bluuebunny/crossref_metadata_2025 huggingface dataset:
Comparative Study of Diverse Copper Zeolites for the Conversion of Methane into Methanol
Authors: Park Min Bum , Ahn Sang Hyun , Mansouri Ali , Ranocchiari Marco , van Bokhoven Jeroen A.
Published: June 2017

The characterization and reactive properties of copper zeolites with twelve framework topologies (MOR, EON, MAZ, MEI, BPH, FAU, LTL, MFI, HEU, FER, SZR, and CHA) are compared in the stepwise partial oxidation of methane into methanol. Cu2+ ion‐exchanged zeolite omega, a MAZ‐type material, reveals the highest yield (86 μmol g(cat.)−1) among these materials after high‐temperature activation and liquid methanol extraction. The high yield is ascribed to the relatively high density of copper–oxo active species, which form in its three‐dimensional 8‐membered (MB) ring channels. In situ UV/Vis studies show that diverse copper species form in different zeolites after high‐temperature activation, suggesting that there are no universally active species. Nonetheless, there are some dominant factors required for achieving high methanol yields: 1) highly dispersed copper–oxo species; 2) large amount of exchanged copper in small‐pore zeolites; 3) moderately high temperature of activation; and 4) use of proton form zeolite precursors. Cu‐omega and Cu‐mordenite, with the proton form of mordenite as the precursor, yield methanol after activation in oxygen and reaction with methane at only 200 °C, that is, under isothermal conditions.
Different Shades of Li4Ti5O12 Composites: The Impact of the Binder on Interface Layer Formation
Authors: Nordh Tim , Jeschull Fabian , Younesi Reza , Koçak Tayfun , Tengstedt Carl , Edström Kristina , Brandell Daniel
Published: June 2017

Replacing the traditional PVdF(‐HFP) electrode binder with water‐soluble alternatives can potentially render electrode fabrication more environmentally benign. Herein, the surface layer formation of stored and cycled samples of two water‐based Li4Ti5O12 composites employing either poly(sodium acrylate) (PAA−Na) or sodium carboxymethyl cellulose (CMC−Na) as binders are studied with X‐ray photoelectron spectroscopy. In all three formulations, the surface layer composition formed upon storage differed notably from the solid‐electrolyte interphase (SEI) layer formed on cycled samples. The surface layer under open‐circuit conditions seems to originate mostly from the electrolyte salt (LiPF6) degradation. The comparison with cycled samples after 10 and 100 cycles shows a continuous build‐up of an SEI layer on PAA−Na and PVdF‐HFP electrodes. In contrast, on CMC−Na containing electrodes the SEI composition remains nearly unchanged. The results correlate well with the electrochemical behavior.
Molecules Designed to Contain Two Weakly Coupled Spins with a Photoswitchable Spacer
Authors: Uber Jorge Salinas , Estrader Marta , Garcia Jordi , Lloyd‐Williams Paul , Sadurní Anna , Dengler Dominik , van Slageren Joris , Chilton Nicholas F. , Roubeau Olivier , Teat Simon J. , Ribas‐Ariño Jordi , Aromí Guillem
Published: June 2017

Controlling the charges and spins of molecules lies at the heart of spintronics. A photoswitchable molecule consisting of two independent spins separated by a photoswitchable moiety was designed in the form of new ligand H4L, which features a dithienylethene photochromic unit and two lateral coordinating moieties, and yields molecules with [MM⋅⋅⋅MM] topology. Compounds [M4L2(py)6] (M=Cu, 1; Co, 2; Ni, 3; Zn, 4) were prepared and studied by single‐crystal X‐ray diffraction (SCXRD). Different metal centers can be selectively distributed among the two chemically distinct sites of the ligand, and this enables the preparation of many double‐spin systems. Heterometallic [MM′⋅⋅⋅M′M] analogues with formulas [Cu2Ni2L2(py)6] (5), [Co2Ni2L2(py)6] (6), [Co2Cu2L2(py)6] (7), [Cu2Zn2L2(py)6] (8), and [Ni2Zn2L2(py)6] (9) were prepared and analyzed by SCXRD. Their composition was established unambiguously. All complexes exhibit two weakly interacting [MM′] moieties, some of which embody two‐level quantum systems. Compounds 5 and 8 each exhibit a pair of weakly coupled S=
spins that show quantum coherence in pulsed Q‐band EPR spectroscopy, as required for quantum computing, with good phase memory times (TM=3.59 and 6.03 μs at 7 K). Reversible photoswitching of all the molecules was confirmed in solution. DFT calculations on 5 indicate that the interaction between the two spins of the molecule can be switched on and off on photocyclization.
Hydrogenation of aromatics compounds: Calculation of thermodynamic properties using molecular index connectivity
Authors: Santos Bruno M. , Zotin José L. , Ndiaye Papa M. , da Silva Mônica A. P.
Published: June 2017

In this work, calculation of relevant thermodynamics properties, for hydrogenation reaction of aromatics compounds, was performed using the approach of molecular topology. Among the several molecular topological indexes, the molecular connectivity indexes have been used widely for calculation methods like quantitative structure properties relationships (QSPR) and quantitative structure and activity relationships (QSAR). Standard enthalpy of formation (ΔH°f), standard Gibbs free energy of formation (ΔG°f), and heat capacity at constant pressure (Cp°) at 298.15 K for naphthalene, 1‐methylnaphthalene, 2‐methylnaphthalene, tetralin, and t‐decalin and equilibrium reaction constants were calculated and compared with experimental data reported in literature. Additionally, the results obtained for naphthalene, tetralin, and t‐decalin were compared to those obtained from Benson's method. Results show that the thermodynamics properties calculated from molecular connectivity index presented an error less than 2 % and are closer to experimental data than those from Benson's method, showing that molecular connectivity index is a promising tool for estimation of thermodynamic properties to be used in design of chemical process.
Preparation and in vitro evaluation of hydrophobic‐modified montmorillonite stabilized pickering emulsion for overdose acetaminophen removal
Authors: Zhang Wenjun , Li Min , Fan Xianlin , Sun Xiao , He Gaohong
Published: June 2017

