bluuebunny/crossref_metadata_2025 huggingface dataset:
Microbial granulation for lactic acid production
Authors: Kim Dong‐Hoon , Lee Mo‐Kwon , Hwang Yuhoon , Im Wan‐Taek , Yun Yeo‐Myeong , Park Chul , Kim Mi‐Sun
Published: April 2015

This work investigated the formation of microbial granules to boost the productivity of lactic acid (LA). The flocculated form of LA‐producing microbial consortium, dominated by Lactobacillus sp. (91.5% of total sequence), was initially obtained in a continuous stirred‐tank reactor (CSTR), which was fed with 2% glucose and operated at a hydraulic retention time (HRT) of 12 h and pH 5.0 ± 0.1 under a thermophilic condition (50°C). The mixed liquor in the CSTR was then transferred to an up‐flow anaerobic sludge blanket reactor (UASB). The fermentation performance and granulation process were monitored with a gradual decrease of HRT from 8.0 to 0.17 h, corresponding to an increase in the substrate loading from 60 to 2,880 g glucose L−1d−1. As the operation continued, the accumulation of biomass in the UASB was clearly observed, which changed from flocculent to granular form with decrease in HRT. Up to the HRT decrease to 0.5 h, the LA concentration was maintained at 19–20 g L−1 with over 90% of substrate removal efficiency. However, further decrease of HRT resulted in a decrease of LA concentration with increase in residual glucose. Nevertheless, the volumetric LA productivity continuously increased, reaching 67 g L‐fermenter−1h−1 at HRT 0.17 h. The size of LA‐producing granules and hydrophobicity gradually increased with decrease in HRT, reaching 6.0 mm and 60%, respectively. These biogranules were also found to have high settling velocities and low porosities, ranging 2.69–4.73 cm s−1 and 0.39–0.92, respectively. Biotechnol. Bioeng. 2016;113: 101–111. © 2015 Wiley Periodicals, Inc.
Covalent immobilization of pullulanase on alginate and study of its hydrolysis of pullulan
Authors: Ali Ghina , Dulong Virginie , Gasmi Sarah N. , Rihouey Christophe , Picton Luc , Le Cerf Didier
Published: April 2015

The immobilization of pullulanase from Klebsiella pneumoniae by grafting was investigated. Pullulanase was linked after activation of alginate via a covalent bond between the amine groups of the enzyme and the carboxylic acid groups of alginate. The immobilization yield was 60%. The activity of free pullulanase and immobilized pullulanase was followed by the quantification of reducing ends by colorimetric assay and the determination of the molar masses of the hydrolyzed pullulan by SEC/MALS/DRI. Compared to free pullulanase, the kinetics is largely slowed. The evolution of the weight average molar mass of pullulan leading to high production of shorter oligosaccharides during hydrolysis is not the same as that obtained with free enzyme. Immobilized pullulanase retained 75% and 30% of its initial activity after 24 h and 14 days of incubation at 60°C, respectively while free pullulanase lost its activity after 5 h of hydrolysis at the same temperature. The kinetic parameters of immobilized pullulanase were also investigated by isothermal titration calorimetry (ITC). The affinity of immobilized enzyme to its substrate was reduced compared to the free pullulanase due to steric hindrance and chemical links. © 2015 American Institute of Chemical Engineers Biotechnol. Prog., 31:883–889, 2015
Defining the Interaction of Human Soluble Lectin ZG16p and Mycobacterial Phosphatidylinositol Mannosides
Authors: Hanashima Shinya , Götze Sebastian , Liu Yan , Ikeda Akemi , Kojima‐Aikawa Kyoko , Taniguchi Naoyuki , Varón Silva Daniel , Feizi Ten , Seeberger Peter H. , Yamaguchi Yoshiki
Published: April 2015

ZG16p is a soluble mammalian lectin that interacts with mannose and heparan sulfate. Here we describe detailed analysis of the interaction of human ZG16p with mycobacterial phosphatidylinositol mannosides (PIMs) by glycan microarray and NMR. Pathogen‐related glycan microarray analysis identified phosphatidylinositol mono‐ and di‐mannosides (PIM1 and PIM2) as novel ligand candidates of ZG16p. Saturation transfer difference (STD) NMR and transferred NOE experiments with chemically synthesized PIM glycans indicate that PIMs preferentially interact with ZG16p by using the mannose residues. The binding site of PIM was identified by chemical‐shift perturbation experiments with uniformly 15N‐labeled ZG16p. NMR results with docking simulations suggest a binding mode of ZG16p and PIM glycan; this will help to elucidate the physiological role of ZG16p.
Asymmetric NaBH4 1,4‐Reduction of C3‐Disubstituted 2‐Propenoates Catalyzed by a Diamidine Cobalt Complex
Authors: Shuto Yoshihiro , Yamamura Tomoya , Tanaka Shinji , Yoshimura Masahiro , Kitamura Masato
Published: April 2015

A new Co complex of a unique diamidine ligand catalyzes asymmetric NaBH4 reduction of C3‐disubstituted (E)‐ and (Z)‐2‐propenoates, including C3‐oxygen‐ and nitrogen‐substituted substrates with high enantioselectivity. Analysis by X‐ray diffraction, 1H NMR spectroscopy, ring‐opening radical‐clock and D‐labeling reactions, and the structure/selectivity relationship suggest that a mechanism of CoH‐involved non‐single‐electron transfer 1,4‐addition differentiates the C2 enantioface. Involvement of CoH species has been supported by quantitative isolation of a new type of CoH2(BH3)2 complex.
Catalytic Surface Promotion of Composite Cathodes in Protonic Ceramic Fuel Cells
Authors: Solís Cecilia , Navarrete Laura , Bozza Francesco , Bonanos Nikolaos , Serra José M.
Published: April 2015

