bluuebunny/crossref_metadata_2025 huggingface dataset:
Ih Block Reveals Separation of Timescales in Pyloric Rhythm Response to Temperature Changes in Cancer borealis
Authors: Schapiro Kyra A , Rittenberg JD , Kenngott Max , Marder Eve
Published: September 2024

Motor systems operate over a range of frequencies and relative timing (phase). We studied the contribution of the hyperpolarization-activated inward current (I
h
) to frequency and phase in the pyloric rhythm of the stomatogastric ganglion (STG) of the crab,
Cancer borealis
as temperature was altered from 11°C to 21°C. Under control conditions, the frequency of the rhythm increased monotonically with temperature, while the phases of the pyloric dilator (PD), lateral pyloric (LP), and pyloric (PY) neurons remained constant. When we blocked I
h
with cesium (Cs
+
) PD offset, LP onset, and LP offset were all phase advanced in Cs
+
at 11°C, and the latter two further advanced as temperature increased. In Cs
+
the steady state increase in pyloric frequency with temperature diminished and the Q
10
of the pyloric frequency dropped from ∼1.75 to ∼1.35. Unexpectedly in Cs
+
, the frequency displayed non-monotonic dynamics during temperature transitions; the frequency initially dropped as temperature increased, then rose once temperature stabilized, creating a characteristic “jag”. Interestingly, these jags were still present during temperature transitions in Cs
+
when the pacemaker was isolated by picrotoxin, although the temperature-induced change in frequency recovered to control levels. Overall, these data suggest that I
h
plays an important role in the ability of this circuit to produce smooth transitory responses and persistent frequency increases by different mechanisms during temperature fluctuations.
Dazzling damselfish: investigating motion dazzle as a defence strategy in humbug damselfish (Dascyllus aruanus)
Authors: Tosetto Louise , Hart Nathan S. , Ryan Laura A.
Published: September 2024

Many animals possess high-contrast body patterns. When moving, these patterns may create confusing or conflicting visual cues that affect a predator’s ability to visually target or capture them, a phenomenon called motion dazzle. The dazzle patterns may generate different forms of optical illusion that can mislead observers about the shape, speed, trajectory and range of the animal. Moreover, it is possible that the disruptive visual effects of the high contrast body patterns can be enhanced when moving against a high contrast background. In this study, we used the humbug damselfish (Dascyllus aruanus) to model the apparent motion cues of its high contrast body stripes against high contrast background gratings of different widths and orientations, from the perspective of a predator. We found with higher frequency gratings, when the background is indiscriminable to a viewer, that the humbugs may rely on the confusing motion cues created by internal stripes. With lower frequency gratings, where the background is likely perceivable by a viewer, the humbugs can rely more on confusing motion cues induced by disruption of edges from both the background and body patterning. We also assessed whether humbugs altered their behaviour in response to different backgrounds. Humbugs remained closer and moved less overall in response to backgrounds with a spatial structure similar to their own striped body pattern, possibly to stay camouflaged against the background and thus avoid revealing themselves to potential predators. At backgrounds with higher frequency gratings, humbugs moved more which may represent a greater reliance on the internal contrast of the fish’s striped body pattern to generate motion dazzle. It is possible that the humbug stripes provide multiple protective strategies depending on the context and that the fish may alter their behaviour depending on the background to maximise their protection.
Visión común y gestión curricular: potenciadores del desarrollo de competencias en la formación técnico profesional
Authors:   , Piña Soto Priscilla
Published: September 2024

Este trabajo corresponde a un estudio de caso con una modalidad de investigación-acción y tiene como objetivo fortalecer las metodologías implementadas en la enseñanza de las competencias de empleabilidad de los estudiantes de un colegio Particular Subvencionado de Formación Técnico Profesional (FTP) de la comuna de San Bernardo, a través de la construcción de una visión común en la integración de las competencias propias de cada especialidad con los Objetivos Transversales Genéricos. Para ello, se utilizaron entrevistas semiestructuradas que brindaron antecedentes para identificar el problema y, posteriormente, se desarrollaron talleres y un grupo focal con el departamento de profesores TP. El análisis de los datos se hizo por medio de un análisis del contenido con un sistema de categorías simple orientado por la teoría ecológica de Bronfenbrenner, lo que permitió establecer conclusiones en los niveles macro, meso y micro. Los resultados reflejan que la existencia de lineamientos comunes, el fortalecimiento de los grupos profesionales de trabajo y la entrega de orientaciones en la gestión curricular de los docentes podría potenciar la enseñanza de los OTG y obtener mejores resultados.
Bioinsumos na agricultura: panorama tecnológico das patentes biológicas
Authors: Santos João Pedro dos , Oliveira Ana Laura Paula de , Putti Fernando Ferrari
Published: September 2024

A produção de bioinsumos tem ganhado espaço na agricultura brasileira com uma alternativa sustentável, auxiliando na demanda de práticas agrícolas que reduzam o uso dos agroquímicos. O uso de bioinsumos é atribuído a fatores como a melhoria na saúde do solo, o aumento da resistência das plantas a pragas e doenças, e a adoção de tecnologias inovadoras no manejo agrícola. Assim, o objetivo deste trabalho foi quantificar, junto à base de dados do INPI, Espacenet e WIPO a totalidade de registros de patentes vinculadas à bioinsumos no país, verificando se há correlação entre o número de registros e o aumento da produtividade agrícola. Foram consultados registros de patentes no período entre 2004 e 2024. O Programa Nacional de Bioinsumos, instituído em 2020, impulsionou a inovação no setor, resultando em um aumento significativo no número de patentes registradas. Além disso, pode-se concluir que o aumento do número de patentes no período analisado coincide com a crescente adoção de bioinsumos na agricultura, o que está relacionado à melhoria da produtividade e à sustentabilidade das práticas agrícolas no Brasil. Essa evolução tecnológica no setor exerce um papel importante para a promoção de soluções inovadoras e sustentáveis no agronegócio.
Development and Content Validation of Iliotibial Band Friction Syndrome Index (IBFS-I)
Authors: Sandeep Ritika, , Saha Joydip , Mishra Lalit , Bhowmik Sunanda
Published: September 2024

