bluuebunny/crossref_metadata_2025 huggingface dataset:
Examining number: A soft Idea
Authors: Switzer J. Matt , Buchheister Kelley , Dougherty Barbara
Published: September 2014

This department publishes brief news articles, announcements, and guest editorials on current mathematics education issues that stimulate the interest of TCM readers and cause them to think about an issue or consider a specific viewpoint about some aspect of mathematics education.
Math is Beautiful
Authors: Enns Ed
Published: September 2014

Each month, elementary school teachers have access to a problem along with suggested instructional notes. Teachers are asked to use the problem in their own classroom and report solutions, strategies, reflections, and misconceptions to the journal audience. This month's task focuses on how stained-glass artists repeat geometric shapes in interesting ways to create their beautiful designs.
Decoding dimensions of the Dakota
Authors: Farmer Sherri , Kastberg Signe E.
Published: September 2014

This part of the department showcases students' in-depth thinking and work on problems previously published in Teaching Children Mathematics. The September 2013 problem scenario highlights a sightseeing trip to New York City and the resulting mathematical wonderings about the historic Dakota apartment building. An Indiana teacher reports on how her fourth graders engaged with this investigation of differences and relationships between perimeter and area.
The Aerospace Engineering Challenge
Authors: English Lyn D. , King Donna T. , Hudson Peter , Dawes Les
Published: September 2014

Integrating Science, Technology, and Engineering in Mathematics authors share ideas and activities that stimulate student interest in the integrated fields of science, technology, engineering, and mathematics (STEM) in K—grade 6 classrooms. This article describes an activity that introduced fourth-grade students to the work of aerospace engineers and to the science, technology, and mathematics principles associated with flight.
Walgreens Connected Care
Authors: DuChane Janeen , Clark Bobby , Staskon Francis , Miller Rick , Love Kathleen , Duncan Ian
Published: September 2014

Background: The Walgreens Connected Care Multiple Sclerosis (CCMS) treatment management program provides enhanced levels of monitoring, oversight, and care for patients taking MS disease-modifying agents. This study compared rates of adherence to MS medications for patients participating in the CCMS program for at least 6 months with those for patients participating for less than 6 months. For a subsample of patients, we also examined the relationship between adherence and the presence of fatigue or depression.

Methods: This was a retrospective study of patients new to the CCMS program and followed up for 1 year of participation. Adherence to MS medications was measured as the proportion of days covered, with propensity scores used to match the CCMS intervention group to the less-managed comparison group. The impact of program participation on the relationship between depression or fatigue and adherence over time was a separate analysis.

Results: Mean proportion of days covered rates improved significantly in the group managed for at least 6 months compared with those who were less managed. Positive screenings for fatigue and depression reduced adherence in the less-managed group but not in patients with longer participation in the program.

Conclusions: Overall, the CCMS program significantly increased adherence to MS medications. This improved adherence was not negatively impacted by positive screenings for fatigue and depression.
Patient Preferences for Attributes of Multiple Sclerosis Disease-Modifying Therapies
Authors: Wilson Leslie S. , Loucks Aimee , Gipson Gregory , Zhong Lixian , Bui Christine , Miller Elizabeth , Owen Mary , Pelletier Daniel , Goodin Douglas , Waubant Emmanuelle , McCulloch Charles E.
Published: September 2014

Background: Timely individualized treatment is essential to improving relapsing-remitting multiple sclerosis (RRMS) patient health outcomes, yet little is known about how patients make treatment decisions. We sought to evaluate RRMS patient preferences for risks and benefits of treatment.

Methods: Fifty patients with RRMS completed conjoint analysis surveys with 16 hypothetical disease-modifying therapy (DMT) medication profiles developed using a fractional factorial design. Medication profiles were assigned preference ratings from 0 (not acceptable) to 10 (most favorable). Medication attributes included a range of benefits, adverse effects, administration routes, and market durations. Analytical models used linear mixed-effects regression.

Results: Participants showed the highest preference for medication profiles that would improve their symptoms (β = 0.81–1.03, P < .001), not a proven DMT outcome. Preventing relapses, the main clinical trial outcome, was not associated with significant preferences (P = .35). Each year of preventing magnetic resonance imaging changes and disease symptom progression showed DMT preferences of 0.17 point (β = 0.17, P = .002) and 0.12 point (β = 0.12, P < .001), respectively. Daily oral administration was preferred over all parenteral routes (P < .001). A 1% increase in death or severe disability decreased relative DMT preference by 1.15 points (P < .001).

Conclusions: Patient preference focused on symptoms and prevention of progression but not on relapse prevention, the proven drug outcome. Patients were willing to accept some level of serious risk for certain types and amounts of benefits, and they strongly preferred daily oral administration over all other options.
A Randomized Placebo-Controlled Trial of Duloxetine for Central Pain in Multiple Sclerosis
Authors: Brown Theodore R. , Slee April
Published: September 2014

Background: Pain is common in multiple sclerosis (MS). Duloxetine has a potential therapeutic role in treating MS-related pain.

Methods: Thirty-eight MS patients were randomized 1:1 to receive duloxetine (n = 18) or matched placebo (n = 20). The dosing regimen was 30 mg daily for 1 week, then 60 mg daily for 5 weeks. The primary outcome measure was change in worst pain for week 6 relative to baseline recorded on a daily pain diary.

