bluuebunny/crossref_metadata_2025 huggingface dataset:
Massively Evoking Immunogenic Cell Death by Focused Mitochondrial Oxidative Stress using an AIE Luminogen with a Twisted Molecular Structure
Authors: Chen Chao , Ni Xiang , Jia Shaorui , Liang Yong , Wu Xiaoli , Kong Deling , Ding Dan
Published: November 2019

Immunogenic cell death (ICD) provides momentous theoretical principle for modern cancer immunotherapy. However, the currently available ICD inducers are still very limited and photosensitizer‐based ones can hardly induce sufficient ICD to achieve satisfactory cancer immunotherapy by themselves. Herein, an organic photosensitizer (named TPE‐DPA‐TCyP) with a twisted molecular structure, strong aggregation‐induced emission activity, and specific ability is reported for effectively inducing focused mitochondrial oxidative stress of cancer cells, which can serve as a much superior ICD inducer to the popularly used ones, including chlorin e6 (Ce6), pheophorbide A, and oxaliplatin. Furthermore, more effective in vivo ICD immunogenicity of TPE‐DPA‐TCyP than Ce6 is also demonstrated using a prophylactic tumor vaccination model. The underlying mechanism of the effectiveness and robustness of TPE‐DPA‐TCyP in inducing antitumor immunity and immune‐memory effect in vivo is verified by immune cell analyses. This study thus reveals that inducing focused mitochondrial oxidative stress is a highly effective strategy to evoke abundant and large‐scale ICD.
Enhanced Nucleation of Atomic Layer Deposited Contacts Improves Operational Stability of Perovskite Solar Cells in Air
Authors: Raiford James A. , Boyd Caleb C. , Palmstrom Axel F. , Wolf Eli J. , Fearon Benjamin A. , Berry Joseph J. , McGehee Michael D. , Bent Stacey F.
Published: November 2019

Metal‐halide perovskites show promise as highly efficient solar cells, light‐emitting diodes, and other optoelectronic devices. Ensuring long‐term stability is now a major priority. In this study, an ultrathin (2 nm) layer of polyethylenimine ethoxylated (PEIE) is used to functionalize the surface of C60 for the subsequent deposition of atomic layer deposition (ALD) SnO2, a commonly used electron contact bilayer for p–i–n devices. The enhanced nucleation results in a more continuous initial ALD SnO2 layer that exhibits superior barrier properties, protecting Cs0.25FA0.75Pb(Br0.20I0.80)3 films upon direct exposure to high temperatures (200 °C) and water. This surface modification with PEIE translates to more stable solar cells under aggressive testing conditions in air at 60 °C under illumination. This type of “built‐in” barrier layer mitigates degradation pathways not addressed by external encapsulation, such as internal halide or metal diffusion, while maintaining high device efficiency up to 18.5%. This nucleation strategy is also extended to ALD VOx films, demonstrating its potential to be broadly applied to other metal oxide contacts and device architectures.
Water insecurity: An agenda for research and call to action for human biology
Authors: Wutich Amber
Published: November 2019

Water insecurity—the lack of adequate and safe water for a healthy and productive life—is one of the greatest threats facing humans in the coming century. By 2030, half of the world is expected to be living in water‐stressed conditions, given current climate change scenarios. A key goal of the UN Water Action Decade and Sustainable Development Goal 6 is to improve water security for the three billion people globally affected, but the future looks grim. For many communities, from Cape Town, South Africa to Flint, United States, the imagined dystopian future of severe water shortages has already arrived—shaped not so much by lack of water, but by aging infrastructure, underfunded utilities, social exclusion, politicized commodification, and environmental racism. Stepping off from my biocultural research in Cochabamba, Bolivia, I discuss how recent research is dramatically advancing our understanding of water insecurity, such as new findings around the biocultural causes and consequences of dehydration, contamination, and water stress. But, much more needs be done to support local communities in creating fair and just water systems. I discuss how human biologists can make crucial contributions toward the advancement of a much‐needed science of water insecurity, while highlighting some practical and ethical challenges to advancing a core mission of providing safe, sufficient water to all.
Pregnancy parturition scars in the preauricular area and the association with the total number of pregnancies and parturitions
Authors: Igarashi Yuriko , Shimizu Kunio , Mizutaka Shogo , Kagawa Kotaro
Published: November 2019

Objectives

The aim of the present study was to clarify the association between the degree of development of pregnancy parturition scars (PPSs) and the total number of pregnancies and parturitions (TNPPs) on the basis of new identification standards for PPS in the preauricular area.

