bluuebunny/crossref_metadata_2025 huggingface dataset:
Achieving 6.7% Efficiency in P3HT/Indene‐C70 Bisadduct Solar Cells through the Control of Vertical Volume Fraction Distribution and Optimized Regio‐Isomer Ratios
Authors: Kutsarov Dimitar I. , Rašović Ilija , Zachariadis Alexandros , Laskarakis Argiris , Lebedeva Maria A. , Porfyrakis Kyriakos , Mills Christopher A. , Beliatis Michail J. , Fisher Brett , Bruchlos Kirsten , Ludwigs Sabine , Logothetidis Stergios , Silva S. Ravi P.
Published: November 2016

Indene C60 and C70 bisadducts (IC60BA and IC70BA) have relatively high lowest unoccupied molecular orbital energies. In poly(3‐hexylthiophene) (P3HT)‐based polymer solar cells (PSCs), this produces an increase in open‐circuit voltage (VOC) and power conversion efficiency (PCE). However, ICBA synthesis produces a mixture of regio‐isomers with different indene spatial orientations (2, 5, and 12 o'clock) that alter the IC70BA molecular packing when mixed with P3HT. In this paper, how the IC70BA regio‐isomerism affects the PSC performance is examined by investigating the molecular packing of P3HT:IC70BA layers with different regio‐isomeric ratios. For the first time, non‐destructive spectroscopic ellipsometry is used to investigate the effect of the fabrication conditions on the P3HT/IC70BA vertical volume fraction distribution and the results are attributed to the spatial arrangement of the regio‐isomers. It is demonstrated that this unambiguously affects the PSC performance. As a result, record device efficiencies are repeatedly attained for standard architecture P3HT:IC70BA PSCs with photoactive areas of 0.43 cm2, achieving 5.9 (±0.4)% PCE (n = 15). With control of the IC70BA constituent, device PCEs vary from below 2.2% to peak values above 6.7%, among the highest recorded PCEs for a P3HT combination, highlighting the importance of the molecular phase separation for high‐efficiency devices.
Numerical investigation on CO2 absorbed in aqueous N‐methyldiethanolamine + piperazine
Authors: Huang Jicai , Gong Maoqiong , Sun Zhaohu , Dong Xueqiang , Shen Jun , Wu Jianfeng
Published: November 2016

A multiphase and multicomponent mass transfer model of CO2 absorbed in aqueous N‐methyldiethanolamine and piperazine (PZ) was built in the study. In the model, a simple method of mass transfer between phases was proposed. Besides, the hydrodynamics, thermodynamics, and complex reversible chemical reaction were considered simultaneously. The model was validated by comparing with the previous experimental data which showed that simulated results can represent the experimental data with reasonable accuracy. Based on the model, the effects of gas velocity, liquid load and CO2 loading on the absorption rate, and enhancement factor were analyzed. Model results showed that the enhancement factor increased with a rising gas velocity while decreased with a rising liquid load or CO2 loading. The change of enhancement factor with CO2 loading was similar to that of equilibrium concentration of PZ which indicated that PZ was significant to the absorption process. Furthermore, the distributions of specie concentrations were discussed in detail. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2386–2393, 2017
The role of acuity of illness at presentation in early mortality in black children with acute myeloid leukemia
Authors: Winestone Lena E. , Getz Kelly D. , Miller Tamara P. , Wilkes Jennifer J. , Sack Leah , Li Yimei , Huang Yuan‐Shung , Seif Alix E. , Bagatell Rochelle , Fisher Brian T. , Epstein Andrew J. , Aplenc Richard
Published: November 2016

Black patients with acute myeloid leukemia (AML) experience higher mortality than White patients. We compared induction mortality, acuity of illness prior to chemotherapy, and insurance type between Black and White patients to assess whether acuity of presentation mediates the disparity. Within a retrospective cohort of 1,122 children with AML treated with two courses of standard induction chemotherapy between 2004 and 2014 in the Pediatric Health Information System (PHIS) database, the association between race (Black versus White) and inpatient mortality during induction was examined. Intensive Care Unit (ICU)‐level resource utilization during the first 72 hours following admission for initial AML chemotherapy was evaluated as a potential mediator. The total effect of race on mortality during Induction I revealed a strong association (unadjusted HR 2.75, CI: 1.18, 6.41). Black patients had a significantly higher unadjusted risk of requiring ICU‐level resources within the first 72 hours after initial presentation (17% versus 11%; RR 1.52, CI: 1.04, 2.24). Mediation analyses revealed the indirect effect of race through acuity accounted for 61% of the relative excess mortality during Induction I. Publicly insured patients experienced greater induction mortality than privately insured patients regardless of race. Black patients with AML have significantly greater risk of induction mortality and are at increased risk for requiring ICU‐level resources soon after presentation. Higher acuity amongst Black patients accounts for a substantial portion of the relative excess mortality during Induction I. Targeting factors affecting acuity of illness at presentation may lessen racial disparities in AML induction mortality.
Excess mortality in the myelodysplastic syndromes
Authors: Nomdedeu Meritxell , Pereira Arturo , Ramos Fernando , Valcárcel David , Costa Dolors , Arnan Montserrat , Calvo Xavier , Pomares Helena , Luño Elisa , Díaz‐Campelo María , Collado Rosa , de Paz Raquel , Falantes José‐Francisco , Pedro Carme , Marco Josefa , Oirtzabal Itziar , Sánchez‐García Joaquín , Tormo Mar , Cedena María‐Teresa , Nomdedeu Benet , Sanz; Guillermo ,   on behalf of the Spanish MDS Group
Published: November 2016