Results: Of 38 randomized patients, 14 (78%) patients randomized to duloxetine and 18 (90%) randomized to placebo completed treatment per protocol. These participants had an average age of 55.5 years, 25% were male, and 66% had relapsing-remitting MS (RRMS). Baseline characteristics were similar. Discontinuations were due primarily to drug intolerance. Among those who completed treatment, worst pain at 6 weeks was reduced by 29% (±20%) for duloxetine versus 12% (±18%) for placebo (P = .016). Average daily pain at 6 weeks was reduced by 39% (±29%) in the duloxetine group compared to 10% (±18.8%) in the placebo group (P = .002). There were no significant changes (week 6 vs. baseline) or between-group differences for subject global impression, Beck Depression Inventory, 36-item Short Form Health Status Survey (SF-36), or sleep quality score.

Conclusions: Fewer patients could tolerate duloxetine compared to placebo. Among patients who completed 6 weeks of treatment, there were significant reductions in average and worst daily pain scores with duloxetine compared to placebo. This study suggests that duloxetine has a direct pain-relieving effect in MS.
No evident association between efavirenz use and suicidality was identified from a disproportionality analysis using the FAERS database
Authors: Napoli Andrew A , Wood Jennifer J , Coumbis John J , Soitkar Amit M , Seekins Daniel W , Tilson Hugh H
Published: September 2014

Objective

To assess the potential association of selected antiretrovirals (ARVs), including efavirenz, with suicidality.

Design

Retrospective analysis of the Food and Drug Administration Adverse Event Reporting System (FAERS), by performing a Multi‐Item Gamma Poisson Shrinker (MGPS) disproportionality analysis.

Methods

MGPS disproportionality analysis, a technique to identify associations between drugs and adverse events, was performed using cumulative data from the FAERS database collected up to August 2012. This method yields an Empirical Bayesian Geometric Mean score and corresponding 90% confidence interval (EB05, EB95). EB05 scores ≥2 were pre‐defined as a signal for a potential drug‐event association. The FAERS database includes spontaneous adverse‐event reports from consumers and healthcare professionals. All FAERS reports of suicidality (including suicidal ideation, suicide attempt and completed suicide or a composite of these) in patients taking efavirenz (as single agent or in fixed‐dose combination), atazanavir, darunavir, etravirine, nevirapine and raltegravir were identified. A number of parallel analyses were performed to assess the validity of the methodology: fluoxetine and sertraline, antidepressants with a known association with suicidality, and raltegravir, an ARV with rhabdomyolysis and myopathy listed as “uncommon” events in the US‐prescribing information.

Results

A total of 29,856 adverse event reports were identified among patients receiving efavirenz, atazanavir, darunavir, etravirine, nevirapine and raltegravir, of which 457 were reports of suicidality events. EB05 scores observed for the composite suicidality term for efavirenz (EB05=0.796), and other ARVs (EB05=0.279–0.368), were below the pre‐defined threshold. Fluoxetine and sertraline gave EB05 scores for suicidality >2. Raltegravir gave EB05 scores >2 for myopathy and rhabdomyolysis.

Conclusions

The pre‐determined threshold for signals for suicidality, including suicidal ideation, suicide attempt, completed suicide and a composite suicidality endpoint, was not exceeded for efavirenz and other ARVs in this analysis. Efavirenz has been associated with suicidality in clinical trials. Further studies that adjust for confounding factors are needed to better understand any potential association with ARVs and suicidality.
USDA‐ARS Riesel Watersheds, Riesel, Texas, USA: Water quality research database
Authors: Harmel R. Daren , Haney Richard L. , Smith Douglas R. , White Michael , King Kevin W.
Published: September 2014

The 75 year legacy database including discharge, sediment loss, land management, and meteorological data for the USDA‐ARS Riesel Watersheds, Riesel, TX, USA has been available on the web for more than a decade (www.ars.usda.gov/spa/hydro‐data) and used in numerous studies and publications; however, only recently have these data been added to the Sustaining the Earth's Watersheds, Agricultural Research Data System (STEWARDS) database (www.nrrig.mwa.ars.usda.gov/stewards/stewards.html). In addition, water quality data including dissolved inorganic N and P compounds measured from more than 1000 storm runoff events, 1300 base flow sampling events (lateral subsurface return flow or seepage flow), and 157 precipitation events through 2012 were added. The objectives of this manuscript are to present relevant background information on these data, summarize the data collection and analysis methodology, present the measured data along with cursory analyses, and convey the commitment of the USDA‐ARS Riesel Watersheds to long‐term data accessibility and database enhancement for water quality data and research.
Global dry deposition of nitrogen dioxide and sulfur dioxide inferred from space‐based measurements
Authors: Nowlan C. R. , Martin R. V. , Philip S. , Lamsal L. N. , Krotkov N. A. , Marais E. A. , Wang S. , Zhang Q.
Published: September 2014

