bluuebunny/crossref_metadata_2025 huggingface dataset:
In situ carbon deposition in polyetherimide/SAPO‐34 mixed matrix membrane for efficient CO2/CH4 separation
Authors: Sen Mitali , Das Nandini
Published: July 2017

A simple method of pore modification complied with defect removal polymer zeolite mixed matrix membrane was developed by in situ carbon (C) deposition. The C deposition was achieved by the controlled decomposition of polymer matrix by heat treatment. In this study, polyetherimide/silicoaluminophosphate‐34 mixed matrix membrane (MMM) was fabricated on clay‐alumina support tube, followed by carbonization of the polymer matrix for gas separation application. MMM without heat treatment were also synthesized for comparison by conventional method. The membranes were characterized by X‐ray diffraction, field emission scanning electron microscopy, and X‐ray photoelectron spectroscopy. Due to carbonization, in situ C nanoparticles were deposited in to the interfacial pores, and filler particles were oriented in preferable direction. The presence of CO, CN, and graphitic carbon in the matrix, may be an indication of partial carbonization and restoration of adherence of polymer with substrate. The separation factor for CO2/CH4 achieved 39.15 with a permeance value of 23.01 × 10−8mol/(m2 s Pa) for CO2 at 30 °C and 200 kPa feed pressure. For the first time, this work shows an improvement toward permeability of MMM by simple carbonization of polymer matrix with commendable values as compare to the reported literature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45508.
Nonhalogen flame retarded poly(butylene terephthalate) composite using aluminum phosphinate and phosphorus‐containing deoxybenzoin polymer
Authors: Hu Xilong , Wang Yan , Yu Junrong , Zhu Jing , Hu Zuming
Published: July 2017

Synergistic charring effect was observed between aluminum diethlyphosphinate (AlPi) and 4,4‐bishydroxydeoxybenzoin‐polyphosphonate (BHDB‐PPN) in the poly(butylene terephthalate) composite. By combining them together, robust UL 94 V0 rating was achieved at 0.8 mm thickness for poly(butylene terephthalate)/AlPi/BHDB‐PPN composite which exhibited better mechanical properties than the samples without BHDB‐PPN. The thermal degradation behavior of BHDB‐PPN was investigated by analyzing its evolution and residues under different temperatures. It was found that the radical termination reaction of formed benzyl group may play a critical role in the high charring capacity of BHDB‐PPN. Part of the volatile diethlyphosphinate fragments reacted with the degradation intermediates from BHDB‐PPN to form big chain structure for further carbonization was a possible reason for the synergistic charring effect between AlPi and BHDB‐PPN. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45537.
Experimental investigation of the effects of different chemical absorbents on wetting and morphology of poly(vinylidene fluoride) membrane
Authors: Rezaiyan Zeynab , Keshavarz Peyman , Khorram Mohammad
Published: July 2017

Membrane wetting is of one the most important factor that affects the CO2 absorption efficiency in membrane contactors due to the increase of mass transfer resistance. In this study, the effects of different absorbents on the wettability of poly(vinylidene fluoride) membranes were investigated. Four absorbents including monoethanolamine, potassium carbonate–piperazine (PZ), potassium carbonate–monoethanolamine, and methyldiethanolamine–PZ were applied to investigate the effects of different absorbents on membrane wetting. Membrane properties before and after contact with absorbents were investigated using methods of thermogravimetric analysis, Fourier transform infrared spectroscopy, electron scanning microscope, and contact angle measurements. The results revealed that methyldiethanolamine and mixed absorbents containing methyldiethanolamine caused the most morphological changes in membrane. The results showed that reduction percentages of contact angle for water, K2CO3/PZ, K2CO3/MEA, MEA, and MDEA/PZ solutions were 14.52, 16.9, 21.19, 23.7, and 28.33, respectively, after 30 days immersion. The results also showed that potassium carbonate–PZ solution caused the least change in membrane wettability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45543.
Cellular and genetic models of H6PDH and 11β‐HSD1 function in skeletal muscle
Authors: Zielinska Agnieszka E. , Fletcher Rachel S. , Sherlock Mark , Doig Craig L. , Lavery Gareth G.
Published: July 2017

Glucocorticoids are important for skeletal muscle energy metabolism, regulating glucose utilization, insulin sensitivity, and muscle mass. Nicotinamide adenine dinucleotide phosphate‐dependent 11β‐hydroxysteroid dehydrogenase type 1 (11β‐HSD1)‐mediated glucocorticoid activation in the sarcoplasmic reticulum (SR) is integral to mediating the detrimental effects of glucocorticoid excess in muscle. 11β‐Hydroxysteroid dehydrogenase type 1 activity requires glucose‐6‐phosphate transporter (G6PT)‐mediated G6P transport into the SR for its metabolism by hexose‐6‐phosphate dehydrogenase (H6PDH) for NADPH generation. Here, we examine the G6PT/H6PDH/11β‐HSD1 triad in differentiating myotubes and explore the consequences of muscle‐specific knockout of 11β‐HSD1 and H6PDH. 11β‐Hydroxysteroid dehydrogenase type 1 expression and activity increase with myotube differentiation and in response to glucocorticoids. Hexose‐6‐phosphate dehydrogenase shows some elevation in expression with differentiation and in response to glucocorticoid, while G6PT appears largely unresponsive to these particular conditions. When examining 11β‐HSD1 muscle‐knockout mice, we were unable to detect significant decrements in activity, despite using a well‐validated muscle‐specific Cre transgene and confirming high‐level recombination of the floxed HSD11B1 allele. We propose that the level of recombination at the HSD11B1 locus may be insufficient to negate basal 11β‐HSD1 activity for a protein with a long half‐life. Hexose‐6‐phosphate dehydrogenase was undetectable in H6PDH muscle‐knockout mice, which display the myopathic phenotype seen in global KO mice, validating the importance of SR NADPH generation. We envisage these data and models finding utility when investigating the muscle‐specific functions of the 11β‐HSD1/G6PT/H6PDH triad.
Recuperating lung decoction attenuates inflammation and oxidation in cigarette smoke‐induced COPD in rats via activation of ERK and Nrf2 pathways
Authors: Li Chunlei , Yan Yue , Shi Qi , Kong Yanhua , Gao Longxia , Bao Haipeng , Li Youlin
Published: July 2017

