bluuebunny/crossref_metadata_2025 huggingface dataset:
Dissecting Bottromycin Biosynthesis Using Comparative Untargeted Metabolomics
Authors: Crone William J. K. , Vior Natalia M. , Santos‐Aberturas Javier , Schmitz Lukas G. , Leeper Finian J. , Truman Andrew W.
Published: July 2016

Bottromycin A2 is a structurally unique ribosomally synthesized and post‐translationally modified peptide (RiPP) that possesses potent antibacterial activity towards multidrug‐resistant bacteria. The structural novelty of bottromycin stems from its unprecedented macrocyclic amidine and rare β‐methylated amino acid residues. The N‐terminus of a precursor peptide (BtmD) is converted into bottromycin A2 by tailoring enzymes encoded in the btm gene cluster. However, little was known about key transformations in this pathway, including the unprecedented macrocyclization. To understand the pathway in detail, an untargeted metabolomic approach that harnesses mass spectral networking was used to assess the metabolomes of a series of pathway mutants. This analysis has yielded key information on the function of a variety of previously uncharacterized biosynthetic enzymes, including a YcaO domain protein and a partner protein that together catalyze the macrocyclization.
Cure‐on‐demand wood adhesive based on the frontal polymerization of acrylates
Authors: Holt TreyVon , Fazende Kylee , Jee Elizabeth , Wu Qinglin , Pojman John A.
Published: July 2016

We demonstrated for the first time a cure‐on‐demand wood adhesive using thermal frontal polymerization with Southern Pine wood. Monomer structure, initiator loading, and filler loading all had an impact on the strength of the adhesive and the cure‐on‐demand ability. More flexible, ethoxylated monomers produced stronger adhesives; though, the ethoxylate groups reduce the ability of the system to be polymerized frontally. Addition of a highly reactive comonomer (acrylic acid) to increase molecular weight between crosslinks along with the ethoxylated triacrylate increased the propensity for frontal polymerization and made a tougher polymer. Increasing initiator loading could help ensure front propagation, but a maximum initiator loading was reached where the gaseous byproducts of the peroxide initiator made the network highly porous and thus lacking strength. Fillers such as kaolin and sawdust helped overcome decreases in strength at high initiator loadings. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44064.
Oxidative β‐Csp3−H Functionalization of tBuOH: A Selective Radical/Radical Cross‐Coupling Access to β‐Hydroxy Thioethers
Authors: Li Yuxiu , Liu Dong , Liu Chao , Lei Aiwen
Published: July 2016

An oxidative β‐Csp3−H functionalization of tert‐butanol (tBuOH) for the construction of C−S bonds through an iodine‐catalyzed Csp3−H/S−H coupling was successfully achieved. Different kinds of mercaptans were shown to be good coupling partners, affording the desired products in good yields. This protocol not only offers a novel method for the synthesis of β‐hydroxy thioethers, but also provides an effective strategy for selective radical/radical cross‐coupling.
RhI‐Catalyzed Intramolecular Carbonylative C−H/C−I Coupling of 2‐Iodobiphenyls Using Furfural as a Carbonyl Source
Authors: Furusawa Takuma , Morimoto Tsumoru , Nishiyama Yasuhiro , Tanimoto Hiroki , Kakiuchi Kiyomi
Published: July 2016

Synthesis of fluoren‐9‐ones by a Rh‐catalyzed intramolecular C−H/C−I carbonylative coupling of 2‐iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate‐determining step is not a C−H bond cleavage but, rather, the oxidative addition of the C−I bond to a RhI center.
Standardization of chemical analytical techniques for pyrolysis bio‐oil: history, challenges, and current status of methods
Authors: Ferrell Jack R. , Olarte Mariefel V. , Christensen Earl D. , Padmaperuma Asanga B. , Connatser Raynella M. , Stankovikj Filip , Meier Dietrich , Paasikallio Ville
Published: July 2016

In this perspective, we discuss the standardization of analytical techniques for pyrolysis bio‐oils, including the current status of methods, and our opinions on future directions. First, the history of past standardization efforts is summarized, and both successful and unsuccessful validation of analytical techniques highlighted. The majority of analytical standardization studies to‐date has tested only physical characterization techniques. Here, we present results from an international round robin on the validation of chemical characterization techniques for bio‐oils. Techniques tested included acid number, carbonyl titrations using two different methods (one at room temperature and one at 80 °C), 31P NMR for determination of hydroxyl groups, and a quantitative gas chromatography–mass spectrometry (GC‐MS) method. Both carbonyl titration and acid number methods have yielded acceptable inter‐laboratory variabilities. 31P NMR produced acceptable results for aliphatic and phenolic hydroxyl groups, but not for carboxylic hydroxyl groups. As shown in previous round robins, GC‐MS results were more variable. Reliable chemical characterization of bio‐oils will enable upgrading research and allow for detailed comparisons of bio‐oils produced at different facilities. Reliable analytics are also needed to enable an emerging bioenergy industry, as processing facilities often have different analytical needs and capabilities than research facilities. We feel that correlations in reliable characterizations of bio‐oils will help strike a balance between research and industry, and will ultimately help to ‐determine metrics for bio‐oil quality. Finally, the standardization of additional analytical methods is needed, particularly for upgraded bio‐oils. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd
In vivo use of the CYP inhibitor 1‐aminobenzotriazole to increase long‐term exposure in mice
Authors: Watanabe Ayahisa , Mayumi Kei , Nishimura Kyohei , Osaki Hiromi
Published: July 2016