A method is developed to estimate global NO2 and SO2 dry deposition fluxes at high spatial resolution (0.1°×0.1°) using satellite measurements from the Ozone Monitoring Instrument (OMI) on the Aura satellite, in combination with simulations from the Goddard Earth Observing System chemical transport model (GEOS‐Chem). These global maps for 2005–2007 provide a data set for use in examining global and regional budgets of deposition. In order to properly assess SO2 on a global scale, a method is developed to account for the geospatial character of background offsets in retrieved satellite columns. Globally, annual dry deposition to land estimated from OMI as NO2 contributes 1.5 ± 0.5 Tg of nitrogen and as SO2 contributes 13.7 ± 4.0 Tg of sulfur. Differences between OMI‐inferred NO2 dry deposition fluxes and those of other models and observations vary from excellent agreement to an order of magnitude difference, with OMI typically on the low end of estimates. SO2 dry deposition fluxes compare well with in situ Clear Air Status and Trends Network‐inferred flux over North America (slope = 0.98, r = 0.71). The most significant NO2 dry deposition flux to land per area occurs in the Pearl River Delta, China, at 13.9 kg N ha−1 yr−1, while SO2 dry deposition has a global maximum rate of 72.0 kg S ha−1 yr−1 to the east of Jinan in China's Shandong province. Dry deposition fluxes are explored in several urban areas, where NO2 contributes on average 9–36% and as much as 85% of total NOy dry deposition.
First spaceborne observation of the entire concentric airglow structure caused by tropospheric disturbance
Authors: Akiya Y. , Saito A. , Sakanoi T. , Hozumi Y. , Yamazaki A. , Otsuka Y. , Nishioka M. , Tsugawa T.
Published: September 2014

Spaceborne imagers are able to observe the airglow structures with wide field of views regardless of the tropospheric condition that limits the observational time of the ground‐based imagers. Concentric wave structures of the O2 airglow in 762 nm wavelength were observed over North America on 1 June 2013 from the International Space Station. This was the first observation in which the entire image of the structure was captured from space, and its spatial scale size was determined to be 1200 km radius without assumptions. The apparent horizontal wavelength was 80 km, and the amplitude in the intensity was approximately 20% of the background intensity. The propagation velocity of the structure was derived as 125 ± 62 m/s and atmospheric gravity waves were estimated to be generated for 3.5 ± 1.7 h. Concentric structures observed in this event were interpreted to be generated by super cells that caused a tornado in its early phase.
Observations on stratified flow over a bank at low Froude numbers
Authors: Jarosz Ewa , Wijesekera Hemantha W. , Teague William J. , Fribance Diane B. , Moline Mark A.
Published: September 2014

In June 2011, a 9 day oceanographic survey was conducted over the East Flower Garden Bank, a coral reef, located on the outer shelf in the northwestern Gulf of Mexico. Current, temperature, conductivity, and microstructure measurements were collected to characterize flow evolution, turbulence, and mixing over the bank. During the experiment, the flow was highly stratified, subcritical (Froude number below 0.4), hydrostatic, and nonlinear with rotational effects being important. Observations showed that flow structure, turbulence, and mixing were highly dependent on the direction and strength of the current; thus, they varied spatially and temporarily. Responses resulting from interactions between the free‐stream flow and the obstacle were significantly different on the upstream and downstream sides of the bank. Blocking and diverging of the flow just below the bank height was observed on the upstream side. On the downstream side, a wake with imbedded vortices developed. Moreover, turbulence was amplified over the bank top and on its downstream side. Turbulent dissipation rates were as high as 10−6 W kg−1 and resulted in measured rates of energy dissipation and mixing by turbulence per unit width as high as 40 W m−1. Mixing on the downstream side was elevated with eddy diffusivities reaching 10−3 m2 s−1, well above a typical value of 10−5 m2 s−1 commonly found in the ocean thermocline and over shelves with flat topography. On the upstream side, estimated eddy diffusivities were close to that for the ocean thermocline, i.e., they were generally less than 0.5×10−4 m2 s−1.
Natural Giesekus fluids: Shear and extensional behavior of food gum solutions in the semidilute regime
Authors: Torres Maria D. , Hallmark Bart , Wilson D. Ian , Hilliou Loic
Published: September 2014

The shear and extensional behavior of two aqueous gum solutions, namely (1) 1–20 g/L guar gum (Torres et al., Food Hydrocolloids. 2014;40:85–95) and (2) κ/ι‐hybrid carrageenan solutions (5–20 g/L), are shown to exhibit Giesekus‐fluid behavior when in the semidilute regime. In this regime, a common set of Giesekus fluid parameters described both shear and extensional behavior. A new analytical result describing the extension of a Giesekus fluid in the filament stretching geometry is presented. This also gave reasonable predictions of the Trouton ratio. Higher concentration guar solutions, in the entangled regime, yielded different Giesekus fluid parameters for extension to those for simple shear. The extensional data for all concentrations of both gums collapsed to a common functional form, similar to that reported for cake batters (Chesterton et al., J Food Eng. 2011;105(2):332–342); the limits of the new filament thinning expression provide insight into this behavior. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3902–3915, 2014
Influence of unsteady mass transfer on dynamics of rising and sinking droplet in water: Experimental and CFD study
Authors: Rao Abhijit , Reddy Rupesh K. , Valsaraj Kalliat T. , Nandakumar Krishnaswamy , Pandey Shashank , Wu Chunliang
Published: September 2014