Composite cathodes based on an electronic conductor and a protonic conductor show advantages for protonic ceramic fuel cells. In this work, the performance of a La5.5WO11.25−δ/La0.8Sr0.2MnO3+δ (LWO/LSM) composite cathode in a fuel cell based on an LWO protonic conducting electrolyte is shown and catalytically improved. The limiting processes were first unambiguously associated to surface steps, and the reaction rate was significantly enhanced by 1) tailoring the catalytic activity through electrode surface impregnation with intrinsically catalytic nanoparticles and 2) electrochemical activation of surface species by imposing a net current through the electrode.
Effect of Adding CeO2 to RuO2–IrO2 Mixed Nanocatalysts: Activity towards the Oxygen Evolution Reaction and Stability in Acidic Media
Authors: Audichon Thomas , Morisset Sophie , Napporn Teko W. , Kokoh K. Boniface , Comminges Clément , Morais Cláudia
Published: April 2015

Trimetallic Ru‐, Ir‐, and Ce‐oxide materials were synthesized by using a hydrolysis method in ethanol medium and characterized to obtain information on their crystallographic structure, morphology, and chemical composition. Voltammetric measurements allowed us to evaluate the properties of these catalysts through the determination of their capacitance, active site number, and accessibility. The effect of cerium on the oxygen evolution reaction (OER) was also evaluated electrochemically and the catalytic layer stability was measured by using a repetitive cyclic voltammetry procedure. The catalysts stability in an acidic medium is not significantly affected by cerium addition. Moreover, the oxygen mobility in the ceria crystallographic structure may contribute to an enhanced electrocatalytic activity per active site. Tafel slope values were determined from electrochemical impedance spectroscopy fitting parameters and indicate the same OER rate‐determining step for mono‐, bi‐, and trimetallic catalysts.
Synthesis, Crystal Structure and Magnetic Properties of a Novel Heterobimetallic Rhenium(IV)–Dysprosium(III) Chain
Authors: Pejo Carolina , Guedes Guilherme P. , Novak Miguel A. , Speziali Nivaldo L. , Chiozzone Raúl , Julve Miguel , Lloret Francesc , Vaz Maria G. F. , González Ricardo
Published: April 2015

The use of the mononuclear rhenium(IV) precursor [ReBr5(H2pydc)]− (H2pydc=3,5‐pyridinedicarboxylic acid) as a metalloligand towards dysprosium(III) afforded the first heterobimetallic ReIV–DyIII complex. Crystal structures and static and dynamic magnetic properties of both rhenium‐containing species are reported herein. The 5d–4f compound shows an extended 1D structure and the AC magnetic measurements reveal frequency dependence at low temperature suggesting slow relaxation of the magnetization.
Organocatalytic Highly Enantioselective Substitution of 3‐(1‐Tosylalkyl)indoles with Oxindoles Enables the First Total Synthesis of (+)‐Trigolutes B
Authors: Huang Jian‐Zhou , Zhang Chen‐Long , Zhu Yi‐Fan , Li Lu‐Lu , Chen Dian‐Feng , Han Zhi‐Yong , Gong Liu‐Zhu
Published: April 2015

A highly enantioselective organocatalytic substitution of 3‐(1‐tosylalkyl)indoles with oxindoles has been established by using chiral bifunctional organocatalysts, providing an efficient entry to multiply functionalized 3,3′‐disubstituted oxindoles, and was exploited as the key step to enable the first asymmetric total synthesis of optically pure (+)‐trigolutes B to be accomplished in a concise manner, within seven steps with an 18 % overall yield.
Crown‐Shaped Tungstogermanates as Solvent‐Controlled Dual Systems in the Formation of Vesicle‐Like Assemblies
Authors: Artetxe Beñat , Reinoso Santiago , San Felices Leire , Gutiérrez‐Zorrilla Juan M. , García José A. , Haso Fadi , Liu Tianbo , Vicent Cristian
Published: April 2015

Reaction of early lanthanides, GeO2, and Na2WO4 in a NaOAc buffer results in large crown‐shaped polyoxometalates based on [Ln2GeW10O38]6− subunits. By using Ni2+ as a crystallizing agent, [Na⊂Ln12Ge6W60O228(H2O)24]35− (Na⊂Ln12) hexamers formed by alternating β(1,5)/β(1,8) subunits were obtained for Ln=Pr, Nd. The addition of K+ led to a similar anion for Ln=Sm, namely, [K⊂Sm12Ge6W60O228(H2O)22]35− (K⊂Sm12) and [K⊂K7Ln24Ge12W120O444(OH)12(H2O)64]52− (K⊂Ln24) dodecamers that consist of a central core identical to K⊂Sm12 decorated with six external γ(3,4) subunits for Ln=Pr, Nd. These anions dissociate in water into hexameric cores and monomeric entities, as shown by ESI mass spectrometry. The former self‐assemble into spherical, hollow, and single‐layered blackberry‐type structures with radii of approximately 75 nm, as monitored by laser light scattering (LLS) and TEM techniques. Analogous studies performed for K⊂Nd24 in water/acetone mixtures show that the dodecamers remain stable and form in turn their own type of blackberries with sizes that increase from approximately 20 to 50 nm with increasing acetone content. This control over both the composition and size of the vesicle‐like assemblies is achieved for the first time by modifying the architecture of the species that undergoes supramolecular association through the solvent polarity.
Micelle‐Triggered β‐Hairpin to α‐Helix Transition in a 14‐Residue Peptide from a Choline‐Binding Repeat of the Pneumococcal Autolysin LytA
Authors: Zamora‐Carreras Héctor , Maestro Beatriz , Strandberg Erik , Ulrich Anne S. , Sanz Jesús M. , Jiménez M. Ángeles
Published: April 2015

