bluuebunny/crossref_metadata_2025 huggingface dataset:
Identification of inactive conformation‐selective interleukin‐2‐inducible T‐cell kinase (ITK) inhibitors based on second‐harmonic generation
Authors: Hantani Yoshiji , Iio Kiyosei , Hantani Rie , Umetani Kayo , Sato Toshihiro , Young Tracy , Connell Katelyn , Kintz Sam , Salafsky Joshua
Published: July 2018

Many clinically approved protein kinase inhibitors stabilize an inactive conformation of their kinase target. Such inhibitors are generally highly selective compared to active conformation inhibitors, and consequently, general methods to identify inhibitors that stabilize an inactive conformation are much sought after. Here, we have applied a high‐throughput, second‐harmonic generation (SHG)‐based conformational approach to identify small molecule stabilizers of the inactive conformation of interleukin‐2‐inducible T‐cell kinase (ITK). A single‐site cysteine mutant of the ITK kinase domain was created, labeled with an SHG‐active dye, and tethered to a supported lipid bilayer membrane. Fourteen tool compounds, including stabilizers of the inactive and active conformations as well as nonbinders, were first examined for their effect on the conformation of the labeled ITK protein in the SHG assay. As a result, inactive conformation inhibitors were clearly distinguished from active conformation inhibitors by the intensity of SHG signal. Utilizing the SHG assay developed with the tool compounds described above, we identified the mechanism of action of 22 highly selective, inactive conformation inhibitors within a group of 105 small molecule inhibitors previously identified in a high‐throughput biochemical screen. We describe here the first use of SHG for identifying and classifying inhibitors that stabilize an inactive vs. an active conformation of a protein kinase, without the need to determine costructures by X‐ray crystallography. Our results suggest broad applicability to other proteins, particularly with single‐site labels reporting on specific protein movements associated with selectivity.
CyberKnife® fixed cone and Iris™ defined small radiation fields: Assessment with a high‐resolution solid‐state detector array
Authors: Biasi Giordano , Petasecca Marco , Guatelli Susanna , Martin Ebert A. , Grogan Garry , Hug Benjamin , Lane Jonathan , Perevertaylo Vladimir , Kron Tomas , Rosenfeld Anatoly B.
Published: July 2018

Purpose

The challenges of accurate dosimetry for stereotactic radiotherapy (SRT) with small unflattened radiation fields have been widely reported in the literature. In this case, suitable dosimeters would have to offer a submillimeter spatial resolution. The CyberKnife® (Accuray Inc., Sunnyvale, CA, USA) is an SRT‐dedicated linear accelerator (linac), which can deliver treatments with submillimeter positional accuracy using circular fields. Beams are delivered with the desired field size using fixed cones, the InCise™ multileaf collimator or a dynamic variable‐aperture Iris™ collimator. The latter, allowing for field sizes to be varied during treatment delivery, has the potential to decrease treatment time, but its reproducibility in terms of output factors (OFs) and dose profiles (DPs) needs to be verified.

Methods

A 2D monolithic silicon array detector, the “Octa”, was evaluated for dosimetric quality assurance (QA) for a CyberKnife system. OFs, DPs, percentage depth‐dose (PDD) and tissue maximum ratio (TMR) were investigated, and results were benchmarked against the PTW SRS diode. Cross‐plane, in‐plane and 2 diagonal dose profiles were measured simultaneously with high spatial resolution (0.3 mm). Monte Carlo (MC) simulations with a GEANT4 (GEometry ANd Tracking 4) tool‐kit were added to the study to support the experimental characterization of the detector response.

Results

For fixed cones and the Iris, for all field sizes investigated in the range between 5 and 60 mm diameter, OFs, PDDs, TMRs, and DPs in terms of FWHM measured by the Octa were accurate within 3% when benchmarked against the SRS diode and MC calculations.

Conclusions

The Octa was shown to be an accurate dosimeter for measurements with a 6 MV FFF beam delivered with a CyberKnife system. The detector enabled real‐time dosimetric verification for the variable aperture Iris collimator, yielding OFs and DPs consistent with those obtained with alternative methods.
The Risk of Ischemic and Hemorrhagic Stroke in Patients With Idiopathic Inflammatory Myopathies: A Swedish Population‐Based Cohort Study
Authors: Moshtaghi‐Svensson John , Lundberg Ingrid E. , Von Euler Mia , Arkema Elizabeth V. , Holmqvist Marie
Published: July 2018

Objective

To study the occurrence of ischemic stroke and hemorrhagic stroke in patients with idiopathic inflammatory myopathies (IIMs) compared to that in the general population and to investigate how it varies by sex, age, clinical subdiagnosis, and time since IIM diagnosis.

Methods

All patients in Sweden with newly diagnosed IIM were identified from the National Patient Register, and general population comparators were identified from the Total Population Register. The study population was followed prospectively until death, emigration, December 2013, or first incident stroke. Incidence rates, rate differences, and hazard ratios (HRs) comparing patients with IIMs to the general population were estimated and stratified by age, sex, type of IIM, and time since diagnosis. To account for the competing risk of death, the subdistribution HR was estimated using Fine and Gray models.

Results

We observed 34 and 229 stroke events in 663 IIM patients and 6,673 comparators, respectively. The HR was elevated for ischemic stroke (HR 2.1 [95% confidence interval (95% CI) 1.4, 3.0]). Few hemorrhagic stroke events were identified, but an increased risk was observed (HR 1.9 (95% CI 0.7, 5.5]). The association remained elevated for both outcomes when taking the competing risk of death into account. For ischemic stroke, the rate difference was highest in the oldest age group (≥68 years), while the HR was highest in the youngest age group (<56 years).

