bluuebunny/crossref_metadata_2025 huggingface dataset:
Supersonic Cold Spraying for Energy and Environmental Applications: One‐Step Scalable Coating Technology for Advanced Micro‐ and Nanotextured Materials
Authors: An Seongpil , Joshi Bhavana , Yarin Alexander L. , Swihart Mark T. , Yoon Sam S.
Published: November 2019

Supersonic cold spraying is an emerging technique for rapid deposition of films of materials including micrometer‐size and sub‐micrometer metal particles, nanoscale ceramic particles, clays, polymers, hybrid materials composed of polymers and particulates, reduced graphene oxide (rGO), and metal–organic frameworks. In this method, particles are accelerated to a high velocity and then impact a substrate at near ambient temperature, where dissipation of their kinetic energy produces strong adhesion. Here, recent progress in fundamentals and applications of cold spraying is reviewed. High‐velocity impact with the substrate results in significant deformation, which not only produces adhesion, but can change the particles' internal structure. Cold‐sprayed coatings can also exhibit micro‐ and nanotextured morphologies not achievable by other means. Suspending micro‐ or nanoparticles in a liquid and cold‐spraying the suspension produces fine atomization and even deposition of materials that could not otherwise be processed. The scalability and low cost of this method and its compatibility with roll‐to‐roll processing make it promising for many applications, including ultrathin flexible materials, solar cells, touch‐screen panels, nanotextured surfaces for enhanced heat transfer, thermal and electrical insulation films, transparent conductive films, materials for energy storage (e.g., Li‐ion battery electrodes), heaters, sensors, photoelectrodes for water splitting, water purification membranes, and self‐cleaning films.
Directional Janus Metasurface
Authors: Chen Ke , Ding Guowen , Hu Guangwei , Jin Zhongwei , Zhao Junming , Feng Yijun , Jiang Tian , Alù Andrea , Qiu Cheng‐Wei
Published: November 2019

Janus monolayers, a class of two‐faced 2D materials, have received significant attention in electronics, due to their unusual conduction properties stemming from their inherent out‐of‐plane asymmetry. Their photonic counterparts recently allowed for the control of hydrogenation/dehydrogenation processes, yielding drastically different responses for opposite light excitation spins. A passive Janus metasurface composed of cascaded subwavelength anisotropic impedance sheets is demonstrated. By introducing a rotational twist in their geometry, asymmetric transmission with the desired phase function is realized. Their broken out‐of‐plane symmetry realizes different functions for opposite propagation directions, enabling direction‐dependent versatile functionalities. A series of passive Janus metasurfaces that enable functionalities including one‐way anomalous refraction, one‐way focusing, asymmetric focusing, and direction‐controlled holograms are experimentally demonstrated.
FDTS‐Modified SiO2/rGO Wrinkled Films with a Micro‐Nanoscale Hierarchical Structure and Anti‐Icing/Deicing Properties under Condensation Condition
Authors: Chu Zhenming , Jiao Weicheng , Huang Yifan , Ding Guomin , Zhong Xue , Yan Meiling , Zheng Yongting , Wang Rongguo
Published: November 2019

Icing accretion on the surface of an aircraft not only increases the weight but also causes changes in the surface shape, so there is an urgent need for anti‐icing/deicing without shutdown. Here, a graphene‐based film with light weight, super‐hydrophobicity, high electric heat, and durability, which has both anti‐icing properties and electrothermal deicing capability, is proposed. The film is prepared with 1H,1H,2H,2H‐perfluorodecyltrichlorosilane (FDTS)‐modified SiO2/rGO wrinkles, and it has a micro‐nanoscale hierarchical structure. Moreover, the superhydrophobic properties of the film can be controlled by adjusting the wrinkle size. Because of its good water repellency, the film can prevent and delay the freezing of water droplets at low temperatures. At −10 °C, compared to a smooth rGO film, the icing time of 10 µL supercooled water droplet on the micro‐nanoscale hierarchical structured film can be delayed by ≈8.3 times, and the ice adhension decreases greatly. In addition, the film exhibits high‐efficiency electrothermal properties. At −10 °C, under a low voltage of 15 V, the film can be heated rapidly to achieve rapid deicing and defrosting. The graphene‐based micro‐nanoscale hierarchical structure shows great potential in the field of sky anti‐icing and real‐time deicing.
3D Helical Micromixer Fabricated by Micro Lost‐Wax Casting
Authors: Tachibana Daiki , Matsubara Ken , Matsuda Ryosuke , Furukawa Taichi , Maruo Shoji , Tanaka Yoshimi , Fuchiwaki Ohmi , Ota Hiroki
Published: November 2019

Micromixers produced by micro fabrication techniques have attracted attention for micro total analysis systems and lab‐on‐a‐chip applications in point‐of‐care testing. However, the fabrication and setup of micromixers have become more complex and more difficult. Considering the practical use of micromixers in medical and industrial applications, their designs can be simplified while maintaining high mixing efficiency. Rapid prototyping, represented by 3D printing having micro‐scale resolutions, is one promising technology to replace conventional fabrication methods such as soft lithography. Here, a 3D helical micromixer fabricated by micro‐scale lost‐wax casting is reported. The molds for lost‐wax casting are fabricated by fine 3D printing of a hard wax resin which can be removed from a polydimethylsiloxane block just by heating and washing with water, and a fine and smooth structure is realized. The optimized helical micromixer fabricated by lost‐wax casting promotes mixing efficiency compared with other micromixers. In addition, a monolithic microchannel having the helical 3D bridge structure is presented in this study. The demonstration is an important advancement toward the industrial applications of micromixers fabricated by micro‐scale 3D printing. The ability to fabricate complex structures can simply lead to the creation of more sophisticated mixers in the future.
Developments and Perspectives in 3d Transition‐Metal‐Based Electrocatalysts for Neutral and Near‐Neutral Water Electrolysis
Authors: Anantharaj Sengeni , Aravindan Vanchiappan
Published: November 2019

