bluuebunny/crossref_metadata_2025 huggingface dataset:
Effects of maximum residue limit of triflumezopyrim exposure on fitness of the red imported fire ant Solenopsis invicta
Authors: Li Qiting , Zhao Fei , Li Jiayi , Tao QiuHong , Gao JiaQian , Lu Yong-Yue , Wang Lei
Published: December 2019

The impact of exposure to free feeding concentrations of triflumezopyrim to the red imported fire ant, Solenopsis invicta, in maximum residue tolerances for 56 days was investigated to understand whether triflumezopyrim, a novel neonicotinoid, poses unacceptable risks to the environment. Our results demonstrated that neither 0.5 μg/ml nor 0.2 μg/ml triflumezopyrim have a significant impact on the growth of the S. invicta colony and their food consumption (sugar water and locusts) during the length of treatment. While both 0.5 μg/ml and 0.2 μg/ml triflumezopyrim improved the grasping ability of S. invicta, and 0.5 μg/ml not 0.2 μg/ml triflumezopyrim increased their rate of locomotion. In addition, although 0.5 μg/ml and 0.2 μg/ml triflumezopyrim increased their individual aggressiveness index, the probability of the survival of S. invicta was not impacted by triflumezopyrim treatments in aggressive group encounters. This study suggests that triflumezopyrim did not have a negative impact on the fitness of S. invicta at 0.5 μg/ml and 0.2 μg/ml exposures.
Inhibition of UBE2L6 attenuates ISGylation and impedes ATRA‐induced differentiation of leukemic cells
Authors: Orfali Nina , Shan‐Krauer Deborah , O’Donovan Tracey R. , Mongan Nigel P. , Gudas Lorraine J. , Cahill Mary R. , Tschan Mario P. , McKenna Sharon L.
Published: December 2019

Ubiquitin/ISG15‐conjugating enzyme E2L6 (UBE2L6) is a critical enzyme in ISGylation, a post‐translational protein modification that conjugates the ubiquitin‐like modifier, interferon‐stimulated gene 15 (ISG15), to target substrates. Previous gene expression studies in acute promyelocytic leukemia (APL) cells showed that all‐trans‐retinoic acid (ATRA) altered the expression of many genes, including UBE2L6 (200‐fold) and other members of the ISGylation pathway. Through gene expression analyses in a cohort of 98 acute myeloid leukemia (AML) patient samples and in primary neutrophils from healthy donors, we found that UBE2L6 gene expression is reduced in primary AML cells compared with normal mature granulocytes. To assess whether UBE2L6 expression is important for leukemic cell differentiation—two cell line models were employed: the human APL cell line NB4 and its ATRA‐resistant NB4R counterpart, as well as the ATRA‐sensitive human AML HL60 cells along with their ATRA‐resistant subclone—HL60R. ATRA strongly induced UBE2L6 in NB4 APL cells and in ATRA‐sensitive HL60 AML cells, but not in the ATRA‐resistant NB4R and HL60R cells. Furthermore, short hairpin (sh)RNA‐mediated UBE2L6 depletion in NB4 cells impeded ATRA‐mediated differentiation, suggesting a functional role for UBE2L6 in leukemic cell differentiation. In addition, ATRA induced ISG15 gene expression in NB4 APL cells, leading to increased levels of both free ISG15 protein and ISG15 conjugates. UBE2L6 depletion attenuated ATRA‐induced ISG15 conjugation. Knockdown of ISG15 in NB4 APL cells inhibited ISGylation and also attenuated ATRA‐induced differentiation. In summary, we demonstrate the functional importance of UBE2L6 in ATRA‐induced neutrophil differentiation of APL cells and propose that this may be mediated by its catalytic role in ISGylation.
Genetics of Gallstone Disease
Authors: Weber Susanne N. , Lammert Frank
Published: December 2019

Gallstone disease is one of the most frequent diseases, with up to 20% of adults developing gallstones and >20% of them symptoms. The treatment of symptomatic stones and their complications by endoscopy and surgery causes high costs in health care systems. Linkage studies in families and twins demonstrated that gallstones are, in part, genetically determined. Genome‐wide association studies have identified a panel of more than 30 ‘lithogenic genes’ that confer gallstone susceptibility in humans. The largest population attributable risk is conferred by variant p.D19H of the hepatobiliary and intestinal cholesterol transporter ABCG5/G8. Deficiency of a second hepatobiliary ABC transporter, the phosphatidylcholine translocase ABCB4, causes a peculiar type of gallstone disease and chronic cholangiopathy. Other lithogenic genes affect metabolic and inflammatory pathways along the gut–liver axis. Understanding the pathobiology of gallstones might help to overcome the current invasive treatment of gallstone disease by personalised effective prevention strategies for patients at risk.

Key Concepts

Gallstone disease is a complex disease affected by exogenous and genetic risk factors.

The hepatobiliary cholesterol transporter
ABCG5/G8
represents the major lithogenic gene in humans.

ABCB4 deficiency causes
low phospholipid‐associated cholelithiasis
(
LPAC
).

α
1
‐Antitrypsin (
SERPINA1
) and adiponutrin (
PNPLA3
) mutations do not only cause chronic liver diseases but modify gallstone disease.