Experimental and numerical investigations were conducted to study the effect of unsteady mass transfer on the dynamics of an organic droplet released in quiescent water. The situation is important and relevant to deep sea oil spill scenario. The droplet contains two components, one is heavier (immiscible) than water and other is lighter (miscible). When released, with an initial mixture density (890–975 kg/m3) lower than that of surrounding water, droplet rises in the column. The mass transfer of lighter solute component into water causes the droplet density to increase and droplet sinks when the density exceeds that of water. A mass‐transfer correlation accounting for the loss of the solute, based on Reynolds, Grashoff, and Schmidt numbers was developed. A two‐dimensional axisymmetric Computational Fluid Dynamics (CFD) model accounting for species transport was developed to emulate the experimental observations. The study also helped in identifying dominant mass‐transfer mechanisms during different stages of droplet motion. © 2014 American Institute of Chemical Engineers AIChE J, 61: 342–354, 2015
Common germline variation at the TERT locus contributes to familial clustering of myeloproliferative neoplasms
Authors: Jäger Roland , Harutyunyan Ashot S. , Rumi Elisa , Pietra Daniela , Berg Tiina , Olcaydu Damla , Houlston Richard S. , Cazzola Mario , Kralovics Robert
Published: September 2014

The C allele of the rs2736100 single nucleotide polymorphism located in the second intron of the TERT gene has recently been identified as a susceptibility factor for myeloproliferative neoplasms (MPN) in the Icelandic population. Here, we evaluate the role of TERT rs2736100_C in sporadic and familial MPN in the context of the previously identified JAK2 GGCC predisposition haplotype. We have confirmed the TERT rs2736100_C association in a large cohort of Italian sporadic MPN patients. The risk conferred by TERT rs2736100_C is present in all molecular and diagnostic MPN subtypes. TERT rs2736100_C and JAK2 GGCC are independently predisposing to MPN and have an additive effect on disease risk, together explaining a large fraction of the population attributable fraction (PAF = 73.06%). We found TERT rs2736100_C significantly enriched (P = 0.0090) in familial MPN compared to sporadic MPN, suggesting that low‐penetrance variants may be responsible for a substantial part of familial clustering in MPN. Am. J. Hematol. 89:1107–1110, 2014. © 2014 The Authors. American Journal of Hematology published by Wiley Periodicals, Inc.
Endocrine function and bone disease during long‐term chelation therapy with deferasirox in patients with β‐thalassemia major
Authors: Casale Maddalena , Citarella Serena , Filosa Aldo , De Michele Elisa , Palmieri Francesco , Ragozzino Alfonso , Amendola Giovanni , Pugliese Umberto , Tartaglione Immacolata , Della Rocca Filomena , Cinque Patrizia , Nobili Bruno , Perrotta Silverio
Published: September 2014

Iron overload in β‐thalassemia major (TM) typically results in iron‐induced cardiomyopathy, liver disease, and endocrine complications. We examined the incidence and progression of endocrine disorders (hypothyroidism, diabetes, hypoparathyroidism, hypogonadism), growth and pubertal delay, and bone metabolism disease during long‐term deferasirox chelation therapy in a real clinical practice setting. We report a multicenter retrospective cohort study of 86 transfusion‐dependent patients with TM treated with once daily deferasirox for a median duration of 6.5 years, up to 10 years. No deaths or new cases of hypothyroidism or diabetes occurred. The incidence of new endocrine complications was 7% (P = 0.338, for change of prevalence from baseline to end of study) and included hypogonadism (n = 5) and hypoparathyroidism (n = 1). Among patients with hypothyroidism or diabetes at baseline, no significant change in thyroid parameters or insulin requirements were observed, respectively. Mean lumbar spine bone mineral density increased significantly (P < 0.001) and the number of patients with lumbar spine osteoporosis significantly decreased (P = 0.022) irrespective of bisphosphonate therapy, hormonal replacement therapy, and calcium or vitamin D supplementation. There were no significant differences in the number of pediatric patients below the 5th centile for height between baseline and study completion. Six pregnancies occurred successfully, and four of them were spontaneous without ovarian stimulation. This is the first study evaluating endocrine function during the newest oral chelation therapy with deferasirox. A low rate of new endocrine disorders and a stabilization of those pre‐exisisting was observed in a real clinical practice setting. Am. J. Hematol. 89:1102–1106, 2014. © 2014 Wiley Periodicals, Inc.
Uncovering the Stoichiometry of Pyrococcus furiosus RNase P, a Multi‐Subunit Catalytic Ribonucleoprotein Complex, by Surface‐Induced Dissociation and Ion Mobility Mass Spectrometry
Authors: Ma Xin , Lai Lien B. , Lai Stella M. , Tanimoto Akiko , Foster Mark P. , Wysocki Vicki H. , Gopalan Venkat
Published: September 2014

We demonstrate that surface‐induced dissociation (SID) coupled with ion mobility mass spectrometry (IM‐MS) is a powerful tool for determining the stoichiometry of a multi‐subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg2+. We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5′ maturation. Previous step‐wise, Mg2+‐dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21⋅RPP29 and POP5⋅RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21⋅RPP29 and (POP5⋅RPP30)2 complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM‐MS in resolving conformational heterogeneity and yielding insights on RNP assembly.
Monitoring the Transition from Spherical to Polymer‐like Surfactant Micelles Using Small‐Angle X‐Ray Scattering
Authors: Jensen Grethe Vestergaard , Lund Reidar , Gummel Jérémie , Narayanan Theyencheri , Pedersen Jan Skov
Published: September 2014