Choline‐binding modules (CBMs) have a ββ‐solenoid structure composed of choline‐binding repeats (CBR), which consist of a β‐hairpin followed by a short linker. To find minimal peptides that are able to maintain the CBR native structure and to evaluate their remaining choline‐binding ability, we have analysed the third β‐hairpin of the CBM from the pneumococcal LytA autolysin. Circular dichroism and NMR data reveal that this peptide forms a highly stable native‐like β‐hairpin both in aqueous solution and in the presence of trifluoroethanol, but, strikingly, the peptide structure is a stable amphipathic α‐helix in both zwitterionic (dodecylphosphocholine) and anionic (sodium dodecylsulfate) detergent micelles, as well as in small unilamellar vesicles. This β‐hairpin to α‐helix conversion is reversible. Given that the β‐hairpin and α‐helix differ greatly in the distribution of hydrophobic and hydrophilic side chains, we propose that the amphipathicity is a requirement for a peptide structure to interact and to be stable in micelles or lipid vesicles. To our knowledge, this “chameleonic” behaviour is the only described case of a micelle‐induced structural transition between two ordered peptide structures.
Directed Hydrogenations and an Ireland–Claisen Rearrangement Linked to Evans–Tishchenko Chemistry: The Highly Efficient Total Synthesis of the Marine Cyclodepsipeptide Doliculide
Authors: Chen Tao , Altmann Karl‐Heinz
Published: April 2015

Two new convergent total syntheses have been developed for the cytotoxic, actin microfilament‐stabilizing marine cyclodepsipeptide doliculide (1). A key strategic element of both routes is the establishment of the central stereogenic center of the characteristic polydeoxypropionate stereotriad by means of a hydroxyl‐directed catalytic hydrogenation of a trisubstituted double bond. The requisite olefin substrates were obtained through a modified Suzuki–Miyaura coupling or through Ireland–Claisen rearrangement of a propionate ester, respectively; the latter was the direct result of a highly selective Evans–Tishchenko reduction of a hydroxy ketone that had been obtained in a stereoselective Paterson aldol reaction. Doliculide (1) was finally obtained in a total number of 17 or 15 (14) linear steps, respectively, which represents a substantial improvement over previous syntheses of this highly bioactive natural product.
Enantiomeric Cyclic Peptides with Different Caco‐2 Permeability Suggest Carrier‐Mediated Transport
Authors: Marelli Udaya Kiran , Bezençon Jacqueline , Puig Eduard , Ernst Beat , Kessler Horst
Published: April 2015

Recently, oral absorption of cyclic hexapeptides was improved by N‐methylation of their backbone amides. However, the number and position of N‐methylations or of solvent exposed NHs did not correlate to intestinal permeability, measured in a Caco‐2 model. In this study, we investigate enantiomeric pairs of three polar and two lipophilic peptides to demonstrate the participation of carrier‐mediated transporters. As expected, all the enantiomeric peptides exhibited identical lipophilicity (logD7.4) and passive transcellular permeability determined by the parallel artificial membrane permeability assay (PAMPA). However, the enantiomeric polar peptides exhibited different Caco‐2 permeability (Papp) in both directions a–b and b–a. The same trend was observed for one of the lipophilic peptide, whereas the second lipophilic enantiomer pair showed identical Caco‐2 permeability (within the errors). These findings provide the first evidence for the involvement of carrier‐mediated transport for peptides, especially for those of polar nature.
Solid Polymer Substrates and Coated Fibers Containing 2,4,6‐Trinitrobenzene Motifs as Smart Labels for the Visual Detection of Biogenic Amine Vapors
Authors: Pablos Jesús L. , Vallejos Saúl , Muñoz Asunción , Rojo María J. , Serna Felipe , García Félix C. , García José M.
Published: April 2015

Attempts to polymerize trinitrobenzene derivatives (TNB) have been fruitless so far. Accordingly, polymers containing TNB have not been exploited in spite of their envisaged potential applications. Here, we describe two ways for preparing polymers with TNB moieties thus overcoming the previously reported polymerization impairments. We also report on the exploitation of the materials, both obtained as tractable transparent films and coated fibers, as smart labels for the visual detection of amine vapors. More precisely, amines in the atmosphere surrounding the sensory materials diffuse into them reacting with the TNB motifs forming highly colored Meisenheimer complexes, giving rise to development of color and to the naked eye sensing phenomenon. This is the case of highly volatile amines, such as trimethylamine, produced in food spoilage, specifically in the deterioration of fish or meat, for which the color development of the smart labels can be used as a visual test for food freshness.
Chirality and Gravitational Parity Violation
Authors: Bargueño Pedro
Published: April 2015

In this review, parity‐violating gravitational potentials are presented as possible sources of both true and false chirality. In particular, whereas phenomenological long‐range spin‐dependent gravitational potentials contain both truly and falsely chiral terms, it is shown that there are models that extend general relativity including also coupling of fermionic degrees of freedom to gravity in the presence of torsion, which give place to short‐range truly chiral interactions similar to that usually considered in molecular physics. Physical mechanisms which give place to gravitational parity violation together with the expected size of the effects and their experimental constraints are discussed. Finally, the possible role of parity‐violating gravity in the origin of homochirality and a road map for future research works in quantum chemistry is presented. Chirality 27:375–381, 2015.© 2015 Wiley Periodicals, Inc.
Scale‐sifting multiscale nonlinear process quality monitoring and fault detection
Authors: Liu Yang , Zhang Guoshan
Published: April 2015

