bluuebunny/crossref_metadata_2025 huggingface dataset:
Innate Lymphoid Cells and T Cells Contribute to the Interleukin‐17A Signature Detected in the Synovial Fluid of Patients With Juvenile Idiopathic Arthritis
Authors: Rosser Elizabeth C. , Lom Hannah , Bending David , Duurland Chantal L. , Bajaj‐Elliott Mona , Wedderburn Lucy R.
Published: October 2018

Objective

Evidence suggests that aberrant function of innate lymphoid cells (ILCs), whose functional and transcriptional profiles overlap with those of Th cell subsets, contributes to immune‐mediated pathologies. To date, analysis of juvenile idiopathic arthritis (JIA) immune pathology has concentrated on the contribution of CD4+ T cells; we have previously identified an expansion of Th17 cells within the synovial fluid (SF) of JIA patients. We undertook this study to extend this analysis to further investigate the role of ILCs and other interleukin‐17 (IL‐17)–producing T cell subsets in JIA.

Methods

ILCs and CD3+ T cell subsets were defined in peripheral blood mononuclear cells (PBMCs) from healthy adults, healthy children, and JIA patients and in SF mononuclear cells (SFMCs) from JIA patients using flow cytometry. Defined subsets in SFMCs were correlated with clinical measures including physician's global assessment of disease activity on a visual analog scale, number of joints with active disease, and erythrocyte sedimentation rate. Transcription factor and cytokine profiles of sorted ILCs were assessed by quantitative reverse transcriptase–polymerase chain reaction.

Results

Group 1 ILCs (ILC1s), NKp44− group 3 ILCs (natural cytotoxicity receptor–negative [NCR−] ILC3s), and NKp44+ ILC3s (NCR+ ILC3s) were enriched in JIA SFMCs compared to PBMCs, which corresponded to an increase in transcripts for TBX21, IFNG, and IL17A. Of the ILC subsets, the frequency of NCR− ILC3s in JIA SFMCs displayed the strongest positive association with clinical measures, which was mirrored by an expansion in IL‐17A+CD4+, IL‐17A+CD8+, and IL‐17A+ γδ T cells.

Conclusion

We demonstrate that the strength of the IL‐17A signature in JIA SFMCs is determined by multiple lymphoid cell types, including NCR− ILC3s and IL‐17A+CD4+, IL‐17A+CD8+, and IL‐17A+ γδ T cells. These observations may have important implications for the development of stratified therapeutics.
Recent Advances in Metal‐Organic Framework Derivatives as Oxygen Catalysts for Zinc‐Air Batteries
Authors: Zhong Yijun , Xu Xiaomin , Wang Wei , Shao Zongping
Published: October 2018

Electrochemical energy storage systems with high power output, large energy density, and stable performance are urgently needed. Zn–air batteries are one of the most promising candidates owing to abundant and inexpensive resources used, decent energy density, and the high reduction potential of Zn. The most significant challenge of primary and rechargeable aqueous Zn‐air batteries is the relatively high overpotential due to the sluggish kinetics of oxygen reactions on the air cathode. Highly efficient oxygen catalysts derived from metal‐organic framework (MOF) precursors have demonstrated remarkable capabilities for facilitating the oxygen reactions. In this contribution, we review the recent progress in state‐of‐the‐art MOF‐derived materials for use as oxygen catalysts in primary and rechargeable Zn‐air batteries. We first summarize the development of several important MOF derivatives, including transition metal‐nitrogen‐carbon (TM−N−C) composites, carbon‐based transition metal compounds, and metal‐free carbons. The advantages and disadvantages of these MOF‐derived catalysts are also discussed. Strategies for optimization of the gas‐liquid diffusion and the long‐range electronic transportation on the air cathode with these MOF‐derived catalysts are also demonstrated. Finally, the main challenges and some perspectives for developing advanced MOF‐derived catalysts applied in Zn–air batteries are provided.
Design‐based inference on Bernstein type estimators for continuous populations
Authors: Franceschi Sara , Marcheselli Marzia , Naddeo Stefania , Pisani Caterina
Published: October 2018

The estimation of the values of a variable at any point of a study area is performed using Bernstein polynomials when the sampling scheme is implemented by selecting a point in each polygon of a regular grid overimposed onto the area. The evaluation of the precision of the resulting estimates is investigated under a completely design‐based framework. Moreover, as the main contribution to the mean squared error of the Bernstein‐type estimator is due to the bias, also a pseudo‐jackknife estimator is proposed. The performance of both estimators is investigated theoretically and by means of a simulation study. An application to a soil survey performed in Berkshire Downs in Oxfordshire (UK) is considered.
Correlation between Copper Oxide Particle Size and Selectivity towards Propylene Oxide in Selective Oxidation of Propene
Authors: Diekmann Marek , Koch Gregor , König Michaela , Ressler Thorsten
Published: October 2018

Copper oxide catalysts supported on nanostructured silica SBA‐15 were synthesized with varying copper loadings in a range from 1.1 to 19.4 wt.%. Catalysts were structurally characterized by N2 physisorption, X‐ray diffraction and ex situ as well as in situ diffuse reflectance UV‐Vis spectroscopy. Copper oxide species contained Cu2+ in an octahedral configuration with a tetragonal distortion. Increasing the copper loading resulted in a decreasing optical band gap, which is associated with a growing particle size. Additionally, CuO/SBA‐15 samples were examined by temperature‐programmed reduction confirming a narrow particle size distribution. Structural evolution and catalytic activity were investigated during selective oxidation of propene focusing on product distribution of nucleophilic and electrophilic oxidation. Catalytic testing was carried out using an on‐line GC and MS coupled to a laboratory fixed‐bed reactor. All catalysts selectively oxidized propene to acrolein and propylene oxide (PO). With time on stream activity decreased while selectivity towards acrolein and PO increased. While selectivity towards PO increased with copper loading and, hence, copper oxide particle size, selectivity towards acrolein was largely independent of copper loading.
NiCo2O4@NiMoO4 Supported on Nickel Foam for Electrocatalytic Water Splitting
Authors: Du Xiaoqiang , Fu Jianpeng , Zhang Xiaoshuang
Published: October 2018