Despite over a century of modern surfactant science, the kinetic pathways of morphological transitions in micellar systems are still not well understood. This is mainly as a result of the lack of sufficiently fast methods that can capture the structural changes of such transitions. Herein, a simple surfactant system consisting of sodium dodecyl sulfate (SDS) in aqueous NaCl solutions is investigated. Combining synchrotron radiation small‐angle X‐ray scattering (SAXS) with fast stopped‐flow mixing schemes allows monitoring the process where polymer‐like micelles are formed from globular micelles when the salt concentration is suddenly increased. The results show that “worm‐like” micelles are formed by fusion of globular micelles and short cylinders in a fashion that bears similarities to a step‐like polymerization process.
Synthesis and Structural Characterization of Three Unique Helicobacter pylori α‐Cholesteryl Phosphatidyl Glucosides
Authors: Nguyen Huy Q. , Davis Ryan A. , Gervay‐Hague Jacquelyn
Published: September 2014

Steryl glycosides produced by bacteria play important biological roles in the evasion and modulation of host immunity. Step‐economical syntheses of three cholesteryl‐6‐O‐phosphatidyl‐α‐D‐glucopyranosides (αCPG) unique to Helicobacter pylori have been achieved. The approach relies upon regioselective deprotection of per‐O‐trimethylsilyl‐α‐D‐cholesterylglucoside at C6 followed by phosphoramidite coupling. Global TMS ether deprotection in the presence of oxygen and subsequent deprotection of the cyano ethyl phosphoester afforded the target compounds in 16–21 % overall yield starting from D‐glucose. The structures of these natural products were determined using a combination of 2D NMR methods and mass spectrometry. These robust synthesis and characterization protocols provide analogues to facilitate glycolipidomic profiling and biological studies.
Polydimethylsiloxane: A General Matrix for High‐Performance Chromatographic NMR Spectroscopy
Authors: Huang Shaohua , Gao Jun , Wu Rui , Li Shengying , Bai Zhengwu
Published: September 2014

The detection and structural characterization of the components of a mixture is a challenging task. Therefore, the development of a facile and general method that enables both the separation and the structural characterization of the components is desired. Diffusion‐ordered NMR spectroscopy (DOSY) with the aid of a matrix is a promising tool for this purpose. However, because the currently existing matrices only separate limited components, the application of the DOSY technique is restricted. Herein we introduce a new versatile matrix, poly(dimethylsiloxane), which can fully separate many mixtures of different structural types by liquid‐state NMR spectroscopy. With poly(dimethylsiloxane), liquid‐state chromatographic NMR spectroscopy could become a general approach for the structural elucidation of mixtures of compounds.
Synthesis of Polyketide Stereoarrays Enabled by a Traceless Oxonia‐Cope Rearrangement
Authors: Yang Lin , He Guoli , Yin Ruifeng , Zhu Lili , Wang Xiaoxia , Hong Ran
Published: September 2014

Polyketide antibiotics bearing skipped polyols represent a synthetic challenge. A SiCl4‐promoted oxonia‐Cope rearrangement of syn,syn‐2‐vinyl‐1,3‐diols was developed to forge an array of 1,5‐pentenediols, thus providing versatile motifs for the preparation of 1,2,3,5‐stereoarrays in a highly stereoselective manner. Further exploration with Sn(OTf)2 realized the rearrangement of a cross‐aldehyde which tactically warrants the utility of the current approach to access complex polyketides. The origin of high stereoselectivity is attributed to a chairlike anti‐conformation of the oxonium ion intermediate.
A General Entry to Antifeedant Sesterterpenoids: Total Synthesis of (+)‐Norleucosceptroid A, (−)‐Norleucosceptroid B, and (−)‐Leucosceptroid K
Authors: Hugelshofer Cedric L. , Magauer Thomas
Published: September 2014

The first asymmetric total synthesis of the antifeedant terpenoids (+)‐norleucosceptroid A, (−)‐norleucosceptroid B, and (−)‐leucosceptroid K has been accomplished. This highly concise synthetic route was guided by our efforts to develop a platform for the collective synthesis of a whole family of antifeedant natural products. The synthesis features a Hauser–Kraus‐type annulation followed by an unprecedented, highly efficient intramolecular dilactol aldol‐type condensation reaction to produce the 5,6,5 skeleton. The developed synthetic route proceeds for norleucosceptroid A and B in 16 steps (longest linear sequence) from known compounds.
Self‐Replication and Amplification of Enantiomeric Excess of Chiral Multifunctionalized Large Molecules by Asymmetric Autocatalysis
Authors: Kawasaki Tsuneomi , Nakaoda Mai , Takahashi Yutaro , Kanto Yusuke , Kuruhara Nanako , Hosoi Kenji , Sato Itaru , Matsumoto Arimasa , Soai Kenso
Published: September 2014

Self‐replication of large chiral molecular architectures is one of the great challenges and interests in synthetic, systems, and prebiotic chemistry. Described herein is a new chemical system in which large chiral multifunctionalized molecules possess asymmetric autocatalytic self‐replicating and self‐improving abilities, that is, improvement of their enantioenrichment in addition to the diastereomeric ratio. The large chiral multifunctionalized molecules catalyze the production of themselves with the same structure, including the chirality of newly formed asymmetric carbon atoms, in the reaction of the corresponding achiral aldehydes and reagent. The chirality of the large multifunctionalized molecules controlled the enantioselectivity of the reaction in a highly selective manner to construct multiple asymmetric stereogenic centers in a single reaction.
In Vivo Residue‐Specific Dopa‐Incorporated Engineered Mussel Bioglue with Enhanced Adhesion and Water Resistance
Authors: Yang Byeongseon , Ayyadurai Niraikulam , Yun Hyungdon , Choi Yoo Seong , Hwang Byeong Hee , Huang Jun , Lu Qingye , Zeng Hongbo , Cha Hyung Joon
Published: September 2014