In the future, polygenic risk scores for gallstone disease might guide prevention and non‐invasive treatment strategies.
Characterization of the In Situ‐Formed Oxide Layer at the Steel Melt/Carbon‐Bonded Alumina Interface
Authors: Zienert Tilo , Dudczig Steffen , Malczyk Piotr , Brachhold Nora , Aneziris Christos G.
Published: December 2019

The surface structure development of the in situ‐formed oxide layer on carbon‐bonded alumina refractory samples immersed in liquid 42CrMo4 steel at a temperature of 1650 °C is studied. The surface morphology is characterized using areal parameters such as the developed interfacial area ratio Sdr, the texture aspect ration Str, the arithmetic mean peak curvature Spc, the density of peaks Spd, and the maximum height Sz defined in ISO 25178‐2:2012 and on the basis of own defined parameters using laser‐optical measured line profiles of the surface's height. The development of the surface morphology is found to be independent of the oxygen content of the steel melt at immersion time. The formed crystal structures are based on alumina and an (Al, Fe, Mg, Mn)‐containing spinel. The spinel's lattice parameters are found to vary between 8.0367 and 8.1194 Å corresponding to oxygen contents of the steel melt between 30 and 85 ppm.
Full‐Scale Osteochondral Regeneration by Sole Graft of Tissue‐Engineered Hyaline Cartilage without Co‐Engraftment of Subchondral Bone Substitute
Authors: Nie Xiaolei , Yang Jian , Chuah Yon Jin , Zhu Wenzhen , Peck Yvonne , He Pengfei , Wang Dong‐An
Published: December 2019

In this study, full‐scale osteochondral defects are hypothesized, which penetrate the articular cartilage layer and invade into subchondral bones, and can be fixed by sole graft of tissue‐engineered hyaline cartilage without co‐engraftment of any subchondral bone substitute. It is hypothesized that given a finely regenerated articular cartilage shielding on top, the restoration of subchondral bones can be fulfilled via spontaneous self‐remodeling in situ. Hence, the key challenge of osteochondral regeneration lies in restoration of the non‐self‐regenerative articular cartilage. Here, traumatic osteochondral lesions to be repaired in rabbit knee models are endeavored using novel tissue‐engineered hyaline‐like cartilage grafts that are produced by 3D cultured porcine chondrocytes in vitro. Comparative trials are conducted in animal models that are implanted with living hyaline cartilage grafts (LhCG) and decellularized LhCG (dLhCG). Sound osteochondral regeneration is gradually revealed from both LhCG and dLhCG‐implanted samples 50–100 d after implantation. Quality regeneration in both zones of articular cartilage and subchondral bones are validated by the restored osteochondral composition, structure, phenotype, and mechanical property, which validate the hypothesis of this study.
Improving the Curing and Mechanical Properties of Short Carbon Fibers/Epoxy Composites by Grafting Nano ZIF‐8 on Fibers
Authors: Zhan Yixing , Wang Yating , Wang Ming , Ding Xiaoqing , Wang Xinlong
Published: December 2019

The nano metal–organic framework particles (nano ZIF‐8) are grafted onto the surface of short carbon fibers (SCFs) by a facile in situ growth method in order to functionalize SCFs. The morphology, crystal structure, and chemical element composition of modified SCFs (ZIF‐8@SCFs) are investigated. The grafted nano‐ZIF‐8 could remarkably enhance the roughness, polarity, and wettability of SCFs surface and promote the curing reaction of epoxy composites. The tensile strength, flexural strength, elastic modulus, toughness, and impact strength of the epoxy composites with 1 wt% ZIF‐8@SCFs are increased by 25%, 31%, 51%, 28%, and 42% compared to that of the composites with 1 wt% SCFs, respectively. Furthermore, the storage modulus (E′) and glass transition temperature (Tg) are enhanced from 2558 MPa and 108.2 °C to 3000 MPa and 147.6 °C. The significant improvement in mechanical and thermomechanical properties of the prepared composites could be ascribed to the ameliorated wettability, enhanced mechanical interlock, and increased chemical bonding induced by ZIF‐8@SCFs.
Noble Metal Free, Visible Light Driven Photocatalysis Using TiO2 Nanotube Arrays Sensitized by P‐Doped C3N4 Quantum Dots
Authors: Kumar Pawan , Kar Piyush , Manuel Ajay P. , Zeng Sheng , Thakur Ujwal K. , Alam Kazi M. , Zhang Yun , Kisslinger Ryan , Cui Kai , Bernard Guy M. , Michaelis Vladimir K. , Shankar Karthik
Published: December 2019

Bulk g‐C3N4 is an earth‐abundant, easily synthesizable, and exceptionally stable photocatalyst with an electronic bandgap of 2.7 eV. Herein, the concepts of P‐doping and size quantization are combined to synthesize highly fluorescent P‐doped carbon nitride quantum dots (CNPQDs) with a bandgap of 2.1 eV. CNPQDs are hosted on anatase‐phase and rutile‐phase TiO2 nanotube array scaffolds, and examined as photoanodes for sunlight‐driven water‐splitting and as photocatalysts for surface catalytic reactions. Square‐shaped rutile phase TiO2 nanotube arrays (STNAs) decorated with CNPQDs (CNPQD‐STNA) generate 2.54 mA cm−2 photocurrent under AM1.5 G simulated sunlight. A champion hydrogen evolution rate of 22 µmol h−1 corresponds to a Faradaic efficiency of 93.2%. In conjunction with Ag nanoparticles (NPs), the CNPQD‐STNA hybrid is also found to be an excellent plexcitonic photocatalyst for the visible light‐driven transformation of 4‐nitrobenzenethiol (4‐NBT) to dimercaptoazobenzene (DMAB), producing reaction completion at a laser power of 1 mW (532 nm) while Ag NP/TNA and Ag NP/STNA photocatalysts cannot complete this transformation even at 10 mW laser power. The results point the way forward for photochemically robust, noble metal free, visible light harvesting photoacatalysts based on nanostructured heterojunctions of graphenic frameworks with TiO2.
Synthesis of 2,2,2‐Trifluoroethyl Oxazoles, Oxazolines and Furans via Alkyne Oxytrifluoromethylation
Authors: Dong Jia‐Jia , Zhang Song‐Lin
Published: December 2019

This study reports an oxytrifluoromethylation method for construction of oxazoles and furans motif and the concurrent incorporation of a 2,2,2‐trifluoroethyl group at the aromatic C5‐position. High‐valent copper(III) trifluoromethyl compounds are crucial to this reaction that induces oxy‐trifluoromethylation of alkynes with a pendant amide/enol group functioning as the oxygen‐nucleophile. A wide substrate scope is demonstrated with high efficiency and with broad functional group tolerance. Late‐stage functionalization of dehydrocholic acid, a complex drug compound, is accomplished to show the potential of this method for practical drug design.