1‐Aminobenzotriazole (ABT) is a well‐known in vivo nonspecific inhibitor of cytochrome P450 (CYP) enzymes. An effective dosing regimen of ABT for a multiple‐administration study is needed to conduct pharmacological studies for proof‐of‐concept, although it has been established for single‐administration study, to characterize the pharmacokinetics of drug candidates. This study demonstrated a suitable dosing vehicle of ABT for continuous administration and increased exposure to antipyrine, which is a nonspecific probe of CYP, using ABT for a long period in mice. The dosing vehicle of ABT was 0.5% (w/v) hydroxypropyl methylcellulose and 0.5% (v/v) Tween 80 in N,N‐dimethylacetamide/20% hydroxypropyl‐β‐cyclodextrin aqueous solution (2:8, v/v) based on the duration of apparent solubility. After implantation of an ALZET osmotic pump with ABT, the plasma concentrations of ABT were maintained at more than 4.1 μg/ml over 336 h. Compared with the vehicle group, the CLtot of antipyrine with ABT decreased to approximately one‐fourth, and the BA of antipyrine with ABT increased up to 3‐fold. In addition, the enhancement of exposure of antipyrine by ABT was maintained over the 336 h. The body weight, food consumption and hematological parameters of mice did not change with ABT administration for 16 days. These findings demonstrated that pretreatment of ABT can increase long‐term exposure using continuous administration with the ALZET osmotic pump in mice with no overt toxicity. It is concluded that the in vivo use of 1‐aminobenzotriazole can be applied to pharmacological studies for proof‐of‐concept, thus contributing to the selection of drug candidates at an early drug discovery stage. Copyright © 2016 John Wiley & Sons, Ltd.
Revisiting the Effects of Anger on Risk‐Taking: Empirical and Meta‐Analytic Evidence for Differences Between Males and Females
Authors: Ferrer Rebecca A. , Maclay Alexander , Litvak Paul M. , Lerner Jennifer S.
Published: July 2016

That anger elicited in one situation can carry over to drive risky behavior in another situation has been described since the days of Aristotle. The present studies examine the mechanisms through which and the conditions under which such behavior occurs. Across three experiments, as well as a meta‐analytic synthesis of the data, results reveal that incidental anger is significantly more likely to drive risky decision making among males than among females. Moreover, the experiments document that, under certain circumstances, such risk‐taking pays off financially. Indeed, the present experiments demonstrate that, because the expected‐value‐maximizing strategy in these studies rewarded risk‐taking, angry‐male individuals earned more money than did both neutral‐emotion males and angry females. In sum, these studies found evidence for robust disparities between males and females for anger‐driven risk‐taking. Importantly, although men did not experience more anger than women, they did show a heightened tendency to respond to anger with risk‐taking. Published 2016. This article has been contributed to by US Government employees and their work is in the public domain in the USA.
Study on the interaction between anti‐tuberculosis drug ethambutol and bovine serum albumin: multispectroscopic and cyclic voltammetric approaches
Authors: Magdum Prashant A. , Gokavi Naveen M. , Nandibewoor Sharanappa T.
Published: July 2016

The binding of bovine serum albumin (BSA) to ethambutol (EMB) was investigated using spectroscopic methods, viz., fluorescence, Fourier transform infrared (FTIR), ultraviolet (UV)/vis absorption and cyclic voltammetry techniques. Spectroscopic analysis of the emission quenching at different temperatures revealed that the quenching mechanism of serum albumin by EMB is static, which was also confirmed by lifetime measurements. The number of binding sites, n, and binding constant, K, were obtained at various temperatures. The distance, r, between EMB and the protein was evaluated according to the Förster energy transfer theory. Based on displacement experiments using site probes, viz., warfarin, ibuprofen and digitoxin, the site of binding of EMB in BSA was proposed to be Sudlow's site I. The effect of EMB on the conformation of BSA was analyzed by using synchronous fluorescence spectra (SFS) and 3D fluorescence spectra. The results of fluorescence, UV/vis absorption and FTIR spectra showed that the conformation of BSA was changed in the presence of EMB. The thermodynamic parameters including enthalpy change (ΔH0), entropy change (ΔS0) and free energy change (ΔG0) for BSA–EMB were calculated according to the van't Hoff equation and are discussed.
The Metalloprotease Neprilysin Degrades and Inactivates Apelin Peptides
Authors: McKinnie Shaun M. K. , Fischer Conrad , Tran Kelvin M. H. , Wang Wang , Mosquera Fabricio , Oudit Gavin Y. , Vederas John C.
Published: July 2016

The apelinergic system is a mammalian peptide hormone network with key physiological roles. Apelin isoforms and analogues are believed to be promising therapeutics for cardiovascular disease. Despite extensive studies on apelin‐13 degradation patterns, only one protease, angiotensin‐converting enzyme 2 (ACE2), had been implicated in its physiological regulation. Through use of a peptide‐based fluorescent probe, we identified the metalloprotease neprilysin (NEP, a target for Entresto used in treatment of heart failure) as an enzyme that cleaves apelin isoforms. In vitro NEP proteolysis generated fragments that lacked the ability to bind to the apelin receptor, thereby making NEP the first protease to fully inactivate apelin. The involvement of NEP in the apelinergic system contributes to the understanding of its role in cardiovascular physiology.
The Potent Inhibitory Effect of a Naproxen‐Appended Cobalt(III)‐Cyclam Complex on Cancer Stem Cells
Authors: Cressey Paul B. , Eskandari Arvin , Bruno Peter M. , Lu Chunxin , Hemann Michael T. , Suntharalingam Kogularamanan
Published: July 2016