Technology for producing highly pure hydrogen (99.999%) by water electrolysis is a field of importance in terms of the planets' current energy scenario. A much needed transition from a carbon economy to a hydrogen economy further adds importance to the field of hydrogen generation from water for a sustainable future. To avoid energy losses in the production process, the use of highly acidic (Proton Exchange Membrane (PEM) water electrolyzer) and alkaline (alkaline water electrolyzer) electrolytes is conventional practice in this field. Unfortunately, there are several other issues associated with the use of acidic and alkaline electrolytes such as the requirement of specific ion exchanging membranes with good stability, acid or alkali stable catalysts and corrosive environment withstanding cell stacks, etc. To overcome these issues, researchers have shown interest in the field of electrochemical water splitting in neutral and near‐neutral conditions. In this review, the chronological development of 3d transition‐metal‐based electrocatalysts for neutral and near‐neutral water splitting is extensively discussed with emphases on screening methodologies, mechanisms, structure‐activity correlations, and detailed catalyst specific evolution. In addition, catalysts reported so far, are also benchmarked based on their performance separately for different electrolytes used.
Bioinspired Binders Actively Controlling Ion Migration and Accommodating Volume Change in High Sulfur Loading Lithium–Sulfur Batteries
Authors: Jin Biyu , Yang Lifeng , Zhang Jiawen , Cai Yongjie , Zhu Juan , Lu Jianguo , Hou Yang , He Qinggang , Xing Huabin , Zhan Xiaoli , Chen Fengqiu , Zhang Qinghua
Published: November 2019

High‐loading lithium–sulfur batteries have gained considerable fame for possessing high area capacity, but face a stern challenge from capacity fading because of serious issues, including “polysulfides shuttling,” insulating S/Li2S, large volume changes, and the shedding of S/C particles during drying or the cell encapsulation process. Herein, a bioinspired water‐soluble binder framework is constructed via intermolecular physical cross‐linking of functional side chains hanging on the terpolymer binder. Experimental results and density‐functional theory (DFT) calculations reveal that this network binder featuring superior volume change accommodation can also capture lithium polysulfides (LiPSs) through strong anchoring of O, N+ actives to LiPSs by forming Li···O and N+···Sx2− bonds. In addition, the abundant negative charged sulfonate coordination sites and good electrolyte uptake of the designed binder endow the assembled cells with high lithium ion conductivity and fast lithium ion diffusion. Consequently, a remarkable capacity retention of 98% after 350 cycles at 1 C and a high areal capacity of 12.8 mA h cm−2 with high sulfur loading of 12.0 mg cm−2 are achieved by applying the environmentally friendly binder.
Determinants of low birth weight in India: An investigation from the National Family Health Survey
Authors: Khan Nizamuddin , Mozumdar Arupendra , Kaur Supreet
Published: November 2019

Objective

This study aimed to estimate the change in prevalence of low birth weight (LBW) over the last decade in India and to identify its associated factors—biological, demographic, socio‐economic, and programmatic.

Methods

We used the data from the National Family Health Survey of 2005‐2006 (NFHS‐3) and 2015‐2016 (NFHS‐4). The sample of this study included 11 300 children from NFHS‐3 and 99 894 from NFHS‐4 data; all these children were the last full‐term singleton live‐births, born within the last 3 years prior to the survey.

Results

In India, the prevalence of LBW has significantly declined from 20.4% (95%CI 19.4‐21.4) to 16.4% (95% CI 16.1‐16.8) in the last decade. The prevalence of LBW remained high in girl children (OR = 1.2, 95% CI 1.2‐1.3; P < .001), whose mothers were adolescent (OR = 1.2, 95% CI 1.1‐1.3; P < .001), and were stunted (OR = 1.3, 95% CI 1.3‐1.3; P < .001). Prevalence of LBW declined among second or higher birth order child (OR = 0.8, 95% CI 0.8‐0.9; P < .001), whose mothers educated up to secondary level and above (OR = 0.6 to 0.8), belonged to rich wealth quintiles (OR = 0.9 to 0.8), were from rural area (OR = 0.9, 95% CI 0.9‐1.0; P < .001), received better nutrition and adequate antenatal care (OR = 0.8, 95% CI 0.8‐0.8; P < .001), and were from eastern, northeastern, and southern regions of India (OR = 0.9 to 0.5).

Conclusion

Although the prevalence of LBW in India has declined over the past decade, the extent of the decline is modest. In the coming years, health programs in India need to gear up with greater convergence between maternal health services and maternal nutrition to reduce LBW.
Clinical report and biochemical analysis of a patient with fumarate hydratase deficiency
Authors: Grocott Olivia , Phanor Sabrina K. , Fung France , Thibert Ronald L. , Berkmen Melanie B.
Published: November 2019

Fumarate hydratase deficiency (FHD) is a rare metabolic disease caused by two defective copies of the FH gene, which encodes the Krebs cycle enzyme fumarase. FHD is associated with brain and developmental abnormalities, seizures, and high childhood mortality. We describe the symptoms and treatment of a patient with FHD. While infantile spasms are common in FHD, the patient presented with epileptic spasms later in childhood. Also unexpectedly, the patient responded excellently to lacosamide for her non‐convulsive status epilepticus and epileptic spasms after three first‐line medication trials failed. We biochemically analyzed the patient's two fumarase variants (E432Kfs*17 and D65G). While E432Kfs*17 was extremely enzymatically defective, D65G exhibited only a mild defect, possibly playing a role in the patient's longer survival.
5‐HT2AR and BDNF gene variants in eating disorders susceptibility
Authors: Ceccarini M. Rachele , Tasegian Anna , Franzago Marica , Patria F. Filomena , Albi Elisabetta , Codini Michela , Conte Carmela , Bertelli Matteo , Dalla Ragione Laura , Stuppia Liborio , Beccari Tommaso
Published: November 2019