Pickering emulsion stabilized with hydrophobic‐modified montmorillonite (HMMT) was proposed for treating acute overdose acetaminophen intoxication, with a rapid removal rate, better stability, and good biocompatibility. The tiny HMMT was able to adsorb at the oil‐water interface of the Pickering emulsion to reduce the interfacial energy along with the formation of solid particle layer, in order to enhance the stability of the emulsion and improve the removal performance. With a fast removal rate, the detoxifying Pickering emulsion removed 0.5 g/L acetaminophen in the simulated gastric fluid to 0.13 g/L in 6 min, which is less than the intoxication content of 0.15 g/L, with a leakage ratio of lower than 4 % in simulated intestinal fluid over 4 h. Such a detoxifying emulsion was prepared at 55 °C with 2 % organoclay (HMMT) as the emulsifier, 6 % tributyl phosphate (TBP) as the extractant, and 0.1 mol/L NaOH as the inner phase in the volume ratio of 5:7. All the results denoted that the Pickering emulsion could be a promising candidate for the acute oral intoxication treatment.
Primary care visit use after positive fecal immunochemical test for colorectal cancer screening
Authors: Hillyer Grace Clarke , Jensen Christopher D. , Zhao Wei K. , Neugut Alfred I. , Lebwohl Benjamin , Tiro Jasmin A. , Kushi Lawrence H. , Corley Douglas A.
Published: June 2017

BACKGROUND

For some patients, positive cancer screening test results can be a stressful experience that can affect future screening compliance and increase the use of health care services unrelated to medically indicated follow‐up.

METHODS

Among 483,216 individuals aged 50 to 75 years who completed a fecal immunochemical test to screen for colorectal cancer at a large integrated health care setting between 2007 and 2011, the authors evaluated whether a positive test was associated with a net change in outpatient primary care visit use within the year after screening. Multivariable regression models were used to evaluate the relationship between test result group and net changes in primary care visits after fecal immunochemical testing.

RESULTS

In the year after the fecal immunochemical test, use increased by 0.60 clinic visits for patients with true‐positive results. The absolute change in visits was largest (3.00) among individuals with positive test results who were diagnosed with colorectal cancer, but significant small increases also were found for patients treated with polypectomy and who had no neoplasia (0.36) and those with a normal examination and no polypectomy performed (0.17). Groups of patients who demonstrated an increase in net visit use compared with the true‐negative group included patients with true‐positive results (odds ratio [OR], 1.60; 95% confidence interval [95% CI], 1.54‐1.66), and positive groups with a colorectal cancer diagnosis (OR, 7.19; 95% CI, 6.12‐8.44), polypectomy/no neoplasia (OR, 1.37; 95% CI, 1.27‐1.48), and normal examination/no polypectomy (OR, 1.24; 95% CI, 1.18‐1.30).

CONCLUSIONS

Given the large size of outreach programs, these small changes can cumulatively generate thousands of excess visits and have a substantial impact on total health care use. Therefore, these changes should be included in colorectal cancer screening cost models and their causes investigated further. Cancer 2017;123:3744–3753. © 2017 American Cancer Society
Hypomethylating agent therapy use and survival in older patients with chronic myelomonocytic leukemia in the United States: A large population‐based study
Authors: Zeidan Amer M. , Hu Xin , Long Jessica B. , Wang Rong , Ma Xiaomei , Podoltsev Nikolai A. , Huntington Scott F. , Gore Steven D. , Davidoff Amy J.
Published: June 2017

BACKGROUND

Despite the approval of azacitidine in 2004 and the approval of decitabine in 2006 in the United States for chronic myelomonocytic leukemia (CMML), the overall survival (OS) benefit with hypomethylating agent (HMA) therapy is unclear.

METHODS

Older adults (age ≥ 66 years) who had been diagnosed with CMML from 2001 to 2011 were selected from the Surveillance, Epidemiology, and End Results–Medicare database, and propensity score matching was used to match patients who had been diagnosed after HMA approval (2007‐2011) and had received HMA treatment with patients diagnosed before HMA approval (2001‐2003). Cox proportional hazards models with the matched sample were used to assess the change in OS. A second matched cohort of patients who did not receive HMA after approval and patients diagnosed before HMA approval was used to evaluate survival change attributable to other potential differences between the 2 time periods, such as improved supportive care.

RESULTS

Among 1378 older adults diagnosed with CMML, the median OS was 13 months, and 18.8% received HMAs. In the primary matched analysis, with 225 HMA users diagnosed in 2007‐2011 and 395 patients diagnosed in 2001‐2003, the median OS times were 17 and 11 months, respectively (hazard ratio, 0.72; 95% confidence interval [CI], 0.58‐0.91; P = .005). In a secondary analysis, the risk of death did not differ between 395 propensity score–matched HMA nonusers diagnosed in 2007‐2011 and 484 patients diagnosed in 2001‐2003 (hazard ratio, 1.09; 95% CI, 0.91‐1.32; P = .34).