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Enantioselective Heck Arylation of Acyclic Alkenol Aryl Ethers: Synthetic Applications and DFT Investigation of the Stereoselectivity
Authors: Polo Ellen Christine , Wang Martí Fernández , Angnes Ricardo Almir , Braga Ataualpa A. C. , Correia Carlos Roque Duarte
Published: December 2019

Herein we report the enantioselective Heck‐Matsuda arylation of acyclic E and Z‐alkenyl aryl ethers. The reactions were carried out under mild conditions affording the enantioenriched benzyl ethers in a regioselective manner, moderate to good yields (up to 73%), and in good to excellent enantiomeric ratios (up to 97:3). The enantioselective Heck‐Matsuda arylation has shown a broad scope (25 examples), and some key Heck‐Matsuda adducts were further converted into more complex and valuable scaffolds including their synthetic application in the synthesis of (R)‐Fluoxetine, (R)‐Atomoxetine, and in the synthesis of an enantioenriched benzo[c]chromene. Finally, in silico mechanistic investigations into the reaction's enantioselectivity were performed using density functional theory.

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Rare‐Earth‐Metal‐Catalyzed Synthesis of Azaindolines and Naphthyridines via C−H Cyclization of Functionalized Pyridines
Authors: Ye Pengqing , Shao Yinlin , Zhang Fangjun , Zou Jinxuan , Ye Xuanzeng , Chen Jiuxi
Published: December 2019

We report herein a rare‐earth‐metal‐catalyzed insertion of a 2‐pyridine C(sp2)−H bond into an intramolecular unactivated vinyl bond. This reaction provides streamlined access to a range of azaindolines in moderate to excellent yields. The salient features of this reaction include simple and mild reaction conditions, 100% atom efficiency, and wide substrate scope. This methodology is also used to construct other nitrogen‐containing compounds such as naphthyridine derivatives. A plausible mechanism for the formation of azaindolines involving initial C−H bond activation by the lanthanide complex followed by C=C insertion into a Ln−C bond to form an alkyl lanthanide species that subsequently undergoes cyclization is proposed.

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Cobalt‐Free High‐Capacity Ni‐Rich Layered Li[Ni0.9Mn0.1]O2 Cathode
Authors: Aishova Assylzat , Park Geon‐Tae , Yoon Chong S. , Sun Yang‐Kook
Published: December 2019

Li[Ni0.9Co0.1]O2 (NC90), Li[Ni0.9Co0.05Mn0.05]O2 (NCM90), and Li[Ni0.9Mn0.1]O2 (NM90) cathodes are synthesized for the development of a Co‐free high‐energy‐density cathode. NM90 maintains better cycling stability than the two Co‐containing cathodes, particularly under harsh cycling conditions (a discharge capacity of 236 mAh g−1 with a capacity retention of 88% when cycled at 4.4 V under 30 °C and 93% retention when cycled at 4.3 V under 60 °C after 100 cycles). The reason for the enhanced stability is mainly the ability of NM90 to absorb the strain associated with the abrupt anisotropic lattice contraction/extraction and to suppress the formation of microcracks, in addition to enhanced chemical stability from the increased presence of stable Mn4+. Although the absence of Co deteriorates the rate capability, this can be overcome as the rate capability of the NM90 approaches that of the NCM90 when cycled at 60 °C. The long‐term cycling stability of NM90 is confirmed in a full cell, demonstrating that it is one of the most promising Co‐free cathodes for high‐energy‐density applications. This study not only provides insight into redefining the role of Mn in a Ni‐rich cathode, it also represents a clear breakthrough in achieving a commercially viable Co‐free Ni‐rich layered cathode.
Hopper flows of mixtures of spherical and rod‐like particles via the multisphere method
Authors: Lattanzi Aaron M. , Stickel Jonathan J.
Published: December 2019

The discharge of granular media from hoppers plays a vital role in many solids handling operations. The dynamic flow of poly‐disperse nonspherical particles differs markedly from mono‐disperse spheres and highlights the need to rigorously account for particle shape effects. The multisphere discrete element method (MS‐DEM) was utilized here to examine the bulk packing fraction, discharge rate, collisional stress tensor, and order parameter of a bi‐disperse sphere‐rod mixture evacuating a hopper. A modified form of the Myers and Sellers correlation with variable shape factor is capable of replicating the MS‐DEM discharge data. The collisional stress tensor is observed to be highly symmetric for mono‐disperse spheres but becomes asymmetric when rod‐like particles are introduced. The order parameter within the hopper increases significantly during discharge and the rod‐like particles undergo shear induced alignment with their long dimensions orthogonal to the outflow plane.
Mesoporous zirconium–silica nanocomposite modified with heteropoly tungstophosphoric acid catalyst for ultra‐deep oxidative desulfurization
Authors: Yuzbashi S. , Mousazadeh M.H. , Ramezani N. , Sid Kalal H. , Sabour B.
Published: December 2019