Introduction: Activity-related lateral knee discomfort is a common symptom of Iliotibial Band Friction Syndrome (ITBFS), a condition characterised by excessive friction between the iliotibial band and the lateral femoral condyle. Literature indicates that ITBFS is highly prevalent in road cyclists, military recruits, and habitual runners respectively. But there is scarcity of readily usable tool to identify the extent of ITBS. This study was designed to develop and validate the content of a scale for ITBFS diagnosis. Aim: To develop and content validate of the developed tool which will help the physiotherapist to asses easier and earlier. Materials and Methods: This study involves expert opinions from seven different physiotherapy experts in an offline mode. Study was done in 3 phases: Phase 1: The extensive literature exploration Phase 2: Development of questionnaire Phase 3: Content validation of the developed questionnaire. The Delphi method was used to validate the content, which involves expert review panel, examining the domain and its items, assigning a score to each item, and computing the scale level content validity index (S-CVI) and item content validity index (I-CVI). It was performed using Delphi method which includes seeking expert opinion from 7 different expert from the field of physiotherapy on an offline mode, selecting expert review panel, reviewing domain and items, providing score to each item and calculating I-CVI (item content validity index) and scale level content validity index (S-CVI). Results: I-CVI was calculated using (I-CVI= agreed item/number of expert) and found to be 0.98 and S-CVI using (S-CVI=sum of I-CVI scores/Number of items) and found to be 0.9. This developed questionnaire is having excellent I-CVI and S-CVI. The physiotherapists may use the IBFS-I scale for the early identification of ITBFS. Conclusion: The IBFS-I scale may help physiotherapists diagnose ITBFS early. This scale may prove to be an effective tool in assisting the therapist in determining the degree of ITBFS in individuals
Association between Body Mass Index and Heart Rate in School-going Children
Authors: . Tanishak , Bhowmik Sunanda
Published: September 2024

Introduction: The link between Body Mass Index (BMI) and Heart Rate (HR) in school-age children is an important area of study due to its potential impact on health fitness. BMI, a measure of body fat based on height and weight, and heart rate, an indicator of cardiovascular health, are being investigated together to gain a better understanding of children’s overall well-being and potential risks for heart-related issues. Aim: To determine if there is association between body mass index and Heart Rate (HR) in School-going children. Materials and Methods: This was a correlation study, 284 schoolgoing children aged between 6 to 12 years were selected according to the inclusion criteria, and categorised into underweight (uwBMI),normal weight (nBMI), and overweight (owBMI). Their age, height, and weight, gender also was recorded. They underwent a Modified Shuttle Test Paeds (MSTP) procedure three trials each for 3 minute, Pre and Post intervention HR was recorded through a pulse oximeter. Results: The findings of this study suggest poor association for HR Pre_uwBMI was (r=0.38); HR Post_uwBMI was (r=0.71), HR pre_nBMI was (r=0.55), HR post_nBMI was (r=0.44), HR pre_owBMI was (r=0.17); HR post_owBMI was (r=0.28) respectively (p-value_<0.005). Conclusion: This study concludes that, there was no association among different BMI on heart rate of students aged between 06- 12 years
Comparative Study of Different Rapid Multiplication Methods in Black Pepper (Piper nigrum L.) cv. Panniyur - 1
Authors: Khatke Deepali B. , R. C Gajbhiye, , S. B Thorat, , N. V Dalvi, , A. V Mane,
Published: September 2024

The present investigation was conducted during the year 2023-2024. The experiment was conducted in randomized block design with seven treatments namely T1: Raised bed method, T2: Soil mound method, T3: Wooden log method, T4: Serpentine method, T5: Split halves of PVC method, T6: Modified serpentine method, T7: Trench method and each treatment were replicated four times. Among the various treatments studied, the treatment T4 (Serpentine method) recorded maximum number of cuttings per harvest, total number of cuttings harvested per year, sprouting percentage at 30 days after planting (DAP), survival percentage at 45 DAP.
Effect of Different Levels of Uptake Stimulants on the Yield of Dolichos Bean (Lablab purpureus)
Authors: Kumar Narendra , Dekhane Swapnil
Published: September 2024

This case study investigates the impact of different levels of uptake stimulants on the growth and yield of a leguminous vegetable crop Dolichos bean (Lablab purpureus). The field experiment was conducted during the Rabi season of 2024 at agricultural land of ASPEE Foundation based in Palghar, Maharashtra. The study utilized a Randomized Block Design (RBD) with three replications and seven treatments. Each treatment received drenched well-formulated nutrients in different concentration. The highest pod yield was recorded 2.187 ton/ha with the application of 2 ml P star used per liter of water(T2).
For the considered Bauni variety of Dolichos bean, the soil parameters of experimental field are as follows: pH 7.28, Organic Carbon (OC) 0.17%, Electrical Conductivity (EC) 0.84 dS/m, Nitrogen (N) 85.29 kg/ha, Phosphorus (P) 92.19 kg/ha, and Potassium (K) 394.17 kg/ha.
This indicates that the application of appropriate treatments using appropriate crop protection equipment with integrated nutrient management (INM) significantly enhanced both growth and yield parameters of Dolichos bean such as number of pods per cluster, pod weight, number of seeds per pod, pod yield per plant and pod Yield (kg/ha).
Mi RNA's are a Novel Class of Regulatory Genes Associated with Kidney Disease
Authors: Potagani Eswara Rao , Rajarajeshwari D. , Lalitha Laxmi , Kumar R. Viswa , Naidu M. Prasad
Published: September 2024