We report the potency against cancer stem cells (CSCs) of a new cobalt(III)‐cyclam complex (1) that bears the nonsteroidal anti‐inflammatory drug, naproxen. The complex displays selective potency for breast CSC‐enriched HMLER‐shEcad cells over breast CSC‐depleted HMLER cells. Additionally, it inhibited the formation of three‐dimensional tumour‐like mammospheres, and reduced their viability to a greater extent than clinically used breast cancer drugs (vinorelbine, cisplatin and paclitaxel). The anti‐mammosphere potency of 1 was enhanced under hypoxia‐mimicking conditions. Detailed mechanistic studies revealed that DNA damage and cyclooxygenase‐2 (COX‐2) inhibition contribute to the cytotoxic mechanism of 1. To the best of our knowledge, 1 is the first cobalt‐containing compound to show selective potency for CSCs over bulk cancer cells.
Comparison of the ipsi‐lateral versus contra‐lateral retrograde approach of percutaneous coronary interventions in chronic total occlusions
Authors: Mashayekhi Kambis , Behnes Michael , Valuckiene Zivile , Bryniarski Leszek , Akin Ibrahim , Neuser Hans , Neumann Franz‐Josef , Reifart Nicolaus
Published: July 2016

Background

Retrograde recanalization of coronary chronic total occlusions (CTO) via contralateral (CL) collateral connections (CCs) is successful in 60–70% of patients in whom conventional antegrade approach fails or is unpromising. This study describes our experience with retrograde CTO‐PCI via ipsi‐lateral (IL) CCs in patients with unfavorable CL CCs.

Methods

Between January 2013 and September 2015, 392 consecutive CTO procedures were performed by two high volume CTO‐operators and the relevant data were fed into an online registry (ERCTO® EuroCTO‐club). Most patients (222/392; 57%) were approached antegradely, whereas 43% were attempted retrogradely (170/392). After exclusion of all procedures performed via bypass‐grafts (n = 12), PCI via CL CCs, the CL‐group (n = 114/158; 72%), was compared with the IL‐group that was attempted via IL CCs (n = 44/158; 28%).

Results

Both groups were similar with respect to risk factors and morphologic criteria of CTO‐severity. The initial primary strategy was successful in 78% in the CL‐group and in 68% in the IL‐group. In both patient groups, the initial strategy had to be switched in five patients from CL toward IL (4.4%, n = 5/114) and from IL to CL (11.3% n = 5/44). The rate of major complications was 7% (CL) and 5% (IL), respectively (n.s.). After retrograde failure and cross‐over to an antegrade controlled re‐entry strategy the overall success rates increased to 92% (CL) and 93% (IL).

Conclusions

In experienced hands retrograde CTO‐PCI via IL CCs appears as safe and successful as the CL approach. © 2016 Wiley Periodicals, Inc.
Safety and efficacy profile of bioresorbable‐polylactide‐polymer‐biolimus‐A9‐eluting stents versus durable‐polymer‐everolimus‐ and zotarolimus‐eluting stents in patients with acute coronary syndrome
Authors: Jaguszewski Milosz , Dörig Manuela , Frangieh Antonio H. , Ghadri Jelena‐Rima , Cammann Victoria Lucia , Diekmann Johanna , Napp L. Christian , D'Ascenzo Fabrizio , Imori Yoichi , Obeid Slayman , Maier Willibald , Lüscher Thomas F. , Templin Christian
Published: July 2016

Background

Comparative data on long‐term safety and efficacy of bioresorbable‐polymer‐BES versus durable‐polymer‐EES/ZES in ACS setting have hitherto been lacking. We sought to assess the safety and efficacy of bioresorbable‐polymer‐biolimus‐A9‐eluting stents (BES) compared with thin‐strut‐durable‐polymer‐everolimus‐ and zotarolimus‐eluting stents (EES/ZES) in patients with acute coronary syndrome (ACS) undergoing PCI.

Methods and Results

Between 2007 and 2012, 1,547 patients were implanted with new‐generation drug‐eluting stents (DES). Out of these, 369 received BES and 1,178 EES/ZES. The primary endpoint was probable/definite stent thrombosis (ST) while the secondary endpoint was a composite of all‐cause death, myocardial infarction (MI), target vessel revascularization (TVR) and definite ST up to 5 years. As stent assignment was not random, we performed a propensity score matching (PSM), with 1:3 ratio, to account for potential confounders. Primary analysis demonstrated no significant differences between both groups for the primary endpoint of ST (BES vs. EES/ZES: 1.6% vs. 1.9%; mean‐event‐time = 1,797 days vs. 1,795 days, respectively; P = 0.75) and composite safety endpoint (BES vs. EES/ZES: 12.5% vs. 12.9%; mean‐event‐time = 1,631 days vs. 1,620 days, respectively; P = 0.88). Results regarding the 5‐year‐ST‐ and safety endpoint remained non‐significant after PSM (P = 0.85, P = 0.56; respectively). After stratification based on cardiovascular risk, no difference regarding ST and composite outcome measure has been documented between both stent groups in high‐risk‐ and low‐risk patients. The type of stent did neither predict ST (HR 1.11, 95%CI 0.45–2.74, P = 0.82) nor composite safety endpoint (HR 0.93, 95%CI 0.67–1.30, P = 0.69).

