphyrin derivatives were synthesized and their optical property changes with pH value were investigated. Their pH‐dependent assembly/disassembly behaviors caused significant changes in both absorption and fluorescence spectra, thus making them promising bimodal ratiometric probes for both colorimetric and fluorescent pH sensing. Different substituent identity and position confer these probes with different sensitive pH‐sensing ranges, and the substituent position gives a larger effect. By selecting different porphyrins, different signal intensity ratios and different fluorescence excitation wavelengths, sensitive pH sensing can be achieved in the range of 2.1–8.0. Having demonstrated the excellent reversibility, good accuracy and low cytotoxicity of the probes, they were successfully applied in pH sensing inside living cells.
Aromaticity Switching in Porphyrinoids
Authors: Pawlicki Miłosz , Latos‐Grażyński Lechosław
Published: March 2015

The aromaticity of porphyrinoids can be substantially altered by reversible modification of their original electronic structures. Well‐defined modulators can be used as a means to initiate these modifications, including redox processes, acid–base chemistry, and conformational phenomena. This Focus Review emphasizes the situation for which a single macrocyclic frame alternatively adopts diatropic and paratropic features and both situations are readily and mutually exchangeable. Eventually, such a porphyrinoid transformation can be explored as a suitable element to construct switchable optoelectronic materials.
Continuous precipitation of IgG from CHO cell culture supernatant in a tubular reactor
Authors: Hammerschmidt Nikolaus , Hintersteiner Beate , Lingg Nico , Jungbauer Alois
Published: March 2015

We successfully transferred a two‐stage batch precipitation‐based antibody capture step to continuous mode using continuous tubular reactors. The precipitation process solely employs a cheap mineral salt (CaCl2) and an organic solvent (ethanol) and could replace the costly protein A capture step in the purification of recombinant antibodies from cell culture supernatant. The time from startup untill attaining steady state conditions was reached in less than 15 minutes and both reactors were operated for several hours at steady state without manual intervention, delivering antibody at a constant yield and purity. An overall yield of > 90 percent, with a host cell protein reduction from 42 777 to 9000 ppm and a DNA reduction from 359 ppm to 7 ppm, could be achieved for the antibody investigated. The precipitated antibody can be dissolved at very high concentrations (> 40 g/L) in numerous buffer systems of various pH and high and low ionic strength, thereby rendering a subsequent concentration or buffer exchange step redundant. This system enables cell culture supernatants with low or high antibody titer to be processed with constant reactor size and without changing any parameters or increasing precipitant consumption. Aggregate levels were below 1% under all conditions tested. Purification by precipitation did not affect binding to CD16a or the isoform distribution of the antibody.
Intraoperative radiotherapy in early breast cancer
Authors: Esposito E , Anninga B , Harris S , Capasso I , D'Aiuto M , Rinaldo M , Douek M
Published: March 2015

Background

Intraoperative radiotherapy (IORT) constitutes a paradigm shift from the conventional 3–5 weeks of whole-breast external beam radiotherapy (EBRT). IORT enables delivery of radiation at the time of excision of the breast tumour, targeting the area at highest risk of recurrence, while minimizing excessive radiation exposure to healthy breast tissue. The rationale for IORT is based on the observation that over 90 per cent of local recurrences after breast-conserving surgery occur at or near the original operation site.

Methods

This article reviews trials of IORT delivered with different techniques and devices.

Results

IORT is a very attractive option for delivering radiotherapy, reducing the traditional fractionated treatment to a single fraction administered at the time of surgery. IORT has been shown to be associated with reduced toxicity and has several potential benefits over EBRT. Only two randomized clinical trials have been published to date. The TARGIT-A and ELIOT trials have demonstrated that IORT is associated with a low rate of local recurrence, although higher than that after EBRT (TARGIT-A: 3·3 versus 1·3 per cent respectively, P = 0·042; ELIOT: 4·4 versus 0·4 per cent, P < 0·001). However, the local recurrence rate for IORT fell within the predefined 2·5 per cent non-inferiority margin in TARGIT-A, and the 7·5 per cent equivalence margin in ELIOT.