We demonstrate a novel multiscale nonlinear process monitoring and fault detection method, called the scale‐sifting multiscale algorithm(SMA). The key innovative feature of SMA is essential scale data reconstruction without prior knowledge of signals monitored compared with state‐of‐the‐art multiscale monitoring methods. The SMA includes a scale‐sifting benchmark, data decomposition and data reconstruction, and dynamic kernel partial least squares. The scale‐sifting benchmark is developed to sift out special scales with the essential features of abnormal situations. Then, the data are reconstructed corresponding to selected scales. Finally, dynamic KPLS is applied to analyze data reconstructed for online quality process monitoring and fault detection. The application results illustrate the effectiveness of the proposed method
Participants' barriers to diagnostic resolution and factors associated with needing patient navigation
Authors: Krok‐Schoen Jessica L. , Brewer Brittany M. , Young Gregory S. , Weier Rory C. , Tatum Cathy M. , DeGraffinreid Cecilia R. , Paskett Electra D.
Published: April 2015

BACKGROUND

Patient navigation (PN) may improve cancer care by identifying and removing patient‐reported barriers to care. In 2012, the American College of Surgeons Commission on Cancer (CoC) announced that health care facilities seeking CoC accreditation must have PN processes in place by January 1, 2015. Given these unfunded mandates, hospitals are looking for cost‐effective ways to implement PN. This study examined demographic and psychosocial predictors of barriers to diagnostic resolution among individuals with a cancer screening abnormality enrolled in the Ohio Patient Navigation Research Project.

METHODS

Data were obtained from patients who received care at 1 of 9 Ohio Patient Navigation Research Project intervention clinics. Descriptive statistics and logistic regression models were used.

RESULTS

There were 424 participants, and 151 (35.6%) reported a barrier to diagnostic resolution within 90 days of study consent. The most commonly reported barriers were misconceptions about a test or treatment (16.4%), difficulty in communicating with the provider (15.0%), and scheduling problems (11.5%). Univariate analyses indicated that race, education, employment, income, insurance, clinic type, friend support, and physical and psychological functioning were significantly associated with reporting a barrier to diagnostic resolution. Multivariate analyses found that comorbidities (odds ratio, 1.65; 95% confidence interval, 1.04‐2.61) and higher intrusive thoughts and feelings (odds ratio, 1.25; 95% confidence interval, 1.10‐1.41) were significantly associated with reporting a barrier to diagnostic resolution.

CONCLUSIONS

The results suggest that demographic and psychosocial factors are associated with barriers to diagnostic resolution. To ensure compliance with the CoC mandate and provide timely care to all patients, CoC‐accredited facilities can systematically identify the patients most likely to have barriers to care and assign them to PN. Cancer 2015;121:2757‐2764. © 2015 American Cancer Society
Morphology, innervation, and peripheral sensory cells of the siphon of aplysia californica
Authors: Carrigan Ian D. , Croll Roger P. , Wyeth Russell C.
Published: April 2015

The siphon of Aplysia californica has several functions, including involvement in respiration, excretion, and defensive inking. It also provides sensory input for defensive withdrawals that have been studied extensively to examine mechanisms that underlie learning. To better understand the neuronal bases of these functions, we used immunohistochemistry to catalogue peripheral cell types and innervation of the siphon in stage 12 juveniles (chosen to allow observation of tissues in whole‐mounts). We found that the siphon nerve splits into three major branches, leading ultimately to a two‐part FMRFamide‐immunoreactive plexus and an apparently separate tyrosine hydroxylase–immunoreactive plexus. Putative sensory neurons included four distinct types of tubulin‐immunoreactive bipolar cells (one likely also tyrosine hydroxylase immunoreactive) that bore ciliated dendrites penetrating the epithelium. A fifth bipolar neuron type (tubulin‐ and FMRFamide‐immunoreactive) occurred deeper in the tissue, associated with part of the FMRFamide‐immunoreactive plexus. Our observations emphasize the structural complexity of the peripheral nervous system of the siphon, and the importance of direct tests of the various components to better understand the functioning of the entire organ, including its role in defensive withdrawal responses. J. Comp. Neurol. 523:2409–2425, 2015. © 2015 Wiley Periodicals, Inc.
A BDDC Algorithm with Deluxe Scaling for Three‐Dimensional H(curl) Problems
Authors: Dohrmann Clark R. , Widlund Olof B.
Published: April 2015

In this paper, we present and analyze a BDDC algorithm for a class of elliptic problems in the three‐dimensional H(curl) space. Compared with existing results, our condition number estimate requires fewer assumptions and also involves two fewer powers of log(H/h), making it consistent with optimal estimates for other elliptic problems. Here, H/h is the maximum of Hi/hi over all subdomains, where Hi and hi are the diameter and the smallest element diameter for the subdomain Ωi. The analysis makes use of two recent developments. The first is a new approach to averaging across the subdomain interfaces, while the second is a new technical tool that allows arguments involving trace classes to be avoided. Numerical examples are presented to confirm the theory and demonstrate the importance of the new averaging approach in certain cases. © 2016 Wiley Periodicals, Inc.
Acetyl Methyl Torsion in N‐Ethylacetamide: A Challenge for Microwave Spectroscopy and Quantum Chemistry
Authors: Kannengießer Raphaela , Lach Marcel J. , Stahl Wolfgang , Nguyen Ha Vinh Lam
Published: April 2015

The gas‐phase structures and parameters describing acetyl methyl torsion of N‐ethylacetamide are determined with high accuracy, using a combination of molecular beam Fourier‐transform microwave spectroscopy and quantum chemical calculations. Conformational studies at the MP2 level of theory yield four minima on the energy surface. The most energetically favorable conformer, which possesses C1 symmetry, is assigned. Due to the torsional barrier of 73.4782(1) cm−1 of the acetyl methyl group, fine splitting up to 4.9 GHz is found in the spectrum. The conformational structure is not only confirmed by the rotational constants, but also by the orientation of the internal rotor. The 14N quadrupole hyperfine splittings are analyzed and the deduced coupling constants are compared with the calculated values.
Preparation of Cyclodextrin–Iron Species in Water by Laser Ablation: Secondary Ion Mass Spectrometry
Authors: Halaszova Sona , Jerigova Monika , Lorenc Dusan , Velic Dusan
Published: April 2015