Conclusion

Our findings indicate that the risk of both ischemic stroke and hemorrhagic stroke is increased in patients with IIMs, but it should be kept in mind that stroke is a rare event. Focus on prevention should be directed toward groups with the highest absolute risk, especially older patients.
FtsZ‐Induced Shape Transformation of Coacervates
Authors: Fanalista Federico , Deshpande Siddharth , Lau Anson , Pawlik Grzegorz , Dekker Cees
Published: July 2018

Recently, both the cellular and synthetic biology communities have expressed a strong interest in coacervates, membrane‐less liquid droplets composed of densely packed multivalent molecules that form as a result of spontaneous phase separation. Here, it is studied how FtsZ, a protein that plays a key role in the bacterial division process, remodels coacervates made of polylysine (pLL) and guanosine triphosphate (GTP). It is shown that FtsZ strongly partitions at the surface of the coacervates and induces their disassembly due to the hydrolysis of GTP by FtsZ. Surprisingly, the coacervates are found to promote lateral interactions between FtsZ filaments, inducing the formation of an emanating network of FtsZ bundles that interconnect neighboring coacervates. Under mechanical stress, coacervates are shown to fracture, resulting in profound invaginations along their circumference. The results bring out the potential of coacervates for their use as membrane‐free scaffolds for building synthetic cells as well as are possibly relevant for coacervation in prokaryotic cells.
Reduction of the Sintering Temperature for the Manufacturing of Carbon‐Rich Dense SiOC Bulk Ceramics
Authors: Mantzel Niko , Schröckert Felix , Bucharsky Ethel Claudia , Schell Karl Guenter , Hoffmann Michael J. , Scheffler Michael
Published: July 2018

A major challenge in the processing of compact polymer derived ceramics is the removal of pores. Even after field‐assisted sintering (FAST) under pressure, a certain level of porosity remains within samples and parts. In order to reduce the porosity, a novel route is developed making use of the addition of trimethyl borate to a polysilsesquioxane‐type preceramic polymer system; trimethyl borate is a molecular boron oxide precursor. It is found that boron‐oxide free samples show a high compression rate during field‐assisted sintering between 1400 and 1600 °C, boron oxide and boron oxide/alumina containing samples show this effect already between 1350 and 1500 °C. In a tentative reaction mechanism, this effect is assigned to the formation of a borosilicate glass by chemical reactions of boron oxide with the silica component of the polysiloxane‐derived ceramic; this glassy phase assists the densification process by viscous flow. The porosity in boron oxide‐containing samples is found to be between 0.3% and 1.4% while boron oxide‐free samples show a total porosity of ≈38% after processing under identical conditions.
Fluorination of Black Phosphorus—Will Black Phosphorus Burn Down in the Elemental Fluorine?
Authors: Plutnar Jan , Šturala Jiří , Mazánek Vlastimil , Sofer Zdeněk , Pumera Martin
Published: July 2018

Black phosphorus (BP) represents a promising tunable bandgap alternative to graphene and other 2D materials in the field of semiconductors. However, its reactivity toward covalent modification of its surface (as a key to its bandgap adjustment) is scarcely reported. Here a method of covalent modification of BP involving reaction with fluorine is reported. Other allotropes of phosphorus are known to react violently with fluorine resulting in its complete burning down and formation of gaseous phosphorus pentafluoride. The results of our fluorination experiments conducted in analogy to the procedures used for fluorination of graphene indicate a successful binding of fluorine to BP. This route of modification of BP opens new possible ways toward covalent modification of the surface of this promising material.
On the Cycling Performance of Na‐O2 Cells: Revealing the Impact of the Superoxide Crossover toward the Metallic Na Electrode
Authors: Lin Xiaoting , Sun Qian , Yadegari Hossein , Yang Xiaofei , Zhao Yang , Wang Changhong , Liang Jianneng , Koo Alicia , Li Ruying , Sun Xueliang
Published: July 2018

Na‐O2 batteries have attracted extensive attention as promising candidates for large‐scale energy storage due to their ultrahigh theoretical energy density. However, the poor cycling performance of Na‐O2 batteries is one of the major challenges facing its future development. A novel Na‐O2 battery using electrically connected carbon paper with Na metal as a protected anode is presented in this study. The O2− crossover from the cathode to anode partially contributes to the limited Coulombic efficiency, as well as the Na corrosion during the cycling process. For the cells with protected Na, the carbon paper maintains a pseudo‐equal potential with the Na metal and works as an artificial protective layer to suppress the detrimental side reactions caused by O2− and O2 crossover toward the Na electrode. Furthermore, the short‐circuiting issue caused by Na dendrite growth also can be completely resolved. Consequently, the Na‐O2 cells with protected Na exhibit two times higher discharge capacity and cycling stability compared with the cells using bare Na. These results indicate the crucial role of the Na anode in determining the overall cell performance and a rational design of anode can dramatically contribute to develop advanced Na‐O2 batteries with longer lifespans and better cycling performance.
Chemically Propelled Motors Navigate Chemical Patterns
Authors: Chen Jiang‐Xing , Chen Yu‐Guo , Kapral Raymond
Published: July 2018