Oxidative/antioxidative imbalance and chronic inflammation are the main contributors to the pathogenesis of chronic obstructive pulmonary disease (COPD). This study evaluated the effect of recuperating lung decoction (RLD) on inflammation and oxidative stress in rats with COPD induced by cigarette smoke and lipopolysaccharides (LPS). We used intravenous infusion of LPS combined with cigarette smoke exposure as a COPD rat model. We observed that RLD treatment increased the protein level of GSH and the ratio of GSH/GSSG but decreased 8‐OHdG and 4‐HNE in the serum. Furthermore, RLD significantly inhibited the expressions of IL‐1β, IL‐6, TNF‐α, and TGF‐β induced by cigarette smoke exposure, reduced the number of inflammatory cells in the bronchoalveolar lavage fluid, and alleviated the severity of cigarette smoke‐induced emphysema. Mechanistically, RLD treatment prevented disease through downregulation of phosphorylated‐ERK and Nrf2 expression, which regulates the production of proinflammatory cytokines. RLD treatment exerted a dramatic therapeutic effect on COPD. This study revealed a mechanism that RLD functions on the regulation of ERK signalling to inhibit inflammation.
Enabling Process Intensification by 3 D Printing of Catalytic Structures
Authors: Konarova Muxina , Aslam Waqas , Ge Lei , Ma Qing , Tang Fengqiu , Rudolph Victor , Beltramini Jorge Norberto
Published: July 2017

Small‐scale, intensified chemical reactors (i.e., process intensification) mediated by structured catalysts substantially diminishes the advantages of large‐scale gas‐to‐liquid (transport fuels) process plants and can be realized at low capital costs, minimum energy consumption, and zero/small CO2 footprints. Current structured‐catalysts approaches are complex and expensive; therefore, simple methods are crucial that are capable of depositing a desired geometry of catalysts into engineered channels. Herein, we developed printable composition by incorporating nickel and molybdenum ions into water‐soluble PVA and starch; the subsequent pyrolysis of organic compounds resulted into three‐dimensional carbon scaffold with micro/macro interconnected pores (dpore, 6.5 Å; dpore, 100 μm) containing up to 25 wt % catalyst loading. 2 D (TEM, SEM) and 3D (X‐ray computed tomography) microstructural analyses and catalytic tests (conversion of syngas to alcohols) were performed for 3 D printed catalysts and compared with conventional pelleted catalysts. At a high feed flow rate (6000 h−1), CO conversion is rapidly reduced to 16 mol % for pelleted catalysts, whereas 3 D printed catalysts converted 35 mol % of CO, with the same catalyst loading.
New Multiresponsive Chromic Soft Materials: Dynamic Interconversion of Short 2,7‐Dicyanomethylenecarbazole‐Based Biradicaloid and the Corresponding Cyclophane Tetramer
Authors: Wang Deliang , Capel Ferrón Cristina , Li Jie , Gámez‐Valenzuela Sergio , Ponce Ortiz Rocio , López Navarrete Juan T. , Hernández Jolín Víctor , Yang Xiaodi , Peña Álvarez Miriam , García Baonza Valentín , Hartl František , Ruiz Delgado M. Carmen , Li Hongxiang
Published: July 2017

This work reports on a quinodimethane‐type molecule, 2,7‐dicyanomethylene‐9‐(2‐ethylhexyl)carbazole (1), one of the shortest π‐conjugated biradicaloids reported to be stable in solution under ambient conditions. This carbazole‐based quinoidal precursor is able to form a macrocyclic σ‐bonded tetramer (2). The resolved single‐crystal X‐ray structure of tetramer 2 shows that four molecules of 1 are linked together through four long (CN)2C−C(CN)2 bonds (1.631 Å) resulting from coupling of the unpaired electrons in biradicaloid 1. Dynamic interconversion between monomer 1 and cyclophane tetramer 2 is achieved by reversible cleavage and recovery of the four (CN)2C−C(CN)2 bonds upon soft external stimuli (light absorption, temperature and pressure), which is accompanied by significant color changes. These novel photo‐, thermo‐, and mechanochromic properties expand the versatility of π‐conjugated biradicaloid compounds as novel functional materials that, in combination with spin chemistry and dynamic covalent chemistry, can be relevant in molecular machines, sensors, and switches.
Chiral Sulfur Functional Groups as Definers of the Chirality at the Metal in Ir and Rh Half‐Sandwich Complexes: A Combined CD/X‐ray Study
Authors: Avello Marta G. , Frutos María , de la Torre María C. , Viso Alma , Velado Marina , de la Pradilla Roberto Fernández , Sierra Miguel A. , Gornitzka Heinz , Hemmert Catherine
Published: July 2017