Splitting water to make hydrogen is one of the most effective ways to solve the energy crisis. In this paper, we started with the catalysts of the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) of electrocatalytic water splitting, studied the catalysts with great stability and practicality, and designed NiCo2O4 nanowires as precursors, on whose surface we set NiMoO4 nanosheets. Cobalt elements were introduced on the nickel foam with electrocatalytic properties, and a flower‐like NiCo2O4@NiMoO4 core‐shell hybrid nanostructure was prepared by a hydrothermal method. The series of core‐shell nanocatalysts were characterized via XRD, SEM, XPS, etc. The electrochemical properties of the obtained catalysts were also measured, and the conclusion that the catalysts could reduce the overpotential of the reaction required was figured out. The conclusion of the overpotential of catalyzing the water splitting reaction provides new ideas for the research of the catalyst for electrocatalytic water splitting reaction.
Recent Advances in the Direct Synthesis of H2O2
Authors: Lewis Richard J. , Hutchings Graham J.
Published: October 2018

Hydrogen peroxide (H2O2) is a highly effective, green oxidant that has found application in sectors ranging from the synthesis of fine chemicals and waste stream treatment to the extraction of precious metals and the bleaching of paper pulp and textiles. The growing demand for H2O2 has seen it become one of the 100 most important chemicals in the world. The direct synthesis of H2O2 from H2 and O2 has been a challenge for the scientific community for over 100 years and represents an attractive alternative to the current means of production. Herein we discuss the historical perspective of the direct synthesis process, the recent literature regarding catalyst design and the role of additives as well as the application of H2O2 as an in situ oxidant. We discuss the key problems that remain and conclude that although there has been progress with respect to the selectivity of hydrogen utilisation, there is a need to now concentrate on catalyst activity as the key remaining problem requiring a solution is the concentration of H2O2 that can be achieved, especially in flow reactors.
Selective Removal of H2S from Gas Streams with High CO2 Concentration Using Hollow‐Fiber Membrane Contractors
Authors: Mirfendereski Seyed Mojtaba , Niazi Zahra , Mohammadi Toraj
Published: October 2018

Selective and simultaneous separation of H2S and CO2 from CH4 was accomplished in a hollow‐fiber membrane contactor (HFMC). The absorption of both H2S and CO2 using an aqueous solution of methyldiethanolamine (MDEA) was almost complete and acid gases were totally removed. Despite the large difference between H2S and CO2 concentrations, the rate of H2S absorption was not significantly influenced by CO2 absorption. The independent effect and interactions of several process variables on the separation performance of H2S and CO2 were investigated. The results indicated that the membrane contactor could be a highly efficient choice for removal of almost all H2S in the presence of a large CO2 content even at high gas/liquid flow ratio. The selectivity of H2S was about three times higher compared to the conventional absorption packed towers.
Highly Sensitive and Selective Electrochemical Detection of Dopamine using Hybrid Bilayer Membranes
Authors: Patrice Fato T. , Zhao Li‐Jun , Fodjo Essy K. , Li Da‐Wei , Qiu Kaipei , Long Yi‐Tao
Published: October 2018

The rapid and precise measurement of dopamine (DA) levels is of great benefit to unveil physiological and pathological processes. The electrochemical detection approaches feature fast DA response, but remain challenging at the moment to realize ultra‐high sensitivity and selectivity to the trace amount of DA, especially in the presence of highly concentrated ascorbic acid (AA, the most common interferent in the human body). To address this issue, a negatively charged hybrid bilayer membrane (HBM) modified gold electrode was designed, which was only attractive to the positive DA but not the negative AA. As a result, this work managed to achieve an ultra‐low detection limit of 0.41 pM DA under the interference of AA of 109 times higher concentration. Such an excellent performance is over three orders of magnitude better than previously reported electrochemical sensing methods, suggesting the promise of applying HBM functionalization in electrochemical and bio‐sensing applications.
Countercation Effect on CO2 Binding to Oxo Titanate with Bulky Anilide Ligands
Authors: Paparo Albert , Silvia Jared S. , Spaniol Thomas P. , Okuda Jun , Cummins Christopher C.
Published: October 2018

This work focuses on nucleophilic activation of CO2 at the anionic terminal oxo titanium tris(anilide) complexes [(Solv)nM][OTi(N[tBu]Ar)3]m with M=Li, Na, K, Mg, MgMe, AlCl2, AlI2; Ar=3,5‐Me2C6H3; Solv=Et2O, THF, 12‐crown‐4, 2,2,2‐cryptand; n, m=1–2. The CO2 binding strength to the terminal oxo ligand of [OTi(N[tBu]Ar)3]− ([1]−) and the stability of the resulting carbonate moiety [O2COTi(N[tBu]Ar)3]− ([2]−) are highly dependent on the Lewis acidity of the countercation. We report herein on CO2 binding as a function of countercation and countercation coordination environment, and comment in this respect on the bottom and upper limits of the cation Lewis acidity. Thermodynamic parameters are provided for oxo complexes with lithium as countercation, that is, [(Et2O)2Li][1] and [(12‐c‐4)Li][1].
Size‐Selective Hydroformylation by a Rhodium Catalyst Confined in a Supramolecular Cage
Authors: Nurttila Sandra S. , Brenner Wolfgang , Mosquera Jesús , van Vliet Kaj M. , Nitschke Jonathan R. , Reek Joost N. H.
Published: October 2018