Conclusion

Longer follow-up data from existing trials, optimization of patient criteria and cost-effectiveness analyses are needed. Based on the current evidence, IORT can be offered as an alternative to EBRT to selected patients within agreed protocols, and outcomes should be monitored within national registries.
‘I Miss My Little One A Lot’: How Father Love Motivates Change in Men Who Have Used Violence
Authors: Broady Timothy R. , Gray Rebecca , Gaffney Irene , Lewis Pamela
Published: March 2015

This paper presents selected findings from a research‐based evaluation of a men's domestic violence intervention programme, which aims to assist men to develop alternative ways of relating to their partners, children and others. The qualitative component of this evaluation involved conducting interviews with 21 group participants after their completion of the course. These interviews investigated several issues, including participants' perceptions of their relationships with their children. The main theme underpinning all discussions of children was an expression of love, in that love for their children served as a motivation to stop using violence and to develop alternative ways of relating to all family members. The paper concludes by discussing the potential of men's relationships with their children as powerful contexts, or points of leverage, through which the impact of their violent behaviour can be realised and confronted. By realising the impact that violent behaviour can have on children's wellbeing and fathers' interpersonal relationships with them, it is argued that intervention programmes can support men to develop more appropriate ways of relating to their children, and thus safeguard children from potential long‐term consequences of domestic abuse. Copyright © 2015 John Wiley & Sons, Ltd.

‘The main theme underpinning all discussions of children was an expression of love’

Key Practitioner Messages

Men attending domestic violence intervention programmes demonstrate a wide range of attitudes towards their partners and former partners, but unanimously report a desire to maintain meaningful relationships with their children.

Men who have used violence in their family relationships can be challenged and motivated to change through realising the impact of their behaviour on their children's wellbeing and their father‐child relationships.

‘Unanimously report a desire to maintain meaningful relationships with their children’
Tunable Photochromism in the Robust Dithienylethene‐Containing Phospholes: Design, Synthesis, Characterization, Electrochemistry, Photophysics, and Photochromic Studies
Authors: Chan Jacky Chi‐Hung , Wong Hok‐Lai , Wong Wing‐Tak , Yam Vivian Wing‐Wah
Published: March 2015

A series of dithienylethene‐containing phosphole derivatives has been designed, synthesized and characterized. One of the compounds has been characterized by X‐ray crystallography. Upon photoexcitation, the compounds exhibit drastic color changes, ascribed to the reversible photochromic behavior. Their photochromic, photophysical and electrochemical properties have been studied. They show photochromic reactivities with high photocyclization quantum yields. Their photophysical and photochromic properties are found to be facilely tuned in this system by substitution at the phosphole backbone, as well as variation on the extent of π‐conjugation of the phosphole backbone. Some selected compounds have been demonstrated to exhibit photochromic properties in polymethylmethacrylate (PMMA) films.
Twist versus Linkage Mode: Which One is Better for the Construction of Blue Luminogens with AIE Properties?
Authors: Yang Jie , Huang Jing , Sun Ning , Peng Qian , Li Qianqian , Ma Dongge , Li Zhen
Published: March 2015

Two new blue luminogens, Py‐4MethylTPE and Py‐4mTPE, constructed with a pyrene core and tetraphenylethene peripheries, have been successfully obtained. These two luminogens show AIE and AEE effects, respectively, as a result of minor differences in their structures. An OLED device based on Py‐4mTPE exhibits a good performance (ηC,max=4.02 cd A−1, λEL,max=436 nm) and reveals the powerful effect of a different linkage mode for the construction of blue AIE luminogens.
Synthesis of One‐Dimensional Schiff Base Polymers that Contain an Oligothiophene Building Block on the Graphite Surface
Authors: Sun Xiu‐Ling , Fan Li‐Xia , Yang Yong‐Jing , Guo Zongxia , Tian Wei Quan , Lei Shengbin
Published: March 2015

Surface‐mediated Schiff base coupling reactions between oligothiophenes equipped with an aldehyde group and aromatic diamines were investigated on highly oriented pyrolytic graphite (HOPG) by means of scanning tunneling microscopy (STM) under ambient conditions. To investigate the evolution process from monomers to resultant polymers and the mechanism of reactions, we controlled the ratio of precursors and the reactive temperature, and we obtained high‐resolution STM images of different stages of the surface reaction. The results suggest that preferential adsorption of one kind of monomer has a great influence on the on‐ surface Schiff base reaction.
Square Tiling by Square Macrocycles at the Liquid/Solid Interface: Co‐crystallisation with One‐ or Two‐Dimensional Order
Authors: Tahara Kazukuni , Gotoda Jun , Carroll Calden N. , Hirose Keiji , De Feyter Steven , Tobe Yoshito
Published: March 2015