Myelodysplastic syndromes (MDS) are the commonest hematologic malignancies in the elderly. Since many patients with MDS actually die from age‐related ailments, the very disease burden of MDS remains largely unknown. This registry‐based study was aimed at investigating the excess mortality attributable to MDS. We analyzed 7,408 adult patients diagnosed with primary MDS from 1980 to 2014. Excess mortality was estimated by comparing the patients' survival with that expected in the matched general population. Median age of patients was 74 years, 58% were males, and 65% belonged to the lower risk categories of the Revised International Prognostic Scoring System (IPSS‐R). Excess mortality accounted for three‐fourths of the all‐cause mortality and was mainly driven by factors unrelated to leukemic transformation. Excess mortality increased with the IPSS‐R risk category [Incidence rate ratio (IRR): 2.1, 95% CI: 1.9–2.3; P < .001]. Older age and male sex retained an independent association with higher excess mortality after discounting demographic effects. Excess mortality increased in the most recent periods just in the higher risk IPSS‐R categories (IRR: 1.2; 95% CI: 1.1–1.3 when comparing periods 2007–14, 2000–06, and 1980–99). In conclusion, MDS carry a significant excess mortality, even in the lower risk categories, that is mainly driven by factors unrelated to leukemic transformation, and increases with older age, male sex, and poorer risk categories. Excess mortality has increased in recent years in the higher risk patients, which might be ascribed to a parallel increase in age‐related comorbidities. Our results claim for more comprehensive treatment strategies for patients with MDS. Am. J. Hematol. 92:149–154, 2017. © 2016 Wiley Periodicals, Inc.
New Di‐, Tri‐, and Tetra‐Core‐Functionalized Naphthalene Diimides from Reactions of Allyl Ethers with Lewis Acids
Authors: Tachapermpon Yordkhuan , Maniam Subashani , Wanichacheva Nantanit , Langford Steven J.
Published: November 2016

Core‐substituted NDIs bearing aryl allyl ethers have a predisposition to deallylation in the presence of Lewis Acids (LA). However, under certain conditions, with appropriate choice of LA, the reaction can be controlled to yield unexpected and highly functionalized dinaphthol systems through a [3,3]‐sigmatropic (Claisen) rearrangement. The major products of the rearrangement study have been characterized by X‐ray crystallographic analysis and the per‐substituted products are shown to undergo ring‐closing metathesis to form heterocyclic core‐extended NDIs. This study highlights a simple method to construct a series of important donor–acceptor building blocks for the preparation of new conjugated materials.
A Smart Phase‐Selective Gelator for Recycling Aromatic Solvents, the Removal of Toxic Dyes, and Molecular Delivery
Authors: Ran Xia , Li Yajie , Gao Qiongqiong , Qiu Weihong , Guo Lijun
Published: November 2016

The phase‐selective gelation properties of a low‐molecular‐mass organogelator, N‐(3,4,5‐tributoxyphenyl)‐N′‐4‐[(4‐hydroxyphenyl)azophenyl] benzohydrazide (BNB‐t4), and its applications in recycling aromatic solvents, removing toxic dyes, and molecular delivery, are reported. The hydroxy head group, hydrazide group, and three butyl chains in this compound provide the collective driving force for self‐assembly and make BNB‐t4 an excellent phase‐selective gelator (PSG). FTIR and UV/Vis spectroscopy suggest that the driving forces for the gelation are hydrogen‐bonding, π–π stacking and Van der Waals interactions. The critical gelation concentration (CGC) of BNB‐t4 in aromatic solvents is very low (e.g., 0.6 mg mL−1 in toluene), which suggests that the BNB‐t4 PSG could extract aromatic solvents from aqueous mixtures. Our results indicate that the entangled fibrous network and its rheological properties enable BNB‐t4 to function as a reversible material for removing toxic dyes from aqueous solution with efficiencies as high as 97 %. Furthermore, its combined phase‐selection and reversible phase‐transition properties confer BNB‐t4 the ability to absorb and release organic compounds with efficiencies of up to 98 %. Taken together, these results demonstrate that BNB‐t4 could be used to construct smart materials for environment remediation and molecular delivery.
Prevention of sinonasal inflammation by a synthetic glycosaminoglycan
Authors: Pulsipher Abigail , Qin Xuan , Thomas Andrew J. , Prestwich Glenn D. , Oottamasathien Siam , Alt Jeremiah A.
Published: November 2016

Background

Glycosaminoglycans (GAGs) are polysaccharides that are distributed on respiratory epithelial cells, endothelial cells, and submucosal glands. Uniquely positioned, certain GAGs exhibit anti‐inflammatory properties in respiratory diseases and serve important roles in repairing mucosal surfaces and modulating mucociliary clearance. We hypothesized that topical administration of a synthetic GAG (GM‐0111) would prevent sinonasal inflammation in a mouse model of rhinosinusitis (RS).

Methods

To test our hypothesis, C57BL/6 mice were intranasally administered fluorescent GM‐0111, and sinonasal tissues were examined for coating and penetration ability. To test therapeutic feasibility, mice (n = 6) were given GM‐0111 or hyaluronic acid (HA; 800 μg dose) prior to inducing RS with inflammatory molecule LL‐37 (115 μg dose). After 24 hours, sinonasal tissues were harvested for histological and biochemical analysis of inflammatory markers (inflammatory cell infiltration, lamina propria [LP] thickening, and neutrophil enzyme myeloperoxidase [MPO]) and cell death.

Results

GM‐0111 was observed within sinonasal tissues 1 hour and 24 hours after intranasal administration, indicating rapid and effective coating and penetration. GM‐0111 prevented sinonasal tissues from developing inflammatory changes, with significant reductions in mast cell infiltration (p < 0.05), LP thickening (p < 0.001), and MPO levels (p < 0.01) when compared to tissues treated with LL‐37 and those pretreated with HA. GM‐0111 reduced cell death within sinonasal tissues in contrast to LL‐37–treated tissues.