Size‐selective hydroformylation of terminal alkenes was attained upon embedding a rhodium bisphosphine complex in a supramolecular metal–organic cage that was formed by subcomponent self‐assembly. The catalyst was bound in the cage by a ligand‐template approach, in which pyridyl–zinc(II) porphyrin interactions led to high association constants (>105 m−1) for the binding of the ligands and the corresponding rhodium complex. DFT calculations confirm that the second coordination sphere forces the encapsulated active species to adopt the ee coordination geometry (i.e., both phosphine ligands in equatorial positions), in line with in situ high‐pressure IR studies of the host–guest complex. The window aperture of the cage decreases slightly upon binding the catalyst. As a result, the diffusion of larger substrates into the cage is slower compared to that of smaller substrates. Consequently, the encapsulated rhodium catalyst displays substrate selectivity, converting smaller substrates faster to the corresponding aldehydes. This selectivity bears a resemblance to an effect observed in nature, where enzymes are able to discriminate between substrates based on shape and size by embedding the active site deep inside the hydrophobic pocket of a bulky protein structure.
Visible‐Light Direct Conversion of Ethanol to 1,1‐Diethoxyethane and Hydrogen over a Non‐Precious Metal Photocatalyst
Authors: Chao Yuguang , Zhang Wenqin , Wu Xuemei , Gong Nana , Bi Zhihong , Li Yunqin , Zheng Jianfeng , Zhu Zhenping , Tan Yisheng
Published: October 2018

Converting renewable biomass and their derivatives into chemicals and fuels has received much attention to reduce the dependence on fossil resources. Photocatalytic ethanol dehydrogenation–acetalization to prepare value‐added 1,1‐diethoxyethane and H2 was achieved over non‐precious metal CdS/Ni‐MoS2 catalyst under visible light. The system displays an excellent production rate and high selectivity of 1,1‐diethoxyethane, 52.1 mmol g−1 h−1 and 99.2 %, respectively. In‐situ electron spin resonance, photoluminescence spectroscopy and transient photocurrent responses were conducted to investigate the mechanism. This study provides a promising strategy for a green application of bioethanol.
Synthesis of the Core Oligosaccharides of Lipooligosaccharides from Campylobacter jejuni: A Putative Cause of Guillain–Barré Syndrome
Authors: Yoshida Fumi , Yoshinaka Hiroki , Tanaka Hidenori , Hanashima Shinya , Yamaguchi Yoshiki , Ishihara Mikio , Saburomaru Miyuki , Kato Yuki , Saito Risa , Ando Hiromune , Kiso Makoto , Imamura Akihiro , Ishida Hideharu
Published: October 2018

The chemical synthesis of the highly branched core oligosaccharides of lipooligosaccharides (LOSs) found in Campylobacter jejuni, which causes Guillain–Barré syndrome by a preceding infection, is described. The target LOS mimics, consisting of eight or nine monosaccharides, were classified into three groups as key building blocks: ganglioside‐core tetra‐/pentasaccharides (GM1‐/GD1a‐like), l‐glycero‐d‐manno‐heptose‐containing trisaccharides, and 3‐deoxy‐d‐manno‐2‐octulosonic acid (KDO) residues. These synthetic fragments were obtained from commercially available monosaccharides. Less obtainable l‐glycero‐d‐manno‐heptose and KDO residues, as key components of the LOSs, were synthesized from p‐methoxyphenyl d‐mannoside and di‐O‐isopropylidene‐protected d‐mannose, respectively. The synthesis of α‐KDO glycoside, as one of the most difficult stereocontrolled glycosidic constructions, was achieved by treating a 2,3‐ene derivative of KDO with phenylselenyl trifluoromethanesulfonate as a suitable α‐directing reagent. All synthetic blocks were constructed through a convergent synthetic route, which resulted in the first synthesis of structurally challenging LOS core glycans containing ganglioside GM1 and GD1a‐core sequences.
Specific Decoration of a Discrete Bismuth Oxido Cluster by Selected Peptides towards the Design of Metal Tags
Authors: Bauer Mona , Remmler Dario , Dallmann André , Jakubowski Norbert , Börner Hans G. , Panne Ulrich , Limberg Christian
Published: October 2018

Metal tags find application in a multitude of biomedical systems and the combination with laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) offers an opportunity for multiplexing. To lay the foundation for an increase of the signal intensities in such processes, we herein present a general approach for efficient functionalization of a well‐defined metal oxido cluster [Bi6O4(OH)4(SO3CF3)6(CH3CN)6]⋅2 CH3CN (1), which can be realized by selecting 7mer peptide sequences via combinatorial means from large one‐bead one‐compound peptide libraries. Selective cluster‐binding peptide sequences (CBS) for 1 were discriminated from non‐binders by treatment with H2S gas to form the reduction product Bi2S3, clearly visible to the naked eye. Interactions were further confirmed by NMR experiments. Extension of a binding peptide with a maleimide linker (Mal) introduces the possibility to covalently attach thiol‐bearing moieties such as biological probes and for their analysis the presence of the cluster instead of mononuclear entities should lead to an increase of signal intensities in LA‐ICP‐MS measurements. To prove this, CBS‐Mal was covalently bound onto thiol‐presenting glass substrates, which then captured 1 effectively, so that LA‐ICP‐MS measurements demonstrated drastic signal amplification compared to single lanthanide tags.
Proposed modifications and incorporation of plasma Epstein‐Barr virus DNA improve the TNM staging system for Epstein‐Barr virus‐related nasopharyngeal carcinoma
Authors: Guo Rui , Tang Ling‐Long , Mao Yan‐Ping , Du Xiao‐Jing , Chen Lei , Zhang Zi‐Chen , Liu Li‐Zhi , Tian Li , Luo Xiao‐Tong , Xie Yu‐Bin , Ren Jian , Sun Ying , Ma Jun
Published: October 2018