Supramolecular complexes between cyclodextrin and iron species are studied by using secondary ion mass spectrometry. The iron species are prepared by pulsed‐laser ablation of bulk iron in water; this gives Fe+ (56 m/z) and FexOy+ (x, y=1–7) species. Cyclodextrin is added to the water either before or after the laser ablation. When it is added before laser ablation, molecular fragments of cyclodextrin are detected as dehydrated glucopyranose units (C6H8O4+) associated with Fe+, FeO+, and Fe2O+ species. The focus is to observe supramolecular host–guest complexes or adducts between intact molecules of cyclodextrin and iron species. When cyclodextrin is added after laser ablation, the relevant peak at 1210 m/z is observed and assigned as C42H67O35FeNa+, which corresponds to a cyclodextrin molecule minus three H atoms. Two possible explanations of this finding are the presence of the host–guest C42H67O35Na–Fe complex, in which Fe is in the cavity, or the presence of the adduct C42H67O34Na–FeO with FeO on the outer surface; the formation of these complexes are supported by the hydrophobicity of Fe and hydrophilicity of FeO, respectively. Due to the presence of 12 % of intact C42H70O35Na–Fe complex and an estimated Fe/FeO ratio of approximately 102, host–guest formation is assumed to be more significant.
Tuning of ZIF‐Derived Carbon with High Activity, Nitrogen Functionality, and Yield – A Case for Superior CO2 Capture
Authors: Gadipelli Srinivas , Guo Zheng Xiao
Published: April 2015

A highly effective and facile synthesis route is developed to create and tailor metal‐decorated and nitrogen‐functionalized active microporous carbon materials from ZIF‐8. Clear metal‐ and pyrrolic‐N‐induced enhancements of the cyclic CO2 uptake capacities and binding energies are achieved, particularly at a much lower carbonization temperature of 700 °C than those often reported (1000 °C). The high‐temperature carbonization can enhance the porosity but only at the expense of considerable losses of sample yield and metal and N functional sites. The findings are comparatively discussed with carbons derived from metal–organic frameworks (MOFs) reported previously. Furthermore, the porosity of the MOF‐derived carbon is critically dependent on the structure of the precursor MOF and the crystal growth. The current strategy offers a new and effective route for the creation and tuning of highly active and functionalized carbon structures in high yields and with low energy consumption.
A Rational Approach to CO2 Capture by Imidazolium Ionic Liquids: Tuning CO2 Solubility by Cation Alkyl Branching
Authors: Corvo Marta C. , Sardinha João , Casimiro Teresa , Marin Graciane , Seferin Marcus , Einloft Sandra , Menezes Sonia C. , Dupont Jairton , Cabrita Eurico J.
Published: April 2015

Branching at the alkyl side chain of the imidazolium cation in ionic liquids (ILs) was evaluated towards its effect on carbon dioxide (CO2) solubilization at 10 and 80 bar (1 bar=1×105 Pa). By combining high‐pressure NMR spectroscopy measurements with molecular dynamics simulations, a full description of the molecular interactions that take place in the IL–CO2 mixtures can be obtained. The introduction of a methyl group has a significant effect on CO2 solubility in comparison with linear or fluorinated analogues. The differences in CO2 solubility arise from differences in liquid organization caused by structural changes in the cation. ILs with branched cations have similar short‐range cation–anion orientations as those in ILs with linear side chains, but present differences in the long‐range order. The introduction of CO2 does not cause perturbations in the former and benefits from the differences in the latter. Branching at the cation results in sponge‐like ILs with enhanced capabilities for CO2 capture.
High‐Surface‐Area Nitrogen‐Doped Reduced Graphene Oxide for Electric Double‐Layer Capacitors
Authors: Youn Hee‐Chang , Bak Seong‐Min , Kim Myeong‐Seong , Jaye Cherno , Fischer Daniel A. , Lee Chang‐Wook , Yang Xiao‐Qing , Roh Kwang Chul , Kim Kwang‐Bum
Published: April 2015

A two‐step method consisting of solid‐state microwave irradiation and heat treatment under NH3 gas was used to prepare nitrogen‐doped reduced graphene oxide (N‐RGO) with a high specific surface area (1007 m2 g−1), high electrical conductivity (1532 S m−1), and low oxygen content (1.5 wt %) for electrical double‐layer capacitor applications. The specific capacitance of N‐RGO was 291 F g−1 at a current density of 1 A g−1, and a capacitance of 261 F g−1 was retained at 50 A g−1, which indicated a very good rate capability. N‐RGO also showed excellent cycling stability and preserved 96 % of the initial specific capacitance after 100 000 cycles. Near‐edge X‐ray absorption fine‐structure spectroscopy results provided evidenced for the recovery of π conjugation in the carbon networks with the removal of oxygenated groups and revealed chemical bonding of the nitrogen atoms in N‐RGO. The good electrochemical performance of N‐RGO is attributed to its high surface area, high electrical conductivity, and low oxygen content.
Interconnected Co‐Entrapped, N‐Doped Carbon Nanotube Film as Active Hydrogen Evolution Cathode over the Whole pH Range
Authors: Xing Zhicai , Liu Qian , Xing Wei , Asiri Abdullah M. , Sun Xuping
Published: April 2015