Materials and Methods

Preauricular grooves were macroscopically observed on the pelves of 103 early modern males and 295 females (62 early modern females; 233 present‐day females). Three categories of PPS in the preauricular area were defined. The association between the degree of development of PPS in the preauricular area and the TNPP was analyzed in 90 present‐day females with detailed lifetime data.

Results

PPS could not estimate the exact TNPP. However, it was shown that no PPS indicated no TNPP, weak PPS indicated a lower TNPP, and developed PPS indicated a higher TNPP.

Discussion

Even though the possibility remains that some PPS indicate no TNPP, the results showed that the percentage of each PPS category indicated fertility in the population, suggesting that the strength of the association between the degree of development of PPS and the TNPP was affected by the classification system, the reliability of lifetime data, and the statistical methods used for analysis.
Highly Selective Production of Ethylene by the Electroreduction of Carbon Monoxide
Authors: Chen Ruixue , Su Hai‐Yan , Liu Deyu , Huang Rui , Meng Xianguang , Cui Xiaoju , Tian Zhong‐Qun , Zhang Dong H. , Deng Dehui
Published: November 2019

Conversion of carbon monoxide to high value‐added ethylene with high selectivity by traditional syngas conversion process is challenging because of the limitation of Anderson‐Schulz–Flory distribution. Herein we report a direct electrocatalytic process for highly selective ethylene production from CO reduction with water over Cu catalysts at room temperature and ambient pressure. An unprecedented 52.7 % Faradaic efficiency of ethylene formation is achieved through optimization of cathode structure to facilitate CO diffusion at the surface of the electrode and Cu catalysts to enhance the C−C bond coupling. The highly selective ethylene production is almost without other carbon‐based byproducts (e.g. C1–C4hydrocarbons and CO2) and avoids the drawbacks of the traditional Fischer–Tropsch process that always delivers undesired products. This study provides a new and promising strategy for highly selective production of ethylene from the abundant industrial CO.
Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron‐Rich Substrates
Authors: Doobary Sayad , Sedikides Alexi T. , Caldora Henry P. , Poole Darren L. , Lennox Alastair J. J.
Published: November 2019

Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an important strategy for their preparation, yet current methods are limited in their alkene‐types and tolerance of electron‐rich, readily oxidized functionalities, as well as in their safety and scalability. Herein, we report a method for the difluorination of a number of unactivated alkene‐types that is tolerant of electron‐rich functionality, giving products that are otherwise unattainable. Key to success is the electrochemical generation of a hypervalent iodine mediator using an “ex‐cell” approach, which avoids oxidative substrate decomposition. The more sustainable conditions give good to excellent yields in up to decagram scales.
Programming DNA Nanoassembly for Enhanced Photodynamic Therapy
Authors: Pan Min , Jiang Qunying , Sun Junlin , Xu Zhen , Zhou Yizhuo , Zhang Li , Liu Xiaoqing
Published: November 2019

Photodynamic therapy (PDT) has extraordinary promise for the treatment of many cancers. However, its clinical progress is impaired by the intrinsic hypoxic tumor microenvironment that limits PDT efficacy and the safety concern associated with biological specificity of photosensitizers or vehicles. Now it is demonstrated that rationally designed DNA nanosponges can load and delivery photosensitizer effectively, target tumor precisely, and relieve hypoxia‐associated resistance remarkably to enhance the efficacy of PDT. Specifically, the approach exhibits a facile assembly process, provides programmable and versatile nanocarriers, and enables robust in vitro and in vivo anti‐cancer efficacy with excellent biosafety. These findings represent a practical and safe approach by designer DNA nanoassemblies to combat cancer effectively and suggest a powerful strategy for broad biomedical application of PDT.
Synthesis, biological screening, and molecular docking of quinazolinone and quinazolinethione as phosphodiesterase 7 inhibitors
Authors: Elfeky Sherin M. , Sobahi Tariq R. , Gineinah Magdy M. , Ahmed Nesreen S.
Published: November 2019