Conclusions

Long‐term safety and efficacy of bioresorbable‐polymer‐BES and durable‐polymer‐EES/ZES appear comparable in patients with ACS. © 2016 Wiley Periodicals, Inc.
Synthesis of a Molecule with Four Different Adjacent Pnictogens
Authors: Hinz Alexander , Schulz Axel , Villinger Alexander
Published: July 2016

The synthesis of a molecule containing four adjacent different pnictogens was attempted by conversion of a Group 15 allyl analogue anion [Mes*NAsPMes*]− (Mes*=2,4,6‐tri‐tert‐butylphenyl) with antimony(III) chloride. A suitable precursor is Mes*N(H)AsPMes* (1) for which several syntheses were investigated. The anions afforded by deprotonation of Mes*N(H)AsPMes* were found to be labile and, therefore, salts could not be isolated. However, the in situ generated anions could be quenched with SbCl3, yielding Mes*N(SbCl2)AsPMes* (4).
Betaine and Carnitine Derivatives as Herbicidal Ionic Liquids
Authors: Pernak Juliusz , Niemczak Michał , Chrzanowski Łukasz , Ławniczak Łukasz , Fochtman Przemysław , Marcinkowska Katarzyna , Praczyk Tadeusz
Published: July 2016

This study focused on the synthesis and subsequent characterization of herbicidal ionic liquids based on betaine and carnitine, two derivatives of amino acids, which were used as cations. Four commonly used herbicides (2,4‐D, MCPA, MCPP and Dicamba) were used as anions in simple (single anion) and oligomeric (two anions) salts. The obtained salts were subjected to analyzes regarding physicochemical properties (density, viscosity, refractive index, thermal decomposition profiles and solubility) as well as evaluation of their herbicidal activity under greenhouse and field conditions, toxicity towards rats and biodegradability. The obtained results suggest that the synthesized herbicidal ionic liquids displayed low toxicity (classified as category 4 compounds) and showed similar or improved efficacy against weed compared to reference herbicides. The highest increase was observed during field trials for salts containing 2,4‐D as the anion, which also exhibited the highest biodegradability (>75 %).
Noble‐Metal‐Free Photocatalytic H2 Generation: Active and Inactive ‘Black’ TiO2 Nanotubes and Synergistic Effects
Authors: Liu Ning , Schneider Christopher , Freitag Detlef , Zolnhofer Eva M. , Meyer Karsten , Schmuki Patrik
Published: July 2016

Over the past five years a number of different synthesis approaches has been reported to obtain so‐called ‘black’ titania. One of the outstanding features of the material is that certain synthesis processes lead to the formation of an intrinsic co‐catalytic center and thus enable noble‐metal free photocatalytic H2‐generation. In the present work, using TiO2 nanotube layers, we compare three common ‘blackening’ approaches, namely i) the original high‐pressure hydrogenation (HPT‐H2), ii) a classic high temperature reduction in Ar, and iii) an electrochemical (cathodic) reduction. We demonstrate that except for high pressure hydrogenation also cathodic reduction leads to an activation of TiO2 ‐ that is, it exhibits noble‐metal‐free photocatalytic H2 generation. Moreover, we show that a combination of cathodic reduction/high pressure hydrogenation leads to a synergistic effect, that is, a significant enhancement of the combined co‐catalytic activity.
Polytrope Kinetikmessung zur Bewertung von Ionenaustauscherharzen für die Veresterung von Acrylsäure mit n‐Butanol
Authors: Antweiler Nicolai , Wang Zhiqi , Agar David W.
Published: July 2016

Es wurde ein Katalysatorscreening stark saurer Ionenaustauscherharze zur Veresterung von Acrylsäure mit n‐Butanol zu Acrylsäurebutylester und Wasser durchgeführt. Die Kinetiken wurden in einem Temperaturbereich von 70 bis 100 °C untersucht und die Selektivitäten bestimmt. Eine Beschreibung über das Langmuir‐Hinshelwood‐Hougen‐Watson‐Modell liefert eine gute Übereinstimmung. Unter Verwendung des ausgewählten Modells erfolgte die Auslegung einer Reaktivrektifikationskolonne. Aufgrund der ähnlichen Fluiddynamik und der zeitökonomischen Generierung vieler Messpunkte wurde die Temperature‐scanning‐Methode (TSM) unter Verwendung eines Rohrreaktors eingesetzt.
Sustainable microalgae‐based palm oil mill effluent treatment process with simultaneous biomass production
Authors: Halim Fatimah T. A. , Guo Xiaoyi , Su Gaomin , Ngee Hannah L. , Zeng Xianhai , He Ning , Lin Lu , Danquah Michael K.
Published: July 2016

The production of copious quantities of waste palm oil mill effluent (POME) is an unavoidable consequence of palm oil industries, and requires effective treatment before discharge into the environment. Microalgae possess a significant nutrient bio‐sorption capacity in addition to high photosynthetic and carbon bio‐sequestration rates, and hence can be exploited for sustainable POME treatment operations. Bioprocess research on the use of microalgal cells to remove specific chemical species from POME is limited. This work investigated the application of the microalgae Chlorella vulgaris and Nannochloropsis sp. for nitrogen and phosphorus removal from POME with simultaneous biomass production. Both microalgae species displayed maximum total nitrogen and phosphorus removal efficiencies at 50 % POME concentration within 8 days. Studies on nitrogen and phosphorous addition demonstrated that a N/P molar ratio of 10:1 improved biomass accumulation with 90.0 % nitrogen and 82.1 % phosphorus removals. These results showed that high treatment efficiencies can be obtained using C. vulgaris and Nannochloropsis sp. for applications in industrial POME treatment.
Degradation of Recalcitrant Textile Dyes by Coupling Fungal and Photocatalytic Membrane Reactors
Authors: Deveci Ece Ümmü , Dizge Nadir , Yatmaz Hüseyin Cengiz , Tansel Berrin
Published: July 2016