Background

The prognosis of patients who have Epstein‐Barr virus (EBV)‐related nasopharyngeal carcinoma (NPC) in which the tumor tissues harbor EBV have a better prognosis than those without EBV‐related NPC. Therefore, the eighth edition of the TNM staging system could be modified for EBV‐related NPC by incorporating the measurement of plasma EBV DNA.

Methods

In total, 979 patients with NPC who received intensity‐modulated radiotherapy (IMRT) were retrospectively reviewed. Recursive partitioning analysis was conducted based on tumor (T) classification, lymph node (N) classification, and EBV DNA measurement to derive objectively the proposed stage groupings. The validity of the proposed stage groupings was confirmed in a prospective cohort of 550 consecutive patients who also received with IMRT.

Results

The pretreatment plasma EBV DNA level was identified as a significant, negative prognostic factor for progression‐free survival and overall survival in univariate analysis (all P < .001) and multivariate analysis (all P < .05). Recursive partitioning analysis of the primary cohort to incorporate EBV DNA generated the following proposed stage groupings: stage RI (T1N0), RIIA (T2‐T3N0 or T1‐T3N1, EBV DNA ≤2000 copies/mL), stage RIIB (T2‐T3N0 or T1‐T3N1, EBV DNA >2000 copies/mL; T1‐T3N2, EBV DNA ≤2000 copies/mL), stage RIII (T1‐T3N2, EBV DNA >2000 copies/mL; T4N0‐N2), and stage RIVA (any T and N3). In the validation cohort, the 5‐year progression‐free survival rate was 100%, 87.9%, 76.7%, 68.7%, and 50.4% for proposed stage RI, RIIA, RIIB, RIII, and RIV NPC, respectively (P < .001). Compared with the eighth edition TNM stage groupings, the proposed stage groupings incorporating EBV DNA provided better hazard consistency, hazard discrimination, outcome prediction, and sample size balance.

Conclusions

The proposed stage groupings have better prognostic performance than the eighth edition of the TNM staging system. EBV DNA titers should be included in the TNM staging system to assess patients who have EBV‐related NPC.
A suspected lunar volcano identification algorithm based on convolutional neural network by the rapid location of light shadow impacts
Authors: Li Xiaoyi , Li Jiaqi , Tian Xiaolin
Published: October 2018

The impact crater is the most common geological unit in the lunar surface, an important object to study the geological evolution history of the Moon, and the foundational basis for the geological dating of the Moon. Thus, the identification of impact craters is of important significance. As a new field with rapid development for more than ten years, deep learning has received attention from an increasing number of researchers because of its obvious advantages compared with the superficial model in terms of both feature extraction and modeling. To address various defects of the current method for the identification and feature extraction of impact craters, including its low efficiency and limited application range, this paper proposes a type of new impact crater identification using the convolutional neural network based on illumination and shadow quick‐positioning. First, we quickly locate the impact crater using the effect of illumination on the impact crater. Second, we train the impact crater images using the convolutional neural network to perform the feature extraction. Then, we identify impact craters in images. Finally, we classify the identified impact craters based on the roughness feature and find impact craters with unsmooth bottoms. Compared with the traditional algorithm, the algorithm of this paper breaks away from the important index of border but has a high identification rate under the specific resolution rate and can classify the identified impact craters. Such impact craters with unsmooth bottoms may overflow and form from the Earth's mantle at the bottom or may be the remnant of volcanic vents since ancient times, which are of great research significance.
RT‐JADE: A preemptive real‐time scheduling middleware for mobile agents
Authors: Filgueiras Tatiana Pereira , Rodrigues Leonardo M. , de Oliveira Rech Luciana , de Souza Luciana Moreira Sá , Netto Hylson Vescovi
Published: October 2018

Mobile agents are examples of distributed systems which may dispute for the same resources on their hosts. Treating such concurrency adequately is essential, particularly in real‐time applications. Due to intrinsic time restrictions, mobile agents in real‐time environments are only considered successful if they fulfill their mission by respecting their deadlines. Scheduling algorithms with different policies can be applied in these scenarios. However, the efficiency of these algorithms may deviate according to the missions and deadlines of the mobile agents. Also, these algorithms can be preemptive, or calculate the order of executions without interrupting an ongoing task. In this paper, we propose a middleware extension to the JADE platform that brings real‐time scheduling support with preemption to mobile agents. The proposed solution uses best effort scheduling policy in the context of soft real‐time applications. We evaluate the performance of the scheduling algorithms, with and without preemption, and the impact of the selected algorithms on mission fulfillment. The results of the proposed middleware showed a great improvement on mission accomplishment when compared to the FIFO algorithm provided by the JADE platform.
Interfacial CoOx Layers on TiO2 as an Efficient Catalyst for Solvent‐Free Aerobic Oxidation of Hydrocarbons
Authors: Wang Hai , Wang Liang , Zhang Jian , Wang Chengtao , Liu Ziyu , Gao Xinhua , Meng Xiangju , Yoo Seung Jo , Kim Jin‐Gyu , Zhang Wei , Xiao Feng‐Shou
Published: October 2018