Mesoionic carbenes (MICs) derived from triazolium salts that contain chiral sulfoxide or sulfoximine functional groups were used to construct enantiopure chiral‐at‐metal IrIII and RhIII half‐sandwich complexes through the synthetic sequence of MIC complexation/C−H aromatic activation. The process was efficient and diastereoselective for the formation of enantiopure five‐membered metallacycles. The use of the enantiomers of the chiral sulfur groups allowed us to prepare complexes that had opposite configurations at the metal center. Complete retention of the configuration at the metal center was observed during the formation of cationic IrIII complexes and upon insertion of alkynes into the IrIII−C bond, as demonstrated by a combined circular dichroism/X‐ray study. These results point to a vicinal‐assisted SN1‐like mechanism.
Disulfide Bond Mimetics: Strategies and Challenges
Authors: Gori Alessandro , Gagni Paola , Rinaldi Silvia
Published: July 2017

The activity profile of many biologically relevant proteins and peptides often relies on a precise 3D structural organization. In this context, disulfide bonds are natural covalent constraints that play a key role in driving and stabilizing the folding pattern of these molecules. Despite its prominent significance as structural motif, the disulfide bond itself is inherently unstable under physiological conditions, posing a major limit to the use and development of disulfide‐rich peptides and proteins as molecular tools and drug lead compounds. To tackle this restriction, disulfide engineering with stable functional analogues has arisen a considerable interest. Here, the most popular approaches to disulfide replacement are reviewed and discussed with particular emphasis on advantages and limitations under both functional and synthetic perspectives.
Highly Diastereo‐ and Enantioselective Synthesis of Tetrahydro‐5H‐Indolo[2,3‐b]quinolines through Copper‐Catalyzed Propargylic Dearomatization of Indoles
Authors: Shao Wen , You Shu‐Li
Published: July 2017

The first copper‐catalyzed intermolecular asymmetric propargylic dearomatization/annulation cascade sequence of indoles via a copper‐allenylidene amphiphilic intermediate has been achieved. This protocol provides a direct asymmetric synthetic method for the preparation of tetrahydro‐5H‐indolo[2,3‐b]quinolines, the core structure of indole alkaloids communesins A–H and perophoramidine. This method features excellent yields, high diastereoselectivity (up to >19:1 d.r.) and enantioselectivity (up to 94 % ee), mild conditions and wide substrate scope.
Selective Conversion of P=O‐Bridged Rhodamines into P=O‐Rhodols: Solvatochromic Near‐Infrared Fluorophores
Authors: Grzybowski Marek , Taki Masayasu , Yamaguchi Shigehiro
Published: July 2017

The substitution of an oxygen atom in rhodols with a phosphine oxide (P=O) moiety affords P=O‐bridged rhodols as a new type of near‐infrared (NIR) fluorophore. This compound class can be readily accessed upon exposure of the corresponding rhodamines to aqueous basic conditions. The electron‐withdrawing effect of the P=O group facilitates the hydrolytic deamination, and, moreover, prolonged exposure to aqueous basic conditions generates P=O‐bridged fluoresceins, that is, a series of three P=O‐bridged xanthene dyes is available in one simple operation. The P=O‐bridged rhodols show significant bathochromic shifts of the longest‐wavelength absorption maximum (Δλ=125 nm; >3600 cm−1) upon changing the solvent from toluene to water, whereas the emission is shifted less drastically (Δλ=70 nm; 1600 cm−1). The hydrogen bonding between the P=O and C=O groups with protic solvents results in substantial stabilization of the LUMO level, which is responsible for the solvatochromism.
Optimization of throughput in semipreparative chiral liquid chromatography using stacked injection
Authors: Taheri Mohammadreza , Fotovati Mohsen , Hosseini Seyed‐Kiumars , Ghassempour Alireza
Published: July 2017

An interesting mode of chromatography for preparation of pure enantiomers from pure samples is the method of stacked injection as a pseudocontinuous procedure. Maximum throughput and minimal production costs can be achieved by the use of total chiral column length in this mode of chromatography.

To maximize sample loading, often touching bands of the two enantiomers is automatically achieved. Conventional equations show direct correlation between touching‐band loadability and the selectivity factor of two enantiomers. The important question for one who wants to obtain the highest throughput is “How to optimize different factors including selectivity, resolution, run time, and loading of the sample in order to save time without missing the touching‐band resolution?” To answer this question, tramadol and propranolol were separated on cellulose 3,5‐dimethyl phenyl carbamate, as two pure racemic mixtures with low and high solubilities in mobile phase, respectively. The mobile phase composition consisted of n‐hexane solvent with alcohol modifier and diethylamine as the additive. A response surface methodology based on central composite design was used to optimize separation factors against the main responses. According to the stacked injection properties, two processes were investigated for maximizing throughput: one with a poorly soluble and another with a highly soluble racemic mixture. For each case, different optimization possibilities were inspected. It was revealed that resolution is a crucial response for separations of this kind. Peak area and run time are two critical parameters in optimization of stacked injection for binary mixtures which have low solubility in the mobile phase.
Psychiatric conditions as predictors of rehospitalization among African American patients hospitalized with heart failure
Authors: Lu Marvin Louis Roy , De Venecia Toni Anne , Goyal Abhinav , Rodriguez Ziccardi Mary , Kanjanahattakij Napatt , Shah Mahek Kishor , Davila Carlos D. , Figueredo Vincent M.
Published: July 2017

Introduction

African Americans (AAs) have the highest risk of developing heart failure (HF) among all ethnicities in the United States and are associated with higher rates of readmissions and mortality. This study aims to determine the prevalence and relationship of common psychiatric conditions to outcomes of patients hospitalized with HF.

Hypothesis

Psychiatric conditions lead to worse outcomes in HF patients.