N‐Substituted isatoic anhydrides were used as starting materials for the synthesis of compounds 5–16 through alkali hydrolysis, Schiff base reactions, and oxidation. Compounds 18–23 were obtained by thionation of their oxo isosteres using Lawesson's reagent. Cyclocondesation of anthranilic acid with thiourea afforded compounds 25–27, which were S‐alkylated to afford compounds 28–30, which were thionated using Lawesson's reagent to afford 31–33. The compounds were tested for their in vitro inhibitory activity against the phosphodiesterase 7A (PDE7A) enzyme compared with the selective PDE7 inhibitor BRL50481. All the compounds showed the inhibitory activity on the enzyme at micromolar levels. Compounds 9 and 25 showed the highest inhibitory activity on the enzyme: IC50 = 0.096 and 0.074 μM, respectively, comparable to BRL50481 (IC50 = 0.072 μM). The binding mode and binding affinity of the target compounds at the enzyme PDE7A‐binding site were studied through molecular docking. Compounds 9 and 25 showed good recognition at the enzyme‐binding site and were capable of binding in an inhibitory mode similar to the reference compound BRL50481, forming the necessary interactions with the key amino acids. Docking studies and enzyme assay were in agreement.
Assessment of biological activities of chitosan Schiff base tagged with medicinal plants
Authors: Khan Arshad Mehmood , Abid Obaid ur Rehman , Mir Sadullah
Published: November 2019

A chitosan Schiff base with an aromatic aldehyde was synthesized and characterized by FTIR and NMR spectroscopies. Furthermore, the degree of substitution was calculated based on the ratios of the area of the proton of the imine (Aimine) and the area of the peak of the proton of the pyranose ring (AH‐2). The antimicrobial activities were determined against bacterial and fungal strains, as well as multiple drug‐resistant (MDR) bacteria. The chitosan Schiff base was also tagged with medicinal plants, for example, Curcuma longa, Peganum harmala, Lepidium sativam, and cruciferous vegetables, and the biological activities determined against pathogenic bacterial and fungal strains. The chitosan Schiff base showed maximum zone of inhibition of 22 mm against Staphylococcus aureus with a minimum zone of inhibition of 15 mm against Bacillus cereus. The chitosan Schiff base was fused with C longa, isothiocyanates and a combined mixture of P harmala and L sativam that has shown activities against Escherichia coli with a zone of inhibition of 28, 24, and 30 mm, respectively. The Schiff base of chitosan fused with medicinal plants also showed significant inhibitory activities against MDR bacteria.
The ALERT model of care for the assessment and personalized management of patients with lymphoedema
Authors: Boyages J , Koelmeyer L A , Suami H , Lam T , Ngo Q D , Heydon-White A , Czerniec S , Munot S , Ho-Shon K , Mackie H
Published: November 2019

Background

This study documents the development and evaluation of a comprehensive multidisciplinary model for the assessment and personalized care of patients with lymphoedema.

Methods

The Australian Lymphoedema Education Research and Treatment (ALERT) programme originated as an advanced clinic for patients considering surgery for lymphoedema. The programme commenced liposuction surgery in May 2012 and then introduced lymph node transfer in 2013 and lymphovenous anastomosis (LVA) in 2016. An outpatient conservative treatment clinic was established in 2016. ALERT commenced investigations with indocyanine green (ICG) lymphography in late 2015, leading to the creation of a diagnostic assessment clinic offering ICG in 2017.

Results

Since 2012, 1200 new patients have been referred to ALERT for assessment of lymphoedema for a total of 5043 episodes of care. The introduction of ICG lymphography in 2015 initially allowed better screening for LVA, but is now used not only to guide surgical options, but also as a diagnostic tool and to guide manual lymphatic drainage massage. The total number of new patients who attended the surgical assessment clinic to December 2018 was 477, with 162 patients (34·0 per cent) undergoing surgery.