Construction of efficient interfaces to improve the performance of supported metal catalysts is a challenging but effective technique. A newly synthesized catalyst with layered cobalt oxide on the surface of titania (layer‐CoOx/TiO2) is highly selective towards the aerobic oxidation of C−H bonds in a series of hydrocarbons under sustainable conditions. The layer‐CoOx/TiO2 easily outperforms the state‐of‐the‐art noble metal catalysts and homogeneous cobalt salts used in industry. In‐depth structural and functional characterization reveal that the layer‐CoOx/TiO2 readily reacts with O2 for the adsorption and activation of C−H bonds. The layered structure of CoOx can maximize the interfacial effect of CoOx/TiO2 leading to a good performance for the oxidation of C−H bonds.
Hard Carbon as Sodium‐Ion Battery Anodes: Progress and Challenges
Authors: Xiao Biwei , Rojo Teófilo , Li Xiaolin
Published: October 2018

Hard carbon (HC) is the state‐of‐the‐art anode material for sodium‐ion batteries due to its excellent overall performance, wide availability, and relatively low cost. Recently, tremendous effort has been invested to elucidate the sodium storage mechanism in HC, and to explore synthetic approaches that can enhance the performance and lower the cost. However, disagreements remain in the field, particularly on the fundamental questions of ion transfer and storage and the ideal HC structure for high performance. This Minireview aims to provide an analysis and summary of the theoretical limitations of HC, discrepancies in the storage mechanism, and methods to improve the performance. Finally, future research on developing ideal structured HCs, advanced electrolytes, and optimized electrolyte–electrode interphases are proposed on the basis of recent progress.
Enhanced Production of γ‐Valerolactone with an Internal Source of Hydrogen on Ca‐Modified TiO2 Supported Ru Catalysts
Authors: Wojciechowska Joanna , Jędrzejczyk Marcin , Grams Jacek , Keller Nicolas , Ruppert Agnieszka M.
Published: October 2018

Calcium‐modified titania supported Ru catalysts were synthesized and evaluated for the hydrogenation of levulinic acid with formic acid as an internal hydrogen source and water as a green solvent. A new elegant photoassisted method was developed for the synthesis of uniform‐size and evenly distributed Ru particles on the titania surface. Compared with the counterpart catalysts prepared by classical wet impregnation, enhanced levulinic acid conversion and γ‐valerolactone yield were obtained and further improved through modification of the support by introduction of calcium into the titania support. This synthesis approach resulted in a change of the surface and bulk properties of the support, namely a decrease in the anatase crystallite size and the formation of a new calcium titanate phase. As a consequence, the properties of the catalysts were modified, and smaller ruthenium particles that had stronger interactions with the support were obtained. This affected the strength of the CO adsorption on the catalyst surface and facilitated the reaction performance. The optimum size of Ru particles that allowed for most efficient levulinic acid conversion was established.
Catalytic Hydrotreatment of Humins to Bio‐Oil in Methanol over Supported Metal Catalysts
Authors: Cheng Ziwei , Saha Basudeb , Vlachos Dionisios G.
Published: October 2018

Invited for this month's cover is the group of Dionisios G. Vlachos at the Catalysis Center for Energy Innovation (CCEI), University of Delaware. The image shows the catalytic hydrotreatment of humins byproduct derived from the aqueous processing of carbohydrates to form valuable chemicals. The Full Paper itself is available at 10.1002/cssc.201801535.
Size‐dependent movement explains why bigger is better in fragmented landscapes
Authors: Hillaert Jasmijn , Hovestadt Thomas , Vandegehuchte Martijn L. , Bonte Dries
Published: October 2018

Body size is a fundamental trait known to allometrically scale with metabolic rate and therefore a key determinant of individual development, life history, and consequently fitness. In spatially structured environments, movement is an equally important driver of fitness. Because movement is tightly coupled with body size, we expect habitat fragmentation to induce a strong selection pressure on size variation across and within species. Changes in body size distributions are then, in turn, expected to alter food web dynamics. However, no consensus has been reached on how spatial isolation and resource growth affect consumer body size distributions. Our aim was to investigate how these two factors shape the body size distribution of consumers under scenarios of size‐dependent and size‐independent consumer movement by applying a mechanistic, individual‐based resource–consumer model. We also assessed the consequences of altered body size distributions for important ecosystem traits such as resource abundance and consumer stability. Finally, we determined those factors that explain most variation in size distributions. We demonstrate that decreasing connectivity and resource growth select for communities (or populations) consisting of larger species (or individuals) due to strong selection for the ability to move over longer distances if the movement is size‐dependent. When including size‐dependent movement, intermediate levels of connectivity result in increases in local size diversity. Due to this elevated functional diversity, resource uptake is maximized at the metapopulation or metacommunity level. At these intermediate levels of connectivity, size‐dependent movement explains most of the observed variation in size distributions. Interestingly, local and spatial stability of consumer biomass is lowest when isolation and resource growth are high. Finally, we highlight that size‐dependent movement is of vital importance for the survival of populations or communities within highly fragmented landscapes. Our results demonstrate that considering size‐dependent movement is essential to understand how habitat fragmentation and resource growth shape body size distributions—and the resulting metapopulation or metacommunity dynamics—of consumers.
Accounting for observation processes across multiple levels of uncertainty improves inference of species distributions and guides adaptive sampling of environmental DNA
Authors: Davis Amy J. , Williams Kelly E. , Snow Nathan P. , Pepin Kim M. , Piaggio Antoinette J.
Published: October 2018