An adsorbent catalyst was proposed to reduce the leaching of active species of the catalyst and enhance the kinetics of the oxidative desulfurization (ODS) reaction of dibenzothiophene (DBT) from model diesel fuel. By loading phosphotungstic acid (HPW) species onto a zirconium‐modified hexagonal mesoporous silica (Zr‐HMS), a novel catalyst was synthesized and utilized for the ODS process. An ultrafast ODS kinetics was specifically identified using 20%HPW/Zr‐HMS as catalyst. Within 30 min, more than 95% of the 350 ppm DBT content of the model fuel was oxidized by H2O2. The synthesized catalyst retained its sulfur removal ability even after five subsequent ODS reactions and the leaching of HPW species was found to be suppressed successfully. Overall, this new reusable catalyst provided an alternative for highly efficient ultra‐deep desulfurization process.
Design and synthesis of the honeycomb PtSnNa/ZSM‐5 monolithic catalyst for propane dehydrogenation
Authors: Tong Qing , Zhao Shiyong , Liu Yubing , Xu Bolian , Yu Lei , Fan Yining
Published: December 2019

A novel PtSnNa/ZSM‐5 monolithic catalyst was designed and synthesized for the propane dehydrogenation reaction, which was a significant transformation in industry. Experimental results showed that although the propane conversion and the propylene selectivity gradually fell down along with the reaction time, the descent speed of the PtSnNa/ZSM‐5 monolithic catalyst was slower than that of the granule catalyst and the propane conversion and propylene selectivity of the reaction with monolithic catalyst still remained at a high level after 12 hr. The monolithic catalyst had regular pore structure that facilitated the separation of the product from the catalyst and reduced the limitation on internal and external diffusion and mass transfer, and led to the high catalytic activity and stability. The catalyst could be easily fabricated and was of highly industrial application potential.
Passive monitoring of phenological acoustic patterns reveals the sound of the camouflage grouper, Epinephelus polyphekadion
Authors: Jublier Noémie , Bertucci Frédéric , Kéver Loïc , Colleye Orphal , Ballesta Laurent , Nemeth Richard S. , Lecchini David , Rhodes Kevin L. , Parmentier Eric
Published: December 2019

Passive acoustic monitoring (PAM) is a non‐invasive technique that uses hydrophones to monitor populations and ecosystem dynamics. Although many applications of PAM have been developed in recent years, it has never been used to identify a calling marine species.

The south pass of Fakarava Atoll, French Polynesia, hosts spawning events of many reef fish species, including the camouflage grouper Epinephelus polyphekadion, with a spawning aggregation abundance exceeding 17 000 individuals during the full moons of June and July.

The current study aimed to use PAM to distinguish camouflage grouper sounds among the vocal activities of all fish recorded during the aggregation periods. Audio recordings analysis resulted in the identification of 29 sound types, some of which showed diel and lunar patterns.

Temporal analysis of these sounds in relation to spawning activities allowed the identification of camouflage grouper calls. These calls can be described as a single pulse or a series of ‘boom(s)’ with a pulse duration of ~44 ms and a low dominant frequency of 103 ± 31 Hz. Video recordings show that the camouflage grouper produces the ‘booms’ to initialize spawner ascent and to promote synchronous gamete release into the water column.

The study highlights for the first time that PAM can be used to identify the previously unknown sound of a fish species. Moreover, we can use it to understand the phenology of some biological activities for improving the resolution of fish biodiversity assessments.
Peptidylarginine Deiminase Autoimmunity and the Development of Anti–Citrullinated Protein Antibody in Rheumatoid Arthritis: The Hapten–Carrier Model
Authors: Auger Isabelle , Balandraud Nathalie , Massy Emmanuel , Hemon Marie F. , Peen Elisa , Arnoux Fanny , Mariot Charlotte , Martin Marielle , Lafforgue Pierre , Busnel Jean‐Marc , Roudier Jean
Published: December 2019

Objective

The presence of autoantibodies to citrullinated proteins (ACPAs) often precedes the development of rheumatoid arthritis (RA). Citrullines are arginine residues that have been modified by peptidylarginine deiminases (PADs). PAD4 is the target of autoantibodies in RA. ACPAs could arise because PAD4 is recognized by T cells, which facilitate the production of autoantibodies to proteins bound by PAD4. We previously found evidence for this hapten–carrier model in mice. This study was undertaken to investigate whether there is evidence for this model in humans.

Methods

We analyzed antibody response to PAD4 and T cell proliferation in response to PAD4 in 41 RA patients and 36 controls. We tested binding of 65 PAD4 peptides to 5 HLA–DR alleles (DRB1*04:01, *04:02, *04:04, *01:01, and *07:01) and selected 11 PAD4 peptides for proliferation studies using samples from 22 RA patients and 27 controls. Peripheral blood lymphocytes from an additional 10 RA patients and 7 healthy controls were analyzed by flow cytometry for CD3, CD4, CD154, and tumor necrosis factor expression after PAD4 stimulation.

Results

Only patients with RA had both antibodies and T cell responses to PAD4. T cell response to peptide 8, a PAD4 peptide, was associated with RA (P = 0.02), anti‐PAD4 antibodies (P = 0.057), and the shared epitope (P = 0.05).