CONCLUSIONS

Despite limited evidence, HMAs are commonly used to treat older CMML patients. The use of HMAs was associated with a 28% reduction in the risk of death in adjusted analyses. Improvements in supportive care do not appear to account for temporal improvements in OS. Cancer 2017;123:3754–3762. © 2017 American Cancer Society
The efficacy of Internet‐based cognitive behavioral therapy for severely fatigued survivors of breast cancer compared with care as usual: A randomized controlled trial
Authors: Abrahams Harriët J.G. , Gielissen Marieke F.M. , Donders Rogier R.T. , Goedendorp Martine M. , van der Wouw Agnes J. , Verhagen Constans A.H.H.V.M. , Knoop Hans
Published: June 2017

BACKGROUND

Severe fatigue is a common and distressing symptom affecting approximately one in four survivors of breast cancer. The current study examined the efficacy of Internet‐based cognitive behavioral therapy (ICBT) for severe fatigue in survivors of breast cancer compared with care as usual (CAU).

METHODS

The authors conducted a parallel‐group randomized controlled trial. Severely fatigued, disease‐free survivors of breast cancer who had completed cancer treatment at least 3 months previously were eligible. Participants were randomly allocated to ICBT or CAU using computer‐generated stratified block randomization. The primary outcome of fatigue severity was assessed at baseline and after 6 months, as were the secondary outcomes of functional impairment, psychological distress, and quality of life. Statistical effects were tested with analyses of covariance (intention‐to‐treat analysis).

RESULTS

Participants were recruited between January 2014 and March 2016 and assigned to ICBT (66 patients) or CAU (66 patients). Compared with the participants who had received CAU, those who had received ICBT reported lower fatigue scores at 6 months (mean difference [Δ], 11.5; 95% confidence interval [95% CI], 7.7‐15.3) and a large effect size (Cohen d = 1.0), with the majority of patients (73%) demonstrating clinically significant improvement. ICBT also was found to lead to lower functional impairment (Δ, 297.8; 95% CI, 145.5‐450.1) and psychological distress scores (Δ, 5.7; 95% CI, 3.4‐7.9) and higher quality‐of‐life scores (Δ, 11.7; 95% CI, 5.8‐17.7) compared with CAU, with medium to large effect sizes (Cohen d = 0.6‐0.8).

CONCLUSIONS

ICBT appears to be effective in reducing severe fatigue and related symptoms and meets the current need for easy accessible and more efficient evidence‐based treatment options for severely fatigued survivors of breast cancer. Cancer 2017;123:3825‐34. © 2017 American Cancer Society.
Hodgkin lymphoma classification: Are we at a crossroads?
Authors: Carbone Antonino , Gloghini Annunziata
Published: June 2017

On the basis of the putative origin from germinal center B cells, the gene expression profile, the expression of the B‐cell phenotype, and the propensity to progress toward large B‐cell lymphoma, nodular lymphocyte‐predominant Hodgkin lymphoma should be classified as a special type of B‐cell lymphoma with a follicular center cell origin. To guarantee the appropriate management of patients, information on the nodular growth patterns, the amount of (the number and the size) diffuse areas, and the tumor cell richness should be reported because of the clinical associations of these features.
A consensus review on malignancy‐associated hemophagocytic lymphohistiocytosis in adults
Authors: Daver Naval , McClain Kenneth , Allen Carl E. , Parikh Sameer A. , Otrock Zaher , Rojas‐Hernandez Cristhiam , Blechacz Boris , Wang Sa , Minkov Milen , Jordan Michael B. , La Rosée Paul , Kantarjian Hagop M.
Published: June 2017

Hemophagocytic lymphohistiocytosis (HLH) is a syndrome of severe immune activation and dysregulation resulting in extreme and often life‐threatening inflammation. HLH has been well recognized in pediatric populations, and most current diagnostic and therapeutic guidelines are based on pediatric HLH. Recently there has been recognition of HLH in adults, especially secondary to immune deregulation by an underlying rheumatologic, infectious, or malignant condition. This review is focused on malignancy‐associated HLH (M‐HLH), in which possible mechanisms of pathogenesis include severe inflammation, persistent antigen stimulation by the tumor cells, and loss of immune homeostasis because of chemotherapy, hematopoietic stem cell transplantation, or infection. Previously considered rare, M‐HLH may occur in up to 1% of patients with hematologic malignancies. M‐HLH is often missed or diagnosed late in most published studies, and it has been associated with a poor median survival of less than 2 months. Identification of the clinical and laboratory features specific to M‐HLH in adults may allow early detection, consultation with HLH experts, and intervention. Improved management of adult M‐HLH with optimal combinations of T‐lympholytic and immunosuppressive agents and the incorporation of novel agents based on the pediatric experience hopefully will improve outcomes in adults with M‐HLH. Cancer 2017;123:3229‐40. © 2017 American Cancer Society.
Sustainable Production of o‐Xylene from Biomass‐Derived Pinacol and Acrolein
Authors: Hu Yancheng , Li Ning , Li Guangyi , Wang Aiqin , Cong Yu , Wang Xiaodong , Zhang Tao
Published: June 2017

o‐Xylene (OX) is a large‐volume commodity chemical that is conventionally produced from fossil fuels. In this study, an efficient and sustainable two‐step route is used to produce OX from biomass‐derived pinacol and acrolein. In the first step, the phosphotungstic acid (HPW)‐catalyzed pinacol dehydration in 1‐ethyl‐3‐methylimidazolium chloride ([emim]Cl) selectively affords 2,3‐dimethylbutadiene. The high selectivity of this reaction can be ascribed to the H‐bonding interaction between Cl− and the hydroxy group of pinacol. The stabilization of the carbocation intermediate by the surrounding anion Cl− may be another reason for the high selectivity. Notably, the good reusability of the HPW/[emim]Cl system can reduce the waste output and production cost. In the second step, OX is selectively produced by a Diels–Alder reaction of 2,3‐dimethylbutadiene and acrolein, followed by a Pd/C‐catalyzed decarbonylation/aromatization cascade in a one‐pot fashion. The sustainable two‐step process efficiently produces renewable OX in 79 % overall yield. Analogously, biomass‐derived crotonaldehyde and pinacol can also serve as the feedstocks for the production of 1,2,4‐trimethylbenzene.
Ecosystem size predicts eco‐morphological variability in a postglacial diversification
Authors: Recknagel Hans , Hooker Oliver E. , Adams Colin E. , Elmer Kathryn R.
Published: June 2017