Understanding factors that influence observation processes is critical for accurate assessment of underlying ecological processes. When indirect methods of detection, such as environmental DNA, are used to determine species presence, additional levels of uncertainty from observation processes need to be accounted for. We conducted a field trial to evaluate observation processes of a terrestrial invasive species (wild pigs‐ Sus scrofa) from DNA in water bodies. We used a multi‐scale occupancy analysis to estimate different levels of observation processes (detection, p): the probability DNA is available per sample (θ), the probability of capturing DNA per extraction (γ), and the probability of amplification per qPCR run (δ). We selected four sites for each of three water body types and collected 10 samples per water body during two months (September and October 2016) in central Texas. Our methodology can be used to guide sampling adaptively to minimize costs while improving inference of species distributions. Using a removal sampling approach was more efficient than pooling samples and was unbiased. Availability of DNA varied by month, was considerably higher when water pH was near neutral, and was higher in ephemeral streams relative to wildlife guzzlers and ponds. To achieve a cumulative detection probability >90% (including availability, capture, and amplification), future studies should collect 20 water samples per site, conduct at least two extractions per sample, and conduct five qPCR replicates per extraction. Accounting for multiple levels of uncertainty of observation processes improved estimation of the ecological processes and provided guidance for future sampling designs.
The impact of artificial light at night on nocturnal insects: A review and synthesis
Authors: Owens Avalon C. S. , Lewis Sara M.
Published: October 2018

In recent decades, advances in lighting technology have precipitated exponential increases in night sky brightness worldwide, raising concerns in the scientific community about the impact of artificial light at night (ALAN) on crepuscular and nocturnal biodiversity. Long‐term records show that insect abundance has declined significantly over this time, with worrying implications for terrestrial ecosystems. The majority of investigations into the vulnerability of nocturnal insects to artificial light have focused on the flight‐to‐light behavior exhibited by select insect families. However, ALAN can affect insects in other ways as well. This review proposes five categories of ALAN impact on nocturnal insects, highlighting past research and identifying key knowledge gaps. We conclude with a summary of relevant literature on bioluminescent fireflies, which emphasizes the unique vulnerability of terrestrial light‐based communication systems to artificial illumination. Comprehensive understanding of the ecological impacts of ALAN on diverse nocturnal insect taxa will enable researchers to seek out methods whereby fireflies, moths, and other essential members of the nocturnal ecosystem can coexist with humans on an increasingly urbanized planet.
Rainfall pulse response of carbon fluxes in a temperate grass ecosystem in the semiarid Loess Plateau
Authors: Tang Yakun , Jiang Jun , Chen Chen , Chen Yunming , Wu Xu
Published: October 2018

Rainfall pulses can significantly influence carbon cycling in water‐limited ecosystems. The magnitude of carbon flux component responses to precipitation may vary depending on precipitation amount and antecedent soil moisture, associated with nonlinear responses of plants and soil microbes. The present study was carried out in a temperate grass ecosystem during 2013–2015 in the semiarid Loess Plateau of China, to examine the response of carbon fluxes to precipitation using the “threshold‐delay” model. The unique contribution of environmental variables such as precipitation amount and antecedent soil moisture before rainfall (SWC_antecedent) to carbon fluxes in response to rainfall was also investigated. The lower threshold of effective rainfall was 6.6 mm for gross ecosystem production (GEP), 8.5 mm for net ecosystem production (NEP), and 4.5 mm for ecosystem respiration (RE); and the upper threshold of effective rainfall was 21.4 mm for GEP and NEP, and 16.8 mm for RE. Rainfall amount was positively affected the relative rainfall responses of GEP, NEP, and RE. However, SWC_antecedent at 20 cm soil depth offset the response of GEP to rainfall pulses, and SWC_antecedent at 5 cm soil depth offset the response of NEP and RE to rainfall pulses, with corresponding partial slopes of linear regressions of −0.50, −0.40, and −0.52. These results indicated that NEP was more sensitive to rainfall pulses and RE was more sensitive to SWC_antecedent. These results demonstrate the importance of rainfall events of <10 mm and that the negative effect of SWC_antecedent should also be considered when estimating ecosystem carbon fluxes in this semiarid region.
Synthesis and Characterization of Paraffin/Metal Organic Gel Derived Porous Carbon/Boron Nitride Composite Phase Change Materials for Thermal Energy Storage
Authors: Atinafu Dimberu G. , Dong Wenjun , Wang Jingjing , Huang Xiubing , Wang Jiawei , Gao Hongyi , Wang Ge
Published: October 2018

New shape‐stabilized paraffin/porous carbon materials derived from metal organic gel (cMOG)/boron nitride (BN) composites were prepared by the impregnation method. In the composites, paraffin was used as phase change material, while cMOG as a supporting and loading large paraffin content in the pores owing to high specific surface area and BN employed to enhance the thermal conductivity. The scanning electron microscopy images showed better filler–filler connectivity in BN/cMOG than the individual supporting materials. With the synergy of BN and cMOG, the thermal conductivity of BN/cMOG/PCM composites exhibited up to 232.1 % of pristine PCM and 82.3 % of binary BN/PCM composites at the same wt.‐% of BN. The latent heat as‐synthesized composite attains up to 163.1 J/g with up to 80 wt.‐% of paraffin retained in the composites without any leakage. In addition, the composites revealed enhanced heat transfer performance in both the solid and liquid states. Similarly, the XRD and FTIR analysis showed excellent chemical compatibility between paraffin and the supporting materials. In addition, the composite has high thermal stability, reduced supercooling extent, and better reliability after 200 times thermal cycling, which indicate a promising method for large‐scale thermal energy storage.
Ethanol From Olive Paste During Malaxation, Exploratory Experiments
Authors: Masella Piernicola , Guerrini Lorenzo , Angeloni Giulia , Zanoni Bruno , Parenti Alessandro
Published: October 2018