Misaminoacylation of 3,4‐dihydroxyphenylalanine (Dopa) molecules to tRNATyr by endogenous tyrosyl‐tRNA synthetase allowed the quantitative replacement of tyrosine residues with a yield of over 90 % by an in vivo residue‐specific incorporation strategy, to create, for the first time, engineered mussel adhesive proteins (MAPs) in Escherichia coli with a very high Dopa content, close to that of natural MAPs. The Dopa‐incorporated MAPs exhibited a superior surface adhesion and water resistance ability by assistance of Dopa‐mediated interactions including the oxidative Dopa cross‐linking, and furthermore, showed underwater adhesive properties comparable to those of natural MAPs. These results propose promising use of Dopa‐incorporated engineered MAPs as bioglues or adhesive hydrogels for practical underwater applications.
A Layered Hybrid Perovskite Solar‐Cell Absorber with Enhanced Moisture Stability
Authors: Smith Ian C. , Hoke Eric T. , Solis‐Ibarra Diego , McGehee Michael D. , Karunadasa Hemamala I.
Published: September 2014

Two‐dimensional hybrid perovskites are used as absorbers in solar cells. Our first‐generation devices containing (PEA)2(MA)2[Pb3I10] (1; PEA=C6H5(CH2)2NH3+, MA=CH3NH3+) show an open‐circuit voltage of 1.18 V and a power conversion efficiency of 4.73 %. The layered structure allows for high‐quality films to be deposited through spin coating and high‐temperature annealing is not required for device fabrication. The 3D perovskite (MA)[PbI3] (2) has recently been identified as a promising absorber for solar cells. However, its instability to moisture requires anhydrous processing and operating conditions. Films of 1 are more moisture resistant than films of 2 and devices containing 1 can be fabricated under ambient humidity levels. The larger bandgap of the 2D structure is also suitable as the higher bandgap absorber in a dual‐absorber tandem device. Compared to 2, the layered perovskite structure may offer greater tunability at the molecular level for material optimization.
Reglucosylation of the Benzoxazinoid DIMBOA with Inversion of Stereochemical Configuration is a Detoxification Strategy in Lepidopteran Herbivores
Authors: Wouters Felipe C. , Reichelt Michael , Glauser Gaétan , Bauer Eugen , Erb Matthias , Gershenzon Jonathan , Vassão Daniel G.
Published: September 2014

Benzoxazinoids are chemical defenses against herbivores and are produced by many members of the grass family. These compounds are stored as stable glucosides in plant cells and require the activity of glucosidases to release the corresponding toxic aglucones. In maize leaves, the most abundant benzoxazinoid is (2R)‐DIMBOA‐Glc, which is converted into the toxic DIMBOA upon herbivory. The ways in which three Spodoptera species metabolize this toxin were investigated. (2S)‐DIMBOA‐Glc, an epimer of the initial plant compound, was observed in the insect frass, and the associated glucosyltransferase activity was detected in the insect gut tissue. The epimeric glucoside produced by the insect was found to be no longer reactive towards plant glucosidases and thus cannot be converted into a toxin. Stereoselective reglucosylation thus represents a detoxification strategy in Spodoptera species that might help to explain their success as agricultural pests on benzoxazinoid‐containing crops.
Dissecting Ubiquitin Signaling with Linkage‐Defined and Protease Resistant Ubiquitin Chains
Authors: Schneider Tatjana , Schneider Daniel , Rösner Daniel , Malhotra Saurav , Mortensen Franziska , Mayer Thomas U. , Scheffner Martin , Marx Andreas
Published: September 2014

Ubiquitylation is a complex posttranslational protein modification and deregulation of this pathway has been associated with different human disorders. Ubiquitylation comes in different flavors: Besides mono‐ubiquitylation, ubiquitin chains of various topologies are formed on substrate proteins. The fate of ubiquitylated proteins is determined by the linkage‐type of the attached ubiquitin chains, however, the underlying mechanism is poorly characterized. Herein, we describe a new method based on codon expansion and click‐chemistry‐based polymerization to generate linkage‐defined ubiquitin chains that are resistant to ubiquitin‐specific proteases and adopt native‐like functions. The potential of these artificial chains for analyzing ubiquitin signaling is demonstrated by linkage‐specific effects on cell‐cycle progression.
Epitaxial Seeded Growth of Rare‐Earth Nanocrystals with Efficient 800 nm Near‐Infrared to 1525 nm Short‐Wavelength Infrared Downconversion Photoluminescence for In Vivo Bioimaging
Authors: Wang Rui , Li Xiaomin , Zhou Lei , Zhang Fan
Published: September 2014

Novel β‐NaGdF4/Na(Gd,Yb)F4:Er/NaYF4:Yb/NaNdF4:Yb core/shell 1/shell 2/shell 3 (C/S1/S2/S3) multi‐shell nanocrystals (NCs) have been synthesized and used as probes for in vivo imaging. They can be excited by near‐infrared (800 nm) radiation and emit short‐wavelength infrared (SWIR, 1525 nm) radiation. Excitation at 800 nm falls into the “biological transparency window”, which features low absorption by water and low heat generation and is considered to be the ideal excitation wavelength with the least impact on biological tissues. After coating with phospholipids, the water‐soluble NCs showed good biocompatibility and low toxicity. With efficient SWIR emission at 1525 nm, the probe is detectable in tissues at depths of up to 18 mm with a low detection threshold concentration (5 nM for the stomach of nude mice and 100 nM for the stomach of SD rats). These results highlight the potential of the probe for the in vivo monitoring of areas that are otherwise difficult to analyze.
Effects of dual impeller system of Rushton turbine, concave disk turbine and their combinations on the performance of kojic acid fermentation by Aspergillus flavus Link 44‐1
Authors: Suhaili Nurashikin , Tan Joo Shun , Mohamed Mohd‐Shamzi , Halim Murni , Ariff A.B.
Published: September 2014