White rot fungi have powerful and broad specific extracellular enzymatic systems and can degrade multiple types of recalcitrant compounds including azo dyes, therefore, they are used in the field of bioremediation. In the present study, decolorization and organic matter removal of Acid Red 88 (AR88) and Reactive Red 180 (RR180) dye solutions were performed using the white rot fungus Phanerochaete chrysosporium in a bioreactor. Degradation of the dyes was assessed using a hybrid process consisting of a fungal membrane bioreactor coupled with a photocatalytic membrane reactor. The photocatalytic oxidation step was conducted using the semiconductor ZnO as the catalyst with UVA irradiation. Experimental data with the fungal membrane bioreactor showed that the optimum pH was 4.5 for P. chrysosporium. Integrating photocatalytic step after the fungal membrane process improved the chemical oxygen demand (COD) removal efficiency up to 98 and 96% for RR180 and AR88 dye solutions, respectively. Color removal efficiencies after the photocatalytic degradation were 99.9% for both dye solutions.
Subsets of salivary duct carcinoma defined by morphologic evidence of pleomorphic adenoma, PLAG1 or HMGA2 rearrangements, and common genetic alterations
Authors: Chiosea Simion I. , Thompson Lester D. R. , Weinreb Ilan , Bauman Julie E. , Mahaffey Alyssa M. , Miller Caitlyn , Ferris Robert L. , Gooding William E.
Published: July 2016

BACKGROUND

The authors hypothesized that histogenetic classification of salivary duct carcinoma (SDC) could account for de novo tumors and those with morphologic or molecular evidence (pleomorphic adenoma gene 1 [PLAG1], high‐mobility group AT hook 2 [HMGA2] rearrangement, amplification) of pleomorphic adenoma (PA).

METHODS

SDCs (n = 66) were reviewed for morphologic evidence of PA. PLAG1 and HMGA2 alterations were detected by fluorescence in situ hybridization (FISH). PLAG1‐positive tumors were tested by FISH for fibroblast growth factor receptor 1 (FGFR1) rearrangement. Thirty‐nine tumors were analyzed using a commercial panel for mutations and copy number variations in 50 cancer‐related genes.

RESULTS

On the basis of combined morphologic and molecular evidence of PA, 4 subsets of SDC emerged: 1) carcinomas with morphologic evidence of PA but intact PLAG1 and HMGA2 (n = 22); 2) carcinomas with PLAG1 alteration (n = 18) or 3) HMGA2 alteration (n = 12); and 4) de novo carcinomas, without morphologic or molecular evidence of PA (n = 14). The median disease‐free survival was 37 months (95% confidence interval, 28.4‐45.6 months). Disease‐free survival and other clinicopathologic parameters did not differ for the subsets defined above. Combined Harvey rat sarcoma viral oncogene homolog/phosphatidylinositol‐4,5‐biphosphate 3‐kinase, catalytic subunit α (HRAS/PIK3CA) mutations were observed predominantly in de novo carcinomas (5 of 8 vs 2 of 31 tumors; P = .035). Erb‐B2 receptor tyrosine kinase 2 (ERBB2) copy number gain was not observed in de novo carcinomas (0 of 8 vs 12 of 31 tumors; P = .08). Tumor protein 53 (TP53) mutations were more common in SDC ex pleomorphic adenomas than in de novo carcinomas (17 of 31 vs 1 of 8 tumors; P = .033).

CONCLUSIONS

The genetic profile of SDC varies with the absence or presence of pre‐existing PA and its cytogenetic signature. Most de novo SDCs harbor combined HRAS/PIK3CA mutations and no ERBB2 amplification. Cancer 2016;122:3136–44. © 2016 American Cancer Society.
Association of functional status and treatment choice among older men with prostate cancer in the Medicare Advantage population
Authors: Jacobs Bruce L. , Lopa Samia H. , Yabes Jonathan G. , Nelson Joel B. , Barnato Amber E. , Degenholtz Howard B.
Published: July 2016

BACKGROUND

There are several effective treatments for prostate cancer. To what extent a patient's functional status influences the treatment decision is unknown. This study examined the association between functional status and treatment among older men with prostate cancer.

METHODS

Surveillance, Epidemiology, and End Results–Medicare Health Outcomes Survey data were used to identify men who were 65 years old or older and were diagnosed with prostate cancer between 1998 and 2009. The primary outcome was treatment choice: conservative management, surgery, or radiation within 1 year of the diagnosis. The exposure was the functional status assessed as 4 measures within 3 domains: 1) physical function (activities of daily living [ADLs] and physical component summary score), 2) cognitive function (survey completer: self vs proxy), and 3) emotional well‐being (mental component summary score). A multivariate, multinomial logistic regression was fitted with adjustments for several patient, tumor, and regional characteristics.

RESULTS

This study identified 508 conservative management patients, 195 surgery patients, and 603 radiation patients. Compared with men with no ADL dependency, those with any ADL dependency had lower odds of receiving surgery (odds ratio [OR], 0.61; 95% confidence interval [CI], 0.38‐0.99) or radiation (OR, 0.58; 95% CI, 0.43‐0.78) versus conservative management. ADL dependency did not differ when surgery and radiation were compared. Patients with a proxy survey response were less likely to receive surgery or radiation versus conservative management.

CONCLUSIONS

Functional status is associated with treatment choice for men with prostate cancer. Future research should examine whether this is due to physician recommendations, patient preferences, or a combination. Cancer 2016;122:3199–206. © 2016 American Cancer Society.
Origin of the Surfactant‐Dependent Redox Chemistry of Single‐Wall Carbon Nanotubes
Authors: Hirano Atsushi , Kameda Tomoshi , Yomogida Yohei , Wada Momoyo , Tanaka Takeshi , Kataura Hiromichi
Published: July 2016