The use of electrocatalysts with low metal content (metal‐deficient) or metal free for the hydrogen evolution reaction (HER) can prevent or decrease metal ion release, which reduces environmental impact; development of such catalysts with high activity and durability over the whole pH range is thus highly desired but still remains a huge challenge. Herein, we describe the direct growth of a film consisting of interconnected Co‐entrapped, N‐doped carbon nanotubes on carbon cloth using chemical vapor deposition from dicyanodiamine using a Co3O4 nanowire array as catalyst. This integrated architecture is used as a flexible 3D electrode for the electrolytic hydrogen evolution with outstanding catalytic activity and durability in acidic media. Moreover, this electrode is also highly efficient under neutral and basic conditions. It offers us an attractive carbon‐based metal‐deficient HER catalyst outperforming most transition‐metal and all metal‐free/deficient catalysts.
Optimization of the cytokine secretion assay for human IL‐2 in single and combination assays
Authors: Deng Nan , Mosmann Tim R.
Published: April 2015

The cytokine secretion assay identifies live cytokine‐secreting cells by capturing the secreted cytokine on a surface‐bound capture antibody in dilute suspension culture, followed by detection with a fluorescent anti‐cytokine antibody. However, examining the kinetics of cytokine detection revealed that IL‐2 staining reached a maximum at early times and then declined, whereas staining for other cytokines including interferon (IFNγ) increased for up to 90 min. The decline in IL‐2 staining could have been due to rapid cessation of cytokine synthesis, coupled with internalization of cytokine/antibody complexes from the cell surface. Consistent with this model, addition of the anti‐IL‐2 detection antibody during the cytokine secretion step resulted in higher and more sustained staining. This modified method enhanced staining of IL‐2 and IL‐4, but not IFNγ, tumor necrosis factor alpha (TNFα), or IL‐5. However, the longer secretion times possible in the modified assay also improved detection of other cytokines in multi‐cytokine combinations. © 2015 International Society for Advancement of Cytometry
Template‐Free Synthesis of Three‐Dimensional Nanoporous Bulk Graphitic Carbon Nitride with Remarkably Enhanced Photocatalytic Activity and Good Separation Properties
Authors: Shen Jianchao , Yang Hui , Shen Qianhong , Feng Yu , Cai Qifeng , Yang Huiying
Published: April 2015

A facile template‐free method is presented for the fabrication of three‐dimensional (3D) nanoporous bulk graphitic carbon nitride (g‐C3N4) with an interconnected framework. Various techniques, namely, X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, elemental analysis, specific surface area measurements (Brunauer–Emmett–Teller method), UV/Vis diffuse reflectance spectroscopy, time‐resolved fluorescence decay spectroscopy, electron paramagnetic resonance spectroscopy, and photoelectrochemical measurements, were adopted to analyze the structures and physicochemical properties of the as‐prpared samples. The results show that the nanoporous bulk g‐C3N4 with a particle size of ca. 20 μm exhibits a high specific surface area, which is ca. 30.9 times higher than that of the original material. The g‐C3N4 with such a structure exhibits an improved adsorption capacity for the target pollutants and is readily separable from the photocatalysis reaction system. It is believed that a two‐step protonation process plays a key role in the formation of the structure. Furthermore, this 3D nanoporous bulk g‐C3N4 also shows more‐efficient photogenerated carrier transfer and separation. As a result, the visible‐light photocatalytic activity of g‐C3N4 is significantly enhanced, and the degradation rates of methyl orange (MO) and rhodamine B (RhB) dyes over the nanoporous bulk g‐C3N4 are ca. 5.0 and 22.3 times higher, respectively, than that over the original material.
Synthesis and Selective N,O‐Functionalization of Pyrazolone‐Fused 3‐Aminoazepinones
Authors: Schurgers Ben , Van Lommen Guy , Verniest Guido
Published: April 2015

A new class of pyrazolone‐fused 3‐amino‐1,3,4,7‐tetrahydro‐2H‐azepin‐2‐ones was synthesized from azepane‐based α,β‐unsaturated esters. The latter compounds were obtained efficiently from 2‐Cbz‐amino‐N‐(2‐bromoallyl)‐4‐pentenamide derivatives through initial Pd‐catalyzed methoxycarbonylation followed by ring‐closing metathesis. These new 3‐aminotetrahydroazepinone esters were condensed with hydrazine and oxidized under mild conditions using CuCl2. The resulting bicyclic pyrazolones were transformed into valuable building blocks for medicinal chemistry through O‐triflation and through selective N‐1‐ and O‐alkylation of the pyrazolone core using (bis)electrophiles.
Analysis of post–transoral robotic‐assisted surgery hemorrhage: Frequency, outcomes, and prevention
Authors: Mandal Rajarsi , Duvvuri Umamaheswar , Ferris Robert L. , Kaffenberger Thomas M. , Choby Garret W. , Kim Seungwon
Published: April 2015

Background

Transoral robotic‐assisted surgery (TORS) carries a small, but not insignificant, risk of life‐threatening postsurgical hemorrhage. The purpose of this study was to analyze all post‐TORS hemorrhagic events at our institution to establish preventative recommendations.

Methods

We conducted a retrospective review of 224 consecutive patients who underwent TORS for any indication at a single tertiary care institution.

Results

Twenty‐two patients (n = 22; 9.82%) had varying degrees of postoperative bleeding. An impaired ability to protect the airway at the time of hemorrhage increased the rate of severe complications. Prophylactic transcervical arterial ligation did not significantly decrease overall postoperative bleeding rates (9.1% vs 9.9%; p = 1.00); however, there was a trend toward decreased hemorrhage severity in prophylactically ligated patients (3.0% vs 7.3%; p = .7040).