Conclusion

ACPA immunity is associated with antibodies to PAD4 and T cell responses to PAD4 and PAD4 peptides. These findings are consistent with a hapten–carrier model in which PAD4 is the carrier and citrullinated proteins are the haptens.
Facile Synthesis of Polysubstituted Indolizines via One‐Pot Reaction of 1‐Acetylaryl 2‐Formylpyrroles and Enals
Authors: Gong Minghua , Guo Jingcheng , Jiang Pengrui , Zhang Ye , Fu Zhenqian , Huang Wei
Published: December 2019

An efficient method for the synthesis of polysubstituted indolizines has been developed based on formal [4+2] annulation of 1‐acetylaryl 2‐formylpyrroles with enals, followed by oxidative aromatization. Pyridine‐type six‐membered rings were constructed in this transformation. This transition metal‐free reaction features mild reaction conditions, a broad substrate scope, and excellent functional group tolerance. Notably, the formyl group is well tolerated under reaction conditions.
Optimal design of non‐fragile PID controller
Authors: Elsisi Mahmoud
Published: December 2019

This paper solves the controller gains uncertainty problem, which may lead to undesirable responses and an unstable system when implemented. A non‐fragile or resilient controller can overcome this problem. The paper suggests a new method to design a non‐fragile proportional‐integral‐derivative (PID) controller for voltage regulation. This method is carried out by applying a constrained genetic algorithm (GA) as a powerful optimization technique to determine the optimal gains of the PID controller. In addition, new developed conditions from the Routh– Kharitonov theorem are taken into account during the optimization operation to ensure system stability and system response. A new time domain objective function is proposed to establish the optimal permissible limits of controller gains to ensure a constraint of good response. The results of the proposed non‐fragile PID controller are compared with the non‐constrained GA‐based PID controller, artificial bee colony (ABC) algorithm‐based PID controller, and Ziegler Nichols (ZN)‐based PID controller. This achieves better results compared with different methods. The controller gains uncertainties test is applied to ensure the non‐fragility of the proposed controller. Furthermore, the system parameters variation test is applied to check the robustness of the controller based on the suggested method. The designed PID controller by this method is more resilient and less design time is required. The proposed controller and the system are carried out and studied by utilizing MATLAB/Simulink.
Evaluating reactor hydraulics in a cost‐effective and environment‐friendly way: Numerical tracer study
Authors: Zhang Jie , Xu Xiaofan , Tejada‐Martinez Andres , Zhang Qiong , Wicklein Edward
Published: December 2019

Tracer analysis is commonly used to evaluate the hydraulics of environmental and chemical engineering systems. The traditional tracer analysis is conducted through physical experiments that are usually complex, costly, time‐intensive, and may be impractical. Because of the continued advancement of computing technology, computational fluid dynamics (CFD) has demonstrated its applicability in simulating tracer transport. CFD can provide advantages, including no interruptions of existing water treatment process, no impacts of background concentration, and a relatively low cost. However, no reports have quantitatively studied the cost that CFD can save on tracer analysis. This study first proved the accuracy of CFD tracer analysis for an existing ozone disinfection tank and then compared the economic expenses and environmental impacts of CFD tracer analysis with those of a field tracer analysis. It was found that CFD‐based tracer analysis has accuracy on par with the physical‐based study but at relatively low economic cost and environmental impacts.
A Critique of Formulaic Descriptions of Natural Product Structural Elucidations
Authors: Klika Karel D.
Published: December 2019

A commonly presented account of the structural elucidation of a natural product consists of an initial, highly detailed and fastidious NMR analysis together with HR‐MS data, followed by an X‐ray analysis, followed then by a postulated biosynthetic pathway with perhaps some bioassay results, which may be apt or appear gratuitous. But an X‐ray crystallographic‐determined structure renders any prior NMR‐based structural elucidation redundant, and moreover, an exhaustive and detailed examination of NMR contacts seems tiresome in light of an X‐ray analysis. Suggestions are therefore proffered on how the description of a structural elucidation of a natural product might alternatively be approached rather than seemingly blindly following a prescribed formula, particularly with respect to NMR and (HR‐)MS data. Also considered is which information should be in the manuscript proper and which material is better placed in the Supporting Information.
General Principles for Yield Optimization of Nucleoside Phosphorylase‐Catalyzed Transglycosylations
Authors: Kaspar Felix , Giessmann Robert T. , Hellendahl Katja F. , Neubauer Peter , Wagner Anke , Gimpel Matthias
Published: December 2019

The biocatalytic synthesis of natural and modified nucleosides with nucleoside phosphorylases offers the protecting‐group‐free direct glycosylation of free nucleobases in transglycosylation reactions. This contribution presents guiding principles for nucleoside phosphorylase‐mediated transglycosylations alongside mathematical tools for straightforward yield optimization. We illustrate how product yields in these reactions can easily be estimated and optimized using the equilibrium constants of phosphorolysis of the nucleosides involved. Furthermore, the varying negative effects of phosphate on transglycosylation yields are demonstrated theoretically and experimentally with several examples. Practical considerations for these reactions from a synthetic perspective are presented, as well as freely available tools that serve to facilitate a reliable choice of reaction conditions to achieve maximum product yields in nucleoside transglycosylation reactions.
Donor–Acceptor Type Pendant Conjugated Molecules Based on a Triazine Center with Depressed Intramolecular Charge Transfer Characteristics as Gain Media for Organic Semiconductor Lasers
Authors: Liu Xu , Sang Ming , Lin He , Liu Chengfang , Zhang Jialing , Yi Jianpeng , Gao Kun , Lai Wen‐Yong , Huang Wei
Published: December 2019