Evidence from family and twin studies points to a genetic contribution to the etiology of eating disorders (EDs), confirmed by the association of several single nucleotide polymorphisms (SNPs) with this group of disorders. Previous reports have suggested that the serotonin receptor (5‐HT2AR) and brain‐derived neurotrophic factor (BDNF) genes could be both involved in EDs susceptibility. In order to provide further evidence about such association, we focused our attention on two SNPs located in these genes carrying out a genetic association study on a large Italian cohort composed of 556 ED patients and 355 controls (CTRs). Obtained results confirm the presence of an association between 5‐HT2AR and BDNF genes and the susceptibility to EDs.
Theranostic Layer‐by‐Layer Nanoparticles for Simultaneous Tumor Detection and Gene Silencing
Authors: Boehnke Natalie , Correa Santiago , Hao Liangliang , Wang Wade , Straehla Joelle P. , Bhatia Sangeeta N. , Hammond Paula T.
Published: November 2019

Layer‐by‐layer nanoparticles (NPs) are modular drug delivery vehicles that incorporate multiple functional materials through sequential deposition of polyelectrolytes onto charged nanoparticle cores. Herein, we combined the multicomponent features and tumor targeting capabilities of layer‐by‐layer assembly with functional biosensing peptides to create a new class of nanotheranostics. These NPs encapsulate a high weight percentage of siRNA while also carrying a synthetic biosensing peptide on the surface that is cleaved into a urinary reporter upon exposure to specific proteases overexpressed in the tumor microenvironment. Importantly, this biosensor reports back on a molecular signature characteristic to metastatic tumors and associated with poor prognosis, MMP9 protease overexpression. This nanotheranostic mediates noninvasive urinary‐based diagnostics in mouse models of three different cancers with simultaneous gene silencing in flank and metastatic mouse models of ovarian cancer.
Antiperovskite Intermetallic Nanoparticles for Enhanced Oxygen Reduction
Authors: Zhang Hao , Xia Wei , Shen Haoming , Guo Wenhan , Liang Zibin , Zhang Kexin , Wu Yingxiao , Zhu Bingjun , Zou Ruqiang
Published: November 2019

Antiperovskite Co3InC0.7N0.3 nanomaterials with highly enhanced oxygen reduction reaction (ORR) performance were prepared by tuning nitrogen contents through a metal–organic framework (MOF)‐derived strategy. The nanomaterial surpasses all reported noble‐metal‐free antiperovskites and even most perovskites in terms of onset potential (0.957 V at J=0.1 mA cm−2) and half‐wave potential (0.854 V). The OER and zinc–air battery performance demonstrate its multifunctional oxygen catalytic activities. DFT calculation was performed and for the first time, a 4 e− dissociative ORR pathway on (200) facets of antiperovskite was revealed. Free energy studies showed that nitrogen substitution could strengthen the OH desorption as well as hydrogenation that accounts for the enhanced ORR performance. This work expands the scope for material design via tailoring the nitrogen contents for optimal reaction free energy and hence performance of the antiperovskite system.
“Design of Experiments” as a Method to Optimize Dynamic Disulfide Assemblies: Cages and Functionalizable Macrocycles
Authors: Shear Trevor A. , Lin Fuding , Zakharov Lev N. , Johnson Darren W.
Published: November 2019

Cyclophanes are a venerable class of macrocyclic and cage compounds that often contain unusual conformations, high strain, and unusual properties. However, synthesis of complex, functional derivatives remains difficult due to low functional group tolerance, high dilution, extreme reaction conditions, and sometimes low yields using traditional stepwise synthetic methods. “Design of experiments” (DOE) is a method employed for the optimization of reaction conditions, and we showcase this approach to generate a dramatic increase in the yield of specific targets from two different self‐assembling systems. These examples demonstrate that DOE provides an additional tool in tuning self‐assembling, dynamic covalent systems.
Phosphine‐Catalyzed [4+1] Cycloadditions of Allenes with Methyl Ketimines, Enamines, and a Primary Amine
Authors: Cao Ze‐Hun , Wang Yu‐Hao , Kalita Subarna Jyoti , Schneider Uwe , Huang Yi‐Yong
Published: November 2019

Unprecedented phosphine‐catalyzed [4+1] cycloadditions of allenyl imides have been discovered using various N‐based substrates including methyl ketimines, enamines, and a primary amine. These transformations provide a one‐pot access to cyclopentenoyl enamines and imines, or (chiral) γ‐lactams through two geminal C−C bond or two C−N bond formations, respectively. Several P‐based key intermediates including a 1,4‐(bis)electrophilic α,β‐unsaturated ketenyl phosphonium species have been detected by 31P NMR and HRMS analyses, which shed light on the postulated catalytic cycle. The synthetic utility of this new chemistry has been demonstrated through a gram‐scaling up of the catalytic reaction as well as regioselective hydrogenation and double condensation to form cyclopentanoyl enamines and fused pyrazole building blocks, respectively.
Electrolyte Regulation towards Stable Lithium‐Metal Anodes in Lithium–Sulfur Batteries with Sulfurized Polyacrylonitrile Cathodes
Authors: Chen Wei‐Jing , Li Bo‐Quan , Zhao Chang‐Xin , Zhao Meng , Yuan Tong‐Qi , Sun Run‐Cang , Huang Jia‐Qi , Zhang Qiang
Published: November 2019