We have systematically investigated the self‐assembled monolayers of seven bimolecular mixtures of square‐shaped pyridinophanes and cyclophanes bearing alkoxy or alkoxycarbonyl substituents in the presence of the tropylium ion as a marker of pyridinophanes at liquid/graphite interfaces by means of scanning tunnelling microscopy (STM). The purpose of this work was to elucidate the mixing behaviour of these macrocycles highlighting the formation of one‐ or two‐dimensionally ordered square tilings consisting of alternating alignments of different macrocycles as a result of attractive dipole–dipole or hydrogen‐bonding interactions; four co‐crystals differing in the dimensionality of the ordering of pyridinophane and cyclophane were observed. The different modes of interaction between the functional groups (ether or carbonyl group) in the side‐chains of the pyridinophanes and cyclophanes lead to the formation of co‐crystals with dimensionally different orderings of the two macrocycles. These observations revealed that a slight modification of the molecular structure may dramatically change the mixing behaviour and structures of the co‐crystals.
Cooperative Dehydrogenation of N‐Heterocycles Using a Carbon Nanotube–Rhodium Nanohybrid
Authors: Jawale Dhanaji V. , Gravel Edmond , Shah Nimesh , Dauvois Vincent , Li Haiyan , Namboothiri Irishi N. N. , Doris Eric
Published: March 2015

Rhodium nanoparticles were anchored on carbon nanotubes and the resulting nanohybrid was studied as co‐catalyst, along with tert‐butylcatechol, for the dehydrogenation of various N‐heterocycles. The co‐catalytic system operates in high yields, under the mildest conditions reported so far, and can be applied to a wide variety of secondary amine‐containing scaffolds.
Bismetal Complexes of 5,20‐Bis(5‐formyl‐2‐pyrrolyl)‐[26]hexaphyrin(1.1.1.1.1.1) Exhibiting Strong Near‐Infrared Region Absorptions
Authors: Mori Hirotaka , Osuka Atsuhiro
Published: March 2015

[26]Hexaphyrin(1.1.1.1.1.1) bearing two 5‐formyl‐2‐pyrrolyl groups at the 5‐ and 20‐positions was prepared by cross‐condensation of 5,10‐bis(pentafluorophenyl)‐substituted tripyrrane with 2,5‐diformylpyrrole as an effective binuclear metal‐coordinating ligand, owing to the two hemiporphyrin‐like NNNN pockets. In fact, metalation of this hexaphyrin with ZnII, CuII, and PdII salts proceed smoothly at room temperature to give the corresponding bismetal complexes that displayed remarkably redshifted absorption spectra reaching deep into near infrared region. These redshifted absorption bands are ascribed, through electrochemical investigations and DFT calculations, to two structural motifs: the N‐metalopyrrole substructure that elevates the HOMO level due to the electron‐donating property and the two coordinated metal ions that serve as Lewis acids to lower the LUMO level.
Targeting the Erythrocytic and Liver Stages of Malaria Parasites with s‐Triazine‐Based Hybrids
Authors: Rodrigues Catarina A. B. , Frade Raquel F. M. , Albuquerque Inês S. , Perry Maria J. , Gut Jiri , Machado Marta , Rosenthal Philip J. , Prudêncio Miguel , Afonso Carlos A. M. , Moreira Rui
Published: March 2015

A diversity‐oriented library of s‐triazine‐based hybrids was screened for activity against the chloroquine‐resistant Plasmodium falciparum W2 strain. The most striking result was sub‐micromolar activity against cultured erythrocytic‐stage parasites of hybrid molecules containing one or two 8‐aminoquinoline moieties. These compounds were not clearly toxic to human cells. The most effective blood‐schizontocidal s‐triazine derivatives were then screened for activity against the liver stage of malaria parasites. The s‐triazine hybrid containing two 8‐aminoquinoline moieties and one chlorine atom emerged as the most potent against P. berghei liver‐stage infection, active in the low nanomolar region, combined with good metabolic stability in rat liver microsomes. These results indicate that s‐triazine‐8‐aminoquinoline‐based hybrids are excellent starting points for lead optimization as dual‐stage antimalarials.
High spatial resolution proteomic comparison of the brain in humans and chimpanzees
Authors: Bauernfeind Amy L. , Reyzer Michelle L. , Caprioli Richard M. , Ely John J. , Babbitt Courtney C. , Wray Gregory A. , Hof Patrick R. , Sherwood Chet C.
Published: March 2015