Methods

This single‐center retrospective study enrolled 611 AA patients admitted to an urban teaching community hospital for HF from 2010 to 2013. Patient demographics, clinical variables, and history of psychiatric disorders were obtained. Cox proportional hazards regression was used to assess impact of psychiatric disorders on readmission rates and mortality.

Results

The mean age was 66 ± 15 years; 53% were men. Median follow‐up time from index admission for HF was 3.2 years. Ninety‐seven patients had a psychiatric condition: 46 had depression, 11 had bipolar mood disorder (BMD), and 40 had schizophrenia. After adjustment of known risk factors and clinical metrics, our study showed that AA HF patients with a psychiatric illness were 3.84× more likely to be admitted within 30 days for HF, compared with those without (P < 0.001). Individually, adjusted Cox multivariable logistic regression analysis also showed that, for 30‐day readmission, schizophrenia had a hazard ratio (HR) of 4.92 (P < 0.001); BMD, an HR of 3.44 (P = 0.02); and depression, an HR 3.15 (P = 0.001). No associations were found with mortality.

Conclusions

Psychiatric conditions of schizophrenia, BMD, and depression were significantly associated with a higher 30‐day and overall readmission rate for HF among AA patients.
The Mechanisms of High N2O Emissions from Greenhouse Vegetable Field Soils
Authors: Wang Jing , Zhang Jinbo , Müller Christoph , Cai Zucong
Published: July 2017

Vegetable cultivation in China is characterized by high N application rate, multiple cropping, and frequent irrigation, which may have caused high N2O emission. However, the N2O emission characteristics and the underlying mechanisms responsible for N2O emission under high N application rate in the greenhouse vegetable field soils remains largely unknown. Thus, we conducted a field experiment to monitor N2O emissions using static chamber and gas chromatography techniques. Meanwhile, an incubation experiment was carried out to quantify soil gross N transformation rates and N2O emissions pathways via 15N tracing and N2O source partitioning methods, respectively. The experiment involved three treatments: Conventional farmland cultivated with soybean (CF), greenhouse vegetable field receiving only chemical N fertilizer (CGV), and greenhouse vegetable field receiving both organic manure and chemical N fertilizer (OGV). Our results showed that soil N2O emissions in the greenhouse vegetable fields, especially in OGV treatment, were significantly higher than those in CF treatment. Heterotrophic nitrification was the dominant pathway for N2O emissions accounting for up to 84.0% of the total N2O flux. The gross heterotrophic nitrification rate was 19.52 mg N kg−1 per day (accounting for 81% of the total nitrification rate) in OGV treatment, which was significantly higher than in CGV and CF treatment. As a consequence, the application of nitrification inhibitors might not be an effective mitigation options of N2O emissions from the greenhouse vegetable fields in China.
Characterization of Small‐Molecule Scaffolds That Bind to the Shigella Type III Secretion System Protein IpaD
Authors: Dey Supratim , Anbanandam Asokan , Mumford Ben E. , De Guzman Roberto N.
Published: July 2017

Many pathogens such as Shigella and other bacteria assemble the type III secretion system (T3SS) nanoinjector to inject virulence proteins into their target cells to cause infectious diseases in humans. The rise of drug resistance among pathogens that rely on the T3SS for infectivity, plus the dearth of new antibiotics require alternative strategies in developing new antibiotics. The Shigella T3SS tip protein IpaD is an attractive target for developing anti‐infectives because of its essential role in virulence and its exposure on the bacterial surface. Currently, the only known small molecules that bind to IpaD are bile salt sterols. In this study we identified four new small‐molecule scaffolds that bind to IpaD, based on the methylquinoline, pyrrolidine‐aniline, hydroxyindole, and morpholinoaniline scaffolds. NMR mapping revealed potential hotspots in IpaD for binding small molecules. These scaffolds can be used as building blocks in developing small‐molecule inhibitors of IpaD that could lead to new anti‐infectives.
C‐MYC–positive relapsed and refractory, diffuse large B‐cell lymphoma: Impact of additional “hits” and outcomes with subsequent therapy
Authors: Epperla Narendranath , Maddocks Kami J. , Salhab Mohammed , Chavez Julio C. , Reddy Nishitha , Karmali Reem , Umyarova Elvira , Bachanova Veronika , Costa Cristiana , Glenn Martha , Calzada Oscar , Xavier Ana C. , Zhou Zheng , Hossain Nasheed M. , Hernandez‐Ilizaliturri Francisco J. , Al‐Mansour Zeina , Barta Stefan K. , Chhabra Saurabh , Lansigan Frederick , Mehta Amitkumar , Jaglal Michael V. , Evans Andrew , Flowers Christopher R. , Cohen Jonathon B. , Fenske Timothy S. , Hamadani Mehdi , Costa Luciano J.
Published: July 2017

BACKGROUND

The impact of MYC proto‐oncogene, basic helix‐loop‐helix (MYC) translocations (with or without additional rearrangements involving the B‐cell lymphoma 2 [BCL2] or BCL6 genes) on the response to salvage therapy and survival in patients with diffuse large B‐cell lymphoma (DLBCL) who experience primary treatment failure is not well defined.

METHODS

This was a multicenter, retrospective study of the impact of MYC, BCL2, and BCL6 rearrangements in patients with DLBCL who failed to achieve complete remission or relapsed within 6 months after they completed upfront chemoimmunotherapy.