Very small synthetic motors that use chemical reactions to drive their motion are being studied widely because of their potential applications, which often involve active transport and dynamics on nanoscales. Like biological molecular machines, they must be able to perform their tasks in complex, highly fluctuating environments that can form chemical patterns with diverse structures. Motors in such systems can actively assemble into dynamic clusters and other unique nonequilibrium states. It is shown how chemical patterns with small characteristic dimensions may be utilized to suppress rotational Brownian motions of motors and guide them to move along prescribed paths, properties that can be exploited in applications. In systems with larger pattern length scales, domains can serve as catch basins for motors through chemotactic effects. The resulting collective motor dynamics in such confining domains can be used to explore new aspects of active particle collective dynamics or promote specific types of active self‐assembly. More generally, when chemically self‐propelled motors operate in far‐from‐equilibrium active chemical media the variety of possible phenomena and the scope of their potential applications are substantially increased.
Mitigating overbidding behavior in agribusiness and food marketing research: Results from induced value hybrid auction experiments
Authors: Ortega David L. , Shupp Robert S. , Nayga Rodolfo M. , Lusk Jayson L.
Published: July 2018

Experimental auctions are a popular and useful tool in understanding demand for food and agricultural products. Bidding behavior often deviates from theoretical predictions in traditional Vickrey and Becker–DeGroot–Marschak (BDM) auction mechanisms. We propose and explore the bidding behavior and demand revealing properties of a hybrid first price‐Vickrey auction and a hybrid first price‐BDM mechanism. Results from a between‐sample, induced value experiment reveal that, relative to traditional mechanisms, the hybrid first price‐Vickrey auction and hybrid first price‐BDM mechanism significantly reduce participants’ likelihood of overbidding, and on average yield bids closer to true valuations. We discuss potential limitations to these hybrid mechanisms as well as implications for their use in eliciting homegrown values that are important for agribusiness and food marketing research. [EconLit citations: C8, C9, Q1, Q13]
Photokeratitis among restaurant workers: A case series
Authors: Stripp Matthew P. , Dulaney Anna R. , Beuhler Michael C. , Langley Ricky L.
Published: July 2018

This case report highlights the challenges associated with the diagnosis and workplace evaluation of occupationally acquired ultraviolet (UV) radiation‐induced photokeratitis and associated skin burns in a group of restaurant workers. UV‐C spectrum bulbs were inadvertently shipped and installed in insect light traps. Ocular and dermal symptoms were reported in 18 of 85 restaurant employees to varying degrees of severity over a 2‐day period. One patient was formally diagnosed with a chemical burn/irritation of the cornea. More severe symptoms were reported by individuals working in close proximity to the lights. This clinical picture can resemble mass chemical or irritant exposure when multiple individuals are affected, and a multidisciplinary approach was required for rapid identification of the source to limit morbidity. Prevention strategies for similar events should be considered which can include limiting hardware compatibility and improving warning labels.
Association between workplace discrimination and depressive symptoms among firefighters in South Korea
Authors: Lee Nagyeong , Kim Ji‐Hwan , Kim Ja Young , Kim Seung‐Sup
Published: July 2018

Background

Workplace discrimination is associated with poor mental health. However, there is a lack of studies examining the effects of discrimination on depressive symptoms among firefighters.

Methods

We analyzed a national cross‐sectional survey of 6369 firefighters in South Korea. Workplace discrimination during the past year was measured and main reasons for the discriminatory experience (gender, birth region, age, education, field/office work, job division) were identified separately by gender and job division. Depressive symptoms during the previous week were measured by the CES‐D11.

Results

Overall, 30.3% of firefighters experienced workplace discrimination and the main reasons for discrimination differed by gender and job division. Firefighters who experienced workplace discrimination had a higher likelihood of depressive symptoms than those who did not after adjusting for potential confounders (PR: 1.73; 95%CI: 1.55, 1.92).

Conclusions

This finding suggests that experience of workplace discrimination could aggravate the mental health of firefighters who provide an important public service.
High exposure mining occupations are associated with obstructive lung disease, National Health Interview Survey (NHIS), 2006‐2015
Authors: Mabila Sithembile L. , Almberg Kirsten S. , Friedman Lee , Cohen Robert
Published: July 2018

Background

The association between mining occupation categories and obstructive lung disease (OLD) has not been well explored in the United States.

Methods

National Health Interview Survey (NHIS) data from 2006 to 2015 was used to determine the relationship between mining occupations and diagnosis of chronic bronchitis, emphysema, chronic obstructive pulmonary disease (COPD), and asthma. We classified occupations into low, moderate, high, and very high dust exposure groups. Extraction workers were categorized as very high dust exposure.

Results

We found 4.5% of miners had chronic bronchitis, 3.3% had emphysema, 6.2% had COPD, and 9.9% had asthma. In fully adjusted models, extraction workers had significantly increased odds of having chronic bronchitis (OR = 2.18 [95%CI: 1.02, 4.64]), emphysema (OR = 7.85 [95%CI: 1.70, 36.27]), and COPD (OR = 2.56 [95%CI: 1.29, 5.12]) compared to lower exposure occupations.