Ethanol is a precursor of ethyl esters in olive oil. Its presence is generally ascribed to microbial degradation of damaged olives. At the same time, it is an anaerobic metabolite that naturally accumulates in olive fruit during ripening. As the possible link with olive processing is poorly studied, this laboratory‐scale experiment measures gaseous ethanol in the headspace above olive paste malaxated in sealed conditions. Malaxation take place in the presence or absence of oxygen, using sanitized or untreated olives. The findings show that ethanol accumulates in the headspace in oxygenated trials, reaching roughly 80 μmol kg−1 of olive paste. Under anoxic conditions ethanol accumulation is ten times higher, while olive treatment is not significant. Ethanol kinetics during malaxation are modeled as a biexponential system in which two components are simultaneously present, originating from parallel reactions at different constant rates. The first is the ethanol present in the olives and gradually released in the headspace. The second is ethanol neoformation under anoxic conditions. Under oxygenated conditions, the first component predominates, while under anoxic conditions, the opposite holds.

Practical Application: Online monitoring of gaseous ethanol above olive paste during malaxation could easily be implemented in olive oil processing plants. Ethanol kinetics could indicate the presence of unwanted anoxic conditions and help in setting appropriate oxygen levels in the kneaded paste. Future studies may find a link between ethanol kinetics in the malaxation headspace, and the occurrence of ethyl esters in oils. If this is the case, operators would be able to fine‐tune the process to avoid unwanted effects.

Ethanol is an anaerobic metabolite that naturally accumulates in olive fruit during ripening. Gaseous ethanol is found to be released from the olive paste during malaxation (sealed conditions). Furthermore, under anoxicity, the ethanol release is roughly ten times higher in response to the absence of oxygen, that is, cell anaerobic respiration take place.
Conjugated Autoxidizable Triene‐Based (CAT and ApoCAT) Assays: Their Practical Application for Screening of Crude Plant Extracts with Antioxidant Functions in Relevant to Oil‐in‐Water Emulsions
Authors: Phonsatta Natthaporn , Luangpituksa Pairoj , Figueroa‐Espinoza Maria Cruz , Lecomte Jérôme , Durand Erwann , Villeneuve Pierre , Visessanguan Wonnop , Deetae Pawinee , Uawisetwathana Umaporn , Pongprayoon Wasinee , Panya Atikorn
Published: October 2018

Many previous reports suggested that conventional antioxidant assays could not forecast antioxidant performance of plant extracts, especially when it came to a real food system such as oil‐in‐water emulsion. In this study, antioxidant activities of aqueous and ethanolic plant extracts are investigated using multiple conventional assays (TPC, ABTS, FRAP, ORAC) and the oil‐in‐water (O/W) emulsion‐based high throughput assays (the CAT and ApoCAT) in a comparison with an autoxidative O/W emulsion model monitored by formation of lipid hydroperoxide and TBARS values. Results suggest that only the ApoCAT assay is able to forecast the antioxidative performances of the extracts in O/W emulsions, regardless of the differences in extraction solvents, while the CAT assay can explain only the performance of ethanolic plant extracts in O/W emulsions. According to untargeted metabolite analysis, the antioxidants activities of plant extracts might be strongly influenced by extraction solvents. As a result, not only is the quantity of particular metabolites impacted, but also the whole metabolite (antioxidant) profiles of the extracts are modified. In addition, this study demonstrates that both the chemical reaction scheme and physical‐state of a model are important parameters for designing a better antioxidant assay in the future.

Practical Applications: The ApoCAT assay would be a more practical method for screening antioxidant compounds and/or crude plant extracts than conventional antioxidant assays and the original CAT assay. The antioxidant capacity of plant extracts obtaining from the ApoCAT can be used to represent their antioxidant performances in food emulsions regardless of their extraction solvents.

Several crude plant extracts using different solvents are used to validate the performance of the CAT and the ApoCAT assays in comparisons with multiple conventional antioxidant assays. These assays differ from each other in terms of scheme of reaction and physical state of the test. In addition, oil‐in‐water (O/W) emulsion model is used as a reference method representing the antioxidant activities in food matrices. Principal component analysis (PCA) is performed to better understand the relationship among all assays. The results suggest that only the ApoCAT assay exhibits a close relationship with O/W emulsion model in both crude ethanolic and aqueous plant extracts. Furthermore, putative metabolite profiles of crude plant extracts are identified using LC‐orbitrap MS/MS.
Phytochemical Content, Minor‐Constituent Compositions, and Antioxidant Capacity of Screw‐Pressed Walnut Oil Obtained from Roasted Kernels
Authors: Gao Pan , Cao Yi , Liu Ruijie , Jin Qingzhe , Wang Xingguo
Published: October 2018