RESULTS

The authors examined response to salvage therapy, receipt of hematopoietic cell transplantation (HCT), and survival outcomes in MYC‐negative (n = 120), MYC‐positive single hit (SH) (n = 20), and MYC‐positive double hit/triple hit (DH/TH) (n = 35) cohorts. The overall response rate in these cohorts to first salvage therapy (51%, 50%, and 54%, respectively) and receipt of HCT (52%, 40%, and 43%, respectively) were comparable between the 3 cohorts. The 2‐year overall survival rate was 29.9% in the MYC‐negative cohort, 0% in the MYC‐positive SH cohort, and 9.9% in the MYC‐positive DH/TH cohort (P < .001), and no difference was observed between the SH and DH/TH cohorts (P = .8). The higher risk of death for patients with MYC‐positive SH DLBCL (hazard ratio, 1.70; 95% confidence interval, 0.98‐2.96; P = .06) and those with MYC‐positive DH/TH DLBCL (hazard ratio, 2.22; 95% confidence interval, 1.41‐3.50; P = .001) persisted after adjusting for covariates. For patients who underwent autologous HCT, the 2‐year overall survival rate was 55.4% in the MYC‐negative cohort, 0% in the MYC‐positive SH cohort, and 19.4% in the MYC‐positive DH/TH cohort (P < .001). All 4 MYC‐positive patients who underwent allogeneic HCT relapsed in <4 months.

CONCLUSIONS

Patients with MYC‐positive DLBCL who experience primary treatment failure have response rates to similar to those achieved by salvage therapy compared with their MYC‐negative counterparts, but their survival is dismal irrespective of additional “hits” and HCT, representing an unmet medical need. Cancer 2017;123:4411‐8. © 2017 American Cancer Society.
The lack of a relationship between physician payments from drug manufacturers and Medicare claims for abiraterone and enzalutamide
Authors: Bandari Jathin , Ayyash Omar M. , Turner Robert M. , Jacobs Bruce L. , Davies Benjamin J.
Published: July 2017

BACKGROUND

Interactions between industry and prescribers have raised concerns regarding conflicts of interest. To the best of the authors' knowledge, quantitative data measuring these interactions have been limited until recently. In the current study, the authors sought to determine whether an association exists between industry payments and prescriber behavior with regard to abiraterone and enzalutamide.

METHODS

Two Centers for Medicare and Medicaid Services databases were combined to analyze oncologists and urologists who received industry payments and/or prescribed abiraterone and enzalutamide. Correlation analysis was constructed on prescription count and industry payments. Multivariable median regression examined predictors of change in prescription count per dollar of industry payment. Stratifying prescribers by quantile evaluated threshold effects on prescribers.

RESULTS

The number of prescriptions was similar between prescribers who did and those who did not receive industry payment for both drugs. The median industry payment amount to prescribers differed between prescribers and nonprescribers for abiraterone ($72 vs $56) and enzalutamide ($59 vs $31). Although no statistical association was found to exist between industry payment amount and prescription count for abiraterone prescribers, an association was found to exist for enzalutamide prescribers (rho = 0.31). A small change was found with regard to prescription count per dollar of industry payment for abiraterone (0.0007 prescriptions) and enzalutamide (0.0006 prescriptions). The amount of industry payment needed to predict one additional prescription was found to be lower in the fourth and fifth quantiles compared with the first through third quantiles.

CONCLUSIONS

No difference in prescription count was found to exist between prescribers who received industry payments and those who did not. A positive correlation was noted between industry payments and prescription count for enzalutamide. Ease of adoption may affect differences between the 2 drugs. Cancer 2017;123:4356‐62. © 2017 American Cancer Society.
Two Phase 1, Open‐Label, Mass Balance Studies to Determine the Pharmacokinetics of 14C‐Labeled Isavuconazonium Sulfate in Healthy Male Volunteers
Authors: Townsend Robert , Kato Kota , Hale Christine , Kowalski Donna , Lademacher Christopher , Yamazaki Takao , Akhtar Shahzad , Desai Amit
Published: July 2017

Isavuconazonium sulfate is the water‐soluble prodrug of the active triazole isavuconazole. Two phase 1 studies were conducted to identify the metabolic profile and mass balance of isavuconazole and BAL8728 (inactive cleavage product). Seven subjects in study 1 (isavuconazole mass balance) received a single oral dose of [cyano‐14C]isavuconazonium sulfate corresponding to 200 mg isavuconazole. Six subjects in study 2 (BAL8728 mass balance) received a single intravenous dose of [pyridinylmethyl‐14C]isavuconazonium sulfate corresponding to 75 mg BAL8728. Pharmacokinetic parameters of radioactivity in whole blood and plasma and of isavuconazole and BAL8728 in plasma were assessed. Radioactivity ratio of blood/plasma, percentage of dose, and cumulative percentage of radioactive dose recovered in urine and feces for isavuconazole and BAL8728 were assessed. Metabolic profiling was carried out by high‐performance liquid chromatography and mass spectrometry. Mean plasma isavuconazole pharmacokinetic parameters included apparent clearance (2.3 ± 0.7 L/h), apparent volume of distribution (301.8 ± 105.7 L), and terminal elimination half‐life (99.9 ± 44.6 hours). In study 1, isavuconazole‐derived radioactivity was recovered approximately equally in urine and feces (46.1% and 45.5%, respectively). In study 2, BAL8728‐derived radioactivity was predominantly recovered in urine (96.0%). Isavuconazole (study 1) and M4 (cleavage metabolite of BAL8728; study 2) were the predominant circulating components of radioactivity in plasma.
An evaluation of the effectiveness of psychological therapy in reducing general psychological distress for adults with autism spectrum conditions and comorbid mental health problems
Authors: Blainey Sarah H. , Rumball Freya , Mercer Louise , Evans Lauren Jayne , Beck Alison
Published: July 2017

Objective

To investigate the effectiveness of psychological therapy in reducing psychological distress for adults with autism spectrum conditions (ASC) and co‐morbid mental health conditions in routine clinical practice. To explore the effect of individual characteristics and service factors on change in general distress.