Identifying the processes by which new phenotypes and species emerge has been a long‐standing effort in evolutionary biology. Young adaptive radiations provide a model to study patterns of morphological and ecological diversification in environmental context. Here, we use the recent radiation (ca. 12k years old) of the freshwater fish Arctic charr (Salvelinus alpinus) to identify abiotic and biotic environmental factors associated with adaptive morphological variation. Arctic charr are exceptionally diverse, and in postglacial lakes there is strong evidence of repeated parallel evolution of similar morphologies associated with foraging. We measured head depth (a trait reflecting general eco‐morphology and foraging ecology) of 1,091 individuals across 30 lake populations to test whether fish morphological variation was associated with lake bathymetry and/or ecological parameters. Across populations, we found a significant relationship between the variation in head depth of the charr and abiotic environmental characteristics: positively with ecosystem size (i.e., lake volume, surface area, depth) and negatively with the amount of littoral zone. In addition, extremely robust‐headed phenotypes tended to be associated with larger and deeper lakes. We identified no influence of co‐existing biotic community on Arctic charr trophic morphology. This study evidences the role of the extrinsic environment as a facilitator of rapid eco‐morphological diversification.
Individual quality and age but not environmental or social conditions modulate costs of reproduction in a capital breeder
Authors: Debeffe Lucie , Poissant Jocelyn , McLoughlin Philip D.
Published: June 2017

Costs associated with reproduction are widely known to play a role in the evolution of reproductive tactics with consequences to population and eco‐evolutionary dynamics. Evaluating these costs as they pertain to species in the wild remains an important goal of evolutionary ecology. Individual heterogeneity, including differences in individual quality (i.e., among‐individual differences in traits associated with survival and reproduction) or state, and variation in environmental and social conditions can modulate the costs of reproduction; however, few studies have considered effects of these factors simultaneously. Taking advantage of a detailed, long‐term dataset for a population of feral horses (Sable Island, Nova Scotia, Canada), we address the question of how intrinsic (quality, age), environmental (winter severity, location), and social conditions (group size, composition, sex ratio, density) influence the costs of reproduction on subsequent reproduction. Individual quality was measured using a multivariate analysis on a combination of four static and dynamic traits expected to depict heterogeneity in individual performance. Female quality and age interacted with reproductive status of the previous year to determine current reproductive effort, while no effect of social or environmental covariates was found. High‐quality females showed higher probabilities of giving birth and weaning their foal regardless of their reproductive status the previous year, while those of lower quality showed lower probabilities of producing foals in successive years. Middle‐aged (prime) females had the highest probability of giving birth when they had not reproduced the year before, but no such relationship with age was found among females that had reproduced the previous year, indicating that prime‐aged females bear higher costs of reproduction. We show that individual quality and age were key factors modulating the costs of reproduction in a capital breeder but that environmental or social conditions were not, highlighting the importance of considering multiple factors when studying costs of reproduction.
Alternative reproductive strategies and the maintenance of female color polymorphism in damselflies
Authors: Sánchez‐Guillén Rosa A. , Wellenreuther Maren , Chávez‐Ríos Jesús R. , Beatty Christopher D. , Rivas‐Torres Anais , Velasquez‐Velez María , Cordero‐Rivera Adolfo
Published: June 2017

Genetic polymorphisms are powerful model systems to study the maintenance of diversity in nature. In some systems, polymorphisms are limited to female coloration; these are thought to have arisen as a consequence of reducing male mating harassment, commonly resulting in negative frequency‐dependent selection on female color morphs. One example is the damselfly Ischnura elegans, which shows three female color morphs and strong sexual conflict over mating rates. Here, we present research integrating male tactics, and female evolutionary strategies (female mating behavior and morph‐specific female fecundity) in populations with different morph‐specific mating frequencies, to obtain an understanding of mating rates in nature that goes beyond the mere measure of color frequencies. We found that female morph behavior differed significantly among but not within morphs (i.e., female morph behavior was fixed). In contrast, male tactics were strongly affected by the female morph frequency in the population. Laboratory work comparing morph‐specific female fecundity revealed that androchrome females have lower fecundity than both of the gynochrome female morphs in the short term (3‐days), but over a 10‐day period one of the gynochrome female morphs became more fecund than either of the other morphs. In summary, our study found sex‐specific dynamics in response to different morph frequencies and also highlights the importance of studying morph‐specific fecundities across different time frames to gain a better understanding of the role of alternative reproductive strategies in the maintenance of female‐limited color polymorphism.
Who's My Daddy? Considerations for the influence of sexual selection on multiple paternity in elasmobranch mating systems
Authors: Lyons Kady , Chabot Chris L. , Mull Christopher G. , Paterson Holder Corinne N. , Lowe Christopher G.
Published: June 2017