Conclusions

Occupation is an important predictor of OLD in the mining industry
A Curved Noninteracting 2D Electron Gas with Anisotropic Mass
Authors: Souza Pedro H. , Silva Edilberto O. , Rojas Moises , Filgueiras Cleverson
Published: July 2018

In da Costa's thin‐layer approach, a quantum particle moving in a 3D sample is confined to a curved thin interface. At the end, the interface effects are ignored and the quantum particle is localized on a curved surface. A geometric potential arises and, since it is due to this confinement procedure, it depends on the transverse to the surface mass component. The effects due to an anisotropic effective mass on a noninteracting two‐dimensional electron gas confined to a curved surface are reported. By tailoring the mass, many investigations carried out in the literature can be improved, which in turn can be useful to better designing electronic systems without modifying the geometry of the given system. Some examples are examined, such as a particle on a helicoidal surface, on a cylinder, on a catenoid and on a cone, with some possible applications briefly discussed.
TDEG based framework and tools for innovation in teaching technical drawing: The example of LaMoo project
Authors: Villa Valerio , Motyl Barbara , Paderno Diego , Baronio Gabriele
Published: July 2018

This work presents the development of an integrated framework and related tools for innovation and improvement in the teaching of Technical Drawing. This framework is based on the “Technical Drawing Evaluation Grid—TDEG.” This grid is currently used, by the authors, for the definition and the development of different kinds of tools for supporting both teaching and learning and for the evaluation of Technical Drawing and engineering graphics topics knowledge in general. In particular, this paper focuses on the problems related to knowledge evaluation and assessment of Technical Drawing using online tests. Then, the LaMoo project which is a tool under development for the structured construction of questions for online tests in Moodle environment is presented.
A course delivery method by using a software to predict contaminant migration through a soil layer
Authors: Çokça Erdal , Aktaş Tuğçe
Published: July 2018

The authors propose a course delivery method for the contaminant transport through a saturated soil layer to explain contamination of soils in the Environmental Geotechnology course. In civil and environmental engineering education, analytical simulation models help students to understand the processes. MATLAB©‐based simulation method is proposed in this paper, to enhance learning of students of contaminant migration phenomena, and the simulation program is written by the students within the course based on an existing analytical solution for two‐dimensional transport of contaminants in a saturated soil layer. Students use systematic, step‐by‐step problem solving approach while identifying, formulating and solving the contaminant migration problem. The program is written for pulse source and includes advective and dispersive transport as well as sorption and the simulation is used to obtain the profiles of contaminant concentration as a function of distance from the source and time for a steady groundwater velocity. It is shown that the contaminant concentration profiles obtained by simulation demonstrate the processes involved, by this way, the software tool integrates with the rest of the course content. It was seen by the author that, almost all of the students, who are taking Environmental Geotechnology course, could write matlab codes for contaminant migration if guided properly by the instructor/assistant. In this regard, it seems important to conduct studies which will allow students to increase their matlab programming practice. Also the use of the computer simulation encourages the students to ask “what if” questions and to carry out parametric studies and to learn by “discovery.”
Improve the way you communicate with those outside of athletics
Authors: Hope Joan
Published: July 2018

When you communicate with those inside the world of college athletics, you don't have to put too much thought into how to get your message across because you're all speaking the same language. But when you're trying to convey an important issue about athletics to faculty or staff members in other campus departments, do you sometimes encounter a blank stare?
Novel Catechol Derivatives of Arylimidamides as Antileishmanial Agents
Authors: Rezaei Foroogh , Saghaie Lotfollah , Sabet Razieh , Fassihi Afshin , Hatam Gholamreza
Published: July 2018

Two novel bis‐arylimidamide derivatives with terminal catechol moieties (9a and 10a) and two parent compounds with terminal phenyl groups (DB613 and DB884) were synthesized as dihydrobromide salts (9b and 10b). The designed compounds were hybrid molecules consisting of a catechol functionality embedded in an arylimidamide moiety. All compounds were examined for in vitro antiparasitic activity upon promastigotes of Leishmania major and L. infantum as well as axenic amastigotes of L. major. It was shown that conversion of terminal phenyl groups into catechol moieties resulted in more than 10‐fold improvement in potency, coupled with lower cytotoxicity against fibroblast cells, compared to the corresponding parent compounds. The furan‐containing analog 9a exhibited the highest activity with submicromolar IC50 values, ranging from 0.29 to 0.36 μm, which is comparable in efficacy to the reference drug amphotericin B (IC50 0.28 – 0.33 μm). The results justify further study of this class of compounds. It seems that the combination of catechol chelating groups with potent antiparasitic agents could improve the efficacy by presenting novel hybrid compounds.
Hypopharyngeal lipoma—A diagnostic work up
Authors: Jia Wei , Navaratnam Annakan , Lingam Ravi Kumar
Published: July 2018

Key Clinical Message

It is important to examine the pharynx through nasoendoscopic examination in patients that present with dysphagia, to look for pharyngeal masses. Magnetic resonance imaging can accurately diagnose lipoma in the pharynx region.
Mn(III)‐Porphyrin Containing Heterogeneous Catalyst based on Microporous Polymeric Constituents as a New Class of Catalyst Support
Authors: Yi Jigyoung , Jeong Ha Young , Shin Dae Yong , Kim Cheal , Lee Suk Joong
Published: July 2018

Mn(III)‐porphyrin containing #heterogeneous catalyst based on microporous polymeric constituents as a new class of #catalyst support from Korea University and Seoul National University of Science and Technology
A Ceramic‐PVDF Composite Membrane with Modified Interfaces as an Ion‐Conducting Electrolyte for Solid‐State Lithium‐Ion Batteries Operating at Room Temperature
Authors: Yu Jing , Kwok Stephen C. T. , Lu Ziheng , Effat Mohammed B. , Lyu Yu‐Qi , Yuen Matthew M. F. , Ciucci Francesco
Published: July 2018