Method

In a specialist psychological therapies service for adults with ASC, the Clinical Outcomes in Routine Evaluation‐Outcome Measure (CORE‐OM) self‐report questionnaire of psychological distress is completed by clients at start and end of therapy. Change over time and reliable and clinical change was assessed for 81 of a total of 122 clients (66.4%). Factors which may influence change over time were explored using available clinical information.

Results

Overall, there was a significant reduction in CORE‐OM score during therapy with a small effect size. Most clients showed an improvement in psychological distress over therapy (75.4% improved, with 36.9% of these showing reliable changes). Significant and comparable reductions from pre‐therapy to post‐therapy were seen across the sample, showing that individual differences did not mediate therapy effectiveness. CORE‐OM scores mediate the association between age of ASD diagnosis and hours of therapeutic input required, with greater age at diagnosis and higher distress associated with longer therapy duration.

Conclusions

Our preliminary findings suggest that psychological therapy may be effective in reducing general distress for clients with ASC and co‐morbid mental health conditions and should be routinely offered. Individuals who are diagnosed with ASD in adulthood are likely to require a longer course of therapy when their general distress scores are high.
Control and synchronization of the generalized Lorenz system with mismatched uncertainties using backstepping technique and time‐delay estimation
Authors: Kim Dongwon , Jin Maolin , Chang Pyung Hun
Published: July 2017

We propose a robust control technique for regulation and synchronization of the generalized Lorenz system (GLS) that covers the Lorenz system, Chen system and Lü system. The proposed control provides synergy through the combination of the backstepping control and time‐delay estimation (TDE) technique. TDE is used to estimate and cancel nonlinearities and uncertainties while the backstepping method is adopted to provide robustness against matched and mismatched uncertainties. As a result, we observe in numerical simulation that the proposed technique shows better performances in regulating and synchronizing the GLS with mismatched uncertainties, in comparison with existing schemes. The efficacy of the proposed technique is also validated with a circuit‐implemented chaotic system. Copyright © 2017 John Wiley & Sons, Ltd.
Winter bait stations as a multispecies survey tool
Authors: Robinson Lacy , Cushman Samuel A. , Lucid Michael K.
Published: July 2017

Winter bait stations are becoming a commonly used technique for multispecies inventory and monitoring but a technical evaluation of their effectiveness is lacking. Bait stations have three components: carcass attractant, remote camera, and hair snare. Our 22,975 km2 mountainous study area was stratified with a 5 × 5 km sampling grid centered on northern Idaho and including portions of Washington, Montana, and British Columbia. From 2010–14, we conducted 563 sampling sessions at 497 bait stations in 453 5 × 5 km cells. We evaluated the effectiveness of cameras and hair snare DNA collection at stations to detect species and individual animals, factors affecting DNA viability, the effectiveness of re‐visiting stations, and the influence of elevation, seasonality, and latency on species detections. Cameras were more effective at detecting multiple species than DNA hair snaring. Length of deployment time and elevation increased genetic species ID success but individual ID success rates were increased only by collecting hairs earlier in the season. Re‐visiting stations did not change camera or genetic species detection results but did increase the number of individual genotypes identified. Marten and fisher were detected quickly while bobcat and coyote showed longer latency to detection. Seasonality significantly affected coyote and bobcat detections but not marten, fisher, or weasel. Multispecies bait station study design should incorporate mixed elevation sites with stratified seasonality. Priority should be given to including cameras as components of bait stations over hair snares, unless there is a specific genetic goal to the study. A hair snare component should be added, however, if individual ID or genetic data are necessary. Winter stations should be deployed a minimum of 45–60 days to allow for detection of low density species and species with long latency to detection times. Hair samples should be collected prior to DNA‐degrading late season rain events. Re‐visiting stations does not change which species are detected at stations; therefore, studies with objectives to delineate species presence or distribution will be more effective if they focus on deploying more stations across a broader landscape in lieu of surveying the same site multiple times.
Different facets of tree sapling diversity influence browsing intensity by deer dependent on spatial scale
Authors: Ohse Bettina , Seele Carolin , Holzwarth Frédéric , Wirth Christian
Published: July 2017

Browsing of tree saplings by deer hampers forest regeneration in mixed forests across Europe and North America. It is well known that tree species are differentially affected by deer browsing, but little is known about how different facets of diversity, such as species richness, identity, and composition, affect browsing intensity at different spatial scales. Using forest inventory data from the Hainich National Park, a mixed deciduous forest in central Germany, we applied a hierarchical approach to model the browsing probability of patches (regional scale) as well as the species‐specific proportion of saplings browsed within patches (patch scale). We found that, at the regional scale, the probability that a patch was browsed increased with certain species composition, namely with low abundance of European beech (Fagus sylvatica L.) and high abundance of European ash (Fraxinus excelsior L.), whereas at the patch scale, the proportion of saplings browsed per species was mainly determined by the species’ identity, providing a “preference ranking” of the 11 tree species under study. Interestingly, at the regional scale, species‐rich patches were more likely to be browsed; however, at the patch scale, species‐rich patches showed a lower proportion of saplings per species browsed. Presumably, diverse patches attract deer, but satisfy nutritional needs faster, such that fewer saplings need to be browsed. Some forest stand parameters, such as more open canopies, increased the browsing intensity at either scale. By showing the effects that various facets of diversity, as well as environmental parameters, exerted on browsing intensity at the regional as well as patch scale, our study advances the understanding of mammalian herbivore–plant interactions across scales. Our results also indicate which regeneration patches and species are (least) prone to browsing and show the importance of different facets of diversity for the prediction and management of browsing intensity and regeneration dynamics.
Herbivores alter plant–wind interactions by acting as a point mass on leaves and by removing leaf tissue
Authors: Kothari Adit R. , Burnett Nicholas P.
Published: July 2017