Conclusion

We report a new synthetic GAG (GM‐0111) that uniformly coats and penetrates into the sinonasal mucosa to prevent sinonasal inflammation and cell death in a mouse model of RS.
Face, content, and construct validation of a low‐cost, non‐biologic, sinus surgery task trainer and knowledge‐based curriculum
Authors: Harbison Richard A. , Johnson Kaalan E. , Miller Craig , Sardesai Maya G. , Davis Greg E.
Published: November 2016

Background

The purpose of this study was to evaluate face and content validity of a low‐cost, low‐technology, non‐biologic endoscopic sinus surgery (ESS) task trainer and knowledge‐based curriculum followed by construct validation of the task trainer.

Methods

A sinus surgery task trainer and curriculum were developed. Attending otolaryngologists were surveyed regarding the utility of the task trainer and curriculum. A cross‐sectional construct validation study was performed including medical students, residents, and attending otolaryngologists. Nine tasks were performed on the task trainer and graded using a global rating scale (GRS). Predictors of task trainer performance were evaluated, and spatial performance was measured. Regression analyses were performed to assess main associations.

Results

All attending physicians (n = 7) agreed that the task trainer accelerates the learning curve and incorporates essential ESS techniques and that the knowledge‐based curriculum describes anatomical and technical knowledge germane to ESS. Twelve medical students, 9 otolaryngology residents, and 5 attending otolaryngologists completed task trainer testing. GRS score varied by level of training after adjusting for potential confounders (slope = 2.63; p = 0.001). There was evidence of an association between a history of video gaming (slope = 1.33; p = 0.077), sports experience (slope = 2.08; p = 0.033), and sinus surgery simulation (slope = 2.72; p = 0.023) with GRS score, although not statistically significant.

Conclusion

This study demonstrated validity of a knowledge‐based sinus surgery curriculum and low‐cost, sinus task trainer supporting use in early training. Participants with prior video gaming, sports participation, and sinus surgery simulation experience perform better at baseline on the task trainer.
Fractal analysis of en face tomographic images obtained with full field optical coherence tomography
Authors: Gao Wanrong , Zhu Yue
Published: November 2016

The quantitative modeling of the imaging signal of pathological areas and healthy areas is necessary to improve the specificity of diagnosis with tomographic en face images obtained with full field optical coherence tomography (FFOCT). In this work, we propose to use the depth‐resolved change in the fractal parameter as a quantitative specific biomarker of the stages of disease. The idea is based on the fact that tissue is a random medium and only statistical parameters that characterize tissue structure are appropriate. We successfully relate the imaging signal in FFOCT to the tissue structure in terms of the scattering function and the coherent transfer function of the system. The formula is then used to analyze the ratio of the Fourier transforms of the cancerous tissue to the normal tissue. We found that when the tissue changes from the normal to cancerous the ratio of the spectrum of the index inhomogeneities takes the form of an inverse power law and the changes in the fractal parameter can be determined by estimating slopes of the spectra of the ratio plotted on a log‐log scale. The fresh normal and cancer liver tissues were imaged to demonstrate the potential diagnostic value of the method at early stages when there are no significant changes in tissue microstructures.
Mikroemulsionen: neue Möglichkeiten zur Erweiterung der Synthese anorganischer Nanopartikel
Authors: Wolf Silke , Feldmann Claus
Published: November 2016

Mikroemulsionen (ME) sind ideal, um hochwertige anorganische Nanopartikel zu erhalten. Als thermodynamisch stabile Systeme mit einer Phase aus Nanometer‐großen Tröpfchen, die als Nanoreaktoren dienen, bieten sie für die Nanopartikelsynthese eine Reihe an Vorteilen. ME haben aber auch Nachteile, z. B. ihre Komplexität als Mehrkomponentensysteme, die geringe erhältliche Nanopartikelmenge, die begrenzte thermische Stabilität, der häufige Ausschluss hydrolysierbarer oder oxidierbarer Verbindungen von der Synthese, die partiell sehr aufwendige Abtrennung der Nanopartikel sowie die Entfernung Oberflächen‐gebundener Tenside nach der Synthese. Dieser Aufsatz soll einige Strategien zur Erweiterung der ME‐basierten Synthese anorganischer Nanopartikel aufzeigen. Dazu zählen die Kristallisation von Nanopartikeln mittels “Hochtemperatur‐ME”, die Synthese nanoskaliger Hohlkugeln, die Verwendung von H2O2 oder flüssigem NH3 als polare Tröpfchenphasen sowie die Synthese von unedlen Metallen und Nitriden in ME.
Nahezu vollständig intaktes und sauberes oxo‐funktionalisiertes Graphen – Synthese und elektronenstrahlinduzierte Reduktion
Authors: Butz Benjamin , Dolle Christian , Halbig Christian E. , Spiecker Erdmann , Eigler Siegfried
Published: November 2016