Conclusion

The ALERT programme has developed a multidisciplinary model of care for personalized lymphoedema treatment options based on clinical, imaging and ICG lymphography. Patients are selected for surgery based on several individual factors.
Collateral grade of the Willis' circle predicts outcomes of acute intracranial internal carotid artery occlusion before thrombectomy
Authors: Zhao Hongchen , Wang Baolin , Xu Ganggang , Dong Yi , Dong Qiang , Cao Wenjie
Published: November 2019

Background and Purpose

Endovascular mechanical thrombectomy (EVMT) shows significant promise in improving acute ischemic stroke (AIS) with proximal artery occlusion, but outcomes have been variable. We explored the patients treated by thrombectomy to investigate the association between a favorable clinical outcome of EVMT in intracranial internal carotid artery occlusion (iICAO) and a set of predictors.

Methods

A total of 38 iICAO patients treated by EVMTs were analyzed. Primary collateral grades (PCG) at baseline based on the integrity of Willis' circle were categorized into three degrees. The favorable outcomes, measured by modified Rankin scale (mRS), were defined as ≤2 at 90 days. The reperfusion was one of the most important confounders, defined as modified thrombolysis in cerebral infarction (mTICI) ≥ 2b. The other risk factors included demographic characteristics, vascular risk factors, stroke severity, procedural EVMT, and PCG at baseline was adjusted to reveal the association with favorable outcomes.

Results

Of 38 iICAO patients, 65.8% (25 in 38) achieved reperfusion. However, only 31.6% (12/38) achieved favorable outcomes at 90 days. With a PCG3, 61.5% of them achieved favorable outcomes, while only 37.5% of those with PCG2 and PCG1 achieved favorable outcomes (p = .003). In multivariable logistic regression, PCG was revealed as a predictor for favorable outcomes (OR 5.278, p = .019) after adjusting the reperfusion and other factors.

Conclusions

The PCG based on the integrity of Willis' circle might be an underlying predictor of the prognosis of AIS in patients with iICAO after EVMT. The function of intact anterior communicating artery (AcoA) and ipsilateral posterior communicating artery (PcoA) in favoring prognosis of the iICAO patients might need to be validation in future study.
Site‐Specific Isotopic Labeling (SSIL): Access to High‐Resolution Structural and Dynamic Information in Low‐Complexity Proteins
Authors: Urbanek Annika , Elena‐Real Carlos A. , Popovic Matija , Morató Anna , Fournet Aurélie , Allemand Frédéric , Delbecq Stephane , Sibille Nathalie , Bernadó Pau
Published: November 2019

Remarkable technical progress in the area of structural biology has paved the way to study previously inaccessible targets. For example, large protein complexes can now be easily investigated by cryo‐electron microscopy, and modern high‐field NMR magnets have challenged the limits of high‐resolution characterization of proteins in solution. However, the structural and dynamic characteristics of certain proteins with important functions still cannot be probed by conventional methods. These proteins in question contain low‐complexity regions (LCRs), compositionally biased sequences where only a limited number of amino acids is repeated multiple times, which hamper their characterization. This Concept article describes a site‐specific isotopic labeling (SSIL) strategy, which combines nonsense suppression and cell‐free protein synthesis to overcome these limitations. An overview on how poly‐glutamine tracts were made amenable to high‐resolution structural studies is used to illustrate the usefulness of SSIL. Furthermore, we discuss the potential of this methodology to give further insights into the roles of LCRs in human pathologies and liquid–liquid phase separation, as well as the challenges that must be addressed in the future for the popularization of SSIL.
Coexistence of acute takotsubo syndrome and acute coronary syndrome
Authors: Sharkey Scott W. , Kalra Ankur , Henry Timothy D. , Smith Timothy D. , Pink Victoria R. , Lesser John R. , Garberich Ross F. , Maron Martin S. , Maron Barry J.
Published: November 2019

Background

Takotsubo syndrome (TS) is an acute cardiac condition with presentation indistinguishable from acute coronary syndrome (ACS), and mechanism independent of epicardial coronary obstruction. Acute coronary artery plaque rupture/occlusion is not expected in TS. Nonetheless, the physiologic stress of ACS might itself trigger TS, leading to coexistence of both conditions, and diagnostic uncertainty.

Methods

From 2011 to 2014, we encountered 137 consecutive patients with typical TS (without acute coronary plaque rupture/occlusion). During this time, among a population of 3,506 consecutive ACS patients, nine (0.3%) presented with features of both ACS and TS, that is, acute onset, troponin elevation, acute plaque rupture/occlusion, and reversible LV ballooning not corresponding to culprit coronary distribution.