Introduction: Micro RNA's have been associated with chronic kidney disease progression and mortality. However, mi RNA 223 and mi RNA 192 role in CKD is poorly evaluated.
Aim: The learning aims to find the part of mi RNA 223 and 192 in CKD patients.
Methods: A cross-sectional observational study that included 450 study subjects out of which, 400 were cases and 50 were controls. Biochemical parameters were assessed by ELISA and mi RNA expression levels were evaluated by quantitative PCR.
Results: It was found that mi RNA 223 and 192 were significantly increased in the advancing stages of CKD when compared to controls.
Conclusion: mi RNA 192 and mi RNA 223 can be used as diagnostic markers of CKD.
Effect of Plant Growth Substances on Rhizogenesis of Stem Cuttings in Pointed Gourd (Trichosanthes dioica Roxb.)
Authors: S. Maneesha , T. S. K. K. Kiran Patro , K. Usha Kumari , D. R. Salomi Suneetha
Published: September 2024

An experiment was conducted to know the influence of growth regulators IBA, NAA and salicylic acid with different concentrations on rooting of stem cuttings in pointed gourd (Trichosanthes dioica Roxb.) in College of Horticulture, Venkataramannagudem, during the year 2023-2024. The experiment was laid out by following Factorial Randomized Block Design (FRBD) with twenty treatment combinations which consists of two factors, Factor-1: types of cuttings (male and female) and Factor-2: growth substances (10). By adopting standard methodology, observations on root and shoot growth were recorded and statistically analyzed. Studies on the effects of various growth substances on the formation of roots in cuttings of pointed gourd vines showed that IBA at 150 ppm recorded highest percentage of rooting, the longest root, the number of roots per cutting the number of leaves per cutting, the length of the shoot and the percentage of establishment in main field among various growth substances. In comparison to female cuttings, male cuttings showed a considerably higher percentage of rooting, as well as more roots per cutting, longest root, longest shoot, more leaves per cutting and a higher percentage of establishment in the main field. IBA 150 ppm + male cuttings recorded considerably more roots per cutting and the longest root than the other combinations, according to the interaction between growth substance and type of cutting.
Dynamics of Salinization of Agricultural Areas in Koba (Boffa)
Authors: Camara Saran , Bah Thierno Boubacar , SYLLA Fatoumata , DIALLO Amirou , MARA Fanta
Published: September 2024

Climate change scenarios indicate an increase in soil salinization as a result of sea-level rise and its impact on coastal areas. In Guinea, our understanding of this phenomenon is limited. This article looks at the extent of salinization phenomenon and proposes farmers' solutions to deal with it in Koba area in Boffa, in the Republic of Guinea. The aim of this work is to analyze the changing dynamics of salinization in agricultural areas of Koba in this context of climate change. By the end, in addition to that, a cartographic survey approach with an image processing on QGis 3.4 was used as working method. This result show that salinization in Koba is progressing rapidly and that marine intrusion is now annual rather than cyclical (every 7 years). Several hectares of land have been abandoned because of the rising salinity, which progresses towards the mainland from year to year. In the space of 36 years, 3,196 hac. (6%) of land have been abandoned, which is equivalent to 88.6 hac. Per year (0.17% per year) in Koba. The solutions proposed which deals with the rise in salinity under the influence of climate change in area with early warning systems for forecasting, water management at plot level, combining activities and changing activity if necessary. Local knowledge (the position of birds' nests on plains, direction taken by ants, etc.) is also a key factor.
Observations of ion‐neutral coupling associated with strong electrodynamic disturbances during the 2015 St. Patrick's Day storm
Authors: Zhang Shun‐Rong , Erickson Philip J. , Zhang Yongliang , Wang Wenbin , Huang Chaosong , Coster Anthea J. , Holt John M. , Foster John F. , Sulzer Michael , Kerr Robert
Published: January 2017

We use incoherent scatter radar observations at Millstone Hill (MHO) and Arecibo (AO) and topside ionosphere in situ Defense Meteorological Satellite Program (DMSP) observations during the great geomagnetic storm on 17–18 March 2015 to conduct a focused study on ion‐neutral coupling and storm time ionosphere and thermosphere dynamics. Some of these observations were made around the time of large ionospheric drifts within a subauroral polarization stream (SAPS). During the storm main phase, we identify multiple disturbance characteristics in the North American late afternoon and dusk sector. (1) Strong subauroral westward drifts occurred between 20 and 24 UT near MHO, accompanied by a storm enhanced density plume passage over MHO in the afternoon with a poleward/upward ion drift. The strongly westward flow reached 2000 m/s speed near the poleward plume edge. (2) Prompt penetration electric field signatures, appearing as poleward/upward ion drifts on the dayside over both MHO and AO, were consistent with DMSP vertical drift data and contributed to plume development. (3) Meridional wind equatorward surges occurred during daytime hours at MHO, followed by 2–3 h period oscillations at both MHO and AO. The zonal electric field at AO was strongly correlated with the wind oscillation. (4) Large ion temperature enhancements as well as 50+ m/s upward ion drifts throughout the E and F regions were observed during the SAPS period. These were presumably caused by strong frictional heating due to large plasma drifts. The heating effects appeared to drive significant atmospheric upwelling, and corresponding ion upflow was also observed briefly. This study highlights some of the important effects of fast plasma transport as well as other disturbance dynamics on ion‐neutral coupling during a single intensification period within a great geomagnetic storm.
Three‐compartment structure of subsurface‐intensified mesoscale eddies in the ocean
Authors: Zhang Zhengguang , Zhang Yu , Wang Wei
Published: January 2017