Die Steuerung der chemischen Eigenschaften von Graphen ist ein wachsendes Forschungsfeld mit möglichen Anwendungen in den Material‐ und Biowissenschaften. Ziel ist eine Forschung jenseits von Graphenoxid, um den defektreichen Charakter von herkömmlichem Graphenoxid zu vermeiden. Hier wird die Optimierung der Synthese von oxo‐funktionalisiertem Graphen (oxo‐G) zur Herstellung hochwertiger einlagiger Flocken beschrieben. Die Identifizierung und Vermeidung unerwünschter Rückstände wird diskutiert. Das Produkt ermöglicht eine direkte Untersuchung mittels atomar auflösender Transmissionselektronenmikroskopie (HR‐TEM). HR‐TEM liefert den Beleg für die außergewöhnliche Integrität des Kohlenstoffgerüsts der oxo‐G‐Flocken. Die ungleichmäßige nanoskalige Verteilung von Oxo‐Funktionen auf den hochreinen oxo‐G‐Flocken bestätigt theoretische Vorhersagen. Gezielte Elektronenbestrahlung führt zur definierten Defunktionalisierung des Materials, was einen neuen Weg zu sauberem Graphen ebnet. Diese Ergebnisse sind ein Durchbruch für die Ausführung örtlich begrenzter chemischer Reaktionen an Graphen.
Photocatalytic C−C Bond Cleavage and Amination of Cycloalkanols by Cerium(III) Chloride Complex
Authors: Guo Jing‐Jing , Hu Anhua , Chen Yilin , Sun Jianfeng , Tang Haoming , Zuo Zhiwei
Published: November 2016

A general strategy for the cleavage and amination of C−C bonds of cycloalkanols has been achieved through visible‐light‐induced photoredox catalysis utilizing a cerium(III) chloride complex. This operationally simple methodology has been successfully applied to a wide array of unstrained cyclic alcohols, and represents the first example of catalytic C−C bond cleavage and functionalization of unstrained secondary cycloalkanols.
Quantitative Method to Investigate the Balance between Metabolism and Proteome Biomass: Starting from Glycine
Authors: Gu Haiwei , Carroll Patrick A. , Du Jianhai , Zhu Jiangjiang , Neto Fausto Carnevale , Eisenman Robert N. , Raftery Daniel
Published: November 2016

The balance between metabolism and biomass is very important in biological systems; however, to date there has been no quantitative method to characterize the balance. In this methodological study, we propose to use the distribution of amino acids in different domains to investigate this balance. It is well known that endogenous or exogenous amino acids in a biological system are either metabolized or incorporated into free amino acids (FAAs) or proteome amino acids (PAAs). Using glycine (Gly) as an example, we demonstrate a novel method to accurately determine the amounts of amino acids in various domains using serum, urine, and cell samples. As expected, serum and urine had very different distributions of FAA‐ and PAA‐Gly. Using Tet21N human neuroblastoma cells, we also found that Myc(oncogene)‐induced metabolic reprogramming included a higher rate of metabolizing Gly, which provides additional evidence that the metabolism of proliferating cells is adapted to facilitate producing new cells. It is therefore anticipated that our method will be very valuable for further studies of the metabolism and biomass balance that will lead to a better understanding of human cancers.
Industrial Applications of Gold Catalysis
Authors: Ciriminna Rosaria , Falletta Ermelinda , Della Pina Cristina , Teles Joaquim Henrique , Pagliaro Mario
Published: November 2016

Gold catalysis has recently found its first large‐scale applications in the chemical industry. This Minireview provides a critical analysis of the success factors and of the main obstacles that had to be overcome on the long way from the discovery to the commercialization of gold catalysts. The insights should be useful to researchers in both academia and industry working on the development of tomorrow's gold catalysts to tackle significant environmental and economic issues.
Efficient Coupling Reaction of Quinone Monoacetal with Phenols Leading to Phenol Biaryls
Authors: Kamitanaka Tohru , Morimoto Koji , Tsuboshima Kohei , Koseki Daichi , Takamuro Hitoho , Dohi Toshifumi , Kita Yasuyuki
Published: November 2016

A simple and efficient synthesis of phenol biaryls by the cross‐couplings of quinone monoacetals (QMAs) and phenols is reported. The Brønsted acid catalytic system in 1,1,1,3,3,3‐hexafluoro‐2‐propanol was found to be particularly efficient for this transformation. This reaction can be extended to the synthesis of various phenol biaryls, including sterically hindered biaryls, with yields ranging from 58 to 90 % under mild reaction conditions and in a highly regiospecific manner.
Selective Production of Carbon Monoxide via Methane Oxychlorination over Vanadyl Pyrophosphate
Authors: Paunović Vladimir , Zichittella Guido , Verel Réne , Amrute Amol P. , Pérez‐Ramírez Javier
Published: November 2016

A catalytic process is demonstrated for the selective conversion of methane into carbon monoxide via oxychlorination chemistry. The process involves addition of HCl to a CH4–O2 feed to facilitate C−H bond activation under mild conditions, leading to the formation of chloromethanes, CH3Cl and CH2Cl2. The latter are oxidized in situ over the same catalyst, yielding CO and recycling HCl. A material exhibiting chlorine evolution by HCl oxidation, high activity to oxidize chloromethanes into CO, and no ability to oxidize CO, is therefore essential to accomplish this target. Following these design criteria, vanadyl pyrophosphate (VPO) was identified as an outstanding catalyst, exhibiting a CO yield up to approximately 35 % at 96 % selectivity and stable behavior. These findings constitute a basis for the development of a process enabling the on‐site valorization of stranded natural‐gas reserves using CO as a highly versatile platform molecule.
Protein‐Sized Bright Fluorogenic Nanoparticles Based on Cross‐Linked Calixarene Micelles with Cyanine Corona
Authors: Shulov Ievgen , Rodik Roman V. , Arntz Youri , Reisch Andreas , Kalchenko Vitaly I. , Klymchenko Andrey S.
Published: November 2016