Results

The nine patients (seven female) with TS‐ACS coexistence, average age 70 ± 13 years, presented with chest pain (n = 6), nausea/vomiting (n = 2), or cardiac arrest (n = 1), ST‐elevation (n = 5), all with troponin elevation (peak 1.3 ± 1.2 ng/ml). Each had single vessel coronary disease; right coronary (n = 3), circumflex (n = 3), mid‐LAD (n = 2), ramus intermedius (n = 1), with percutaneous coronary intervention in seven patients (78%). Initial ejection fraction was 26 ± 7%, with apical ballooning in eight patients and mid‐LV ballooning in one patient. Each patient had LV ballooning resolution and ejection fraction normalization to 57 ± 3%, hospital survival was 89%.

Conclusions

Among patients with ACS, a subset have evidence of coexisting TS, findings which further expand the clinical profile of both conditions, raising the possibility that ACS itself may trigger TS.
Molecular Release Associated with Interfacial pH Change Stimulated by a Small Electrical Potential Applied
Authors: Bellare Madhura , Kadambar Vasantha Krishna , Bollella Paolo , Katz Evgeny , Melman Artem
Published: November 2019

Electrochemically stimulated molecular release from a modified electrode surface has been studied. The system was based on a buckypaper electrode modified with a molecular layer, which included a linker with a hydrolyzable phenolic ester bond connecting a fluorescent dye to the electrode surface, and with bilirubin oxidase catalyzing O2 reduction. The O2 reduction resulted in the local pH increase, which resulted in hydrolytic cleavage of the linker and release of the dye. The source of electrons for the reduction process can be electronic (potentiostat) or chemical (NADH). The potential applied on the modified electrode (0 V vs. Ag/AgCl) or generated in situ in the presence of NADH was very small, thus allowing the electrochemical process without complications of any side reaction. While the fluorescent dye released from the electrode represents a convenient model, various (bio)molecular species (e. g., drugs) can be released in the similar process. The designed signal‐controlled release system represents a general platform for various (bio)molecular delivering processes.
Non‐covalent Interactions and Charge Transfer between Propene and Neutral Yttrium‐Doped and Pure Gold Clusters
Authors: Barabás Júlia , Vanbuel Jan , Ferrari Piero , Janssens Ewald , Höltzl Tibor
Published: November 2019

The dopant and size‐dependent propene adsorption on neutral gold (Aun) and yttrium‐doped gold (Aun−1Y) clusters in then=5–15 size range are investigated, combining mass spectrometry and gas phase reactions in a low‐pressure collision cell and density functional theory calculations. The adsorption energies, extracted from the experimental data using an RRKM analysis, show a similar size dependence as the quantum chemical results and are in the range of ≈0.6–1.2 eV. Yttrium doping significantly alters the propene adsorption energies forn=5, 12 and 13. Chemical bonding and energy decomposition analysis showed that there is no covalent bond between the cluster and propene, and that charge transfer and other non‐covalent interactions are dominant. The natural charges, Wiberg bond indices, and the importance of charge transfer all support an electron donation/back‐donation mechanism for the adsorption. Yttrium plays a significant role not only in the propene binding energy, but also in the chemical bonding in the cluster‐propene adduct. Propene preferentially binds to yttrium in small clusters (n<10), and to a gold atom at larger sizes. Besides charge transfer, relaxation also plays an important role, illustrating the non‐local effect of the yttrium dopant. It is shown that the frontier molecular orbitals of the clusters determine the chemical bonding, in line with the molecular‐like electronic structure of metal clusters.
Hatted 1T/2H‐Phase MoS2 on Ni3S2 Nanorods for Efficient Overall Water Splitting in Alkaline Media
Authors: Zhao Yang , Wei Shizhong , Wang Feihong , Xu Liujie , Liu Yong , Lin Junpin , Pan Kunming , Pang Huan
Published: November 2019