The screw‐pressed walnut oil produced from unroasted kernels and roasted kernels subjected to roasting at 140, 160, and 180 °C for 5, 10, and 15 min is analyzed and compared. The effects of roasting on the chemical compositions (acid value, peroxide value, fatty acid composition, tocopherols, phytosterols, squalene, and polyphenols), oxidative stability index (OSI), and free radical scavenging capacity (via DPPH, ABTS, FRAP, and ORAC assays) of walnut oil is investigated. It is observed that roasting yields slight changes in the acid values and fatty acid contents of walnut oils. Upon roasting walnut kernels at 180 °C for 10 and 15 min, the peroxide values (5.10 and 5.87 mmol kg−1) of oil are significantly increased. Roasting is observed to cause an increase in the amount of tocopherols (470.16–508.68 mg kg−1), phytosterols (1740.91–2048.05 mg kg−1), and polyphenols (30.08–44.82 mg GAE/kg) in the oil whereas the level of squalene (3.17–5.90 mg kg−1) decreases. In addition, the oxidative stability and antioxidant capacity of walnut oil increases with roasting, which could increase the amount of natural antioxidants in walnut oil, and produce Maillard reaction products with antioxidant effects.

Practical Applications: Cold‐pressed oil is a good source of bioactive components and is favored by consumers. Screw‐pressed walnut oil obtained from roasted kernels has higher amounts of micronutrients, such as tocopherols, polyphenols, and phytosterols. These compounds exhibit strong antioxidant properties and thus are considered as health‐promoting substances. In effect, roasting is a suitable cold‐press pre‐processing method to produce walnut oil for application in healthcare.

An analytic comparison is made of cold‐pressed walnut oil produced from unroasted kernels and roasted kernels that had previously undergone roasting. The qualitative and quantitative effects of roasting temperature and duration on the content of natural antioxidants in walnut oil are determined. Roasting walnut oil has significantly higher oxidative stability and free radical scavenging capacity than unroasted walnut oil.
β‐sitosterol Lipid Nano Carrier Based on Propolis Wax and Pomegranate Seed Oil: Effect of Thermal Processing, pH, and Ionic Strength on Stability and Structure
Authors: Soleimanian Yasamin , Goli Sayed Amir Hossein , Varshosaz Jaleh , Maestrelli Francesca
Published: October 2018

The β‐sitosterol‐loaded nanostructured lipid carrier (NLC) is formulated using propolis wax (PW) alone or in the mixture (1:1 w/w) with glyceryl behenate (GB), and pomegranate seed oil stabilized with Tween 80 and lecithin. The influence of thermal treatment (60‐90 °C, pH 7, 20 min), pH (2, 4, 6, and 8) and ionic strength (0–200 mM NaCl, pH 7) on physical stability, structure, and β‐sitosterol degradation is evaluated. The NLCs are physically and chemically stable during heating at low temperatures (≤70 °C) while thermal treatment at 80–90 °C leads to an increase in size and a slight decrease in β‐sitosterol content. The particle size of PW and PW + GB NLCs increases from 96 and 105 nm at pH 7 to 108 and 114 nm at pH 2, respectively, which may limit NLC long‐term stability in highly acidic products. On the other hand, there is no significant difference in particle size and PDI with respect to electrolyte concentration. The NLC does not undergo polymorphic transitions by changes in pH and ionic strength. However, crystallinity decreases with increasing electrolyte concentration which is further confirmed by differential scanning calorimetry results. The β‐sitosterol NLC relatively showed a suitable potential for industrial applications.

Practical Applications: β‐sitosterol has many valuable physiological functions in humans which has made it an attractive nutraceutical ingredient for food fortifications. Nevertheless, incorporation of β‐sitosterol in food and beverages is rather challenging since it is almost insoluble in water and only slightly soluble in oils. NLC based on PW and PSO offer a promising means for delivery of β‐sitosterol to aqueous‐based foods and developing functional health promoting products by virtue of supplementary health benefits in addition to those of β‐sitosterol. However, functionality and dispersibility of formulations could be affected by environmental stresses typically experienced by foods during production and storage. Thus, behavior of emulsions at different conditions should be examined. NLC with relatively good physical and chemical stability to thermal processing, pH, and salt can be created using Tween 80 and lecithin as interfacial coating and PW as lipid matrix which ensures the successful delivery of β sitosterol to various food formats.

Nanostructured lipid carriers made with propolis wax (PW) alone or in the mixture with glyceryl behenate (GB) and pomegranate seed oil and loaded with β‐sitosterol. Influence of environmental stresses typically encountered by food products on stability.
Voltammetric Determination of Amino Acids Based on the Measurement of Reduction Prepeak of Quinone Caused by Surplus Acid after Neutralization
Authors: Kotani Akira , Kitamura Kanae , Kusu Fumiyo , Yamamoto Kazuhiro , Hakamata Hideki
Published: October 2018

In the voltammetric reduction of quinone, such as 3,5‐di‐tert‐butyl‐1,2‐benzoquinone (DBBQ), in the presence of HCl, a reduction prepeak of DBBQ caused by HCl can be observed on a voltammogram. Here, we have shown that the prepeak height of DBBQ is linearly decreased with increasing concentrations of amino acid in an electrolyte solution when this voltammetry is performed after neutralization between amino acids and excess HCl. This finding is based on a concept of acid‐base back titration of amino acids with excess HCl where surplus HCl gives a reduction prepeak of DBBQ. In this study, the reduction behaviors of DBBQ in the presence of amino acids and HCl have been provided to develop a novel electroanalytical method for the determining of amino acids. Electrochemical detection of 20 kinds of α‐amino acids, including less electroactive ones, has been achieved using a bare plastic formed carbon working electrode. Moreover, a flow injection analysis with electrochemical detection system using a glassy carbon working electrode is developed based on the present detection principle, and it has been applied to the determination of glutamine in an L‐glutamine granulated powder.