The key challenge in the field of fluorescent nanoparticles (NPs) for biological applications is to achieve superior brightness for sizes equivalent to single proteins (3–7 nm). We propose a concept of shell‐cross‐linked fluorescent micelles, in which PEGylated cyanine 3 and 5 bis‐azides form a covalently attached corona on micelles of amphiphilic calixarene bearing four alkyne groups. The fluorescence quantum yield of the obtained monodisperse NPs, with a size of 7 nm, is a function of viscosity and reached up to 15 % in glycerol. In the on‐state they are circa 2‐fold brighter than quantum dots (QD‐585), which makes them the smallest PEGylated organic NPs of this high brightness. FRET between cyanine 3 and 5 cross‐linkers at the surface of NPs suggests their integrity in physiological media, organic solvents, and living cells, in which the NPs rapidly internalize, showing excellent imaging contrast. Calixarene micelles with a cyanine corona constitute a new platform for the development of protein‐sized ultrabright fluorescent NPs.
Catalytic [2+2+1] Synthesis of Fused Thiophenes Using Thiocarbonyls as Sulfur Donors
Authors: Matsui Kazuma , Shibuya Masatoshi , Yamamoto Yoshihiko
Published: November 2016

The use of N‐(p‐chlorophenyl)methylbenzoxazole‐2‐thione as a sulfur‐atom donor enables the catalytic [2+2+1] cycloaddition of diynes in wet DMF at 80 °C when open to air, thus affording diverse fused thiophenes with good yields and wide functional‐group compatibility. A plausible mechanism, involving a cationic ruthenacycle intermediate, was also proposed on the basis of several control experiments.
Microbial levan biopolymer production and its use for the synthesis of an antibacterial iron(II,III) oxide–levan nanocomposite
Authors: Taran Mojtaba , Etemadi Saba , Safaei Mohsen
Published: November 2016

Levan biopolymer is an exopolysaccharide characterized with biocompatibility and unique properties that is widely used in different industries. In this study, this biopolymer was used to synthesize a nanocomposite containing magnetic nanoparticles of iron with antibacterial effects. The effects of three factors at three levels of sucrose (5, 7, and 9 g), KH2PO4 (0.3, 0.5, and 0.7 g), and soy flour (3, 5, and 7 g) were evaluated to produce levan exopolysaccharide by Bacillus polymyxa PTCC1020. Nine experiments were designed with different environmental conditions via the Taguchi method. The nanoparticles of iron oxide were synthesized with the coprecipitation method. In addition, nanocomposites containing magnetic nanoparticles of iron and levan biopolymer were produced. The highest level of levan extraction was observed with conditions of 5 g of soy flour (second level), 0.7 g of KH2PO4 (third level), and 5 g of sucrose (first level) as 27 g/L. The Fourier transform infrared analysis and ultraviolet–visible spectroscopy showed the formation of nanocomposites containing magnetic particles of iron. The results indicate that the synthesized nanocomposites had antibacterial effects on both Escherichia coli and Staphylococcus aureus. We concluded that levan and Fe3O4 could be used to synthesize antibacterial nanocomposites with high potential for various industrial applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44613.
Alkoxysilane modification of a Ti‐based catalyst system for ethylene dimerization: A step forward in enhancing productivity and selectivity
Authors: Bigdeli Peyman , Abdouss Majid , Abedi Sadegh
Published: November 2016

Alkoxysilanes were used as novel enhancing agents in the Ti‐based catalyst for the highly selective ethylene dimerization to butene‐1. The dimerization of ethylene was carried out using the homogeneous Ti(OBu)4/THF/TEA/alkoxysilane catalyst system, where Ti(OBu)4, THF (tetrahydrofuran), TEA (triethylaluminum), and alkoxysilane were used as catalyst, additive, activator, and modifier, respectively. The nature and concentration of alkoxysilanes on the dimerization rate, catalyst yield, by‐products production, and selectivity to butene‐1 were investigated in detail. It was found that the performance of alkoxysilanes assisted with the class of the Ti‐based catalyst system, developed in this work, has been furthered by high productivity and selectivity with respect to the bare catalyst system. It proved that alkoxysilanes could play an excellent improving role in the selective ethylene dimerization process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44615.
The Mobility of the Human Face: More than Just the Musculature
Authors: Burrows Anne M. , Rogers‐Vizena Carolyn R. , Li Ly , Mendelson Bryan
Published: November 2016

The human face has the greatest mobility and facial display repertoire among all primates. However, the variables that account for this are not clear. Humans and other anthropoids have remarkably similar mimetic musculature. This suggests that differences among the mimetic muscles alone may not account for the increased mobility and facial display repertoire seen in humans. Furthermore, anthropoids themselves outpace prosimians in these categories: humans > other anthropoids > prosimians. This study was undertaken to clarify the morphological underpinnings of the increased mobility and display repertoire of the human face by investigating the SMAS (the superficial musculo‐aponeurotic system), a connective tissue layer enclosing the mimetic musculature located between the skin and deep fascia/periosteum. Full‐thickness samples from the face near the zygoma region from the anthropoidsHomo sapiens(humans, N = 3),Pan troglodytes(chimpanzees, N = 3),Hylobates muelleri(gibbons, N = 1), andMacaca mulatta(rhesus macaque, N = 3) and the prosimiansTarsius bancanus(tarsiers, N = 1), andOtolemur crassicaudatus(galagos, N = 2) were used. All samples were processed for paraffin‐based histology and stained sections were viewed under light microscopy to determine if a SMAS layer could be identified. Results indicate that a SMAS layer was present in all anthropoid species but neither of the prosimian species. This connective tissue layer may be a factor in the increased facial mobility and facial display repertoire present in these species. Anat Rec, 299:1779–1788, 2016. © 2016 Wiley Periodicals, Inc.
Membranous Support for Eyes of Strepsirrhine Primates and Fruit Bats
Authors: Harvey Brianna M. , Bhatnagar Kunwar P. , Schenck Robert J. , Rosenberger Alfred L. , Rehorek Susan J. , Burrows Anne M. , DeLeon Valerie B. , Smith Timothy D.
Published: November 2016