A new hatted 1T/2H‐phase MoS2 on Ni3S2 nanorods, as a bifunctional electrocatalyst for overall water splitting in alkaline media, is prepared through a simple one‐pot hydrothermal synthesis. The hat‐rod structure is composed mainly of Ni3S2, with 1T/2H‐MoS2 adhered to the top of the growth. Aqueous ammonia plays an important role in forming the 1T‐phase MoS2 by twisting the 2H‐phase transition and expanding the interlayer spacing through the intercalation of NH3/NH4+. Owing to the special “hat‐like” structure, the electrons conduct easily from Ni foam along Ni3S2 to MoS2, and the catalyst particles maintain sufficient contact with the electrolyte, with gaseous molecules produced by water splitting easily removed from the surface of the catalyst. Thus, the electrocatalytic performance is enhanced, with an overpotential of 73 mV, a Tafel slope of 79 mV dec−1, and excellent stability, and the OER demonstrates an overpotential of 190 mV and Tafel slope of 166 mV dec−1.
Kinetically Controlled, Highly Chemoselective Acylation of Functionalized Grignard Reagents with Amides by N−C Cleavage
Authors: Li Guangchen , Szostak Michal
Published: November 2019

The direct transition‐metal‐free acylation of amides with functionalized Grignard reagents by highly chemoselective N−C cleavage under kinetic control has been accomplished. The method offers rapid and convergent access to functionalized biaryl ketones through transient tetrahedral intermediates. The direct access to functionalized Grignard reagents by in situ halogen–magnesium exchange promoted by the versatile turbo‐Grignard reagent (iPrMgCl⋅LiCl) permits excellent substrate scope with respect to both the amide and Grignard coupling partners. These reactions enable facile, operationally simple and chemoselective access to tetrahedral intermediates from amides under significantly milder conditions than chelation‐controlled intermediates. This novel direct two‐component coupling sets the stage for using amides as acylating reagents in an alternative paradigm to the metal‐chelated approach, acyl metals and Weinreb amides.
A DNA Switch for Detecting Single Nucleotide Polymorphism within a Long DNA Sequence Under Denaturing Conditions
Authors: Zhang Wenqing , Li Jiuxing , Salena Bruno , Li Yingfu
Published: November 2019

Invited for the cover of this issue is the group of Yingfu Li at McMaster University. The image depicts a molecular switch for ultra‐specific detection of DNA utilizing a guanine‐quadruplex (up‐right structure) resistant to denaturation by urea (ball‐and‐stick structures). Read the full text of the article at 10.1002/chem.201903536.
Cambiarenes: Single‐Step Synthesis and Selective Zwitterion Binding of a Clip‐Shaped Macrocycle with a Redox‐Active Core
Authors: Petersen Riley J. , Rozeboom Brett J. , Oburn Shalisa M. , Blythe Nolan J. , Rathje Tanner L. , Luna Javier A. , Kibby Steven K. , O'Brien Emily A. , Rohr Kayleigh G. , Carpenter Joshua R. , Sanders Taylor L. , Johnson Andrew M. , Hutchins Kristin M. , Shaw Scott K. , MacGillivray Leonard R. , Wackerly Jay Wm.
Published: November 2019

A novel macrocyclic host molecule was synthesized that forms in a single step from commercially available starting materials. The core of the macrocycle backbone possesses two quinone rings and, thus, it is redox‐active. Host–guest binding involving the clip‐shaped cavity indicates selective binding of pyridine N‐oxides based on the electron density of and steric bulk around the anionic oxygen.
Tropfstein im Labor
Authors: Schmidkonz Bertram
Published: November 2019

Die Reaktion von Bariumhydroxid‐Lösung mit Kohlendioxid lässt sich einsetzen, um die Bildung von Tropfsteinen aus Bariumcarbonat in einer sehr einfachen Apparatur zu beobachten.
On the Singular Set of Free Interface in an Optimal Partition Problem
Authors: Alper Onur
Published: November 2019

We study the singular set of free interface in an optimal partition problem for the Dirichlet eigenvalues. We prove that its upper (n − 2)‐dimensional Minkowski content, and consequently its (n − 2)‐dimensional Hausdorff measure, are locally finite. We also show that the singular set is countably (n − 2)‐rectifiable; namely, it can be covered by countably many C1‐manifolds of dimension (n − 2), up to a set of (n − 2)‐dimensional Hausdorff measure zero. Our results hold for optimal partitions on Riemannian manifolds and harmonic maps into homogeneous trees as well. © 2019 Wiley Periodicals, Inc.
Investigation of 4f‐Related Electronic Transitions of Rare‐Earth Doped ZnO Luminescent Materials: Insights from First‐Principles Calculations
Authors: He Lingjun , Meng Junling , Feng Jing , Yao Fen , Zhang Lifang , Zhang Zhixiang , Liu Xiaojuan , Zhang Hongjie
Published: November 2019