In the present work, the effects of dual impeller configurations comprising of Rushton turbine (RT) and Concave‐bladed disk turbine (CD‐6) on the oxygen transfer profile and fermentation performance of kojic acid production by Aspergillus flavus Link 44‐1 was investigated. Batch cultivations of A. flavus Link 44‐1 were performed in 2 L stirred tank bioreactor. The fermentations were conducted using different dual impeller systems; (1) RT‐RT, (2) CD6‐CD6, (3) RT‐CD6, and (4) CD6‐RT (bottom‐top impeller). It was perceived that dual CD‐6 system was able to improve oxygen transfer rate by about 25–45% over the hybrids of RT and CD‐6 and the typically configured dual RT system. While no substantial disparity could be seen on the fungal growth rate by the manipulation of the impeller, high concentration of kojic acid (44.93 g L−1) was attained with the use of dual CD‐6 as the mixer. Efficient agitating system that can facilitate good gas dispersion capability is crucially required in order to counteract the problem of oxygen solubility limitation faced in such viscous fungal fermentation broth. The results from this work suggested the promising capability of dual CD‐6 configuration in enhancing productivity of kojic acid fermentation in stirred tank bioreactor. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Influences of different gravity environments on the curing process and cured products of carbon‐nanotube‐reinforced epoxy composites
Authors: Li Defeng , Liu Yuyan , Wang Youshan , Kang Hongjun , Wang Lei , Tan Huifeng
Published: September 2014

The influences of different gravity environments on the curing process and the cured products of carbon‐nanotube‐reinforced epoxy composites were investigated in this study. Different gravity environments were simulated with a superconducting magnet on the basis of which resin matrix composites with different amino‐functionalized multiwalled carbon nanotube (NH2‐MWCNT) concentrations of 0.1, 0.3, 0.5, and 1 wt % were tested. Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, thermomechanical analysis (TMA), thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, and three‐point bending tests were used to analyze the characteristics of different curing processes and cured products. From the results, we observed that the curing rate of the epoxy composites was influenced by different gravity values, and there was anisotropy in the NH2‐MWCNT‐reinforced epoxy composites cured in the simulated microgravity environment. More effects of gravity on the curing process and cured products could be obtained through detailed experiments and discussion; this is important and fundamental for improving and enhancing the properties of composite materials used in different gravity environments. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41413.
Effects of mold cavity temperature on surface quality and mechanical properties of nanoparticle‐filled polymer in rapid heat cycle molding
Authors: Zhang Aimin , Zhao Guoqun , Guan Yanjin
Published: September 2014

Acrylonitrile‐butadiene‐styrene (ABS)/poly methyl methacrylate (PMMA) and ABS/PMMA/nano‐CaCO3 composites were prepared in a corotating twin screw extruder. Single‐gate and double‐gate samples were molded based on a rapid heat cycle molding (RHCM) system. Effects of mold cavity temperature on surface quality and mechanical properties of single‐gate and double‐gate samples in RHCM process were conducted. The results showed that surface quality of plastic parts can be improved significantly by increasing mold cavity temperature. Nano‐CaCO3 particles on the surface of plastic parts can be eliminated by using high mold cavity temperature. The roughness and gloss of two kinds of plastic parts (ABS/PMMA and ABS/PMMA/nano‐CaCO3) stabilized at the same level when the mold cavity temperature is above glass transition temperature of resin material. Weld line can be eliminated in RHCM process during high mold cavity temperature. The tensile strength of both ABS/PMMA and ABS/PMMA/nano‐CaCO3 exhibited decreasing trend with the increase of mold cavity temperature. Reduction of internal stress gave rise to the increase of Izod impact strength of ABS/PMMA for both sing‐gate and double‐gate samples. However, influence regularity of mold cavity temperature on Izod impact strength of ABS/PMMA/nano‐CaCO3 is depended on the number of gates. For all the samples in this study, too high of mold cavity temperature (higher than 125°C) deprave Izod impact strength of plastic parts. Both ABS/PMMA and ABS/PMMA/nano‐CaCO3 are not susceptible to weld line. When the mold surface temperature is approximately equal to glass transition temperature of resin material, all the samples are found to give the best combination of properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41420.
Fragmentation and drying ratchet down Great Plains stream fish diversity
Authors: Perkin Joshuah S. , Gido Keith B. , Costigan Katie H. , Daniels Melinda D. , Johnson Eric R.
Published: September 2014

Stream fragmentation alters the structure of aquatic communities on a global scale, generally through loss of native species. Among riverscapes in the Great Plains of North America, stream fragmentation and hydrologic alteration (flow regulation and dewatering) are implicated in the decline of native fish diversity.

This study documents the spatio–temporal distribution of fish reproductive guilds in the fragmented Arkansas and Ninnescah rivers of south‐central Kansas using retrospective analyses involving 63 years of fish community data.