Solid‐state batteries hold great promise because of their safety and high projected energy density. However, the sizeable interfacial resistance between the electrodes and the electrolyte of such batteries is a significant bottleneck in the development of this technology. In this work, we develop a Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and polyvinylidene fluoride (PVDF) solid‐state composite membrane characterized by high conductivity, tensile strength, and flexibility as well as low impedance if interfacially modified by a minute amount of liquid electrolyte. A solid‐state lithium‐ion battery using this electrolyte with LiFePO4 and Li as electrodes delivers excellent rate capability and cycling stability at room temperature. In particular, the battery shows an initial discharge capacity of 155 mAh g−1 and, after 100 cycles at 1C, of 145 mAh g−1. Even at 4C, the discharge capacity is 96 mAh g−1. Our study suggests that the interfacially modified LLZTO‐PVDF membrane is a promising electrolyte for solid‐state lithium‐ion batteries.
Covalency and Ionicity Do Not Oppose Each Other—Relationship Between Si−O Bond Character and Basicity of Siloxanes
Authors: Fugel Malte , Hesse Maxie F. , Pal Rumpa , Beckmann Jens , Jayatilaka Dylan , Turner Michael J. , Karton Amir , Bultinck Patrick , Chandler Graham S. , Grabowsky Simon
Published: July 2018

Covalency and ionicity are orthogonal rather than antipodal concepts. We demonstrate for the case of siloxane systems [R3Si−(O−SiR2)n−O−SiR3] that both covalency and ionicity of the Si−O bonds impact on the basicity of the Si‐O‐Si linkage. The relationship between the siloxane basicity and the Si−O bond character has been under debate since previous studies have presented conflicting explanations. It has been shown with natural bond orbital methods that increased hyperconjugative interactions of LP(O)→σ*(Si‐R) type, that is, increased orbital overlap and hence covalency, are responsible for the low siloxane basicity at large Si‐O‐Si angles. On the other hand, increased ionicity towards larger Si‐O‐Si angles has been revealed with real‐space bonding indicators. To resolve this ostensible contradiction, we perform a complementary bonding analysis, which combines orbital‐space, real‐space, and bond‐index considerations. We analyze the isolated disiloxane molecule H3SiOSiH3with varying Si‐O‐Si angles, andn‐membered cyclic siloxane systems Si2H4O(CH2)n−3. All methods from quite different realms show that both covalent and ionic interactions increase simultaneously towards larger Si‐O‐Si angles. In addition, we present highly accurate absolute hydrogen‐bond interaction energies of the investigated siloxane molecules with water and silanol as donors. It is found that intermolecular hydrogen bonding is significant at small Si‐O‐Si angles and weakens as the Si‐O‐Si angle increases until no stable hydrogen‐bond complexes are obtained beyondφSiOSi=168°, angles typically displayed by minerals or polymers. The maximum hydrogen‐bond interaction energy, which is obtained at an angle of 105°, is 11.05 kJ mol−1for the siloxane–water complex and 18.40 kJ mol−1for the siloxane–silanol complex.
Fluorophobic Effect Promoting Lamellar Self‐Assembly of Donor Acceptor Dyes
Authors: Haenle Johannes Christian , Stöckl Yannick , Forschner Robert , Haenle Elena , Laschat Sabine
Published: July 2018

To combine liquid crystalline and linear optical properties in the same molecule, the fluorophobic effect was probed for the first time in donor acceptor dyes. Thus, a series of mono‐, bi‐, and tricyclic donor acceptor dyes with 1H,1H‐perfluorinated alkyl chains of different lengths as donor units and nitrile, malononitrile or barbiturate as acceptor units was synthesized in 5 steps and 1.4–6.6 % overall yield. UV/Vis and fluorescence spectroscopy, cyclic voltammetry and DFT calculations revealed that absorption and emission maxima, Stokes shifts and LUMO energies were mainly governed by the chromophore size and acceptor strengths. The perfluorinated chain was electronically almost decoupled from the remaining chromophore and induced only slight changes of the absorption maxima as compared to the alkyl substituted counterparts. However, in contrast to the non‐mesomorphic alkyl donor‐substituted derivatives, the perfluorinated donors resulted in self‐assembly into partially interdigitated SmA bilayers according to differential scanning calorimetry (DSC), polarizing optical microscopy (POM), X‐ray diffraction (WAXS, SAXS) studies and electron density profile calculations.
Pharmacogenomics of Vincristine‐Induced Peripheral Neuropathy Implicates Pharmacokinetic and Inherited Neuropathy Genes
Authors: Wright Galen E.B. , Amstutz Ursula , Drögemöller Britt I. , Shih Joanne , Rassekh Shahrad R. , Hayden Michael R. , Carleton Bruce C. , Ross Colin J.D. ,   The Canadian Pharmacogenomics Network for Drug Safety Consortium
Published: July 2018