In nature, plants regularly interact with herbivores and with wind. Herbivores can wound and alter the structure of plants, whereas wind can exert aerodynamic forces that cause the plants to flutter or sway. While herbivory has many negative consequences for plants, fluttering in wind can be beneficial for plants by facilitating gas exchange and loss of excess heat. Little is known about how herbivores affect plant motion in wind. We tested how the mass of an herbivore resting on a broad leaf of the tulip tree Liriodendron tulipifera, and the damage caused by herbivores, affected the motion of the leaf in wind. For this, we placed mimics of herbivores on the leaves, varying each herbivore's mass or position, and used high‐speed video to measure how the herbivore mimics affected leaf movement and reconfiguration at two wind speeds inside a laboratory wind tunnel. In a similar setup, we tested how naturally occurring herbivore damage on the leaves affected leaf movement and reconfiguration. We found that the mass of an herbivore resting on a leaf can change that leaf's orientation relative to the wind and interfere with the ability of the leaf to reconfigure into a smaller, more streamlined shape. A large herbivore load slowed the leaf's fluttering frequency, while naturally occurring damage from herbivores increased the leaf's fluttering frequency. We conclude that herbivores can alter the physical interactions between wind and plants by two methods: (1) acting as a point mass on the plant while it is feeding and (2) removing tissue from the plant. Altering a plant's interaction with wind can have physical and physiological consequences for the plant. Thus, future studies of plants in nature should consider the effect of herbivory on plant–wind interactions, and vice versa.
Open access increases citations of papers in ecology
Authors: Tang Min , Bever James D. , Yu Fei‐Hai
Published: July 2017

Open access (OA) can effectively increase the accessibility and visibility of scientific articles and thus potentially confer them with citation advantages. Such an impact may be more pronounced in developing countries where the cost for journal subscription is comparably expensive and usually unaffordable. By comparing one OA article with one non‐OA article published in the same issue, we tested the impact of OA on citation advantages of articles published in 46 ecology journals indexed in the Journal Citation Reports (JCR). We compared OA to non‐OA articles published in the same issue of these journals, thereby controlling for potentially confounding effects of publication requirement and period. OA articles received significantly more citations than non‐OA articles, and this citation advantage of approximately one citation per year was sustained across publication years from 2009 to 2013. The OA citation advantage did not depend upon income of the country of origin of the citing scientists, and the OA citation advantage was found for citing scientists from North America, Europe, Asia, Africa, and Oceania, but not for Latin America. A total of 10 countries contributed more than 1000 citations each, and the OA citation advantage was found in all the 10 countries except Canada. Therefore, in ecology journals OA confers articles with citation advantages and such an impact accumulates with years and independent of the economic status of the countries. This information may guide decisions of scientific societies, journals, and individual authors as they weigh the relative costs and benefits of open electronic accessibility of scientific research.
Synthesis and Characterization of a Ruthenium(II) Complex for the Development of Supramolecular Photocatalysts Containing Multidentate Coordination Spheres
Authors: Huber Fabian L. , Nauroozi Djawed , Mengele Alexander K. , Rau Sven
Published: July 2017

The synthesis of the new bis‐heteroleptic RuII complex [(tbbpy)2Ru(dptpphz)](PF6)2 (7), that exhibits a tetradentate coordination sphere for a second metal centre, and its characterization are presented. The complex shows similar photostability and redox properties regarding the first ligand‐centred reductions compared to its tpphz analogue. Concentration‐dependent NMR investigations were performed and a dimerization constant (KD = 83 ± 5) could be calculated, which was significantly lower than that of other tpphz systems. Photophysical investigations reveal a stabilizing effect of the two electron‐withdrawing 2‐pyridyl substituents on π–π* transition of the phenazine sphere. The typical H2O‐induced light‐switch effects have also been observed. To further highlight the potential of the tetradentate coordination site, the ZnII adduct of 7 was prepared and preliminary studied.
Transition Metal Complexes of a Monocarba‐closo‐dodecaborate Ligand via B–H Activation
Authors: Shen Yunjun , Liu Jiyong , Sattasatchuchana Tosaporn , Baldridge Kim K. , Duttwyler Simon
Published: July 2017

Rhodium‐ and palladium‐induced B2–H activation of a derivative of the monocarba‐closo‐dodecaborate [CB11H12]– afforded two new transition metal complexes of this cluster. The products were formed in high yields under mild conditions. The complexes were fully characterized by spectroscopic methods, X‐ray crystallography, and computational analysis. The product from the reaction with rhodium was identified as a monomeric RhIII complex, while B–H activation with palladium afforded a dimeric PdII structure. Acetate‐mediated deprotonation–metalation is proposed as the mechanistic pathway.
The Thermodynamic Effects of Ligand Structure on the Molecular Recognition of Mononuclear Ruthenium Polypyridyl Complexes with B‐DNA
Authors: Mikek Clinton G. , DuPont Jesse I. , Machha Venkata R. , White Jake C. , Martin Logan R. , Alatrash Nagham , MacDonnell Frederick M. , Lewis Edwin A.
Published: July 2017