Pelagic‐spawning fishes declined throughout the study area during 1950–2013, including Arkansas River shiner (Notropis girardi) last reported in 1983, plains minnow (Hybognathus placitus) in 2006, and peppered chub (Macrhybopsis tetranema) in 2012. Longitudinal patterns in fish community structure in both rivers consisted of strong breaks associated with dams, and pelagic‐spawning fishes were missing from shorter fragments upstream of those barriers. Among downstream and longer fragments, probability of occurrence for pelagic‐spawning fishes declined or fell to zero during periods of drought.

Based on these data, interactions between fragmentation and drying are hypothesized as operating as an ecological ratchet mechanism in which forward movement toward pelagic‐spawning fish extirpation occurs during desiccation, and reciprocated reverse movement toward recolonization following return of flows is blocked by fragmentation.

The ratchet mechanism is capable of explaining the long‐term 'ratcheting down' of fish diversity in Great Plains rivers and has implications for managing biodiversity in fragmented riverscapes where water is scarce or might become so in the future.

Copyright © 2014 John Wiley & Sons, Ltd.
A Single 2‐(2′‐Hydroxyphenyl)benzothiazole Derivative Can Achieve Pure White‐Light Emission
Authors: Cheng Jinling , Liu Di , Bao Lijun , Xu Kai , Yang Yang , Han Keli
Published: September 2014

The synthesis and photophysics of two novel 2‐(2′‐hydroxyphenyl)benzothiazole (HBT) derivatives are presented. The electron‐withdrawing trifluoromethyl (CF3) group in compound 1 facilitates the deprotonation of the phenolic hydroxy group. Well‐resolved triple fluorescence from the enol, keto, and phenolic anion, which ranges from 350 to 600 nm, was detected for 1 in ethanol, which marks the first time triple fluorescence from an excited‐state intramolecular proton transfer (ESIPT) molecule has been reported. Both triphenylamine and CF3 were introduced into derivative 2. Intramolecular charge transfer and the “red‐edge effect” resulted in the bathochromic shift of dual fluorescence of 2. Triple fluorescence was also observed for 2 in ethanol. In mixed acetonitrile and ethanol, pure white‐light emission with CIE coordinates of (0.33, 0.33) and a quantum yield of 0.25 was achieved for 2. This work provides a new avenue for the rational design of an ESIPT molecule to achieve white‐light generation under mild conditions.
Noncovalent immobilization of cellulases using the reversibly soluble polymers for biopolishing of cotton fabric
Authors: Yu Yuanyuan , Yuan Jiugang , Wang Qiang , Fan Xuerong , Wang Ping , Cui Li
Published: September 2014

The hydrolytic reaction of cellulases can occur in the interior of cellulosic fibers, causing tensile strength loss of the fabrics. Cellulase immobilization is an approach to solve this problem, because enlarging the molecule size of cellulases will limit the hydrolysis to the surfaces of the fibers. In this study, commercial cellulases were noncovalently immobilized onto the reversibly soluble polymers (Eudragit S‐100 and Eudragit L‐100). The characteristics of cellulase‐Eudragit S‐100 (CES) and cellulase‐Eudragit L‐100 (CEL) were evaluated using Fourier transform infrared spectra, circular dichroism spectra, and fluorescence spectra. The CES showed higher stability than CEL and free cellulase, especially at higher pH and temperature. CES and CEL retained 51% and 42% of their original activities after three cycles of repeated uses, respectively. In addition, the effects of cellulase treatment on the cotton yarn and fabric have been investigated. The bending stiffness results showed that the cotton fabric samples treated with the free and immobilized cellulases were softer than untreated samples. However, less fiber damage in terms of weight loss and tensile strength of treated cotton was observed.
Dermatan sulfate epimerase 1 deficient mice as a model for human abdominal wall defects
Authors: Gustafsson Renata , Stachtea Xanthi , Maccarana Marco , Grottling Emma , Eklund Erik , Malmström Anders , Oldberg Åke
Published: September 2014

Background

Dermatan sulfate (DS) is a highly sulfated polysaccharide with a variety of biological functions in extracellular matrix organization and processes such as tumorigenesis and wound healing. A distinct feature of DS is the presence of iduronic acid, produced by the two enzymes, DS‐epimerase 1 and 2, which are encoded by Dse and Dsel, respectively.

Methods

We have previously shown that Dse knockout (KO) mice in a mixed C57BL/6–129/SvJ background have an altered collagen matrix structure in skin. In the current work we studied Dse KO mice in a pure NFR genetic background.

Results

Dse KO embryos and newborns had kinked tails and histological staining revealed significantly thicker epidermal layers in Dse KO mice when compared with heterozygote (Het) or wild‐type (WT) littermates. Immunochemical analysis of the epidermal layers in newborn pups showed increased expression of keratin 5 in the basal layer and keratin 1 in the spinous layer. In addition, we observed an abdominal wall defect with herniated intestines in 16% of the Dse KO embryos. Other, less frequent, developmental defects were exencephaly and spina bifida.

Conclusion

We conclude that the combination of defective collagen structure in the dermis and imbalanced keratinocyte maturation could be responsible for the observed developmental defects in Dse KO mice. In addition, we propose that Dse KO mice could be used as a model in pathogenetic studies of human fetal abdominal wall defects. Birth Defects Research (Part A) 100:712–720, 2014. © 2014 The Authors Birth Defects Research Part A: Clinical and Molecular Teratology Published by Wiley Periodicals, Inc.