Polyandry resulting in multiply‐sired litters has been documented in the majority of elasmobranch species examined to date. Although commonly observed, reasons for this mating system remain relatively obscure, especially in batoids. The round stingray (Urobatis halleri) is an abundant, well‐studied elasmobranch distributed throughout the northeastern Pacific that we used to explore hypotheses regarding multiple paternity in elasmobranchs. Twenty mid‐ to late‐term pregnant females were sampled off the coast of southern California and their litters analyzed for the occurrence of multiple paternity using five nuclear microsatellite loci. In addition, embryo sizes and their position within the female reproductive system (i.e., right or left uterus) were recorded and used to make inferences for patterns of ovulation. Multiple paternity was observed in 90% of litters and male reproductive success within litters was relatively even among sires. High variability in testes mass was observed suggesting that sperm competition is high in this species, although male reproductive success per litter appeared to be relatively even. Using embryo size as a proxy for fertilization, females were found to exhibit a variety of ovulation patterns that could function to limit a male's access to eggs and possibly promote high rates of multiple paternity. Our study highlights that elasmobranch mating systems may be more varied and complex than presumed and further investigation is warranted.
Dioecious plants are more precocious than cosexual plants: A comparative study of relative sizes at the onset of sexual reproduction in woody species
Authors: Ohya Itsuki , Nanami Satoshi , Itoh Akira
Published: June 2017

The reproductive capacities of dioecious plant species may be limited by severe pollen limitation and narrow seed shadows for the two reasons. First, they are unable to self‐pollinate, and seed production occurs only with pollinator movement from males to females. Second, only 50% of the individuals in populations contribute to seed production. Despite these handicaps, dioecious plants maintain their populations in plant communities with cooccurring cosexual plants, and no substantial difference in population growth rates has been found between dioecious and cosexual plants. Hence, dioecious plants are thought to mitigate these disadvantages by adopting ecological traits, such as insect pollination, animal‐dispersed fleshy fruits, and precocious flowering. We studied the relationship between flowering and plant size in 30 woody species with different sex expressions, leaf habits, fruit types, and maximum plant sizes. The study site was located in an evergreen broad‐leaved forest on the island of Honshu, Japan. A phylogenetic linear regression model showed that dioecious species tended to mature at smaller sizes than did cosexual taxa. At the population level, given equal plant densities and reproductive efforts, the precocity of dioecious plants could serve as one of the factors that mitigate the limitations of pollen and seed‐shadow handicaps by increasing the density of reproductive individuals in the population. At the individual level, smaller size of onset of flowering may play a role in enhancing reproductive success over a lifetime by increasing reproductive opportunities. We discussed the possible effect of the relationship between precocity and some ecological traits of dioecious plants, such as small flowers pollinated by unspecialized insects, fleshy fruit dispersed by animals, and their preferential occurrence in the tropics and in island habitats. The universality of precocity among dioecious plants should be investigated in diverse plant communities. Such studies will increase our understanding of the evolution of plant breeding systems.
Magellanic penguin telomeres do not shorten with age with increased reproductive effort, investment, and basal corticosterone
Authors: Cerchiara Jack A. , Risques Rosa Ana , Prunkard Donna , Smith Jeffrey R. , Kane Olivia J. , Boersma P. Dee
Published: June 2017

All species should invest in systems that enhance longevity; however, a fundamental adult life‐history trade‐off exists between the metabolic resources allocated to maintenance and those allocated to reproduction. Long‐lived species will invest more in reproduction than in somatic maintenance as they age. We investigated this trade‐off by analyzing correlations among telomere length, reproductive effort and output, and basal corticosterone in Magellanic penguins (Spheniscus magellanicus). Telomeres shorten with age in most species studied to date, and may affect adult survival. High basal corticosterone is indicative of stressful conditions. Corticosterone, and stress, has been linked to telomere shortening in other species. Magellanic penguins are a particularly good model organism for this question as they are an unusually long‐lived species, exceeding their mass‐adjusted predicted lifespan by 26%. Contrary to our hypothesis, we found adults aged 5 years to over 24 years of age had similar telomere lengths. Telomeres of adults did not shorten over a 3‐year period, regardless of the age of the individual. Neither telomere length, nor the rate at which the telomeres changed over these 3 years, correlated with breeding frequency or investment. Older females also produced larger volume clutches until approximately 15 years old and larger eggs produced heavier fledglings. Furthermore, reproductive success (chicks fledged/eggs laid) is maintained as females aged. Basal corticosterone, however, was not correlated with telomere length in adults and suggests that low basal corticosterone may play a role in the telomere maintenance we observed. Basal corticosterone also declined during the breeding season and was positively correlated with the age of adult penguins. This higher basal corticosterone in older individuals, and consistent reproductive success, supports the prediction that Magellanic penguins invest more in reproduction as they age. Our results demonstrate that telomere maintenance may be a component of longevity even with increased reproductive effort, investment, and basal corticosterone.
Growth and fecundity of fertile Miscanthus × giganteus (“PowerCane”) compared to feral and ornamental Miscanthus sinensis in a common garden experiment: Implications for invasion
Authors: Miriti Maria N. , Ibrahim Tahir , Palik Destiny , Bonin Catherine , Heaton Emily , Mutegi Evans , Snow Allison A.
Published: June 2017