We performed high‐throughput mass spectrometry at high spatial resolution from individual regions (anterior cingulate and primary motor, somatosensory, and visual cortices) and layers of the neocortex (layers III, IV, and V) and cerebellum (granule cell layer), as well as the caudate nucleus in humans and chimpanzees. A total of 39 mass spectrometry peaks were matched with probable protein identifications in both species, allowing for comparison in expression. We explored how the pattern of protein expression varies across regions and cortical layers to provide insights into the differences in molecular phenotype of these neural structures between species. The expression of proteins differed principally in a region‐ and layer‐specific pattern, with more subtle differences between species. Specifically, human and chimpanzee brains were similar in their distribution of proteins related to the regulation of transcription and enzyme activity but differed in their expression of proteins supporting aerobic metabolism. Whereas most work assessing molecular expression differences in the brains of primates has been performed on gene transcripts, this dataset extends current understanding of the differential molecular expression that may underlie human cognitive specializations. J. Comp. Neurol. 523:2043–2061, 2015. © 2015 Wiley Periodicals, Inc.
Methoxy and Methyl Group Rotation: Solid‐State NMR 1H Spin‐Lattice Relaxation, Electronic Structure Calculations, X‐ray Diffractometry, and Scanning Electron Microscopy
Authors: Beckmann Peter A. , Mallory Clelia W. , Mallory Frank B. , Rheingold Arnold L. , Wang Xianlong
Published: March 2015

We report solid‐state 1H nuclear magnetic resonance (NMR) spin‐lattice relaxation experiments, X‐ray diffractometry, field‐emission scanning electron microscopy, and both single‐molecule and cluster ab initio electronic structure calculations on 1‐methoxyphenanthrene (1) and 3‐methoxyphenanthrene (2) to investigate the rotation of the methoxy groups and their constituent methyl groups. The electronic structure calculations and the 1H NMR relaxation measurements can be used together to determine barriers for the rotation of a methoxy group and its constituent methyl group and to develop models for the two coupled motions.
Oxygen Sorption and Desorption Properties of Selected Lanthanum Manganites and Lanthanum Ferrite Manganites
Authors: Nielsen Jimmi , Skou Eivind M. , Jacobsen Torben
Published: March 2015

Temperature‐programmed desorption (TPD) with a carrier gas was used to study the oxygen sorption and desorption properties of oxidation catalysts and solid‐oxide fuel cell (SOFC) cathode materials (La0.85Sr0.15)0.95MnO3+δ (LSM) and La0.60Sr0.40Fe0.80Mn0.20O3‐δ (LSFM). The powders were characterized by X‐ray diffractometry, atomic force microscopy (AFM), and BET surface adsorption. Sorbed oxygen could be distinguished from oxygen originating from stoichiometry changes. The results indicated that there is one main site for oxygen sorption/desorption. The amount of sorbed oxygen was monitored over time at different temperatures. Furthermore, through data analysis it was shown that the desorption peak associated with oxygen sorption is described well by second‐order desorption kinetics. This indicates that oxygen molecules dissociate upon adsorption and that the rate‐determining step for the desorption reaction is a recombination of monatomic oxygen. Typical problems with re‐adsorption in this kind of TPD setup were revealed to be insignificant by using simulations. Finally, different key parameters of sorption and desorption were determined, such as desorption activation energies, density of sorption sites, and adsorption and desorption reaction order.
Air Quality and Temperature Effects on Exercise‐Induced Bronchoconstriction
Authors: Rundell Kenneth W. , Anderson Sandra D. , Sue‐Chu Malcolm , Bougault Valerie , Boulet Louis‐Philippe
Published: March 2015

Exercise‐induced bronchoconstriction (EIB) is exaggerated constriction of the airways usually soon after cessation of exercise. This is most often a response to airway dehydration in the presence of airway inflammation in a person with a responsive bronchial smooth muscle. Severity is related to water content of inspired air and level of ventilation achieved and sustained. Repetitive hyperpnea of dry air during training is associated with airway inflammatory changes and remodeling. A response during exercise that is related to pollution or allergen is considered EIB. Ozone and particulate matter are the most widespread pollutants of concern for the exercising population; chronic exposure can lead to new‐onset asthma and EIB. Freshly generated emissions particulate matter less than 100 nm is most harmful. Evidence for acute and long‐term effects from exercise while inhaling high levels of ozone and/or particulate matter exists. Much evidence supports a relationship between development of airway disorders and exercise in the chlorinated pool. Swimmers typically do not respond in the pool; however, a large percentage responds to a dry air exercise challenge. Studies support oxidative stress mediated pathology for pollutants and a more severe acute response occurs in the asthmatic. Winter sport athletes and swimmers have a higher prevalence of EIB, asthma and airway remodeling than other athletes and the general population. Because of fossil fuel powered ice resurfacers in ice rinks, ice rink athletes have shown high rates of EIB and asthma. For the athlete training in the urban environment, training during low traffic hours and in low traffic areas is suggested. © 2015 American Physiological Society.Compr Physiol5:579‐610, 2015.
Mathematical Modeling in Neuroendocrinology
Authors: Bertram Richard
Published: March 2015