Mesoscale eddies are energetically dominant and pervasive over most of the world's oceans. Among them, many are subsurface intensified with strongest signals in the ocean interior such as mode‐water eddies, which trap water masses with distinctive properties and carry them over long distances. With both Argo profiling floats and atmospheric reanalysis data we showed that the structure of these eddies obeys a universal rule. Hence their three‐dimensional hydrographic fields can be readily reconstructed from very limited information. More interestingly, the volume of water trapped and moved by a mode‐water eddy is much greater than previously thought; it has a three‐compartment structure in the vertical with the mode water being sandwiched between two layers of notably different properties and accounting for only a portion of the total trapped volume.
On the predictive potential of Pc5 ULF waves to forecast relativistic electrons based on their relationships over two solar cycles
Authors: Lam Hing‐Lan
Published: January 2017

A statistical study of relativistic electron (>2 MeV) fluence derived from geosynchronous satellites and Pc5 ultralow frequency (ULF) wave power computed from a ground magnetic observatory data located in Canada's auroral zone has been carried out. The ground observations were made near the foot points of field lines passing through the GOESs from 1987 to 2009 (cycles 22 and 23). We determine statistical relationships between the two quantities for different phases of a solar cycle and validate these relationships in two different cycles. There is a positive linear relationship between log fluence and log Pc5 power for all solar phases; however, the power law indices vary for different phases of the cycle. High index values existed during the descending phase. The Pearson's cross correlation between electron fluence and Pc5 power indicates fluence enhancement 2–3 days after strong Pc5 wave activity for all solar phases. The lag between the two quantities is shorter for extremely high fluence (due to high Pc5 power), which tends to occur during the declining phases of both cycles. Most occurrences of extremely low fluence were observed during the extended solar minimum of cycle 23. The precursory attribute of Pc5 power with respect to fluence and the enhancement of fluence due to rising Pc5 power both support the notion of an electron acceleration mechanism by Pc5 ULF waves. This precursor behavior establishes the potential of using Pc5 power to predict relativistic electron fluence.
Long Minority‐Carrier Diffusion Length and Low Surface‐Recombination Velocity in Inorganic Lead‐Free CsSnI3 Perovskite Crystal for Solar Cells
Authors: Wu Bo , Zhou Yuanyuan , Xing Guichuan , Xu Qiang , Garces Hector F. , Solanki Ankur , Goh Teck Wee , Padture Nitin P. , Sum Tze Chien
Published: January 2017

Sn‐based perovskites are promising Pb‐free photovoltaic materials with an ideal 1.3 eV bandgap. However, to date, Sn‐based thin film perovskite solar cells have yielded relatively low power conversion efficiencies (PCEs). This is traced to their poor photophysical properties (i.e., short diffusion lengths (<30 nm) and two orders of magnitude higher defect densities) than Pb‐based systems. Herein, it is revealed that melt‐synthesized cesium tin iodide (CsSnI3) ingots containing high‐quality large single crystal (SC) grains transcend these fundamental limitations. Through detailed optical spectroscopy, their inherently superior properties are uncovered, with bulk carrier lifetimes reaching 6.6 ns, doping concentrations of around 4.5 × 1017 cm−3, and minority‐carrier diffusion lengths approaching 1 µm, as compared to their polycrystalline counterparts having ≈54 ps, ≈9.2 × 1018 cm−3, and ≈16 nm, respectively. CsSnI3 SCs also exhibit very low surface recombination velocity of ≈2 × 103 cm s−1, similar to Pb‐based perovskites. Importantly, these key parameters are comparable to high‐performance p‐type photovoltaic materials (e.g., InP crystals). The findings predict a PCE of ≈23% for optimized CsSnI3 SCs solar cells, highlighting their great potential.
Comparative Study of Various Pyrazole‐based Anions: A Promising Family of Ionic Derivatives as Insensitive Energetic Materials
Authors: Yin Ping , Mitchell Lauren A. , Parrish Damon A. , Shreeve Jean'ne M.
Published: January 2017

In the design of advanced energetic materials, high‐density explosophores play a pivotal role because of their remarkable enhancement of both density and molecular stability. Using diversified functionalization strategies, a comparative study involving various nitropyrazole anions shows that these are crucially important in determining performance and stability. A promising family of pyrazole‐based energetic ionic derivatives were synthesized and characterized by NMR and IR spectroscopies, and elemental analysis. Among them, 7, 8, 11–13 exhibit favorable overall performance as energetic materials.
Belastungsversuche an einer historischen Eisenbahn‐Gewölbebrücke
Authors: Schacht Gregor , Piehler Jens , Marx Steffen , Müller Jens Z.A.
Published: January 2017