A set of fluorene‐capped pendant conjugated molecules (T‐m and T‐p), which consist of a triazine center with three carbazole substituents as the donor–acceptor (D‐A) type pendant structure, were designed, synthesized, and investigated as gain media for organic semiconductor lasers (OSLs). In particular, varying the capping positions of the fluorene units on the pendant core structures results in significantly different intramolecular charge transfer (ICT) properties, where T‐m manifested depressed ICT characteristic and high fluorescence quantum yield. The lowest amplified spontaneous emission (ASE) threshold in neat films was recorded as 1.9 μJ cm−2 for T‐m and 83.8 μJ cm−2 for T‐p, which indicated that the depressed ICT characteristics in the case of T‐m help to enhance the ASE properties. Remarkably, the ASE threshold remained almost unchanged and the ASE spectra showed very small shifts (within 1 nm) for T‐m with film samples annealed up to 180 °C in open air. In contrast, its linear counterpart 2FEtCz‐m showed a clearly increased ASE threshold upon annealing above 100 °C. The results suggest that the selective construction of conjugated pendant molecules with depressed ICT characteristics is beneficial for finely modulating the optical and electrical properties as well as improving the thermostability and photostability, which manifests the great potential as a robust gain media for OSLs.
Stimuli‐Responsive Fluorescent Nanoswitches: Solvent‐Induced Emission Enhancement of Copper Nanoclusters
Authors: Yuan Jin , Wang Ling , Wang Yitong , Hao Jingcheng
Published: December 2019

Copper nanoclusters (CuNCs) as a new class of fluorescent materials have attracted a great deal of interest due to their outstanding fluorescence properties. In this work, a variety of organic solvents were used to induce self‐assembly of glutathione‐capped CuNCs (GSH‐CuNCs) to form ordered assemblies with enhanced fluorescence properties. Assemblies with multicolor fluorescence emission were constructed on the basis of the aggregation‐induced emission (AIE) of GSH‐CuNCs and the solvent effect. The fluorescence emission from these GSH‐CuNCs assemblies can also be tuned from yellow to purple by changing the organic solvent. A possible mechanism based on the size of the assemblies and electron transfer was explored to explain the solvent effects on GSH‐CuNCs. Stimuli‐responsive nanoswitches with excellent reversibility can be controlled by changing the type of organic solvent and the ratio of the organic solvent to the aqueous solution of GSH‐CuNCs. As the CuNCs assemblies exhibit strong, stable, and color‐tunable fluorescence, they were employed as color‐conversion materials for recognizing different organic solvents.
Usefulness of methylthioadenosine phosphorylase and BRCA‐associated protein 1 immunohistochemistry in the diagnosis of malignant mesothelioma in effusion cytology specimens
Authors: Berg Kyra B. , Churg Andrew M. , Cheung Simon , Dacic Sanja
Published: December 2019

Background

The separation of benign from malignant mesothelial proliferations on effusion cytology can be difficult. Loss of methylthioadenosine phosphorylase (MTAP) by immunohistochemistry is an established marker of malignancy in mesothelial proliferations, but to the authors' knowledge largely has been applied only to biopsies. The current study was conducted to determine the usefulness of MTAP immunohistochemistry in the diagnosis of malignant mesothelioma in effusion cytology specimens.

Methods

A total of 21 effusion cytology cases of malignant mesothelioma were stained for MTAP and BRCA‐associated protein 1 (BAP1), with 15 reactive mesothelial cytology cases used as a control. Fourteen cases had a paired surgical specimen for comparison, and 7 cases were run for CDKN2A deletion by fluorescence in situ hybridization.

Results

Complete loss of MTAP cytoplasmic staining was noted in 7 of 21 effusion samples (33%), and no loss was observed in 11 effusion samples (52%); 11 of these cases had a matching surgical specimen and all 11 specimens demonstrated the same MTAP pattern. Partial loss was observed in 3 effusion specimens (80%, 40%, and 40% intact staining, respectively), but in all 3 the surgical specimen demonstrated 100% staining. None of the 15 reactive mesothelial cytology specimens demonstrated MTAP cytoplasmic loss. CDKN2A FISH demonstrated concordance in 5 of 7 cases (71%). MTAP immunohistochemistry had a sensitivity of 33% and a specificity of 100% for this differential diagnosis.

Conclusions

MTAP staining demonstrated generally good concordance between the cytologic and surgical specimens and appears to be useful in the diagnosis of mesothelioma on effusion specimens. Complete loss of MTAP is a reliable marker of malignancy, but the significance of partial loss of MTAP staining is unclear.
Molecular and histologic outcomes following spinal cord injury in spiny mice, Acomys cahirinus
Authors: Streeter Kristi A. , Sunshine Michael D. , Brant Jason O. , Sandoval Aaron G. W. , Maden Malcolm , Fuller David D.
Published: December 2019

The spiny mouse (Acomys cahirinus) appears to be unique among mammals by showing little scarring or fibrosis after skin or muscle injury, but the Acomys response to spinal cord injury (SCI) is unknown. We tested the hypothesis that Acomys would have molecular and immunohistochemical evidence of reduced spinal inflammation and fibrosis following SCI as compared to C57BL/6 mice (Mus), which similar to all mammals studied to date exhibits spinal scarring following SCI. Initial experiments used two pathway‐focused RT‐PCR gene arrays (“wound healing” and “neurogenesis”) to evaluate tissue samples from the C2–C6 spinal cord 3 days after a C3/C4 hemi‐crush injury (C3Hc). Based on the gene array results, specific genes were selected for RT‐qPCR evaluation using species‐specific primers. The results supported our hypothesis by showing increased inflammation and fibrosis related gene expression (Serpine 1, Plau, and Timp1) in Mus as compared to Acomys (p < .05). RT‐qPCR also showed enhanced stem cell and axonal guidance related gene expression (Bmp2, GDNF, and Shh) in Acomys compared to Mus (p < .05). Immunohistochemical evaluation of the spinal lesion at 4 weeks postinjury indicated less collagen IV immunostaining in Acomys (p < .05). Glial fibrillary acidic protein (GFAP) and ionized calcium binding adaptor molecule 1(IBA1) immunostaining indicated morphological differences in the appearance of astrocytes and macrophages/microglia in Acomys. Collectively, the molecular and histologic results support the hypothesis that Acomys has reduced spinal inflammation and fibrosis following SCI. We suggest that Acomys may be a useful comparative model to study adaptive responses to SCI.
Photoelectrochemical Cells for Artificial Photosynthesis: Alternatives to Water Oxidation
Authors: Ru Ng Andrew Yun , Boruah Bhanupriya , Chin Kek Foo , Modak Jayant M. , Soo Han Sen
Published: December 2019