Conclusion

Prophylactic transcervical arterial ligation may reduce the incidence of severe bleeding following TORS. Post‐TORS patients displaying an inability to protect the airway should be strongly considered for prophylactic tracheostomy to assist airway protection. © 2015 Wiley Periodicals, Inc. Head Neck 38: E776–E782, 2016
Comparison of quality of life between open and endoscopic thyroidectomy for papillary thyroid cancer
Authors: Lee Myung Chul , Park Hoon , Lee Byeong‐Cheol , Lee Guk‐Haeng , Choi Ik Joon
Published: April 2015

Background

Recently, various endoscopic thyroidectomy techniques have been introduced for cosmetic purposes. However, few reports have compared the quality of life (QOL) between post–endoscopic thyroidectomy and post–conventional open thyroidectomy. In this study, we investigated whether endoscopic thyroidectomy was comparable to conventional open thyroidectomy with respect to QOL.

Methods

Between January 2010 and September 2011, 75 patients underwent endoscopic thyroid lobectomy and 233 patients underwent conventional open thyroid lobectomy. The QOL was assessed preoperatively and at 1, 3, and 6 months postoperatively by using the European Organization for Research and Treatment of Cancer Quality of Life Questionnaire‐Core 30‐question (EORTC‐QLQ‐C30) instruments.

Results

Both groups showed similar changes over time in most of the QOL scales. However, patients who underwent endoscopic thyroidectomy showed significantly greater improvement in emotional function at 1 month (p = .039) and physical function at 3 months (p = .032). However, the pain increased more in the patients who underwent endoscopic thyroidectomy at 1 month (p = .042).

Conclusion

Current findings suggest that endoscopic thyroidectomy may offer more rapid recovery of emotional and physical function than open thyroidectomy. © 2015 Wiley Periodicals, Inc. Head Neck 38: E827–E831, 2016
Intraoral lining with the fibular osteomyofascial flap without a skin paddle during maxillary and mandibular reconstruction
Authors: Fan Song , Wang You‐yuan , Wu Dong‐hui , Lai Dong‐li , Feng Yu‐huan , Yu Xin , Lin Zhao‐yu , Zhang Da‐ming , Chen Wei‐liang , Liang Jian‐qiang , Li Jin‐song
Published: April 2015

Background

To achieve an ideal intraoral lining, we harvest the fibular osteomyofascial flap to avoid the common embarrassment caused by the fibular osteomyocutaneous flap, and we report on our experience with this technique in this article.

Methods

Twenty‐eight patients underwent reconstruction of the maxilla and mandible using an osteomyofascial free fibula flap after oncologic ablation. Data, including the size of the fascial flaps, the number of debulking operations, the complications at both the donor and recipient sites, and the dental rehabilitation, were collected.

Results

All fascial flaps survived and were remucosalized, except one with partial necrosis. None of the patients in the osteomyofascial group required an additional debulking operation, and 82% of the patients (23 of 28) had conventional dentures and showed good chewing function and cosmetic results.

Conclusion

The fibular osteomyofascial flap yielded a more anatomic solution for oral mucosal defects, obviating the need for additional debulking and potentially reducing donor‐site wound problems. © 2015 Wiley Periodicals, Inc. Head Neck 38: E832–E836, 2016
Translational treatment paradigm for managing non‐unions secondary to radiation injury utilizing adipose derived stem cells and angiogenic therapy
Authors: Donneys Alexis , Blough Jordan T. , Nelson Noah S. , Perosky Joseph E. , Deshpande Sagar S. , Kang Stephen Y. , Felice Peter A. , Figueredo Christian , Peterson Jonathan R. , Kozloff Kenneth M. , Levi Benjamin , Chepeha Douglas B. , Buchman Steven R.
Published: April 2015

Background

Bony non‐unions arising in the aftermath of collateral radiation injury are commonly managed with vascularized free tissue transfers. Unfortunately, these procedures are invasive and fraught with attendant morbidities. This study investigated a novel, alternative treatment paradigm utilizing adipose‐derived stem cells (ASCs) combined with angiogenic deferoxamine (DFO) in the rat mandible.

Methods

Rats were exposed to a bioequivalent dose of radiation and mandibular osteotomy. Those exhibiting non‐unions were subsequently treated with surgical debridement alone or debridement plus combination therapy. Radiographic and biomechanical outcomes were assessed after healing.

Results

Significant increases in biomechanical strength and radiographic metrics were observed in response to combination therapy (p < .05). Importantly, combined therapy enabled a 65% reduction in persisting non‐unions when compared to debridement alone.

Conclusion

We support the continued investigation of this promising combination therapy in its potential translation for the management of radiation‐induced bony pathology. © 2015 Wiley Periodicals, Inc. Head Neck 38: E837–E843, 2016
Optimal timing of first posttreatment FDG PET/CT in head and neck squamous cell carcinoma
Authors: Leung Alan S. , Rath Tanya J. , Hughes Marion A. , Kim Seungwon , Branstetter Barton F.
Published: April 2015

Background

The optimal timing for the initial posttreatment fluorodeoxyglucose (FDG) positron emission tomography (PET)/CT scan after definitive treatment of head and neck squamous cell carcinoma (HNSCC) is unclear.

Methods

We conducted a retrospective review of 247 patients with definitively treated nonmetastatic HNSCC. First posttreatment PET/CT scans were grouped into: <7 weeks, 7 to 10 weeks, 11 to 14 weeks, and ≥15 weeks. Scans were categorized as positive or negative and accuracy of scans was calculated for each group using biopsy, subsequent imaging, or clinical follow‐up for 1 year after treatment as a reference standard.

Results

Sixty‐seven of the 247 patients (27.1%) had treatment failure. Scans performed at <7 weeks were less accurate than all other time intervals (p < .05). Scans performed at all other intervals were similar in accuracy.