Die Eisenbahn‐Gewölbebrücke über die Aller in Verden wurde im Oktober 2015 nach über 150 Jahren außer Betrieb genommen und im Sommer 2016 endgültig abgebrochen. Durch das entstandene Zeitfenster zwischen Außerbetriebnahme und Abbruch ergab sich bei diesem Bauwerk die außergewöhnliche Chance, das Tragverhalten der Gewölbereihe experimentell mithilfe einer Probebelastung zu untersuchen. Ein Projektteam unter Führung des Instituts für Massivbau der Leibniz Universität Hannover führte im März und im Juni 2016 zwei Belastungsversuche durch und konnte das Tragverhalten des Gewölbes weit oberhalb des Gebrauchslastniveaus unter einer0 maximalen Belastung von ca. 570 t () untersuchen. In den zwei Versuchen konnten unter anderem die Einflüsse der Stirnwand und der Abdichtungsschicht auf das Verformungsverhalten erfasst und durch eine Vielzahl lokaler und globaler Verformungsmessungen quantifiziert werden. Aus den Ergebnissen der Untersuchungen sollen Rechenmethoden und ‐annahmen verbessert werden, damit die Tragsicherheit bestehender Gewölbebrücken zukünftig zuverlässiger und realitätsnäher bewertet werden kann.
Disrupted neural activity patterns to novelty and effort in young adult APOE‐e4 carriers performing a subsequent memory task
Authors: Evans Simon , Dowell Nicholas G. , Tabet Naji , King Sarah L. , Hutton Samuel B. , Rusted Jennifer M.
Published: January 2017

Introduction

The APOE e4 allele has been linked to poorer cognitive aging and enhanced dementia risk. Previous imaging studies have used subsequent memory paradigms to probe hippocampal function in e4 carriers across the age range, and evidence suggests a pattern of hippocampal overactivation in young adult e4 carriers.

Methods

In this study, we employed a word‐based subsequent memory task under fMRI; pupillometry data were also acquired as an index of cognitive effort. Participants (26 non‐e4 carriers and 28 e4 carriers) performed an incidental encoding task (presented as word categorization), followed by a surprise old/new recognition task after a 40 minute delay.

Results

In e4 carriers only, subsequently remembered words were linked to increased hippocampal activity. Across all participants, increased pupil diameter differentiated subsequently remembered from forgotten words, and neural activity covaried with pupil diameter in cuneus and precuneus. These effects were weaker in e4 carriers, and e4 carriers did not show greater pupil diameter to remembered words. In the recognition phase, genotype status also modulated hippocampal activity: here, however, e4 carriers failed to show the conventional pattern of greater hippocampal activity to novel words.

Conclusions

Overall, neural activity changes were unstable in e4 carriers, failed to respond to novelty, and did not link strongly to cognitive effort, as indexed by pupil diameter. This provides further evidence of abnormal hippocampal recruitment in young adult e4 carriers, manifesting as both up and downregulation of neural activity, in the absence of behavioral performance differences.
Discovery of a Potent BTK Inhibitor with a Novel Binding Mode by Using Parallel Selections with a DNA‐Encoded Chemical Library
Authors: Cuozzo John W. , Centrella Paolo A. , Gikunju Diana , Habeshian Sevan , Hupp Christopher D. , Keefe Anthony D. , Sigel Eric A. , Soutter Holly H. , Thomson Heather A. , Zhang Ying , Clark Matthew A.
Published: January 2017

We have identified and characterized novel potent inhibitors of Bruton's tyrosine kinase (BTK) from a single DNA‐encoded library of over 110 million compounds by using multiple parallel selection conditions, including variation in target concentration and addition of known binders to provide competition information. Distinct binding profiles were observed by comparing enrichments of library building block combinations under these conditions; one enriched only at high concentrations of BTK and was competitive with ATP, and another enriched at both high and low concentrations of BTK and was not competitive with ATP. A compound representing the latter profile showed low nanomolar potency in biochemical and cellular BTK assays. Results from kinetic mechanism of action studies were consistent with the selection profiles. Analysis of the co‐crystal structure of the most potent compound demonstrated a novel binding mode that revealed a new pocket in BTK. Our results demonstrate that profile‐based selection strategies using DNA‐encoded libraries form the basis of a new methodology to rapidly identify small molecule inhibitors with novel binding modes to clinically relevant targets.
Tailoring Asymmetric Discharge‐Charge Rates and Capacity Limits to Extend Li‐O2 Battery Cycle Life
Authors: Geaney Hugh , O'Dwyer Colm
Published: January 2017

Widespread issues with the fundamental operation and stability of Li‐O2 cells impact cycle life and efficiency. While the community continues to research ways of mitigating side reactions and improving stability to realize Li‐O2 battery prospects, we show that limiting the depth‐of‐discharge while unbalancing discharge/charge rate symmetry can extend Li‐O2 battery cycle life by ensuring efficient reversible Li2O2 formation, markedly improving cell efficiency. Systematic variation of the discharge/charge currents shows that clogging from discharging the Li‐O2 cell at high current (250 μA) can be somewhat negated by recharging with a lower applied current (50 μA), with a marked improvement in cycle life achievable. Our measurements determined that specific reduction of the depth of discharge in decrements from equivalent capacities of 1000 mAhg−1 to 50 mAhg−1 under symmetric discharge/charge currents of 50 μA strongly affect the cumulative discharge capacity of each cell. A maximum cumulative discharge capacity occurs at ∼10 % depth of discharge (500 mAhg−1) and the cumulative discharge capacity of 39,500 mAhg−1 is significantly greater than that of cells operated at higher and lower depths of discharge. The results emphasize the importance of appropriate discharge/charge rate and depth of discharge selection for other cathode/electrolyte combinations for directly improving the cycle life performance of Li‐O2 batteries.
Systematic Study of Open‐Shell Trigonal Pyramidal Transition‐Metal Complexes with a Rigid‐Ligand Scaffold
Authors: Pinkowicz Dawid , Birk Francisco J. , Magott Michał , Schulte Kelsey , Dunbar Kim R.
Published: January 2017