Photoelectrochemical cells have been used as one of the most common artificial photosynthetic approaches to mimic natural photosynthetic water splitting reactions. However, despite the tremendous advances made to improve the affordability and efficiency of photoelectrochemical water splitting, it is still not an economically feasible method to produce solar fuels currently since only the H2 evolving reduction half‐reaction generates valuable fuels. Therefore, in this review, we intend to highlight other underexplored substrates and reactions for producing solar fuels in photoelectrochemical cells, as well as alternative architectures including temporally independent and biohybrid systems. We show that besides water oxidation, electrocatalytic or photoredox reactions for pollutant degradation, biomass valorization, and organic chemical synthesis can be or have been successfully adapted for photoelectrochemical cells, thus offering a virtually infinite number of possibilities for artificial photosynthetic applications which generate valuable products in both the reduction and oxidation half reactions.
Chi‐squared automatic interaction detector analysis on a choice experiment: An evaluation of responsible initiatives on consumers' purchasing behavior
Authors: Boccia Flavio , Sarnacchiaro Pasquale
Published: December 2019

Corporate social responsibility linked to consumer's behavior is a topic increasingly felt during the last years. By administering a questionnaire to consumers, the aim of the present research is to study impacts of responsible initiatives on consumers' purchasing behavior and, besides, possible willingness to pay higher prices for good practice foods. The investigation was conducted through a choice experiment, considering a representative sample of more than 1,660 families, selected on a functional relation to the objectives of the research in the major Italian cities. So the main goal is to explore consumers' preferences linked to business responsible initiatives: Data were analyzed performing a logistic regression analysis and, in order to perform the segmentation of choice, an analysis based on the chi‐squared automatic interaction detector procedure was carried out, using variables explained in the logistic regression. The conclusions are very significant and can be considered also a matter for further discussion.
Water disclosure in the mining sector: An assessment of the credibility of sustainability reports
Authors: Talbot David , Barbat Guillaume
Published: December 2019

Sustainable water resource management is a major challenge for mining companies. The objective of this article is to analyze the credibility of the information disclosed by companies in this sector as well as the strategies used to justify their water performance. To meet this objective, a qualitative content analysis of 58 Global Reporting Initiative (GRI; G4) reports was carried out. This article demonstrates a strong propensity for mining companies to disclose information that does not comply with the GRI guidelines. Moreover, the use of external verification has no impact on the quality of the information disclosed. This study also highlights several neutralization and obfuscation techniques used to justify negative information related to water performance. The results of this study have important managerial implications, particularly with regard to the effectiveness of reporting compliance with GRI standards.
Regioselective β‐Arylation of α‐Angelica Lactone through Isomerization/Addition under Mild Conditions
Authors: Zhuo Kai‐Feng , Yu Shang‐Hai , Gong Tian‐Jun , Fu Yao
Published: December 2019

The conversion of biomass‐based platform molecules into various high‐value chemicals greatly promotes the utilization of renewable biomass resources. Herein, an example of Rh‐catalyzed β‐arylation of levulinic‐acid‐derived α‐angelica lactone was reported, providing the γ‐lactone‐structure products with high regioselectivity. Both arylboronic and alkenylboronic acids could be applied in this transformation. This reaction tolerated a variety of synthetically important functional groups. Moreover, the obtained γ‐lactone products could be readily converted to high‐value products such as 1,4‐diols and γ‐methoxy‐carboxylates.
A Novel C–N Migration Rearrangement Based on N–F Compounds for the Synthesis of N‐Alkyl Diaryl Ureas
Authors: Zhao Yi‐Xiao , Xie Tian , Yang San‐Ke , Yang Xian‐Jin
Published: December 2019

A novel rearrangement reaction based on the structure of N‐fluoro‐N‐(phenylsulfonyl) benzamides (FPSBA) was developed. In the presence of base, unsymmetrical N‐alkyl diaryl ureas were obtained in good yields which were accomplished through secondary alkyl phenylamines initiated 1,2‐phenyl‐shift migration rearrangement of N‐fluoro‐N‐(phenylsulfonyl) benzamides. The reaction was carried out without using traditional, highly toxic reagents and noble metals. Whereas without rearrangement occurrence for primary phenylamines and aliphatic amines, normal amides and N‐(phenylsulfonyl) benzamides were afforded respectively. Nitrene and phenyl isocyanate included process were prevented and a secondary alkyl phenylamine initiated vicinal SN2' reaction occurred. This rearrangement reaction features an interesting reaction mechanism, mild reaction conditions, simple operation, and useful products.
Three Step Synthesis of Fully and Differently Arylated Pyridines
Authors: Arita Mao , Yokoyama Soichi , Asahara Haruyasu , Nishiwaki Nagatoshi
Published: December 2019