Lithium–sulfur (Li–S) batteries are highly regarded as the next‐generation energy‐storage devices because of their ultrahigh theoretical energy density of 2600 Wh kg−1. Sulfurized polyacrylonitrile (SPAN) is considered a promising sulfur cathode to substitute carbon/sulfur (C/S) composites to afford higher Coulombic efficiency, improved cycling stability, and potential high‐energy‐density Li–SPAN batteries. However, the instability of the Li‐metal anode threatens the performances of Li–SPAN batteries bringing limited lifespan and safety hazards. Li‐metal can react with most kinds of electrolyte to generate a protective solid electrolyte interphase (SEI), electrolyte regulation is a widely accepted strategy to protect Li‐metal anodes in rechargeable batteries. Herein, the basic principles and current challenges of Li–SPAN batteries are addressed. Recent advances on electrolyte regulation towards stable Li‐metal anodes in Li–SPAN batteries are summarized to suggest design strategies of solvents, lithium salts, additives, and gel electrolyte. Finally, prospects for future electrolyte design and Li anode protection in Li–SPAN batteries are discussed.
Responsive Exosome Nano‐bioconjugates for Synergistic Cancer Therapy
Authors: Nie Weidong , Wu Guanghao , Zhang Jinfeng , Huang Li‐Li , Ding Jingjing , Jiang Anqi , Zhang Yahui , Liu Yanhong , Li Jingchao , Pu Kanyi , Xie Hai‐Yan
Published: November 2019

Exosomes hold great potential in therapeutic development. However, native exosomes usually induce insufficient effects in vivo and simply act as drug delivery vehicles. Herein, we synthesize responsive exosome nano‐bioconjugates for cancer therapy. Azide‐modified exosomes derived from M1 macrophages are conjugated with dibenzocyclooctyne‐modified antibodies of CD47 and SIRPα (aCD47 and aSIRPα) through pH‐sensitive linkers. After systemic administration, the nano‐bioconjugates can actively target tumors through the specific recognition between aCD47 and CD47 on the tumor cell surface. In the acidic tumor microenvironment, the benzoic‐imine bonds of the nano‐bioconjugates are cleaved to release aSIRPα and aCD47 that can, respectively, block SIRPα on macrophages and CD47, leading to abolished “don't eat me” signaling and improved phagocytosis of macrophages. Meanwhile, the native M1 exosomes effectively reprogram the macrophages from pro‐tumoral M2 to anti‐tumoral M1.
Functional and Structural Adaptations of Skeletal Muscle in Long‐Term Juvenile Dermatomyositis: A Controlled Cross‐Sectional Study
Authors: Berntsen Kristin Schjander , Raastad Truls , Marstein Henriette , Kirkhus Eva , Merckoll Else , Cumming Kristoffer Toldnes , Flatø Berit , Sjaastad Ivar , Sanner Helga
Published: November 2019

Objective

To compare muscle strength and endurance of the knee extensors between patients with long‐term juvenile dermatomyositis (DM) and controls and between patients with active disease and those with inactive disease, and to explore associations between strength/endurance and 1) clinical parameters, 2) physical activity, and 3) humoral/structural adaptation in the skeletal muscle of patients.

Methods

In a cross‐sectional study (44 patients and 44 age‐ and sex‐matched controls), we tested isometric muscle strength (peak torque, in Nm) and dynamic muscle endurance (total work, in Joules) of the knee extensors, physical activity (measured by accelerometer), and serum myokine levels (by enzyme‐linked immunosorbent assay). Patients were examined with validated tools (clinical muscle tests and measures of disease activity/damage and inactive disease) and using magnetic resonance imaging of the thigh muscles, which included evaluation of the quadriceps cross‐sectional area (CSA). Needle biopsy samples of the vastus lateralis muscle (obtained from 12 patients ages ≥18 years) were assessed by histochemistry.

Results

After a mean ± SD disease duration of 21.8 ± 11.8 years, peak torque was lower in patients with juvenile DM compared to controls (mean difference 29 Nm, 95% confidence interval 13–46; P = 0.001). Similarly, total work of the knee extensors was lower in patients compared to controls (median 738J [interquartile range 565–1,155] versus 1,249J [interquartile range 815–1,665]; P < 0.001). Both peak torque and total work were lower in patients with active juvenile DM compared to those with inactive disease (both P < 0.019); in analyses controlled for quadriceps CSA, only total work remained lower in patients with active disease. Moreover, peak torque and total work correlated with findings from clinical muscle tests in patients with active disease (r = 0.57–0.84). Muscle biopsy results indicated that the fiber type composition was different, but capillary density was similar, between patients with active disease and those with inactive disease.

Conclusion

In patients with long‐term juvenile DM, both muscle strength and endurance of the knee extensors were lower when compared to matched controls, and also lower in patients with active disease compared to those with inactive disease. Our results indicate a need for more sensitive muscle tests in this clinical setting. We hypothesize that impaired muscle endurance in patients with active juvenile DM may be influenced by structural/functional adaptations of muscle tissue independent of muscle size.
Placental transfer of 125iodinated humanized immunoglobulin G2Δa in the cynomolgus monkey
Authors: Catlin Natasha R. , Mitchell Andrea Z. , Potchoiba Michael J. , O'Hara Denise M. , Wang Mengmeng , Zhang Minlei , Weinbauer Gerhard F. , Bowman Christopher J.
Published: November 2019