The redox chemistry of single‐walled carbon nanotubes (SWCNTs) was examined by using optical absorption spectroscopy measurements in the presence of sodium dodecyl sulfate (SDS) and its analog surfactants, that is, sodium 1‐undecanesulfonate (SUS) and sodium dodecylbenzenesulfonate (SDBS). Redox reactions of the SWCNTs were observed in the SDS and SUS solutions, whereas such reactions were suppressed in the SDBS solution. Molecular dynamics simulations were performed to investigate the assembly of the surfactants around an SWCNT. SDS and SUS were shown to primarily form single layers on the SWCNT and certain solvent‐exposed areas, whereas SDBS predictably densely coated the SWCNTs. The results suggest that the SDBS layer on the SWCNT surfaces prevents charge‐transfer reactions; in contrast, the sparse layers of SDS and SUS allow the redox chemistry through the charge‐transfer reactions. Interestingly, a positively charged SWCNT as a model for the oxidized SWCNT showed an increase in the number of surfactant molecules around the SWCNT in the SDS and SUS solutions owing to electrostatic interaction, which is related to the chirality‐dependence of the SWCNT colloidal stability.
Emissive Heterobimetallic Copper(I) Dicyanoaurate‐Based Coordination Polymers
Authors: Ovens Jeffrey S. , Leznoff Daniel B.
Published: July 2016

Five new CuI/[Au(CN)2]−‐based coordination polymer materials—Cu(py)2[Au(CN)2] (1), Cu(PPh3)(MeCN)[Au(CN)2]⋅MeCN (2 a), Cu(PPh3)(MeCN)[Au(CN)2] (2 b), Cu3(THT)4[Au(CN)2]3 (3 a) and Cu(THT)[Au(CN)2] (3 b)—were prepared and characterized in terms of their structural and photoluminescence properties, and thermal stability (py=pyridine, THT=tetrahydrothiophene). While 1 and 2 a/2 b adopted one‐dimensional zig‐zag chain structures with no Au⋅⋅⋅Au (aurophilic) bonding, 3 a and 3 b exhibited much more complex three‐dimensional frameworks featuring numerous aurophilic interactions; bridging THT units formed either eight‐membered Cu4S4 rings (3 a) or helical (Cu/S)n chains (3 b). When these materials are excited using a broad‐band UV source (365 nm), they each emit light of a distinct colour (except for 2 a): light green for 1, pale blue for 2 b, deep blue for 3 a, and violet for 3 b (λmax=506 nm (1), 464 nm (2 b), 457 nm (3 a) and 404 nm (3 b)). The emission band in 1, 2 b and 3 b was assigned to CuI/ligand/CN−‐based MLCT transitions, while the emission band of 3 a appears to be influenced by the presence of the aurophilic interactions in the structure. Materials 1 and 3 a lose their bound pyridine and THT, respectively, at 110 and 95 °C, respectively, indicating their potential utility as sensory materials.
Impacts of beaver dams on channel hydraulics and substrate characteristics in a mountain stream
Authors: Stout T. L. , Majerova M. , Neilson B. T.
Published: July 2016

Beaver dams have significant impacts on the hydrology, temperature, biogeochemical processes, and geomorphology of streams and riparian areas. They have also been used as a viable tool in restoring impaired riverine systems. Because of the dynamic nature of beaver dams, these influences vary and are difficult to quantify. To begin understanding the impacts of beaver dams in mountain streams, we developed 1D hydraulic models for a beaver impacted reach that includes eight dams and a non‐impacted reach to compare hydraulic responses (e.g. channel depth, width, and velocity distributions). We also compared observations of substrate size distributions for different geomorphic/habitat units within each reach. Results from the models indicated shifts in channel hydraulics through statistically significant increases in depths and widths as well as a decrease in flow velocities through the beaver impacted reach. These hydraulic adjustments, as a result of beaver dams, are consistent with observed changes in the increased variability and spatial heterogeneity in sediment size distributions. Through the application of three different modelling approaches, we found that a relatively low number of beaver dams would result in significant changes in channel hydraulics. These results provide preliminary information regarding the number of dams per unit stream length required to begin meeting various restoration goals.
A Facile Synthesis of Co3O4 Hollow Microtubes by Decomposition of a Cobalt Metal–Organic Framework
Authors: Gómez‐Aguirre L. Claudia , Castro‐García Socorro , Sánchez‐Andújar Manuel , Yáñez‐Vilar Susana , Mira Jorge , Bermúdez‐García Juan Manuel , Centeno Teresa A. , Señarís‐Rodríguez María Antonia
Published: July 2016

In this work, we have successfully synthesized hollow microtubular crystals of the metal–organic framework (MOF) [Co2(NH2‐bdc)2(dabco)]·[G] {G = H2O, N,N‐dimethylformamide (DMF); NH2‐bdc =2‐amino‐1,4‐benzenedicarboxylate; dabco = 1,4‐diazabicyclo[2.2.2]octane} by a very simple coordination‐modulation method that avoids the use of an external modulator. Additionally, we have obtained the corresponding hollow microtubular crystals of Co3O4 through the solid‐state thermolysis of the Co‐MOF material at 400 °C. The as‐prepared Co3O4 crystals exhibit the typical magnetic behavior for a nanostructured material with good crystallinity. Thus, this coordination‐modulation method provides a simple route for the preparation of nanostructured porous frameworks and derived oxides and opens a way to prepare new materials with advanced properties.
Impact of the Metal Centre and Functionalization on the Mechanical Behaviour of MIL‐53 Metal–Organic Frameworks
Authors: Yot Pascal G. , Yang Ke , Guillerm Vincent , Ragon Florence , Dmitriev Vladimir , Parisiades Paraskevas , Elkaïm Erik , Devic Thomas , Horcajada Patricia , Serre Christian , Stock Norbert , Mowat John P. S. , Wright Paul A. , Férey Gérard , Maurin Guillaume
Published: July 2016