Vincristine is an effective chemotherapeutic drug for various cancers, including acute lymphoblastic leukemia (ALL). Unfortunately, clinical utility is restricted by dose‐limiting vincristine‐induced peripheral neuropathies (VIPN). We sought to determine the association of VIPN with a recently identified risk variant, CEP72 rs924607, and drug absorption, distribution, metabolism, and excretion (ADME) gene variants in pediatric ALL. This was followed by a meta‐analysis of pharmacogenomic data from over 500 patients. CEP72 rs924607 was significantly associated with VIPN (P = 0.02; odds ratio (OR) = 3.4). ADME analyses identified associations between VIPN and ABCC1 rs3784867 (P = 5.34 × 10−5; OR = 4.9), and SLC5A7 rs1013940 (P = 9.00 × 10−4; OR= 8.6); genes involved in vincristine transport and inherited neuropathies, respectively. Meta‐analysis identified an association with a variant related to TTPA (rs10504361: P = 6.85 × 10−4; OR = 2.0), a heritable neuropathy‐related gene. This study provides essential corroboratory evidence for CEP72 rs924607 and highlights the importance of drug transporter and inherited neuropathy genes in VIPN.
Enhanced Base‐Free Formic Acid Production from CO2 on Pd/g‐C3N4 by Tuning of the Carrier Defects
Authors: Mondelli Cecilia , Puértolas Begoña , Ackermann Miriam , Chen Zupeng , Pérez‐Ramírez Javier
Published: July 2018

CO2 hydrogenation is attracting increasing attention as a sustainable route to produce formic acid, a commodity and potential energy vector. Here, bifunctional catalysts comprising metal nanoparticles deposited on bulk graphitic carbon nitride were assessed under base‐free conditions, identifying supported Pd as the best performer. The catalyst productivity was enhanced by maximizing the edge‐defects of the g‐C3N4 carrier, amino groups able to activate CO2, and by generating welldispersed 5 nm Pd particles, required to split H2. Bottom‐up synthesis methods, that is, hard‐templating and carbon enrichment upon polymerization, and top‐down strategies, that is, thermal exfoliation of the as‐prepared solid, were explored to boost the defects, the nature and density of which were evaluated by thermal and (in situ) spectroscopic techniques. After optimization of temperature, pressure, and reaction time, a 20 times higher turnover frequency compared with the best Pd/g‐C3N4 catalyst reported producing formic acid from CO2 without base was attained. This activity level was retained upon recycling with intermediate catalyst regeneration at mild temperature.
Understanding the recruitment response of juvenile Neotropical trees to logging intensity using functional traits
Authors: Hogan J. Aaron , Hérault Bruno , Bachelot Bénédicte , Gorel Anaїs , Jounieaux Marianne , Baraloto Christopher
Published: July 2018

Selective logging remains a widespread practice in tropical forests, yet the long‐term effects of timber harvest on juvenile tree (i.e., sapling) recruitment across the hundreds of species occurring in most tropical forests remain difficult to predict. This uncertainty could potentially exacerbate threats to some of the thousands of timber‐valuable tree species in the Amazon. Our objective was to determine to what extent long‐term responses of tree species regeneration in logged forests can be explained by their functional traits. We integrate functional trait data for 13 leaf, stem, and seed traits from 25 canopy tree species with a range of life histories, such as the pioneer Goupia glabra and the shade‐tolerant Iryanthera hostmannii, together with over 30 yr of sapling monitoring in permanent plots spanning a gradient of harvest intensity at the Paracou Forest Disturbance Experiment (PFDE), French Guiana. We anticipated that more intensive logging would increase recruitment of pioneer species with higher specific leaf area, lower wood densities, and smaller seeds, due to the removal of canopy trees. We define a recruitment response metric to compare sapling regeneration to timber harvest intensity across species. Although not statistically significant, sapling recruitment decreased with logging intensity for eight of 23 species and these species tended to have large seeds and dense wood. A generalized linear mixed model fit using specific leaf area, seed mass, and twig density data explained about 45% of the variability in sapling dynamics. Effects of specific leaf area outweighed those of seed mass and wood density in explaining recruitment dynamics of the sapling community in response to increasing logging intensity. The most intense treatment at the PFDE, which includes stand thinning of non‐timber‐valuable adult trees and poison‐girdling for competitive release, showed evidence of shifting community composition in sapling regeneration at the 30‐yr mark, toward species with less dense wood, lighter seeds, and higher specific leaf area. Our results indicate that high‐intensity logging can have lasting effects on stand regeneration dynamics and that functional traits can help simplify general trends of sapling recruitment for highly diverse logged tropical forests.
WASPnest: a worldwide assessment of social Polistine nesting behavior
Authors: Miller Sara E. , Bluher Sarah E. , Bell Emily , Cini Alessandro , Silva Rafael Carvalho da , de Souza André Rodrigues , Gandia Kristine M. , Jandt Jennifer , Loope Kevin , Prato Amanda , Pruitt Jonathan N. , Rankin David , Rankin Erin , Southon Robin J. , Uy Floria M. K. , Weiner Susan , Wright Colin M. , Downing Holly , Gadagkar Raghavendra , Cristina Lorenzi M. , Rusina Lidiya , Sumner Seirian , Tibbetts Elizabeth A. , Toth Amy , Sheehan Michael J.
Published: July 2018