Conclusion

First posttreatment PET/CT can be obtained as early as 2 months after therapy. Scans performed earlier than 2 months have lower accuracy. © 2015 Wiley Periodicals, Inc. Head Neck 38: E853–E858, 2016
Prognostic significance of lymph node density in squamous cell carcinoma of the tongue
Authors: Ong Wilson , Zhao Runfeng , Lui Benjamin , Tan Winson , Ebrahimi Ardalan , Clark Jonathan R. , Soo Khee‐Chee , Tan Ngian‐Chye , Tan Hiang‐Khoon , Iyer N. Gopalakrishna
Published: April 2015

Background

The prognostic significance of lymph node density in oral squamous cell carcinoma (OSCC) has been well recognized. However, its use in a specific subsite of the tongue has not been evaluated. The purpose of this study was to determine the prognostic significance of lymph node density in tongue squamous cell carcinoma (SCC).

Methods

A retrospective analysis of 99 patients with tongue SCC who underwent primary curative resection and neck dissection was conducted. Overall survival (OS) and disease‐specific survival (DSS) was used to evaluate the prognostic significance of lymph node density.

Results

Lymph node density (using a cutoff of 0.06) was shown to be an independent predictor of OS and DSS. The impact of lymph node density on OS and DSS remained significant on multivariate analysis, whereas conventional nodal staging was not. An alternative staging strategy incorporating depth of invasion and lymph node density performs better than conventional TNM staging in predicting survival.

Conclusion

Our data suggest that lymph node density is a reliable and applicable predictor of prognosis in patients with tongue SCC. © 2015 Wiley Periodicals, Inc. Head Neck 38: E859–E866, 2016
From Bipartite to Tripartite Devolved HRM in Professional Service Contexts: Evidence from Hospitals in Three Countries
Authors: McDermott Aoife M. , Fitzgerald Louise , Van Gestel Nicolette M. , Keating Mary A.
Published: April 2015

This article explores the devolution of HRM in a hospital context. Based on secondary data and 128 interviews conducted in nine hospitals across three European countries (Ireland, the Netherlands, and the United Kingdom), we examine roles and responsibility for HRM under devolution and coordination between those delivering it. Findings challenge bipartite conceptions of devolution, identifying a tripartite model with (1) HR practitioners, (2) line managers, and (3) senior professionals (managers and specialists) implementing HRM. Involving senior professionals in HRM reflects long‐standing concern regarding managerial legitimacy in overseeing professional work. In the tripartite relationship, each party has scope to contribute to people management: HR practitioners to formulate a strategic framework, HR practices, and provide advisory services; line managers to implement HR practices and interface between HR and frontline professionals; and senior professionals to act as line managers’ advocates and provide expert knowledge and credibility to inform people‐related decision making. However, lack of role clarity and tensions in coordination relate to the differing goals of, and distance between, the HR function, line managers, and senior professionals. Our theoretical reframing of devolution notes potential for tripartite relational involvement to enhance HR performance in professional service contexts, the contingencies affecting this, and potential implications for the HR architecture. © 2015 Wiley Periodicals, Inc.
Biased Facial Expression Interpretation in Shy Children
Authors: Kokin Jessica , Younger Alastair , Gosselin Pierre , Vaillancourt Tracy
Published: April 2015

The relationship between shyness and the interpretations of the facial expressions of others was examined in a sample of 123 children aged 12 to 14 years. Participants viewed faces displaying happiness, fear, anger, disgust, sadness, surprise, as well as a neutral expression, presented on a computer screen. The children identified each expression by pressing a button on an external keyboard. For each expression, children also rated (a) the degree to which they felt the child displaying the expression would like them, (b) the probability that someone at school would look at them with that expression, and (c) their own emotional reaction to interacting with a child displaying the expression. Participants also completed the Children's Shyness Questionnaire and the Children's Rejection Sensitivity Questionnaire. We hypothesized that shyness in children would be related to negatively biased interpretations of facial expressions. Although the accuracy with which the children could identify the facial expressions was not related to their degree of shyness, negative biases were found in their interpretations of the meanings of the expressions. Furthermore, rejection sensitivity significantly mediated many of these biased interpretations. These findings may have implications for interventions for children experiencing shyness and social anxiety, especially social‐skills training approaches. Copyright © 2015 John Wiley & Sons, Ltd.
Identification of novel CD8+ T cell epitopes in human herpesvirus 6B U11 and U90
Authors: Halawi Mustafa , Khan Naeem , Blake Neil
Published: April 2015

Human herpesvirus 6B (HHV6B) infects over 90% of the population, and normally establishes a latent infection, where episodes of reactivation are asymptomatic. However, in immunocompromised patients HHV6B reactivation is associated with high morbidity and mortality. Cellular immunotherapy has been utilised against other herpesvirus in immunocompromised settings. However, limited information on the immune response against HHV6B has hampered the development of immunotherapy for HHV6B‐driven disease. In this study, we have analysed the cellular immune response against four HHV6B antigens in a panel of 30 healthy donors. We show that the base‐line level of T cell reactivity in peripheral blood is very low to undetectable. A short‐term reactivation step enabled expansion of T cell responses, and all donors responded to at least 1 antigen, but more commonly 3 or 4. A hierarchy of immunogenicity was determined with antigens U90 and U54 being co‐dominant, followed by U11 and U39. Putative CD8+ T cell epitopes were mapped to U90 and U11, predicted to be presented in the context of HLA‐A1, A29, B39 and C6. T cells reactive against these novel epitopes were able to recognise virus‐infected cells. Our data is supportive of the application and on‐going development of T cell immunotherapy against HHVB‐driven disease in the immunocompromised host.