Perennial grasses are promising candidates for bioenergy crops, but species that can escape cultivation and establish self‐sustaining naturalized populations (feral) may have the potential to become invasive. Fertile Miscanthus × giganteus, known as “PowerCane,” is a new potential biofuel crop. Its parent species are ornamental, non‐native Miscanthus species that establish feral populations and are sometimes invasive in the USA. As a first step toward assessing the potential for “PowerCane” to become invasive, we documented its growth and fecundity relative to one of its parent species (Miscanthus sinensis) in competition with native and invasive grasses in common garden experiments located in Columbus, Ohio and Ames, Iowa, within the targeted range of biofuel cultivation. We conducted a 2‐year experiment to compare growth and reproduction among three Miscanthus biotypes—”PowerCane,” ornamental M. sinensis, and feral M. sinensis—at two locations. Single Miscanthus plants were subjected to competition with a native grass (Panicum virgatum), a weedy grass (Bromus inermis), or no competition. Response variables were aboveground biomass, number of shoots, basal area, and seed set. In Iowa, all Miscanthus plants died after the first winter, which was unusually cold, so no further results are reported from the Iowa site. In Ohio, we found significant differences among biotypes in growth and fecundity, as well as significant effects of competition. Interactions between these treatments were not significant. “PowerCane” performed as well or better than ornamental or feral M. sinensis in vegetative traits, but had much lower seed production, perhaps due to pollen limitation. In general, ornamental M. sinensis performed somewhat better than feral M. sinensis. Our findings suggest that feral populations of “PowerCane” could become established adjacent to biofuel production areas. Fertile Miscanthus × giganteus should be studied further to assess its potential to spread via seed production in large, sexually compatible populations.
Seasonal changes in leaf chemistry and leaf selection of the Japanese giant flying squirrel upon two tree species
Authors: Ito Mutsumi , Tamura Noriko , Hayashi Fumio
Published: June 2017

Tree leaves are important food sources for arboreal herbivores, such as primates, rodents, and marsupials. These animals do not eat leaves randomly in habitats with many tree species but rather choose based on the chemical components of leaves, such as sugars, fibers, proteins, and toxins. However, the effects of the microscale distribution of these chemicals within each leaf have not been examined for these animals. The giant flying squirrels Petaurista leucogenys are entirely arboreal, nocturnal herbivores, usually feeding on leaves and dropping leaf debris on the ground after partially consuming them. Therefore, we could easily assess which species of trees and which parts of the individual leaves they preferred to eat. We also examined microscale distributions of phenolics, sugar, and water within individual leaves. Of the two dominant food tree species, the deciduous Quercus acutissima was preferred over the evergreen Q. sessilifolia. The latter tree is only used during winter to early spring when the former had no leaves. Our chemical analyses revealed that Q. acutissima contained much more glucose than Q. sessilifolia in all seasons. Three types of leaf debris, eaten apically, basally, or centrally with a hole, were found. In Q. sessilifolia, which had low phenolic concentrations, apical eating was most common, whereas central eating was rare. In Q. acutissima, which had high phenolics, basal or central eating was common. Central feeding may be caused by avoiding the periphery because of a higher phenolic concentration in the leaf margin. Thus, microscale distributions of phenolics within individual leaves affect which parts P. leucogenys eats, whereas leaf sugar concentration is an important factor affecting which species of leaves they eat.
Potassium and Yttrium Complexes of a Rigid Bis‐Phosphido POP‐Donor Ligand
Authors: Motolko Kelly S. A. , Emslie David J. H. , Jenkins Hilary A. , Britten James F.
Published: June 2017

Dilithiation of 4,5‐dibromo‐2,7‐di‐tert‐butyl‐9,9‐dimethyl‐xanthene (XBr2) followed by addition of 2 equiv. of (2,4,6‐triisopropylphenyl)dichlorophosphine (TrippPCl2) afforded 4,5‐bis[(2,4,6‐triisopropylphenyl)chlorophosphino]‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene (XP2Cl2), which was reduced to 4,5‐bis[(2,4,6‐triisopropylphenyl)phosphino]‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene (H2XP2) using excess LiAlH4. Deprotonation of H2XP2 with excess KH in DME provided the dipotassium salt, [K2(XP2)(dme)n] (1; n = 2.5–4), and stirring 1 in THF followed by recrystallization from hexanes yielded tetrametallic [K4(XP2)2(THF)4] (2) which features a central K4P4 cage. Reaction of [YI3(THF)3.5] with [K2XP2(dme)2.5] afforded a mixture of products including [(XP2)YI(THF)2] (3) and (PTripp)3; pure 3 could be isolated in low yield by extraction with a minimum volume of hexanes or O(SiMe3)2. In the solid state, 3 adopts a face‐capped trigonal bipyramidal coordination geometry with a planar xanthene backbone and an angle of 85° between the P(1)/C(4)/C(5)/P(2) and P(1)/Y/P(2) planes.
Synthesis and Reactivity of Thiolate‐Bridged NiIIMI Heterodinuclear Complexes (M = Rh, Ir) with an S‐Bidentate NiP2S2 Metalloligand
Authors: Kure Bunsho , Sano Mikie , Watanabe Natsuki , Nakajima Takayuki , Tanase Tomoaki
Published: June 2017