Cooperative breeding decreases the direct reproductive output of subordinate individuals, but cooperation can be evolutionarily favored when there are challenges or constraints to breeding independently. Environmental factors, including temperature, precipitation, latitude, high seasonality, and environmental harshness have been hypothesized to correlate with the presence of cooperative breeding. However, to test the relationship between cooperation and ecological constraints requires comparative data on the frequency and variation of cooperative breeding across differing environments, ideally replicated across multiple species. Paper wasps are primitively social species, forming colonies composed of reproductively active dominants and foraging subordinates. Adult female wasps, referred to as foundresses, initiate new colonies. Nests can be formed by a single solitary foundress (noncooperative) or by multiple foundress associations (cooperative). Cooperative behavior varies within and among species, making paper wasps species well suited to disentangling ecological correlates of variation in cooperative behavior. This data set reports the frequency and extent of cooperative nest founding for 87 paper wasp species. Data were assembled from more than 170 published sources, previously unpublished field observations, and photographs contributed by citizen scientists to online natural history repositories. The data set includes 25,872 nest observations and reports the cooperative behavioral decisions for 45,297 foundresses. Species names were updated to reflect modern taxonomic revisions. The type of substrate on which the nest was built is also included, when available. A smaller population‐level version of this data set found that the presence or absence of cooperative nesting in paper wasps was correlated with temperature stability and environmental harshness, but these variables did not predict the extent of cooperation within species. This expanded data set contains details about individual nests and further increases the power to address the relationship between the environment and the presence and extent of cooperative breeding. Beyond the ecological drivers of cooperation, these high‐resolution data will be useful for future studies examining the evolutionary consequences of variation in social behavior. This data set may be used for research or educational purposes provided that this data paper is cited.
Enantiomeric quality control of R‐Tofisopam by HPLC using polysaccharide‐type chiral stationary phases in polar organic mode
Authors: Foroughbakhshfasaei Mohammadhassan , Szabó Zoltán‐István , Mirzahosseini Arash , Horváth Péter , Tóth Gergő
Published: July 2018

A novel, fast and economic chiral HPLC method was developed and validated for the resolution of the four isomers of tofisopam. The separation capacity of eleven different chiral columns: six polysaccharide‐type including three amylose‐based (Chiralpak AD, Chiralpak AD‐RH and Chiralpak AS) and three cellulose‐based (Chiralcel OD, Chiralcel OJ and Lux Cellulose‐4); three cyclodextrin‐ (Quest‐BC, Quest‐C2 and Quest‐CM) and two macrocyclic glycopeptide antibiotic‐type (Chirobiotic T and Chirobiotic TAG) were screened using polar organic or reversed‐phase mode. Chiralpak AD, based on amylose tris(3,5‐dimethylphenylcarbamate) as chiral selector with neat methanol was identified as the most promising system. In order to improve resolution, an orthogonal experimental design was employed, altering the concentration of 2‐propanol, column temperature, and flow rate in a multivariate manner. Using the optimized method (85/15 v/v methanol/2‐propanol, 40°C, flow rate: 0.7 mL/min) we were not only able to separate the four isomers but also detect 0.1% S‐enantiomer as chiral impurity in R‐tofisopam. This is important since the latter is under development as a single enantiomeric agent. Thermodynamic investigation revealed an unusual entropy and enthalpy‐entropy co‐driven controlled enantioseparation on Chiralcel OJ and on Chiralpak AD column, respectively. Our newly developed HPLC method was validated according to the ICH guidelines and its application was tested on a pharmaceutical formulation containing the racemic mixture of the drug. As a further novelty, a separate circular dichroism method was applied for the investigation of the interconversion kinetics of tofisopam conformers, which proved to be crucial for sample preparation and method validation.
Culturally Responsive Indigenous Evaluation and Tribal Governments: Understanding the Relationship
Authors:   Waapalaneexkweew (Nicole Bowman, Mohican/Lunaape), Dodge‐Francis Carolee
Published: July 2018

Over the last decade, culturally responsive (CR) indigenous evaluation resources have become more readily available to academia and evaluation practitioners within the mainstream literature. This is a direct result of the growing number of Indigenous evaluators in the field; the increased access and opportunities for Indigenous and non‐Indigenous partners collaborating on evaluation projects and academic initiatives; and changes in policy, programming, and funding that better support CR and/or culturally responsive indigenous evaluation (CRIE) initiatives. This chapter examines four overarching content summary areas for CRIE: historical and legal foundations; design approaches; application; and practical CRIE strategies for strengthening professional practice and building evaluation industry capacities for CRIE.
Efficient Vapor‐Phase Selective Hydrogenolysis of Bio‐Levulinic Acid to γ‐Valerolactone Using Cu Supported on Hydrotalcite Catalysts
Authors: Mitta Harisekhar , Seelam Prem Kumar , Chary K. V. Raghava , Mutyala Suresh , Boddula Rajender , Inamuddin  , Asiri Abdullah M.
Published: July 2018

In this work, Cu nanoparticles (Cu NPs, 2‐20 nm) supported on Hydrotalcite catalysts exhibit enhanced selectivity for γ‐valerolactone (GVL) during hydrogenolysis of levulinic acid (LA). At 260 °C, over 3 wt% Cu achieved 87.5% of LA conversion with a maximum GVL selectivity (95%). In contrast, LA hydrogenolysis over 3Cu/Hydrotalcite catalyst is highly active and stable toward the production of GVL due to balanced acido‐basicity and higher Cu dispersion with ultrasmall particle sizes, which are investigated through the temperature programmed desorption (TPD) of ammonia, N2O titration, and transmission electron microscopy (TEM) analysis. Hydrotalcite in combination with inexpensive Cu catalyst is found to be an efficient and environmentally benign for LA hydrogenolysis.
Serum 25-Hydroxyvitamin D and Intact Parathyroid Hormone Influence Muscle Outcomes in Children and Adolescents
Authors: Wright Christian S , Laing Emma M , Pollock Norman K , Hausman Dorothy B , Weaver Connie M , Martin Berdine R , McCabe George P , Peacock Munro , Warden Stuart J , Hill Gallant Kathleen M , Lewis Richard D
Published: July 2018