Antibody‐like biopharmaceuticals cross the placenta by utilizing existing transport pathways (e.g., FcRn receptor). There are limited data evaluating this transfer during organogenesis in any species. Understanding placental transfer of antibody‐like biopharmaceuticals can help to predict risk of developmental toxicity across species, including humans. To complement previously published placental transfer data in the rat with humanized IgGΔ2 (hIgG2), the timing and magnitude of transfer in the cynomolgus monkey and embryo/fetal biodistribution of maternally administered 125I‐radiolabeled hIgG2 was quantified on gestation days (GD) 35, 40, 50, 70, and 140 using gamma counting and whole body autoradiography 24 hr following intravenous injection. Chorioallantoic placental tissues were collected at all time points for Western Blot analysis with anti‐FcRn antibody. Maternally administered 125I‐hIgG2 was found in embryo/fetal tissues at all time points, including organogenesis. Embryo/fetal plasma 125I‐hIgG2 concentration increased during gestation, but only slightly up to GD 70 in embryo/fetal tissues, with hIgG2 tissue concentrations generally similar between GD70 and 140. The embryo/fetal:maternal 125I‐hIgG2 plasma concentration ratio was approximately 2.3 fold higher on GD 140, in comparison to ratios on GD 40. Importantly, placental FcRn protein expression was confirmed at all timepoints. These data demonstrate placental transfer of hIgG2 in a nonhuman primate model, and at levels comparable to the rat model, raising the potential for adverse developmental outcomes by direct antibody binding to biological targets.
A LabVIEW module to promote undergraduate research in control of AC servo motors of robotics manipulator
Authors: Yahya Samer , Moghavvemi Mahmoud , Almurib Haider A. F. , Al‐Rizzo Hussain
Published: November 2019

This paper presents a project‐based learning pedagogy for undergraduate mechanical engineering students which integrates traditional hardware‐based laboratory with LabVIEW to control the angular position, velocity, and acceleration of AC servo motors of a six‐degree of freedom manipulator. The proposed experimental modules have been proved to be very effective in assisting teams of undergraduate students within the Department of Mechanical, Materials and Manufacturing Engineering at the University of Nottingham, Malaysia Campus, who have used the modules in designing a new mechanical structure of a robot during their capstone design project. The proposed pedagogy inspired undergraduate students to publish their first paper based on the outcomes of their project. The focus on this paper is to present how the students' learning experience has been significantly enforced and their role in developing the modules introduced in this paper. Three modules are presented; the first configures a timer to generate a signal that drives the servo motors. The second drives the servo motor to a specific angular position with a constant angular velocity. Finally, the third is used to control the servo motor to follow any desired angular position, velocity, and acceleration.
The Multifaceted Inhibitory Effects of an Alkylquinolone on the Diatom Phaeodactylum tricornutum
Authors: Dow Lachlan , Stock Frederike , Peltekis Alexandra , Szamosvári Dávid , Prothiwa Michaela , Lapointe Adrien , Böttcher Thomas , Bailleul Benjamin , Vyverman Wim , Kroth Peter G. , Lepetit Bernard
Published: November 2019

The mechanisms underlying interactions between diatoms and bacteria are crucial to understand diatom behaviour and proliferation, and can result in far‐reaching ecological consequences. Recently, 2‐alkyl‐4‐quinolones have been isolated from marine bacteria, both of which (the bacterium and isolated chemical) inhibited growth of microalgae, suggesting these compounds could mediate diatom–bacteria interactions. The effects of several quinolones on three diatom species have been investigated. The growth of all three was inhibited, with half‐maximal inhibitory concentrations reaching the sub‐micromolar range. By using multiple techniques, dual inhibition mechanisms were uncovered for 2‐heptyl‐4‐quinolone (HHQ) in Phaeodactylum tricornutum. Firstly, photosynthetic electron transport was obstructed, primarily through inhibition of the cytochrome b6f complex. Secondly, respiration was inhibited, leading to repression of ATP supply to plastids from mitochondria through organelle energy coupling. These data clearly show how HHQ could modulate diatom proliferation in marine environments.
Single Molecule Conductance of Electroactive Helquats: Solvent Effect
Authors: Kolivoška Viliam , Šebera Jakub , Severa Lukáš , Mészáros Gábor , Sokolová Romana , Gasior Jindřich , Kocábová Jana , Hamill Joseph M. , Pospíšil Lubomír , Hromadová Magdaléna
Published: November 2019

A series of helquat molecules with increasing number of rings n was studied by electrochemical and break junction methods to provide redox characteristics and single molecule conductance properties. Even though selected species do not contain anchoring groups the molecular junction conductance was observed experimentally and depends strongly on the solvent used. Single molecule conductance G is almost two orders of magnitude higher in water environment compared to mesitylene, whereas the distribution of G values is narrow in water and wide in mesitylene solvent. In the non‐polar environment, G increases with increasing n, contrary to generally accepted notion of decreasing tunneling current with increasing molecular length. This behavior is, however, consistent with electrochemical properties, which showed that longer helquats are reduced more easily than the shorter ones. Furthermore, theoretical computations provided most probable molecular junction configurations of helquats in water solvent with excellent agreement between theoretical and experimental G values.
Improving LED Efficiency with the New Polymorph β‐Ca1−xSrxAlSiN3:Eu2+
Authors: Fiedler Tim , Dirksmeyer Stephanie , Seibald Markus , Hummel Franziska , Peschke Simon , Achrainer Gina M. , Bichler Daniel
Published: November 2019