The mononuclear complex [Ni(meppp)] {H2meppp = meso‐1,3‐bis[(2‐mercaptoethyl)(phenyl)phosphino]propane} was used as an S‐bidentate NiP2S2 metalloligand to prepare a series of NiIIMI complexes with various neutral ligands, namely, [Ni(µ‐meppp)ML2]PF6 [M = Rh, L = 1/2cod (1a; cod = 1,5‐cycloocatadiene), CO (1b), XylNC (1c; Xyl = 2,6‐dimethylphenyl), P(OPh)3 (1d); M = Ir, L = 1/2cod (2a), CO (2b), XylNC (2c)]. The reactivities of 1 and 2 toward methyl iodide and tertiary hydrosilanes were examined. Complexes 1c, 2a, and 2b reacted with MeI to afford the oxidative addition products [Ni(µ‐meppp)M(L)2(Me)(I)]PF6 [M = Rh, L = XylNC (3c); M = Ir, L = 1/2cod (4a)] and [Ni(µ‐meppp)Ir(CO)(Me)(I)2] (5). In the reactions with hydrosilanes, only 2c exhibited an interesting reactivity to afford the NiII(µ‐H)IrIII silyl complexes [Ni(µ‐meppp)(µ‐H)Ir(XylNC)2(Si)]PF6 [Si = SiEt3 (6a), SiMe2Ph (6b), SiMePh2 (6c), SiPh3 (6d)]. The reaction proceeded via the intermediate isomers [Ni(meppp)(µ‐H)Ir(XylNC)2(Si)]PF6 (7); intermediate 7d (Si = SiPh3) was characterized and has an NiII(µ‐H)IrIII silyl structure with the hydrido ligand nesting in the reverse side of the Ni(µ‐S)2Ir pocket to that of 6d. These results demonstrated that the reactivities of the bis(thiolate)‐bridged NiIIMI heterodinuclear complexes can be tuned by changing the metal ions and ancillary ligands. In addition, the S‐bidentate NiP2S2 metalloligand [Ni(meppp)] plays an important role in the stabilization of the bridging hydrido ligand in both pockets of the NiII(µ‐H)IrIII core owing to the flexibility of the hinged Ni(µ‐SR)2Ir structure.
Rational Design of a Near‐Infrared Fluorescent Probe Based on a Pyridazinone Scaffold
Authors: Zhou Tongliang , Yang Lingfei , Liang Lei , Liu Hui , Zhu Yuanjun , Shui Mengyang , Yuan Lan , Xu Fengrong , Niu Yan , Wang Chao , Xu Ping
Published: June 2017

A class of pyridazinone derivatives as near‐infrared optical probes in fluorescence microscopy images was designed. The design strategy consisted of the stepwise extension and modification of pyridazinone by expansion of the electron‐donating moiety to a larger π‐conjugated system and anchoring a subcellular directing group such as triphenylphosphine or morpholine. All the desired products were successfully applied in cell imaging with high subcellular colocalization. Furthermore, these fluorescent probes showed excellent performance in mouse‐brain imaging.
AgI‐Promoted Difluoromethylation of Isocyanides To Give Difluoromethylated Phenanthridines
Authors: Wan Wen , Xu Xiaochen , Chen Yunrong , Jiang Haizhen , Wang Yong , Deng Hongmei , Hao Jian
Published: June 2017

An AgI‐mediated ethoxycarbonyldifluoromethylation of isocyanides has been developed. This radical cascade reaction involves the addition of difluoromethylene radical to the isocyanide functionality, and subsequent homolytic aromatic substitution to give difluoromethylated phenanthridines with a good functional‐group tolerance.
A Meldrum's Acid Based Multicomponent Synthesis of N‐Fmoc‐isoxazolidin‐5‐ones: Entry to N‐Fmoc‐β‐amino Acids
Authors: Le Foll Devaux Alexandra , Deau Emmanuel , Corrot Emilie , Bischoff Laurent , Levacher Vincent , Brière Jean‐François
Published: June 2017

A multicomponent Knoevenagel–aza‐Michael cyclocondensation (KaMC) reaction starting from Meldrum's acid has been developed with base‐sensitive N‐Fmoc‐hydroxylamine. The reaction takes place under very mild basic conditions, providing a straightforward synthetic route to various unprecedented N‐Fmoc‐isoxazolidin‐5‐ones. Subsequent chemoselective reductive cleavage of the N–O bond in the presence of Zn/AcOH allowed a short synthesis of the corresponding N‐Fmoc‐β‐amino acids.
LiAlH4‐Induced Thia‐Aza‐Payne Rearrangement of Functionalized 2‐(Thiocyanatomethyl)aziridines into 2‐(Aminomethyl)thiiranes as an Entry to 5‐(Chloromethyl)thiazolidin‐2‐ones
Authors: Dolfen Jeroen , Van Hecke Kristof , D'hooghe Matthias
Published: June 2017

Nonactivated 2‐(thiocyanatomethyl)aziridines with diverse substitution patterns were deployed as substrates to effect a LiAlH4‐promoted thia‐aza‐Payne rearrangement to provide access to functionalized 2‐(aminomethyl)thiiranes in good to excellent yields (78–94 %). The developed strategy involved hydride reduction of the thiocyanato moiety followed by intramolecular aziridine ring opening. Subsequent exposure of the obtained 2‐(aminomethyl)episulfide intermediates to triphosgene resulted in the formation of 5‐(chloromethyl)thiazolidin‐2‐ones.
Metal‐Free Selective Synthesis of 1,4‐Dihydropyridazines from Hydroxypyrrolines and Hydrazines
Authors: Shabalin Dmitrii A. , Dvorko Marina Yu. , Zolotareva Evgeniya E. , Ushakov Igor' A. , Vashchenko Alexander V. , Schmidt Elena Yu. , Trofimov Boris A.
Published: June 2017

An efficient and selective synthesis of 1,4‐dihydropyridazines through the acid‐catalyzed recyclization of 5‐hydroxy‐Δ1‐pyrrolines with hydrazines has been developed. The scope of this reaction was thoroughly explored, resulting in the generation of a library of 1,4‐dihydropyridazines in good to excellent yields (25 examples, 67–100 % yields).
Synthesis and Rearrangement of Cage [4.3.2]Propellanes that Contain a Spiro Linkage
Authors: Kotha Sambasivarao , Rao Cheekatla Subba , Mandal Binita
Published: June 2017

Rearranged cage ketones 6a and 6b are reported in eight linear synthetic steps from 2,5‐dimethoxybenzaldehyde 9 without the use of protecting groups. In this regard, Diels–Alder reaction, [2+2]photocycloaddition and Lewis acid promoted rearrangement with BF3·OEt2 were used as key steps. Surprisingly, during the ring expansion process with Lewis acid, solvent incorporation occurred. This rearrangement approach has provided difficult complex targets through non‐obvious synthetic routes. The rearrangement process demonstrated here opens up a new synthetic strategy to interesting and unusual cage molecules.
Electrochemical Studies on Self‐assembled Monolayer (SAM) Upon Exposure to Anionic Surfactants: PFOA, PFOS, SDS and SDBS
Authors: Fang Cheng , Megharaj Mallavarapu , Naidu Ravi
Published: June 2017