Increases in 25-hydroxyvitamin D concentrations are shown to improve strength in adults; however, data in pediatric populations are scant and equivocal. In this ancillary study of a larger-scale, multi-sited, double-blind, randomized, placebo-controlled vitamin D intervention in US children and adolescents, we examined the associations between changes in vitamin D metabolites and changes in muscle mass, strength, and composition after 12 weeks of vitamin D3 supplementation. Healthy male and female, black and white children and adolescents between the ages of 9 and 13 years from two US states (Georgia 34°N and Indiana 40°N) were enrolled in the study and randomly assigned to receive an oral vitamin D3 dose of 0, 400, 1000, 2000, or 4000 IU/d for 12 weeks between the winter months of 2009 to 2011 (N = 324). Analyses of covariance, partial correlations, and regression analyses of baseline and 12-week changes (post-baseline) in vitamin D metabolites (serum 25(OH)D, 1,25(OH)2D, intact parathyroid hormone [iPTH]), and outcomes of muscle mass, strength, and composition (total body fat-free soft tissue [FFST], handgrip strength, forearm and calf muscle cross-sectional area [MCSA], muscle density, and intermuscular adipose tissue [IMAT]) were assessed. Serum 25(OH)D and 1,25(OH)2D, but not iPTH, increased over time, as did fat mass, FFST, forearm and calf MCSA, forearm IMAT, and handgrip strength (p < 0.05). Vitamin D metabolites were not associated with muscle strength at baseline nor after the 12-week intervention. Changes in serum 25(OH)D correlated with decreases in forearm IMAT, whereas changes in serum iPTH predicted increases in forearm and calf MCSA and IMAT (p < 0.05). Overall, increases in 25(OH)D did not influence muscle mass or strength in vitamin D-sufficient children and adolescents; however, the role of iPTH on muscle composition in this population is unknown and warrants further investigation. © 2018 American Society for Bone and Mineral Research.
Extraction of rotenoids from Derris elliptica using supercritical CO2
Authors: Baldino Lucia , Scognamiglio Mariarosa , Reverchon Ernesto
Published: July 2018

BACKGROUND

Supercritical (SC)‐CO2 extraction of rotenoids from Derris elliptica roots was proposed using fractional separation of the extracts and operating at increasing pressure.

RESULTS

The best processing conditions were found at 200 bar, 40 °C and 1.2 kg h−1 SC‐CO2 flow rate, obtaining a final product with a concentration of 93% w/w of rotenone and rotenoids, and a yield of active principles of 6.70% w/w with respect to the vegetable matrix. Very small quantities of waxes were found, up to 0.05% w/w; this result can be explained considering the reduced surface‐to‐volume ratio of this vegetable material.

CONCLUSION

Extraction kinetics data confirmed that, in this case, the extraction process was controlled by solubility limitation of the active compounds in the supercritical solvent. © 2018 Society of Chemical Industry
Glycerol valorization to lactic acid catalyzed by hydroxyapatite‐supported palladium particles
Authors: Shen Lingqin , Yu Zhongyong , Zhang Di , Yin Hengbo , Wang Chengtao , Wang Aili
Published: July 2018

BACKGROUND

Catalytic formation of lactic acid from biomass glycerol is a sustainable alternative to the conventional fermentation process starting from carbohydrate and the chemical route using HCN and acetaldehyde. Highly concentrated glycerol can be effectively converted to lactic acid using hydroxyapatite‐supported palladium particles in the presence of NaOH.

RESULTS

The 3% hydroxyapatite‐supported palladium catalyst (Pd3/HAP) demonstrates excellent activity (TOF = 1274 h−1 for a batch time of 90 min) with a high selectivity (95%) towards lactic acid at 99% glycerol conversion (230 °C, NaOH:glycerol molar ratio = 1.1, and glycerol/total Pd intake = 1926). Under the same reaction conditions, the selectivities of lactic acid were 82% and 90% on Pd0.75/HAP and Pd1.5/HAP catalysts, respectively. The Pd3/HAP catalyst was recycled five times in a batch set‐up without a significant drop in activity and lactic acid selectivity, which is indicative of good catalyst stability.

CONCLUSIONS

Pd‐based catalysts on available hydroxyapatite supports are efficient catalysts for glycerol selective oxidation. The catalysts possess active PdO and Pd0 species well dispersed on the functionalized hydroxyapatite support. Pd0 nanoparticles and NaOH synergistically catalyze the reaction process. © 2018 Society of Chemical Industry
Analysis of apparent demonstrations of responding in accordance with relational frames of sameness and opposition
Authors: Alonso‐Álvarez Benigno , Pérez‐González Luis Antonio
Published: July 2018

We evaluated whether contextual control over equivalence and nonequivalence and responding by exclusion can explain the outcomes of relational frame theory (RFT) studies on sameness and opposition relations. We trained nine college students to maintain and reverse conditional discriminations with X1 and X2 as contextual stimuli. In Experiment 1, X1 and X2 controlled derived stimulus relations (DSR) analogous to those controlled by Same and Opposite in RFT studies. These results can be explained by at least two hypotheses: X1 and X2 were cues for equivalence and nonequivalence and responding by exclusion, or for sameness and opposition. In Experiment 2, X1 and X2 controlled DSR predicted by the hypothesis that they were cues for equivalence and nonequivalence and responding by exclusion, and not predicted by the hypothesis that they were cues for sameness and opposition. The results of Experiment 2 and the functional equivalence of X1 and X2 with Same and Opposite in Experiment 1 suggest that Same and Opposite were cues for equivalence and nonequivalence and responding by exclusion in RFT studies.