A family of distorted trigonal pyramidal transition‐metal complexes [MII(N3N)Li(THF)] (M=Mn, Fe, Co, Ni) have been studied as candidates for mononuclear single‐molecule magnets. Magnetic anisotropy of the family depends on the electronic configuration of the central ion, with the Co analogue exhibiting pronounced SMM behavior.
Water‐Soluble Spiropyrans with Inverse Photochromism and Their Photoresponsive Electrostatic Self‐Assembly
Authors: Moldenhauer Daniel , Gröhn Franziska
Published: January 2017

A new type of light responsive nanoscale assemblies based on water‐soluble spiropyrans is presented. We have synthesized four anionic spiropyrans bearing multiple sulfonate groups and investigated their photochromic behavior in aqueous solution. Depending on the pH, either inverse photochromism (acidic conditions) or normal photochromism (alkaline conditions) is found. Kinetic data for the interconversion of the spiropyran and merocyanine isomers including the subsequent slow hydrolysis have been obtained by UV/Vis spectroscopy. The results show that the spiropyrans undergo hydrolysis in both alkaline and acidic solution, while in the latter the rate is far slower than in the former. This prolonged hydrolytic stability together with the inverse photochromism under acidic conditions makes the sulfonated spiropyrans suitable to build photoresponsive nanostructures with cationic polyelectrolytes. We show how the self‐assembly process is driven by electrostatic interactions and how the spiropyrans’ photochromic property allows the size control of the supramolecular objects by visible light. The assembly size is characterized by dynamic light scattering and TEM. In addition, UV/Vis and fluorescence spectroscopy and ζ‐potential measurements help to explain the size change upon visible light irradiation.
Conformational Changes and Competitive Adsorption between Serum Albumin and Hemoglobin on Bioceramic Substrates
Authors: Gruian Cristina Mihaela , Rickert Christian , Nicklisch Sascha C. T. , Vanea Emilia , Steinhoff Heinz‐Jürgen , Simon Simion
Published: January 2017

Traditional methods to analyze interactions and conformational changes of proteins adsorbed onto biomaterials are limited by the protein's associations with the substrate material and the complexity of the surrounding media. We have used EPR spectroscopy in combination with site‐directed spin labeling (SDSL) to investigate single protein and competitive adsorption kinetics of horse hemoglobin (Hgb) and bovine serum albumin (BSA) on a silica–calcium–phosphate bioceramic substrate. Combined continuous wave and pulsed (DEER) EPR techniques were employed to monitor local mobility/flexibility changes within the proteins and tertiary structure dynamics upon adsorption. An alternate labeling technique was introduced to allow for specific quantification of each protein adsorbed to the bioceramic surface. We show that at buffer pH 7.4 and 4.7 the amount of adsorbed hemoglobin was increased by a factor of 4–5 compared with BSA. The tertiary structure of hemoglobin was strongly affected upon adsorption, leading to a dissociation of the tetrameric molecule into monomers or αβ dimers. When the bioceramic substrate was previously functionalized with a layer of BSA, dissociation was reduced by 71 % compared with the untreated surface, indicating a “primer” effect of BSA for better adhesion of the globular hemoglobin.
DNA with Different Local Torsional States Affects RecA‐Mediated Recombination Progression
Authors: Lu Chih‐Hao , Li Hung‐Wen
Published: January 2017

DNA topology is thought to affect DNA enzyme activity. The helical structure of duplex DNA dictates the change of topological states during strand separation when DNA is constrained. During the repair of DNA double‐stranded breaks, the RecA nucleoprotein filament invades DNA and carries out consecutive strand exchange reactions coupled with duplex DNA strand separation. It has been suggested that torsional strain could be generated and its accumulation could inhibit strand exchange. We used hairpin and nicked DNA substrates to test how torsional strain alters the RecA‐mediated strand exchange efficiency. Single‐molecule tethered particle motion (TPM) experiments showed that torsionally constrained hairpin DNA substrates returned nearly no successful strand exchange events catalyzed by RecA. Surprisingly, the strand exchange efficiencies increase in the presence of DNA nicks or loop disruption. The dwell time of transient RecA events in hairpin is shorter compared to those found in nicked or fork DNA substrates, which suggests a limited strand exchange progression in hairpin substrates. Our observation shows that RecA generates local torsional strain during strand exchange, and the inability to dissipate this torsional strain inhibits homologous recombination progression. DNA topological states are thus important regulation measures of DNA recombination.
Investigating Solvent Effects of an Ionic Liquid on Pericyclic Reactions through Kinetic Analyses of Simple Rearrangements
Authors: Keaveney Sinead T. , Haines Ronald S. , Harper Jason B.
Published: January 2017

Simple Cope and Claisen rearrangements were investigated in an ionic liquid and a range of molecular solvents through a series of kinetic studies. Analysis of the solvent effects on the Cope rearrangement of 3‐phenyl‐1,5‐hexadiene indicated that a solvophobic effect was responsible for the observed rate enhancement in the ionic liquid, and that this was due to preferential solvation of the transition state. A similar solvophobic effect contributes to the ionic liquid solvent effect on the Claisen rearrangement of allyl vinyl ether, although the ability of the ionic liquid to stabilise the incipient charges in the transition state also likely contributes to the rate increase observed in the ionic liquid solvent. The activation parameter data suggest that in this case the ionic liquid was interacting with species along the reaction coordinate through general coulombic interactions (more acetonitrile‐like) rather than through hydrogen‐bonding interactions (less ethanol‐like).
Strong Asymmetry in the Perepoxide Bifurcation Mechanism: The Large‐Group Effect in the Singlet Oxygen Ene Reaction with Allylic Alcohols
Authors: Griesbeck Axel G. , Goldfuss Bernd , Jäger Christina , Brüllingen Eric , Lippold Tim , Kleczka Margarethe
Published: January 2017