Living primates have relatively large eyes and support orbital tissues with a postorbital bar (POB) and/or septum. Some mammals with large eyes lack a POB, and presumably rely on soft tissues. Here, we examined the orbits of four species of strepsirrhine primates (Galagidae, Cheirogaleidae) and three species of fruit bats (Pteropodidae). Microdissection and light microscopy were employed to identify support structures of the orbit. In bats and primates, there are two layers of fascial sheets that border the eye laterally. The outer membrane is the most superficial layer of deep fascia, and has connections to the POB in primates. In fruit bats, which lacked a POB or analogous ligament, the deep fascia is reinforced by transverse ligaments. Bats and primates have a deeper membrane supporting the eye, identified as the periorbita (PA) based on the presence of elastic fibers and smooth muscle. The PA merges with periostea deep within the orbit, but has no periosteal attachment to the POB of primates. These findings demonstrate that relatively big eyes can be supported primarily with fibrous connective tissues as well as the PA, in absence of a POB or ligament. The well‐developed smooth muscle component within the PA of fruit bats likely helps to protrude the eye, maintaining a more convergent eye orientation, with greater overlap of the visual fields. The possibility should be considered that early euprimates, and even stem primates that may have lacked a POB, also had more convergent eyes than indicated by osseous measurements of orbital orientation. Anat Rec, 299:1690–1703, 2016. © 2016 Wiley Periodicals, Inc.
Ontogeny of the Postorbital Region in Tarsiers and Other Primates
Authors: DeLeon Valerie B. , Smith Timothy D. , Rosenberger Alfred L.
Published: November 2016

Bony structure of the postorbital region is a key trait distinguishing major clades of primates. Strepsirrhines share a postorbital bar, and anthropoids share a complete postorbital septum. At issue is whether the partial postorbital septum of tarsiers unites living tarsiers more closely with anthropoids than with certain large‐eyed Eocene fossils. Previously we reported incomplete postorbital closure in tarsiers at birth. In this article, we document comparative analyses of the postorbital region in a broad range of perinatal primates. Virtual reconstructions of microCT data were used to study three‐dimensional structure of the perinatal cranium in these taxa. We also describe and illustrate formation of the tarsier partial postorbital septum through the perinatal period using a growth series of Tarsius syrichta. Our results support the hypothesis that partial postorbital septation in the tarsier is secondary to eye hypertrophy. Based on these observations, we propose a structural hypothesis for phylogenetic differences observed in the primate postorbital region. Specifically, we propose that key postorbital traits, including the frontal spur in strepsirrhines and the posterior lamina of the zygomatic in anthropoids, develop as a result of the spatial relationships of brain, eyes, and teeth. Haplorhines are united by expansion of the anterior cranial fossa and loss of the frontal spur. Anthropoids are further united to the exclusion of tarsiers by expansion of the temporal lobes and associated formation of the posterior lamina of the zygomatic. Mechanical forces related to these spatial relationships may be modulated by deep fascia of the orbit to induce formation of the postorbital septum. Anat Rec, 299:1631–1645, 2016. © 2016 Wiley Periodicals, Inc.
Vertebral Development and Ossification in the Siberian Sturgeon (Acipenser Baerii), with New Insights on Bone Histology and Ultrastructure of Vertebral Elements and Scutes
Authors: Leprévost Amandine , AzaÏs Thierry , Trichet Michael , Sire Jean‐Yves
Published: November 2016

In order to improve our knowledge on the vertebral development, structure and mineralization in Acipenseriformes, we undertook a study in a growth series of reared Siberian sturgeons (Acipenser baerii) using in toto clear and stain specimens, histological and ultrastructural observations, X‐ray micro‐tomography, and solid state NMR analyses. Scutes were also studied to compare the tissue structure and mineralization of endoskeletal and dermal skeletal elements. This study completes and clarifies previous investigations on vertebral development and architecture in sturgeons, and brings original data on the structure of (i) the perichondral bone that is progressively deposited around the vertebral elements during ontogeny, (ii) the typical cartilage composing these elements, and (iii) the scutes. In addition we provide data on the mineralization process, on the nature of the bone mineral phase, and on the growth dynamics of the vertebral elements. Anat Rec, 300:437–449, 2017. © 2016 Wiley Periodicals, Inc.
Silver(I)‐Promoted Radical Sulfonylation of Allyl/Propargyl Alcohols: Efficient Synthesis of γ‐Keto Sulfones
Authors: Fang Guichun , Liu Jianquan , Shang Weidong , Liu Qun , Bi Xihe
Published: November 2016

An efficient Ag2CO3‐promoted sulfonylation of allyl/propargyl alcohols with sodium sulfinates has been developed. The reaction tolerates a wide range of functional groups to deliver γ‐keto sulfones in high yields (up to 93 %). Propargyl alcohols furnished trimerization product 1,3,5‐triaroylbenzenes in the presence of sodium methanesulfinate under the standard conditions. A mechanism involving a sulfonyl radical was suggested.
Nickel‐Catalyzed Facile [2+2+2] Cyclotrimerization of Unactivated Internal Alkynes to Polysubstituted Benzenes
Authors: Xue Fei , Loh Ying Kai , Song Xiaolu , Teo Wei Jie , Chua J. Y. Darrence , Zhao Jin , Hor T. S. Andy
Published: November 2016