Innovative materials for phosphor‐converted white light‐emitting diodes (pc‐LEDs) are much sought after due to the huge potential of the LED technology to reduce energy consumption worldwide. One of the main levers for further improvements are the conversion phosphors. The system Ca1−xSrxAlSiN3:Eu2+ currently provides one of the most important red‐emitting phosphors for pc‐LEDs. We report the discovery of the new polymorph β‐Ca1−xSrxAlSiN3:Eu2+ which allows for significant improvements to LED efficacies. It crystallizes in the orthorhombic space group Pbcn with lattice parameters a=982.43(10) pm, b=575.2(1) pm and c=516.12(5) pm. Compared to α‐Ca1−xSrxAlSiN3:Eu2+, its emission shows a significantly reduced spectral full‐width at half maximum (FWHM). With that, we demonstrated 3 % efficacy increase for white light‐emitting pc‐LEDs. The new polymorph can easily be industrialised, because the synthesis works on the same equipment as α‐Ca1−xSrxAlSiN3:Eu2+.
Current Challenges in Catalyst Development for PEM Water Electrolyzers
Authors: Bernt Maximilian , Hartig‐Weiß Alexandra , Tovini Mohammad Fathi , El‐Sayed Hany A. , Schramm Carina , Schröter Jonas , Gebauer Christian , Gasteiger Hubert A.
Published: November 2019

This work addresses current challenges in catalyst development for proton exchange membrane water electrolyzers (PEM‐WEs). To reduce the amount of iridium at the oxygen anode to levels commensurate with large‐scale application of PEM‐WEs, high‐structured catalysts with a low packing density are required. To allow an efficient development of such catalysts, activity and durability screening tests are essential. Rotating disk electrode measurements are suitable to determine catalyst activity, while accelerated stress tests on the MEA level are required to evaluate catalyst stability.
Partial order relations for classification comparisons
Authors: Chang Lo‐Bin
Published: November 2019

Abstract

The Bayes classification rule offers the optimal classifier, minimizing the classification error rate, whereas the Neyman–Pearson lemma offers the optimal family of classifiers to maximize the detection rate for any given false alarm rate. These motivate studies on comparing classifiers based on similarities between the classifiers and the optimal. In this article, we define partial order relations on classifiers and families of classifiers, based on rankings of rate function values and rankings of test function values, respectively. Each partial order relation provides a sufficient condition, which yields better classification error rates or better performance on the receiver operating characteristic analysis. Various examples and applications of the partial order theorems are discussed to provide comparisons of classifiers and families of classifiers, including the comparison of cross‐validation methods, training data that contains outliers, and labelling errors in training data. The Canadian Journal of Statistics 48: 152–166; 2020 © 2019 Statistical Society of Canada
A phase 2 clinical trial assessing the efficacy and safety of pembrolizumab and radiotherapy in patients with metastatic triple‐negative breast cancer
Authors: Ho Alice Y. , Barker Christopher A. , Arnold Brittany B. , Powell Simon N. , Hu Zishuo I. , Gucalp Ayca , Lebron‐Zapata Lizza , Wen Hannah Y. , Kallman Cindy , D'Agnolo Alessandro , Zhang Zhigang , Flynn Jessica , Dunn Samantha A. , McArthur Heather L.
Published: November 2019

Background

The current study was conducted to evaluate the efficacy and safety of pembrolizumab‐mediated programmed cell death protein 1 inhibition plus radiotherapy (RT) in patients with metastatic triple‐negative breast cancer who were unselected for programmed death‐ligand 1 expression.

Methods

The current study was a single‐arm, Simon 2‐stage, phase 2 clinical trial that enrolled a total of 17 patients with a median age of 52 years (range, 37‐73 years). An RT dose of 3000 centigrays (cGy) was delivered in 5 daily fractions. Pembrolizumab was administered intravenously at a dose of 200 mg within 3 days of the first RT fraction, and then every 3 weeks ± 3 days until disease progression. The median follow‐up was 34.5 weeks (range, 2.1‐108.3 weeks). The primary endpoint of the current study was the overall response rate (ORR) at week 13 in patients with unirradiated lesions measured using Response Evaluation Criteria in Solid Tumors (RECIST; version 1.1). Secondary endpoints included safety and progression‐free survival. Exploratory objectives were to identify biomarkers predictive of ORR and progression‐free survival.

Results

The ORR for the entire cohort was 17.6% (3 of 17 patients; 95% CI, 4.7%‐44.2%), with 3 complete responses (CRs), 1 case of stable disease, and 13 cases of progressive disease. Eight patients died prior to week 13 due to disease progression. Among the 9 women assessed using RECIST version 1.1 at week 13, 3 (33%) achieved a CR, with a 100% reduction in tumor volume outside of the irradiated portal. The CRs were durable for 18 weeks, 20 weeks, and 108 weeks, respectively. The most common grade 1 to 2 toxicity (assessed according to the National Cancer Institute Common Terminology Criteria for Adverse Events, version 4.0) was dermatitis (29%). Four grade 3 adverse events were attributed to pembrolizumab: fatigue, lymphopenia, and infection. No were no grade 4 adverse events or treatment‐related deaths reported.

Conclusions

The combination of pembrolizumab and RT was found to be safe and demonstrated encouraging activity in patients with poor‐prognosis, metastatic, triple‐negative breast cancer who were unselected for programmed death‐ligand 1 expression. Larger clinical trials of checkpoint blockade plus RT with predictive biomarkers of response are needed.
Visible‐Light‐Driven Selective Oxidative Coupling of Amines to Imines by Bismuth‐Rich Bismuth Oxybromide in Water
Authors: Zhao Wei , Yang Chunxia , Zhang Xu , Deng Yu , Han Chunqiu , Ma Zhaoyu , Wang Li , Ye Liqun
Published: November 2019