The singlet oxygen reactions of sterically crowded allylic alcohols result in the preferential formation of γ‐hydroperoxy alcohols with regioselectivities up to 98:2. The kinetic cis effect still prevails in the first, rate‐determining step of this two‐step non‐intermediate ene mechanism (kE‐5/kZ‐5=1.9). The primary allylic alcohol 3 showed no regioselectivity at all, increasing the steric demands at the α carbon and directing the singlet oxygen addition towards the γ carbon up to 98:2 regioselectivity. DFT calculations rationalized these results and show the decisive role of the symmetry‐breaking bifurcation following the early transition states. The use of the products as substrates for the synthesis of five‐ and seven‐membered ring peroxides, namely 4‐methylene‐1,2‐dioxolanes and 6‐methylene‐1,2,4‐trioxepanes, by rare earth metal complexes as Lewis acids is also demonstrated.
A Novel Nebulizer‐Based Continuous Flow Reactor: Introducing the Use of Pneumatically Generated Aerosols for Highly Productive Photooxidations
Authors: Ioannou Georgios I. , Montagnon Tamsyn , Kalaitzakis Dimitris , Pergantis Spiros A. , Vassilikogiannakis Georgios
Published: January 2017

A very effective and highly innovative continuous flow reactor (CFR) for undertaking important large‐scale photooxidations is presented. Until now, two major issues have obstructed the widespread use of photooxidation CFRs: 1) the detrimental effect of poor oxygen solubility on the rate of biphasic gas–liquid reactions and 2) the rapid attenuation of light by solutions which severely limits dimension‐enlarging opportunities. Both problems are nullified by this novel and yet extremely simple reactor design. The reactor operates by nebulizing a photooxidation solution inside a cylindrical chamber surrounded by a low‐energy LED strip. Thus, the interfacial area between the two phases is maximized, leading to greatly improved reaction rates and excellent light penetration. This pneumatic nebulizer‐based photooxygenation system (NebPhotOX) can use air (as the oxygen source) and very concentrated photooxidation solutions. NebPhotOX has very high productivity and could potentially be scaled up easily to work in an industrial setting.
Efficient Cleavage of Lignin–Carbohydrate Complexes and Ultrafast Extraction of Lignin Oligomers from Wood Biomass by Microwave‐Assisted Treatment with Deep Eutectic Solvent
Authors: Liu Yongzhuang , Chen Wenshuai , Xia Qinqin , Guo Bingtuo , Wang Qingwen , Liu Shouxin , Liu Yixing , Li Jian , Yu Haipeng
Published: January 2017

Lignocellulosic biomass is an abundant and renewable resource for the production of biobased value‐added fuels, chemicals, and materials, but its effective exploitation by an energy‐efficient and environmentally friendly strategy remains a challenge. Herein, a facile approach for efficiently cleaving lignin–carbohydrate complexes and ultrafast fractionation of components from wood by microwave‐assisted treatment with deep eutectic solvent is reported. The solvent was composed of sustainable choline chloride and oxalic acid dihydrate, and showed a hydrogen‐bond acidity of 1.31. Efficient fractionation of lignocellulose with the solvent was realized by heating at 80 °C under 800 W microwave irradiation for 3 min. The extracted lignin showed a low molecular weight of 913, a low polydispersity of 1.25, and consisted of lignin oligomers with high purity (ca. 96 %), and thus shows potential in downstream production of aromatic chemicals. The other dissolved matter mainly comprised glucose, xylose, and hydroxymethylfurfural. The undissolved material was cellulose with crystal I structure and a crystallinity of approximately 75 %, which can be used for fabricating nanocellulose. Therefore, this work promotes an ultrafast lignin‐first biorefinery approach while simultaneously keeping the undissolved cellulose available for further utilization. This work is expected to contribute to improving the economics of overall biorefining of lignocellulosic biomass.
Production of long, laminar plasma jets at atmospheric pressure with multiple cathodes
Authors: Wang Cheng , Cui Haichao , Zhang Zelong , Xia Weiluo , Xia Weidong
Published: January 2017

Plasma jets from conventional non‐transferred arc plasma devices are usually operated in turbulent flows at atmospheric pressure. In this paper, a novel non‐transferred arc plasma device with multiple cathodes is introduced to produce long, laminar plasma jets at atmospheric pressure. A pure helium atmosphere is used to produce a laminar plasma jet with a maximum length of >60 cm. The influence of gas components, arc currents, anode nozzle diameter, and gas flow rate on the jet characteristics is experimentally studied. The results reveal that the length of the plasma jet increases with increasing helium content and arc current but decreases with increasing nozzle diameter. As the gas flow rate increases, the length of the plasma jet initially increases and then decreases. Accordingly, the plasma jet is transformed from a laminar state to a transitional state and finally to a turbulent state. Furthermore, the anode arc root behaviours corresponding to different plasma jet flows are studied. In conclusion, the multiple stationary arc roots that exist on the anode just inside the nozzle entrance are favourable for the generation of a laminar plasma jet in this device.
In vitro phase I metabolism of selective estrogen receptor modulators in horse using ultra‐high performance liquid chromatography‐high resolution mass spectrometry
Authors: Kwok Karen Y. , Chan George H. M. , Kwok Wai Him , Wong Jenny K. Y. , Wan Terence S. M.
Published: January 2017