We investigate the interaction between anionic surfactants (AS) and a self‐assembled monolayer (SAM) using cyclic voltammetry (CV), electrochemical impedance spectrum (EIS) and electrochemical quartz crystal microbalance (EQCM). The AS include two common fluorosurfactants, which have been previously formulated in aqueous film‐forming foam (AFFF): perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), and two common detergents: sodium dodecyl sulphate (SDS) and sodium dodecyl benzenesulfonate (SDBS). The AS can re‐configure the SAM arrangement, particularly on nanoporous gold surface due to the high density of defects and pinholes of SAM, which results in changes to the electrochemical redox kinetics and interface capacitance of the SAM. Based on the experimental results, we hypothesis that AS insert and dope the pristine monolayer, which is evidenced with EQCM and EIS.
Solvent degradation studies using hydrodynamic cavitation
Authors: Suryawanshi Pravin G. , Bhandari Vinay M. , Sorokhaibam Laxmi Gayatri , Ruparelia Jayesh P. , Ranade Vivek V.
Published: June 2017

Hydrodynamic cavitation for the degradation of organic solvents was investigated in detail using a newer form of cavitating device‐vortex diode. The results were also compared with that using conventional cavitating device orifice. Removal of three different organic solvents—acetone, methyl ethyl ketone (MEK), and toluene were studied on a pilot plant with capacity of 1 m3/h. The effect of different operating parameters such as inlet pressure, initial concentration, and reactor type on the degradation rate of solvent was investigated in detail. The results revealed that efficiency of solvent removal varies substantially with the change in physical operating conditions and nature of the solvent. It was found that up to 80% degradation could be achieved for toluene (cavitational yield 32.2 × 10−3 mg/J), substantially higher than that for acetone and MEK indicating the effect of molecular weight/structure in the degradation process. Further, the results clearly indicated chemical oxidation as a predominant mechanism for degradation and not physical destruction. Vortex diode that works on the principle of vortex generation for cavitation, was found to be far superior over conventional cavitating device‐orifice‐ ∼up to eight times higher cavitational yield could be obtained for toluene as compared to orifice. The results of this study provide newer insight into solvent removal using hydrodynamic cavitation and would have bearing on the treatment of solvent containing wastewaters. © 2017 American Institute of Chemical Engineers Environ Prog, 37: 295–304, 2018
Genetic differences between willow warbler migratory phenotypes are few and cluster in large haplotype blocks
Authors: Lundberg Max , Liedvogel Miriam , Larson Keith , Sigeman Hanna , Grahn Mats , Wright Anthony , Åkesson Susanne , Bensch Staffan
Published: June 2017

It is well established that differences in migratory behavior between populations of songbirds have a genetic basis but the actual genes underlying these traits remains largely unknown. In an attempt to identify such candidate genes we de novo assembled the genome of the willow warbler Phylloscopus trochilus, and used whole-genome resequencing and a SNP array to associate genomic variation with migratory phenotypes across two migratory divides around the Baltic Sea that separate SW migrating P. t. trochilus wintering in western Africa and SSE migrating P. t. acredula wintering in eastern and southern Africa. We found that the genomes of the two migratory phenotypes lack clear differences except for three highly differentiated regions located on chromosomes 1, 3, and 5 (containing 146, 135, and 53 genes, respectively). Within each migratory phenotype we found virtually no differences in allele frequencies for thousands of SNPs, even when comparing geographically distant populations breeding in Scandinavia and Far East Russia (>6000 km). In each of the three differentiated regions, multidimensional scaling-based clustering of SNP genotypes from more than 1100 individuals demonstrates the presence of distinct haplotype clusters that are associated with each migratory phenotype. In turn, this suggests that recombination is absent or rare between haplotypes, which could be explained by inversion polymorphisms. Whereas SNP alleles on chromosome 3 correlate with breeding altitude and latitude, the allele distribution within the regions on chromosomes 1 and 5 perfectly matches the geographical distribution of the migratory phenotypes. The most differentiated 10 kb windows and missense mutations within these differentiated regions are associated with genes involved in fatty acid synthesis, possibly representing physiological adaptations to the different migratory strategies. The ∼200 genes in these regions, of which several lack described function, will direct future experimental and comparative studies in the search for genes that underlie important migratory traits.
La Maddalena exploratory tunnel
Authors: Parisi Maria Elena , Brino Lorenzo , Gilli Piergiuseppe , Fornari Enrico , Martinotti Giorgio , Lo Russo Stefano
Published: June 2017

This paper deals with the cross‐border section of the Lyon‐Turin Line, i.e. the 57.5 km long Mont Cenis Base Tunnel between Saint Jean de Maurienne in France and the Susa valley in Italy. Works at Saint Martin La Porte started in 2015 including the 9 km TBM excavation along the south tube of the base tunnel between the access adits of Saint Martin La Porte and La Praz. In order to assemble the TBM, a large underground cavern has been excavated at the end of the Saint Martin La Porte access adit. The size of this cavern, with a length of approximately 45 m, a span of 23 m and a height of 22.2 m, and the geological and geomechanical conditions in the Carboniferous Formation at a depth of about 600 m made this work a challenge. The excavation and support methods adopted are described, together with the rock mass conditions and the observed ground behaviour. The monitoring data obtained during excavation are briefly presented, including the works schedule.