Invited for the cover of this issue is the group of Edwin Lewis, Mississippi State University, in collaboration with Frederick MacDonnell, University of Texas at Arlington, USA. The cover image shows Ru(phen)2(tatpp)]2+ binding to DNA.
Lipids from the marine world: Perspectives of an organic chemist
Authors: Rögnvaldsdottir Edda K. , Magnusson Carlos D. , Haraldsson Gudmundur G.
Published: July 2017

This report describes synthesis of novel structured triacylglycerols (TAGs) and diacylglyceryl ethers (DAGEs) of the 1‐O‐alkyl‐sn‐glycerol type constituting EPA and DHA as the sole fatty acids. One of two TAGs was comprised of a pure EPA located at the 1,3‐positions with pure DHA at the 2‐position and the other had it reversed with a pure DHA at the 1,3‐positions and pure EPA at the 2‐positions. The similarly structured DAGEs were derived from chimyl‐, batyl‐, and selachyl alcohols constituting pure EPA at their sn‐3 position with pure DHA at the sn‐2 position as well as the opposite composition with pure DHA at the sn‐3 position and EPA at the sn‐2 position, the total of six such DAGE products. The syntheses of these compounds were brought about by a two‐step chemoenzymatic process involving a highly regioselective immobilized Candida antarctica lipase to incorporate EPA or DHA activated as acetoxime esters exclusively into the 1,3‐positions of glycerol and the sn‐3 position of the 1‐O‐alkyl‐sn‐glycerols. The second PUFA acyl groups were subsequently introduced to the remaining 2‐positions by EDCI coupling agent to accomplish the title compounds highly efficiently in very high to excellent yields (86–92%).

Practical applications: The work described is based on a previously reported methodology to introduce n‐3 PUFAs activated as oxime esters exclusively into the terminal 1,3‐positions of glycerol and 1‐O‐alkyl‐sn‐glycerols to prepare reversed structured TAGs and DAGEs by use of immobilized Candida antarctica lipase. The methodology is ideal for introducing isotopically labeled fatty acids into predetermined positions of TAGs and DAGEs.

Novel structured triacylglycerols (TAGs) and diacylglyceryl ethers (DAGEs), constituting EPA and DHA as the sole fatty acids, were obtained by a two‐step chemoenzymatic synthesis comprised of an exclusive incorporation of EPA or DHA, activated as acetoxime esters, into the terminal positions of glycerol and 1‐O‐alkyl‐sn‐glycerols by use of immobilized Candida antarctica lipase, and a subsequent introduction of a second PUFA acyl group to the remaining 2‐positions by EDCI coupling agent.
Facile Coupling of Aldehydes with Alcohols: An Evolved Tishchenko Process for the Preparation of Unsymmetrical Esters
Authors: Liu Heng , Eisen Moris S.
Published: July 2017

A facile coupling process between aldehydes and alcohols to afford unsymmetrical esters is presented herein. This transformation is complementary to the Tishchenko reaction and provides access to unsymmetrical esters under very mild conditions. Various aldehydes and alcohols are suitable in this reaction, and the addition of a sacrificial trifluoromethyl ketone allows the process to take place in a highly selective manner. A plausible mechanism based on details obtained by monitoring the reaction progress and deuterium‐labeling studies has been proposed.
Electrochemical Characterization of Coinage Techniques the 17th Century: The maravedís Case
Authors: Doménech‐Carbó Antonio , Doménech‐Carbó María Teresa , Álvarez‐Romero Carla , Montoya Noemí , Pasíes‐Oviedo Trinidad , Buendía Milagros
Published: July 2017

The voltammetry of immobilized particles (VIMP) methodology was applied to the discrimination of Spanish maravedis produced in 10 different mints between 1661 and 1664 using characteristic signatures for the reduction of cuprite and tenorite in the patina of the coins and catalytic effects on the hydrogen evolution reaction (HER). The variation of the apparent tenorite/cuprite ratio with depth was fitted to potential laws differing from one mint to another for A Coruña, Burgos, Córdoba, Cuenca, Granada, Madrid, Trujillo, Segovia, Sevilla and Valladolid coins. Electrochemical data permitted to detect the changes in the composition (with lowering of the silver content) and manufacturing technique (from hammer to mill) occurring in this historical period.
Measurement of heat transfer coefficients in stirred single‐use bioreactors by the decay of hydrogen peroxide
Authors: Müller Matthias , Meusel Wolfram , Husemann Ute , Greller Gerhard , Kraume Matthias
Published: July 2017

Single‐use bioreactors are barely described by means of their heat transfer characteristics, although some of their properties might affect this process. Steady‐state methods that use external heat sources enable precise investigations. One option, commonly present in stirred, stainless steel tanks, is to use adjustable electrical heaters. An alternative are exothermic chemical reactions that offer a higher flexibility and scalability. Here, the catalytic decay of hydrogen peroxide was considered a possible reaction, because of the high reaction enthalpy of –98.2 kJ/mole and its uncritical reaction products. To establish the reaction, a proper catalyst needed to be determined upfront. Three candidates were screened: catalase, iron(III)‐nitrate and manganese(IV)‐oxide. Whilst catalase showed strong inactivation kinetic and general instability and iron(III)‐nitrate solution has a pH of 2, it was decided to use manganese(IV)‐oxide for the bioreactor studies. First, a comparison between electrical and chemical power input in a benchtop glass bioreactor of 3.5 L showed good agreement. Afterwards the method was transferred to a 50 L stirred single‐use bioreactor. The deviation in the final results was acceptable. The heat transfer coefficient for the electrical method was 242 W/m2/K, while the value achieved with the chemical differed by less than 5%. Finally, experiments were carried out in a 200 L single‐use bioreactor proving the applicability of the chemical power input at technical relevant scales.