A catalytic [2+2+2] cyclotrimerization of unactivated internal alkynes providing cyclotrimerization products in excellent yields with high regioselectivity is described. The transformation is accomplished by using a simple catalytic mixture comprising Ni(acac)2, an imidazolium salt and a Grignard reagent at room temperature or 60 °C for 20 min or 1 h.
Nonparametric conditional autoregressive expectile model via neural network with applications to estimating financial risk
Authors: Xu Qifa , Liu Xi , Jiang Cuixia , Yu Keming
Published: November 2016

The parametric conditional autoregressive expectiles (CARE) models have been developed to estimate expectiles, which can be used to assess value at risk and expected shortfall. The challenge lies in parametric CARE modeling is the specification of a parametric form. To avoid any model misspecification, we propose a nonparametric CARE model via neural network. The nonparametric CARE model can be estimated by a classical gradient based nonlinear optimization algorithm, and the consistency of nonparametric conditional expectile estimators is established. We then apply the nonparametric CARE model to estimating value at risk and expected shortfall of six stock indices. Empirical results for the new model is competitive with those classical models and parametric CARE models. Copyright © 2016 John Wiley & Sons, Ltd.
Effects of BMP9 and pulsed electromagnetic fields on the proliferation and osteogenic differentiation of human periodontal ligament stem cells
Authors: Wang Tingting , Wang Pei , Cao Zhizhong , Wang Xingxing , Wang Dalin , Shen Yaxian , Jing Da , Luo Erping , Tang Weizhong
Published: November 2016

Periodontal ligament stem cells (PDLSCs) have been confirmed to have self‐renewal capacity and multidifferentiation potential and are good candidates for periodontal tissue regeneration. Pulsed electromagnetic field (PEMF) has been demonstrated to promote osteogenesis in non‐union fractures, partly by regulating mesenchymal stem cells or osteoblast activity. However, there is no report about the osteo‐inductive effect of PEMF stimulation on human PDLSCs (hPDLSCs). Thus, we tested the hypothesis that PEMF biophysical stimulation alone has an influence on the proliferation and osteogenic differentiation of hPDLSCs. To detect the osteo‐inductive potential of bone morphogenetic protein (BMP9), we transfected the STRO‐1+/CD146+hPDLCSs with BMP9‐expressing recombinant adenoviruses. We examined the proliferation and osteogenic differentiation of hPDLSCs treated with either PEMF (15 Hz, 1 h daily, different intensities), or BMP9, or both stimuli. Cell counting kit‐8 (CCK‐8) assay showed that PEMF of different intensities had no effect on the proliferation of hPDLSCs and did not enhance the proliferative capability of BMP9‐transfected cells. Quantitative real‐time polymerase chain reaction (qRT‐PCR) and Western blotting showed that the combination of both PEMFs (1.8 or 2.4 mT) and BMP9 stimulation had a synergistic effect on early and intermediate osteogenic genes and protein expressions of runt‐related transcription factor 2, alkaline phosphatase, osteopontin, and late mineralized extracellular matrix formation in hPDLSCs. Bioelectromagnetics. 38:63–77, 2017. © 2016 Wiley Periodicals, Inc.
DNA demethylation pathways: Additional players and regulators
Authors: Bochtler Matthias , Kolano Agnieszka , Xu Guo‐Liang
Published: November 2016

DNA demethylation can occur passively by “dilution” of methylation marks by DNA replication, or actively and independently of DNA replication. Direct conversion of 5‐methylcytosine (5mC) to cytosine (C), as originally proposed, does not occur. Instead, active DNA methylation involves oxidation of the methylated base by ten‐eleven translocations (TETs), or deamination of the methylated or a nearby base by activation induced deaminase (AID). The modified nucleotide, possibly together with surrounding nucleotides, is then replaced by the BER pathway. Recent data clarify the roles and the regulation of well‐known enzymes in this process. They identify base excision repair (BER) glycosylases that may cooperate with or replace thymine DNA glycosylase (TDG) in the base excision step, and suggest possible involvement of DNA damage repair pathways other than BER in active DNA demethylation. Here, we review these new developments.
Identification of biomarker‐by‐treatment interactions in randomized clinical trials with survival outcomes and high‐dimensional spaces
Authors: Ternès Nils , Rotolo Federico , Heinze Georg , Michiels Stefan
Published: November 2016

Stratified medicine seeks to identify biomarkers or parsimonious gene signatures distinguishing patients that will benefit most from a targeted treatment. We evaluated 12 approaches in high‐dimensional Cox models in randomized clinical trials: penalization of the biomarker main effects and biomarker‐by‐treatment interactions (full‐lasso, three kinds of adaptive lasso, ridge+lasso and group‐lasso); dimensionality reduction of the main effect matrix via linear combinations (PCA+lasso (where PCA is principal components analysis) or PLS+lasso (where PLS is partial least squares)); penalization of modified covariates or of the arm‐specific biomarker effects (two‐I model); gradient boosting; and univariate approach with control of multiple testing. We compared these methods via simulations, evaluating their selection abilities in null and alternative scenarios. We varied the number of biomarkers, of nonnull main effects and true biomarker‐by‐treatment interactions. We also proposed a novel measure evaluating the interaction strength of the developed gene signatures. In the null scenarios, the group‐lasso, two‐I model, and gradient boosting performed poorly in the presence of nonnull main effects, and performed well in alternative scenarios with also high interaction strength. The adaptive lasso with grouped weights was too conservative. The modified covariates, PCA+lasso, PLS+lasso, and ridge+lasso performed moderately. The full‐lasso and adaptive lassos performed well, with the exception of the full‐lasso in the presence of only nonnull main effects. The univariate approach performed poorly in alternative scenarios. We also illustrate the methods using gene expression data from 614 breast cancer patients treated with adjuvant chemotherapy.
Omega‐3 production by fermentation of Yarrowia lipolytica: From fed‐batch to continuous
Authors: Xie Dongming , Miller Edward , Sharpe Pamela , Jackson Ethel , Zhu Quinn
Published: November 2016