An extended series of MIL‐53(M)_X metal–organic frameworks (MIL = Materials of Institute Lavoisier; M = Al, Cr, Fe, Sc; X = Cl, CH3, NO2) have been systematically investiaged to explore the impact of the nature of both the metal centre and the functions grafted on to the organic linker on the mechanical behaviour of this family of highly flexible hybrid porous frameworks under the application of an external pressure of up to 3 GPa. The high‐pressure X‐ray diffraction measurements allowed the characterization of the pressure‐induced phase transitions of the hydrated structures, the associated volume changes/pressure transitions, and their mechanical resilience through the determination of their bulk moduli.
Alternative Precursors for the Synthesis of Binary Sb2E3 and Bi2E3 (E = S, Se, Te) Nanoparticles by the Hot Injection Method
Authors: Rusek Monika , Bendt Georg , Wölper Christoph , Schulz Stephan
Published: July 2016

Intramolecularly stabilized Sb(OCH2CH2NMe2)3 (1) and Bi(OCH2CH2NMe2)3 (2) readily react with (Me3Si)2S and (Et3Si)2E (E = Se, Te) at moderate temperatures (hot injection method) with elimination of the corresponding silyl ether and subsequent formation of the group 15 chalcogenides Sb2E3 and Bi2E3, which were characterized by XRD, SEM, and energy‐dispersive X‐ray spectroscopy (EDX). In addition, the solid‐state structure of 1 was determined by single‐crystal XRD.
Conducting Behavior and Valence Ordering of a One‐Dimensional MMX‐Type Coordination Polymer under High Pressure
Authors: Otsubo Kazuya , Suto Tomohiko , Kobayashi Atsushi , Ikeda Ryuichi , Hedo Masato , Uwatoko Yoshiya , Kitagawa Hiroshi
Published: July 2016

One‐dimensional (1D) halogen‐bridged mixed‐valent binuclear metal compounds, the so‐called MMX chains, are well known as highly conductive coordination polymers because of the high electronic flexibility within their metal‐dimer unit. Herein, we report on the conducting behavior and electronic state of a highly conductive MMX‐chain compound, Pt2(dta)4I (dta: CH3CS2–) under high pressure. Electrical resistivity measurements showed that this compound exhibits semiconducting behavior in a broad pressure region, despite metallic conduction under ambient pressure. Raman spectra provided clear information about the semiconducting state of this compound under pressure, which was also supported by X‐ray diffraction (XRD) studies. Moreover, we successfully clarified the pressure–temperature phase diagram of this material. By comparing with an analogous material, we found that the difference in the alkyl chain length of the terminal ligand plays an important role for the conducting behavior and the electronic phase under pressure.
Micronized natural talc affects the proteins and pectic cell wall polysaccharides during “Hojiblanca” virgin olive oil extraction
Authors: Sadkaoui Abir , Jiménez Antonio , Pacheco Rafael , Beltrán Gabriel
Published: July 2016

This work studies how using MNT affects cell wall polysaccharides and proteins of “Hojiblanca” paste during virgin olive oil extraction. Four doses of MNT were assessed: 0, 0.25, 0.5, and 1%. Three pectic fractions were extracted from alcohol insoluble solids (AIS): water‐soluble pectin (WSP), chelate‐soluble pectin (CSP), and non‐soluble pectin (NSP). In general, the content of the three pectic fractions decreased throughout the kneading step. This indicated a significant degradation and solubilization of pectins during processing. The same trend was observed for protein content and total pectin content while AIS yield increased. Addition of MNT at doses lower than 0.5% favored the formation of a chemical bound through electrostatic interactions between proteins and pectic polysaccharides which are held together and adsorbed onto the talc surface giving a decrease in their content. Higher MNT doses (1%) produced the opposite behavior. The lowest dose of MNT (0.25%) reduced the oil losses in the pomace. A certain tendency for the loss of oil in the pomace to decrease as the amount of total pectin and protein decreased was observed, indicating that the oil yield is at least in part, related to the pectin and protein content depending on the dose of MNT added during malaxation step.

Practical application: We have demonstrated that the use of talc during the malaxation step greatly lessens the effect of the pectic substrates and proteins, principal emulsifier agents that influence the formation of oil‐in‐water emulsions during oil extraction process and enhance the extraction of the oil from the mesocarp cells by reducing its loose in the pomace. Excess of talk addition presented a reverse effect, though. It is, therefore, of the utmost importance that the information contained in this study is fully taken into account to establish the suitable dose of talc that should be applied when difficult pastes are formed during malaxation step and which at least partially depends on the content of proteins and pectin compounds of the processed olive paste.

Proteins and pectic cell wall polysaccharides as affected by talc addition during virgin olive oil extraction.
Regioselective Synthesis of 2,4‐Substituted Pyrido[1′,2′:1,5]pyrazolo[3,4‐d]pyrimidines through Sequential Pd‐Catalyzed Arylation and SNAr Reactions
Authors: Belaroussi Rabia , El Hakmaoui Ahmed , Akssira Mohamed , Guillaumet Gérald , Routier Sylvain
Published: July 2016

The synthesis and regioselective functionalization of rare 2,4‐disubstituted‐pyrido[1′,2′:1,5]pyrazolo[3,4‐d]pyrimidine derivatives is reported. C‐4 aminations were performed by chlorine nucleophilic substitution SNAr reactions, and their efficiencies were compared with those for direct one‐pot amide C–O activation with bromotripyrrolidinophosphonium hexafluorophosphate (PyBroP) as a reagent. The latter method was used to perform palladium‐catalyzed C‐4 (het)arylation. Finally, two C‐4 amino and aryl derivatives were prepared on a large scale and engaged in desulfurative Liebeskind–Srogl‐type reactions under microwave irradiation to afford the envisioned compound library. Each step was optimized, and the results are discussed.
Palladium‐Catalyzed Regioselective Dehydrogenative C–H/C–H Cross‐Coupling of Pyrroles and Pyridine N‐Oxides
Authors: Liu Shanshan , Tzschucke C. Christoph
Published: July 2016