Selective estrogen receptor modulators (SERMs) are chemicals that possess the anti‐oestrogenic activities that are banned ‘in’ and ‘out’ of competition by the World Anti‐Doping Agency (WADA) in human sports, and by the International Federation of Horseracing Authorities (IFHA) in horseracing. SERMs can be used as performance‐enhancing drugs to boost the level of androgens or to compensate for the adverse effects as a result of extensive use of androgenic anabolic steroids (AASs). SERMs have indeed been abused in human sports; hence, a similar threat can be envisaged in horseracing. Numerous analytical findings attributed to the use of SERMs have been reported by WADA‐accredited laboratories, including 42 cases of tamoxifen and 2 cases of toremifene in 2014. This paper describes the identification of the in vitro phase I metabolites of tamoxifen and toremifene using ultra‐high performance liquid chromatography‐high resolution mass spectrometry (UHPLC‐HRMS), with an aim to identify potential screening targets for doping control in equine sports. A total of 13 and 11 in vitro metabolites have been identified for tamoxifen and toremifene, respectively, after incubation with homogenized horse liver. The more prominent in vitro biotransformation pathways include N‐desmethylation, hydroxylation, and carboxylation. In addition, this is the first report of some novel metabolites for both tamoxifen and toremifene with hydroxylation occurring at the N‐methyl moiety. To our knowledge, this is the first study of the phase I metabolism of tamoxifen and toremifene in horses using homogenized horse liver. Copyright © 2017 John Wiley & Sons, Ltd.
Doping control analysis of lithium in horse urine and plasma by inductively coupled plasma mass spectrometry
Authors: Choi Timmy L. S. , Wong Jenny K. Y. , Ho Emmie N. M. , Kwok Wai Him , Leung Gary N. W. , Curl Peter , Wan Terence S. M.
Published: January 2017

Lithium salts are commonly prescribed to treat bipolar disorder in humans. They are effective for the treatment of acute mania and the prophylaxis of manic relapses through long‐term use. Although there is no reported legitimate therapeutic use of lithium in horses, its potential mood‐stabilizing effect, low cost, and ready availability make lithium salt a potential agent of abuse in equine sports, especially for equestrian competition horses. Lithium can be found in soil, plants, and water, as such it is naturally present in the equine body, thus a threshold is necessary to control its misuse in horses. This paper describes the validation of quantification methods for lithium in equine urine and plasma using inductively coupled plasma mass spectrometry (ICP‐MS). Based on a population study of lithium in horse urine and an administration study using a single oral dose of lithium chloride (100 mg) to mimic the daily lithium intake from a diet rich in lithium, a urinary threshold of 5 μg/mL was proposed. Applying this urinary threshold to two other administration studies (a single oral dose of 65 g of lithium chloride, and a single intravenous dose of 2.54 g of lithium chloride), excessive lithium in urine could be detected for 8 days and 2.5 days respectively. The concentrations of lithium in plasma following these three lithium chloride administration trials were also studied. Copyright © 2017 John Wiley & Sons, Ltd.
Preparation and characterization of glycyrrhetinic‐acid loaded PEG‐modified liposome based on PEG‐7 glyceryl cocoate
Authors: Jia Hong‐Jiao , Jia Fang‐Ya , Zhu Bi‐Jun , Zhang Wan‐Ping
Published: January 2017

The aim of the study was to develop a kind of glycyrrhetinic acid (GA) liposome modified by PEG‐7 glyceryl cocoate for cosmetic use. Encapsulation efficiency, particle morphology, particle size, zeta potential, and Fourier transform infrared spectroscopy (FTIR) were studied to get its physico‐chemical properties. Release property, skin permeation in vitro, and storage stability were also investigated to evaluate the application performance. The results showed that the PEG‐modified liposomes were spherical particles with mean particle size of 117 ± 4.6 nm. Zeta potential and average encapsulation efficiency were −22.5 ± 0.54 mv and 91.9 ± 2.43%, respectively. The FTIR results indicated that GA had been loaded successfully into the liposomes. Compared with the non‐PEG‐modified liposomes, the PEG‐modified GA liposomes showed lower release rate and higher deposition in epidermis/dermis in vitro study, and also possessed better stability according to the little change of particle size during 30 days.

Practical applications: Liposomes are widely used in drug delivery system but rarely used in cosmetics. It is necessary to develop a kind of liposome especially for cosmetic use. Different from other non‐modified liposomes, all of the materials used in this study are non‐toxic which guarantee the safety. The high liposome concentration up to 10% w/w also makes it efficient in large‐scale production. Furthermore, the cooperation of PEG‐7 glyceryl cocoate could prolong the release rate of GA from liposomes, and thus, achieve a better application performance. These results indicate that PEG‐modified liposomes can be a potential delivery system for the water‐insoluble GA and be used in cosmetics.

The forming mechanism of the GA modified liposome in this chart was as follows: the water insoluble GA dissolved in the PEG‐7 glyceryl cocoate and the organic phase of phospholipids was put into the water phase at the same time, the phospholipid molecules wrapped the GA in the bilayers and the PEG‐7 glyceryl cocoate was bonded to the hydrophilic group of liposome vesicles. This structure made the liposome more smaller and higher encapsulation efficiency, and it also brought a prolonged release rate and better drug deposition in epidermis compare with the non‐modified ones.