The omega‐3 fatty acid, cis‐5,8,11,14,17‐eicosapentaenoic acid (C20:5; EPA) has wide‐ranging benefits in improving heart health, immune function, and mental health. A sustainable source of EPA production through fermentation of metabolically engineered Yarrowia lipolytica has been developed. In this paper, key fed‐batch fermentation conditions were identified to achieve 25% EPA in the yeast biomass, which is so far the highest EPA titer reported in the literature. Dynamic models of the EPA fermentation process were established for analyzing, optimizing, and scaling up the fermentation process. In addition, model simulations were used to develop a two‐stage continuous process and compare to single‐stage continuous and fed‐ batch processes. The two stage continuous process, which is equipped with a smaller growth fermentor (Stage 1) and a larger production fermentor (Stage 2), was found to be a superior process to achieve high titer, rate, and yield of EPA. A two‐stage continuous fermentation experiment with Y. lipolytica strain Z7334 was designed using the model simulation and then tested in a 2 L and 5 L fermentation system for 1,008 h. Compared with the standard 2 L fed‐batch process, the two‐stage continuous fermentation process improved the overall EPA productivity by 80% and EPA concentration in the fermenter by 40% while achieving comparable EPA titer in biomass and similar conversion yield from glucose. During the long‐term experiment it was also found that the Y. lipolytica strain evolved to reduce byproduct and increase lipid production. This is one of the few continuous fermentation examples that demonstrated improved productivity and concentration of a final product with similar conversion yield compared with a fed‐batch process. This paper suggests the two‐stage continuous fermentation could be an effective process to achieve improved production of omega‐3 and other fermentation products where non‐growth or partially growth associated kinetics characterize the process. Biotechnol. Bioeng. 2017;114: 798–812. © 2016 Wiley Periodicals, Inc.
Specific targeting of the deubiquitinase and E3 ligase families with engineered ubiquitin variants
Authors: Gorelik Maryna , Sidhu Sachdev S.
Published: November 2016

The ubiquitin proteasome system (UPS) has garnered much attention due to its potential for the development of therapeutics. Following a successful clinical application of general proteasome inhibitors much effort has been devoted to targeting individual UPS components including E3 enzymes and deubiquitinases that control specificity of ubiquitination. Our group has developed a novel approach for targeting the UPS proteins using engineered ubiquitin variants (Ubvs). These drug‐like proteins can serve as valuable tools to study biological function of UPS components and assist in the development of small molecules for clinical use. In this review, we summarize studies of Ubvs targeting members of three major families, including deubiquitinases, HECT E3 ligases, and CRL E3 ligases. In particular, we focus on Ubv binding mechanisms, structural studies, and effects on enzyme function. Furthermore, new insights gained from the Ubvs are discussed in the context of small molecule studies.
A demonstration of athermal effects of continuous microwave irradiation on the growth and antibiotic sensitivity ofPseudomonas aeruginosaPAO1
Authors: Nakouti Ismini , Hobbs Glyn , Teethaisong Yothin , Phipps David
Published: November 2016

Stress, caused by exposure to microwaves (2.45 GHz) at constant temperature (37 ± 0.5°C), alters the growth profile of Pseudomonas aeruginosa PAO1. In the absence of microwave treatment a simple, highly reproducible growth curve was observed over 24 h or more. Microwave treatment caused no reduction in growth during the first 6 h, but at a later stage (>12 h) the growth was markedly different to the controls. Secondary growth, typical of the presence of persisters clearly became apparent, as judged by both the dissolved oxygen and the cell density profiles. These treated cells showed distinct morphological changes, but on regrowth these cells reverted to normal. The microwave induced persisters were subject to antibiotic challenge (tobramycin) and showed increased sensitivity when compared to the unstressed planktonic cells. This is in marked contrast to antibiotic induced persisters which show increased resistance. This provides evidence for both a nonthermal effect of microwaves and a previously undescribed route to a novel form of antibiotic susceptible persister cells. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 33:37–44, 2017
Identification of an IgG CDR sequence contributing to co‐purification of the host cell protease cathepsin D
Authors: Bee Jared S. , Machiesky LeeAnn M. , Peng Li , Jusino Kristin C. , Dickson Matthew , Gill Jeffrey , Johnson Douglas , Lin Hung‐Yu , Miller Kenneth , Heidbrink Thompson Jenny , Remmele Richard L.
Published: November 2016

Recombinant therapeutic monoclonal antibodies (mAbs) must be purified from host cell proteins (HCPs), DNA, and other impurities present in Chinese hamster ovary (CHO) cell culture media. HCPs can potentially result in adverse clinical responses in patients and, in specific cases, have caused degradation of the final mAb product. As reported previously, residual traces of cathepsin D caused particle formation in the final product of mAb‐1. The current work was focused on identification of a primary sequence in mAb‐1 responsible for the binding and consequent co‐purification of trace levels of CHO cathepsin D. Surface plasmon resonance (SPR) was used to detect binding between immobilized CHO cathepsin D and a panel of mAbs. Out of 13 mAbs tested, only mAb‐1 and mAb‐6 bound to cathepsin D. An LYY motif in the HC CDR2 was common, yet unique, to only these two mAbs. Mutation of LYY to AAA eliminated binding of mAb‐1 to cathepsin D providing confirmation that this sequence motif was involved in the binding to CHO cathepsin D. Interestingly, the binding between mAb‐1 and cathepsin D was weaker than that of mAb‐6, which may be related to the fact that two aspartic acid residues near the LYY motif in mAb‐1 are replaced with neutral serine residues in mAb‐6. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 33:140–145, 2017