Photocatalytic selective oxidative coupling of amines is a promising method for imine synthesis. Bismuth‐rich bismuth oxybromide photocatalysts have been found to exhibit improved conversion and selectivity for the visible‐light‐driven selective oxidative coupling of amines to imines in water. Benzylamines with either electron‐withdrawing or electron‐donating groups undergo good conversion (94–99 %) and excellent selectivity (93–98 %) to the corresponding imines. The average apparent quantum efficiency at 455 nm is 57.4 %. Active species trapping experiments, isotope experiments, and in situ infrared spectroscopy reveal that water both serves as solvent and participates in the coupling reaction as a reactant. This work provides a green and environmentally friendly method for the efficient synthesis of imines with bismuth‐rich bismuth oxyhalides and reveals water is involved in the oxidative coupling mechanism of benzylamines.
Leaching Mechanisms of Industrial Powders of Spent Nickel Metal Hydride Batteries in a Pilot‐Scale Reactor
Authors: Zielinski Margot , Cassayre Laurent , Destrac Philippe , Coppey Nicolas , Garin Gilles , Biscans Béatrice
Published: November 2019

In view of a sustainable recycling process, the leaching mechanisms of nickel and rare‐earth elements (REEs) contained within industrial samples of spent nickel metal hydride battery powders were investigated in HCl and H2SO4, under mild temperature (25–60 °C) and pH (3–5.5). First, in‐depth characterization of the heterogeneous battery powder was carried out with powder XRD, SEM, electron probe microanalyzer wavelength‐dispersive spectroscopy (EPMA‐WDS) quantitative analyses of individual particles, and inductively coupled plasma optical emission spectrometry (ICP‐OES) elemental analysis. An unusual result is the identification of particles that exhibit a core–shell structure, which is related to anode active mass aging mechanisms. Then, a leaching study in a 10 L pilot‐scale reactor demonstrated the selective dissolution of REEs, with respect to nickel, at pH 3, which is attributed to 1) the kinetic inhibition of nickel metal dissolution, and 2) the specific core–shell structure of aged mischmetal particles. Furthermore, the use of H2SO4 led to coprecipitation of lanthanide–alkali double sulfates and nickel salts.
An efficient resource allocation to improve QoS of 5G slicing networks using general processor sharing‐based scheduling algorithm
Authors: AlQahtani Salman A.
Published: November 2019

Fifth generation (5G) slicing is an emerging technology for software‐defined networking/network function virtualization–enabled mobile networks. Improving the utilization and throughput to meet the quality of service (QoS) requirements of 5G slicing is very important for the operators of mobile networks. With growing data traffic from different applications of numerous smart mobile devices having several QoS requirements, we expect networks to face problems of congestion and overload that prevent the effective functioning of a radio access network (RAN). This paper proposes a more effective packet‐based scheduling scheme for data traffic by 5G slicing with two operation modes for improving the resource utilization of 5G cloud RAN and providing an efficient isolation of the 5G slices. These two operation modes are referred to as static sharing resource (SSR) scheme and dynamic sharing resources (DSR) scheme. The SSR scheme is a modified version of an existing method. The goal of this approach is to reallocate the shared available resources of 5G network fairly and maximize the utilization of bandwidth while protecting a 5G slice from overwhelming other 5G slices. Throughput and delays of the system model are also discussed to show its performance limits. On the basis of the simulation outcomes, we observed that the proposed DSR scheme outperforms the SSR scheme in terms of provided delay and throughput. In addition, the token bucket parameters together with the assigned capacity weight for each slice can be selected and configured based on the required QoS. Finally, a good estimate for the maximum delay bounds of the slices is provided by the derived theoretical delay bound.
Detection of 5α‐reductase inhibitors by UPLC–MS/MS: Application to the definition of the excretion profile of dutasteride in urine
Authors: Mazzarino Monica , Martellone Lorenzo , Comunità Fabio , de la Torre Xavier , Molaioni Francesco , Botrè Francesco
Published: November 2019

An analytical procedure based on ultra‐performance liquid chromatography‐mass spectrometry was developed to screen and to confirm dutasteride and its metabolites in human urine. Sample preparation included an enzymatic hydrolysis followed by solid‐phase extraction using the strong cation exchange cartridges OASIS® MCX. The chromatographic separation was carried out on C18 column, employing as mobile phases ultra purified water and acetonitrile, both containing 0.1% formic acid. Detection was achieved using a triple quadrupole as a mass spectrometric analyzer, with positive ion electrospray ionization and multiple reaction monitoring as acquisition mode. The analytical procedure developed was validated according to ISO 17025 and World Anti‐Doping Agency guidelines. The extraction efficiency was estimated to be greater than 75% for both dutasteride and its hydroxylated metabolites. Detection capability was determined in the range of 0.1–0.4 ng/mL. Specificity and repeatability of the relative retention times (CV% < 0.5) and of the relative abundances of the characteristic ion transitions selected (CV% < 10) were confirmed to be fit for purpose to ensure the unambiguous identification of dutasteride and its metabolites in human urine. The developed method was used to characterize the urinary excretion profile of dutasteride after both chronic and acute administration of therapeutic doses. After chronic administration, dutasteride and its hydroxylated metabolites were easily detected and confirmed. After acute administration, instead, only the two hydroxylated metabolites were detected for 3–4 days.
Ligand‐Controlled Reactivity and Cytotoxicity of Cyclometalated Rhodium(III) Complexes
Authors: Zhang Wen‐Ying , Bridgewater Hannah E. , Banerjee Samya , Soldevila‐Barreda Joan J. , Clarkson Guy J. , Shi Huayun , Imberti Cinzia , Sadler Peter J.
Published: November 2019