Mathematical models are commonly used in neuroscience, both as tools for integrating data and as devices for designing new experiments that test model predictions. The wide range of relevant spatial and temporal scales in the neuroendocrine system makes neuroendocrinology a branch of neuroscience with great potential for modeling. This article provides an overview of concepts that are useful for understanding mathematical models of the neuroendocrine system, as well as design principles that have been illuminated through the use of mathematical models. These principles are found over and over again in cellular dynamics, and serve as building blocks for understanding some of the complex temporal dynamics that are exhibited throughout the neuroendocrine system. © 2015 American Physiological Society.Compr Physiol5:911‐927, 2015.
Peripheral Chemoreception and Arterial Pressure Responses to Intermittent Hypoxia
Authors: Prabhakar Nanduri R. , Peng Ying‐Jie , Kumar Ganesh K. , Nanduri Jayasri
Published: March 2015

Carotid bodies are the principal peripheral chemoreceptors for detecting changes in arterial blood oxygen levels, and the resulting chemoreflex is a potent regulator of blood pressure. Recurrent apnea with intermittent hypoxia (IH) is a major clinical problem in adult humans and infants born preterm. Adult patients with recurrent apnea exhibit heightened sympathetic nerve activity and hypertension. Adults born preterm are predisposed to early onset of hypertension. Available evidence suggests that carotid body chemoreflex contributes to hypertension caused by IH in both adults and neonates. Experimental models of IH provided important insights into cellular and molecular mechanisms underlying carotid body chemoreflex‐mediated hypertension. This article provides a comprehensive appraisal of how IH affects carotid body function, underlying cellular, molecular, and epigenetic mechanisms, and the contribution of chemoreflex to the hypertension. © 2015 American Physiological Society.
Compr Physiol
5:561‐577, 2015.
Intracellular Signaling of Cardiac Fibroblasts
Authors: Roche Patricia L. , Filomeno Krista L. , Bagchi Rushita A. , Czubryt Michael P.
Published: March 2015

Long regarded as a mere accessory cell for the cardiomyocyte, the cardiac fibroblast is now recognized as a critical determinant of cardiac function in health and disease. A recent renaissance in fibroblast‐centered research has fostered a better understanding than ever before of the biology of fibroblasts and their contractile counterparts, myofibroblasts. While advanced methodological approaches, including transgenics, lineage fate mapping, and improved cell marker identification have helped to facilitate this new work, the primary driver is arguably the contribution of myofibroblasts to cardiac pathophysiology including fibrosis and arrhythmogenesis. Fibrosis is a natural sequel to numerous common cardiac pathologies including myocardial infarction and hypertension, and typically exacerbates cardiovascular disease and progression to heart failure, yet no therapies currently exist to specifically target fibrosis. The regulatory processes and intracellular signaling pathways governing fibroblast and myofibroblast behavior thus represent important points of inquiry for the development of antifibrotic treatments. While steady progress is being made in uncovering the signaling pathways specific for cardiac fibroblast function (including proliferation, phenotype conversion, and matrix synthesis), much of what is currently known of fibroblast signaling mechanisms is derived from noncardiac fibroblast populations. Given the heterogeneity of fibroblasts across tissues, this dearth of information further underscores the need for progress in cardiac fibroblast biological research. © 2015 American Physiological Society.Compr Physiol5:721‐760, 2015.
Alcohol Effects on Cardiac Function
Authors: Gardner Jason D. , Mouton Alan J.
Published: March 2015

The consumption of ethanol can have both beneficial and detrimental effects on the function of the heart and cardiovascular system, depending on the amount consumed. Low‐to‐moderate amounts of ethanol intake are associated with improvements in cardiac function and vascular health. On the other hand, ethanol chronically consumed in large amounts acts as a toxin to the heart and vasculature. The cardiac injury produced by chronic alcohol abuse can progress to heart failure and eventual death. Furthermore, alcohol abuse may exacerbate preexisting heart conditions, such as hypertension and cardiomyopathy. This article focuses on the molecular mechanisms and pathophysiology of both the beneficial and detrimental cardiac effects of alcohol. © 2015 American Physiological Society.Compr Physiol5:791‐802, 2015.