The palladium‐catalyzed cross‐dehydrogenative coupling of N‐alkylpyrroles and pyridine N‐oxides gave the corresponding pyrrolylpyridine N‐oxides. Cu(OAc)2·H2O as a co‐catalyst with air as the terminal oxidant led to preferential coupling in the β‐position, whereas AgOAc as the stoichiometric oxidant resulted in preferential coupling in the α‐position. N‐(Benzyloxymethyl)pyrrole derivatives were deprotected by hydrogenolysis followed by basic hydrolysis.
Dispersive liquid–liquid microextraction of quinolones in porcine blood: Optimization of extraction procedure and CE separation using experimental design
Authors: Vera–Candioti Luciana , Teglia Carla M. , Cámara María S.
Published: July 2016

A dispersive liquid–liquid microextraction procedure was developed to extract nine fluoroquinolones in porcine blood, six of which were quantified using a univariate calibration method. Extraction parameters including type and volume of extraction and dispersive solvent and pH, were optimized using a full factorial and a central composite designs. The optimum extraction parameters were a mixture of 250 μL dichloromethane (extract solvent) and 1250 μL ACN (dispersive solvent) in 500 μL of porcine blood reached to pH 6.80. After shaking and centrifugation, the upper phase was transferred in a glass tube and evaporated under N2 steam. The residue was resuspended into 50 μL of water–ACN (70:30, v/v) and determined by CE method with DAD, under optimum separation conditions. Consequently, a tenfold enrichment factor can potentially be reached with the pretreatment, taking into account the relationship between initial sample volume and final extract volume. Optimum separation conditions were as follows: BGE solution containing equal amounts of sodium borate (Na2B4O7) and di‐sodium hydrogen phosphate (Na2HPO4) with a final concentration of 23 mmol/L containing 0.2% of poly (diallyldimethylammonium chloride) and adjusted to pH 7.80. Separation was performed applying a negative potential of 25 kV, the cartridge was maintained at 25.0°C and the electropherograms were recorded at 275 nm during 4 min. The hydrodynamic injection was performed in the cathode by applying a pressure of 50 mbar for 10 s.
Simple, rapid and, cost‐effective fabrication of PDMS electrophoresis microchips using poly(vinyl acetate) as photoresist master
Authors: Lobo‐Júnior Eulício O. , Gabriel Ellen F. M. , dos Santos Rodrigo A. , de Souza Fabrício R. , Lopes Wanderson D. , Lima Renato S. , Gobbi Angelo L. , Coltro Wendell K. T.
Published: July 2016

This study describes a simple, rapid, and cost‐effective fabrication of PDMS electrophoresis microchips using poly(vinyl acetate) (PVAc) emulsion as photoresist master. High‐relief microfluidic structures were defined on poly(vinyl acetate) previously deposited on printed circuit boards surfaces without cleanroom facilities and sophisticated instrumentation. After a UV exposure, channels with heights ranging from 30 to 140 μm were obtained by controlling the emulsion mass deposited on the master surface. The developing stage was performed using water rather than the organic solvents that are applied for conventional masks. The surface morphology was characterized by optical imaging, profilometry, and SEM. Based on the achieved results, the proposed method offers suitable reproducibility for the prototyping of electrophoresis microchips in PDMS. The feasibility of the resulting PDMS electrophoresis chips was successfully demonstrated with the separation of major inorganic cations within 100 s using a contactless conductivity detection system. The separation efficiencies ranged from ca. 67 900 to 125 600 plates/m. Due to the satisfactory performance and simplified instrumentation, we believe this fabrication protocol presents potential to be implemented in any chemical, biochemical, or biological laboratory.
Nutrient content of fish powder from low value fish and fish byproducts
Authors: Abbey Lawrence , Glover‐Amengor Mary , Atikpo Margaret O. , Atter Amy , Toppe Jogeir
Published: July 2016

Consuming small‐sized fish species whole, and bones of large fish could contribute significantly to reducing the level of micronutrient and protein malnutrition. These fish products are more affordable and could therefore meet the needs of poor, vulnerable groups, particularly in rural and urban areas where limited economic resources prevent dietary diversity. The objectives of the study were to produce fish powder from dried edible byproducts from fish processing factories, an underutilized fish species, burrito and to determine the physical, micromineral, macronutrient and microbiological quality of the dried fish powder. Edible fish processing byproducts and an underutilized fish, burrito (Brachydeuterus auritus) were cleaned thoroughly and dried with a Council for Scientific and Industrial Research‐Food Research Institute (CSIR‐FRI) gas‐fuelled oven at 55°C for 8 h or until dried. The dried products were milled into powder, and packaged into polythene bags. Proximate analysis of the fish powder was done Official Methods of Analysis (AOAC) methods. Minerals and heavy metals in the fish powder were determined by atomic absorption spectrophotometry (AAS). Microbiological quality was determined by Nordic Committee on Food Analysis Method (NMLK) methods. Tuna trimmings contained 80.71 g/100 g protein, whereas burrito contained 70.40 g/100 g protein. Concentrations of cadmium, arsenic, and mercury varied from <1.00 to 1 mg/kg. Lead was found at 0.04 mg/100 g in tuna frames and gills only. All fish byproducts contained high levels of iron, for example, trimmings contained 16.58 mg/100 g, whereas tuna frames and gills also contained 16.82 and 19.54 mg/100 g, respectively. Burrito contained 8.92 mg/100 g. Zinc levels also ranged from 0.41 mg/100 g in tuna trimmings to 1.88 mg/100 g in tuna gills. The powdered samples according to the standards set by Ghana Standard Authority, were acceptable. Consuming small‐ sized fish species whole, and bones of large fish could contribute significantly to reducing the level of micronutrient and protein malnutrition. These are more affordable and could therefore meet the needs of poor, vulnerable groups.