We report the synthesis, characterization and cytotoxicity of six cyclometalated rhodium(III) complexes [CpXRh(C^N)Z]0/+, in which CpX = Cp*, Cpph, or Cpbiph, C^N = benzo[h]quinoline, and Z = chloride or pyridine. Three X‐ray crystal structures showing the expected “piano‐stool” configurations have been determined. The chlorido complexes hydrolyzed faster in aqueous solution, and reacted preferentially with 9‐ethyl guanine or glutathione compared to their pyridine analogues. The 1‐biphenyl‐2,3,4,5‐tetramethylcyclopentadienyl complex [CpbiphRh(benzo‐[h]quinoline)Cl] (3a) was the most efficient catalyst in coenzyme reduced nicotinamide adenine dinucleotide (NADH) oxidation to NAD+ and induced an elevated level of reactive oxygen species (ROS) in A549 human lung cancer cells. The pyridine complex [CpbiphRh(benzo[h]quinoline)py]+ (3b) was the most potent against A549 lung and A2780 ovarian cancer cell lines, being 5‐fold more active than cisplatin towards A549 cells, and acted as a ROS scavenger. This work highlights a ligand‐controlled strategy to modulate the reactivity and cytotoxicity of cyclometalated rhodium anticancer complexes.
Credible and economic multimedia service optimization based on game theoretic in hybrid cloud networks
Authors: Cao Tengfei , Zhong Lujie , Xiao Han , Song Chengru , Yang Shujie , Xu Changqiao
Published: November 2019

The cloud network has the advantages in efficiently offloading the large‐scale Internet traffic, which is considered as a promising architecture to provide the satisfactory multimedia services for mobile users. However, most current studies lack the joint consideration of economic and security of services in hybrid cloud networks. In this paper, a novel multimedia service optimization mechanism is proposed hereby to meet the user's requirements mentioned above while guaranteeing the reliability of service. Firstly, a credible scheme is designed to help the mobile users distinguish the reliable cloud providers. Meanwhile, a blockchain‐based content credibility approach is further designed to guarantee the reliability and integrity of video contents. Moreover, a noncooperative Stackelberg game model is presented to maximize the profit of each party. Furthermore, the equilibrium of this game is achieved by the methods of backward induction and gradient descent. Finally, extensive simulations demonstrate that our solution has efficient performance in terms of secure service ratio, utility, service pricing, etc.
Prediction of clinical benefit from androgen deprivation therapy in salivary duct carcinoma patients
Authors: van Boxtel Wim , Verhaegh Gerald W. , van Engen‐van Grunsven Ilse A. , van Strijp Dianne , Kroeze Leonie I. , Ligtenberg Marjolein J. , van Zon Hans B. , Hendriksen Yara , Keizer Diederick , van de Stolpe Anja , Schalken Jack A. , van Herpen Carla M.
Published: November 2019

Androgen deprivation therapy (ADT) is first‐line palliative treatment in androgen receptor‐positive (AR+) salivary duct carcinoma (SDC), and response rates are 17.6–50.0%. We investigated potential primary ADT resistance mechanisms for their predictive value of clinical benefit from ADT in a cohort of recurrent/metastatic SDC patients receiving palliative ADT (n = 30). We examined mRNA expression of androgen receptor (AR), AR splice variant‐7, intratumoral androgen synthesis enzyme‐encoding genes AKR1C3, CYP17A1, SRD5A1 and SRD5A2, AR protein expression, ERBB2 (HER2) gene amplification and DNA mutations in driver genes. Furthermore, functional AR pathway activity was determined using a previously reported Bayesian model which infers pathway activity from AR target gene expression levels. SRD5A1 expression levels and AR pathway activity scores were significantly higher in patients with clinical benefit from ADT compared to those without benefit. Survival analysis showed a trend toward a longer median progression‐free survival for patients with high SRD5A1 expression levels and high AR pathway activity scores. The AR pathway activity analysis, and not SRD5A1 expression, also showed a trend toward better disease‐free survival in an independent cohort of locally advanced SDC patients receiving adjuvant ADT (n = 14) after surgical tumor resection, and in most cases a neck dissection (13/14 patients) and postoperative radiotherapy (13/14 patients). In conclusion, we are the first to describe that AR pathway activity may predict clinical benefit from ADT in SDC patients, but validation in a prospective study is needed.
The genomic landscape of nonsmall cell lung carcinoma in never smokers
Authors: Boeckx Bram , Shahi Rajendra B. , Smeets Dominiek , De Brakeleer Sylvia , Decoster Lore , Van Brussel Thomas , Galdermans Daniella , Vercauter Piet , Decoster Lynn , Alexander Patrick , Berchem Guy , Ocak Sebahat , Vuylsteke Peter , Deschepper Koen , Lambrechts Marc , Cappoen Nadia , Teugels Erik , Lambrechts Diether , De Greve Jacques
Published: November 2019

Lung cancer is the number one cause of cancer‐related death worldwide with cigarette smoking as its major risk factor. Although the incidence of lung cancer in never smokers is rising, this subgroup of patients is underrepresented in genomic studies of lung cancer. Here, we assembled a prospective cohort of 46 never‐smoking, nonsmall cell lung cancer (NSCLC) patients and performed whole‐exome and low‐coverage whole‐genome sequencing on tumors and matched germline DNA. We observed fewer somatic mutations, genomic breakpoints and a smaller fraction of the genome with chromosomal instability in lung tumors from never smokers compared to smokers. The lower number of mutations, enabled us to identify TSC22D1 as a potential driver gene in NSCLC. On the other hand, the frequency of mutations in actionable genes such as EGFR and ERBB2 and of amplifications in MET were higher, while the mutation rate of TP53, which is a negative prognostic factor, was lower in never smokers compared to smokers. Together, these observations suggest a more favorable prognosis for never smokers with NSCLC. Classification of somatic mutations into six‐substitution type patterns or into 96‐substitution type signatures revealed distinct clusters between smokers and never smokers. Particularly, we identified in never smokers signatures related to aging, homologous recombination damage and APOBEC/AID activity as the most important underlying processes of NSCLC. This further indicates that second‐hand smoking is not driving NSCLC pathogenesis in never smokers.