Condensation of β‐(2‐pyridyl)enamine and α,β‐unsaturated ketone in the presence of FeCl3 under air afforded highly substituted pyridines. In this transformation, FeCl3 acted as not only an acid catalyst but also an oxidant for the intermediate dihydropyridine. The substituents could be easily modified by altering the substrates to obtain tri‐ and tetraarylpyridines including bipyridines and terpyridine. Synthesis of differently substituted pentaarylpyridines was consequently achieved via only three steps from commercially available reagents with simple experimental manipulations.
Recyclable Bismuth Complex Catalyzed 1,6‐Conjugate Addition of Various Nucleophiles to para‐Quinone Methides: Expedient Access to Unsymmetrical Diaryl‐ and Triarylmethanes
Authors: Liang Xianghao , Xu Haiyan , Li Hanlin , Chen Lizhuang , Lu Hongfei
Published: December 2019

An efficient method for the 1,6‐conjugate addition of para‐quinone methides with readily available nucleophiles was developed. This protocol provides a straightforward access to a class of diaryl and triarylmethane derivatives with good to excellent yields in the presence of (C4H12N2)2[BiCl6]Cl·H2O. Moreover, this bismuth catalyst can be recycled for several times.
Some statistical consideration in transcriptome‐wide association studies
Authors: Xue Haoran , Pan Wei ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: December 2019

The methodology of transcriptome‐wide association studies (TWAS) has become popular in integrating a reference expression quantitative trait (eQTL) data set with an independent main GWAS data set to identify (putatively) causal genes, shedding mechanistic insights to biological pathways from genetic variants to a GWAS trait mediated by gene expression. Statistically TWAS is a (two‐sample) 2‐stage least squares (2SLS) method in the framework of instrumental variables analysis for causal inference: in Stage 1 it uses the reference eQTL data to impute a genes expression for the main GWAS data, then in Stage 2 it tests for association between the imputed gene expression and the GWAS trait; if an association is detected in Stage 2, a (putatively) causal relationship between the gene and the GWAS trait is claimed. If a nonlinear model or a generalized linear model (GLM) is fitted in Stage 2 (e.g., for a binary GWAS trait), it is known that using only imputed gene expression, as in standard TWAS, in general does not lead to a consistent (i.e., asymptotically unbiased) estimate for the causal effect; accordingly, a variation of 2SLS, called two‐stage residual inclusion (2SRI), has been proposed to yield better estimates (e.g., being consistent under suitable conditions). Our main goal is to investigate whether it is necessary or even better to apply 2SRI, instead of the standard 2SLS. In addition, due to the use of imputed gene expression (i.e., with measurement errors), it is known that in general some correction to the standard error estimate of the causal effect estimate has to be applied, while in the standard TWAS no correction is applied. Is this an issue? We also compare one‐sample 2SLS with two‐sample 2SLS (i.e., the standard TWAS). We used the Alzheimer's Disease Neuroimaging Initiative (ADNI) data and simulated data mimicking the ADNI data to address the above questions. At the end, we conclude that, in practice with the large sample sizes and small effect sizes of genetic variants, the standard TWAS performs well and is recommended.
Integrating germline and somatic genetics to identify genes associated with lung cancer
Authors: Pattee Jack , Zhan Xiaowei , Xiao Guanghua , Pan Wei
Published: December 2019

Genome‐wide association studies (GWAS) have successfully identified many genetic variants associated with complex traits. However, GWAS experience power issues, resulting in the failure to detect certain associated variants. Additionally, GWAS are often unable to parse the biological mechanisms of driving associations. An existing gene‐based association test framework, Transcriptome‐Wide Association Studies (TWAS), leverages expression quantitative trait loci data to increase the power of association tests and illuminate the biological mechanisms by which genetic variants modulate complex traits. We extend the TWAS methodology to incorporate somatic information from tumors. By integrating germline and somatic data we are able to leverage information from the nuanced somatic landscape of tumors. Thus we can augment the power of TWAS‐type tests to detect germline genetic variants associated with cancer phenotypes. We use somatic and germline data on lung adenocarcinomas from The Cancer Genome Atlas in conjunction with a meta‐analyzed lung cancer GWAS to identify novel genes associated with lung cancer.
Consumer perceptions of community pharmacy‐based promotion of mental health and well‐being
Authors: Hall Bethany , Kelly Fiona , Wheeler Amanda J. , McMillan Sara S.
Published: December 2019

Issue addressed

With nearly half of all Australians likely to experience a mental illness, increasing community‐based mental health promotion is warranted. Community pharmacies are accessible health care destinations that effectively provide a range of public health services. This study explored consumer opinions of mental health promotion in the community pharmacy setting, the activities they have observed and the perceived role/s of pharmacy staff in this area.

Methods

A survey was informed by five interviews with pharmacy consumers and a literature review. Adult pharmacy consumers were recruited nationwide via a Research Panel company between December 2018 and January 2019. Survey data were descriptively analysed and associations confirmed by chi‐square analysis.

Results

Data were analysed from 537 of the 577 respondents; 34.3% of participants had a lived experience of mental illness. Just under a quarter of participants (23.3%) had observed mental health promotion in community pharmacy. Pharmacy was viewed as a suitable environment for this promotion by most respondents (n = 446/516), particularly those with lived experience, with a preference for in‐store leaflets, posters and linking with existing national mental health organisations/campaigns. Lack of privacy and the busy pharmacy environment were identified as barriers for promotion in this setting.

Conclusion

There is a clear potential for mental health promotion within community pharmacies, although the uptake and impact of such activities require further investigation.

So what?

These findings highlight a missed opportunity for pharmacists to engage with consumers about mental health and well‐being, even though community pharmacies are accessible health care destinations.