Rare‐earth (RE) doped zinc oxides (ZnO) are regarded as promising materials for application in versatile color‐tuned devices. However, the understanding of underlying luminescence mechanism and the rule of 4 f‐related electronic transition is still limited, which is full of significance for the exploration of advanced RE‐based ZnO phosphors. Thus, a series of ZnO : RE (RE=Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb) phosphors have been investigated by means of first‐principles calculations. Meanwhile, we also consider the effect of native defects (VO, VZn) on the luminescence of ZnO : RE phosphors. Accordingly, four types of electric‐dipole allowed transition processes are figured out in ZnO : RE family. Additionally, we manifest that the VO can further improve the luminescent performance of ZnO : RE phosphors, and give insightful guidance to design desired RE‐based ZnO materials with excellent luminescence.
Update on metabolism of abemaciclib: In silico, in vitro, and in vivo metabolite identification and characterization using high resolution mass spectrometry
Authors: Thakkar Disha , Kate Abhijeet S.
Published: November 2019

Abemaciclib was approved by the US Food and Drug Administration in 2015 as an advanced treatment for metastatic breast cancer. Identification and characterization of limited numbers of abemaciclib metabolites have been reported in the literature. Therefore, the current study focused on the investigation of the in vitro and in vivo metabolic fate of abemaciclib using high resolution mass spectrometry. Initially, a vulnerable site of metabolism was predicted by the Xenosite web predictor tool. Later, in vitro metabolites were identified from pooled rat liver microsomes, rat S9 fractions, and human liver microsomes. Finally, in vivo metabolites have been detected in plasma, urine, and feces matrix of male Sprague–Dawley rats. A total of 12 putative metabolites (11 phase I and 1 phase II) of abemaciclib and their metabolic pathways were proposed by considering accurate mass, mass fragmentation pattern, nitrogen rule, and ring double bonds of the detected metabolites. Abemaciclib was metabolized via hydroxylation, N‐oxidation, N‐dealkylation, oxidative deamination followed by reduction and sulfate conjugation. In the human liver microsomes, maximum numbers of metabolites (11 metabolites) were observed, from which M7, M8, M9, and M11 were human specific.
Phylogeography and population genetics of pine butterflies: Sky islands increase genetic divergence
Authors: Halbritter Dale A. , Storer Caroline G. , Kawahara Akito Y. , Daniels Jaret C.
Published: November 2019

The sky islands of southeastern Arizona (AZ) mark a major transition zone between tropical and temperate biota and are considered a neglected biodiversity hotspot. Dispersal ability and host plant specificity are thought to impact the history and diversity of insect populations across the sky islands. We aimed to investigate the population structure and phylogeography of two pine‐feeding pierid butterflies, the pine white (Neophasia menapia) and the Mexican pine white (Neophasia terlooii), restricted to these “islands” at this transition zone. Given their dependence on pines as the larval hosts, we hypothesized that habitat connectivity affects population structure and is at least in part responsible for their allopatry. We sampled DNA from freshly collected butterflies from 17 sites in the sky islands and adjacent high‐elevation habitats and sequenced these samples using ddRADSeq. Up to 15,399 SNPs were discovered and analyzed in population genetic and phylogenetic contexts with Stacks and pyRAD pipelines. Low genetic differentiation in N. menapia suggests that it is panmictic. Conversely, there is strong evidence for population structure within N. terlooii. Each sky island likely contains a population of N. terlooii, and clustering is hierarchical, with populations on proximal mountains being more related to each other. The N. menapia habitat, which is largely contiguous, facilitates panmixia, while the N. terlooii habitat, restricted to the higher elevations on each sky island, creates distinct population structure. Phylogenetic results corroborate those from population genetic analyses. The historical climate‐driven fluxes in forest habitat connectivity have implications for understanding the biodiversity of fragmented habitats.
Topotactic Mechanisms Related to the Graphene Planes: Chemical Intercalation of Electron Donors into Graphite
Authors: Cahen Sébastien , Speyer Lucie , Lagrange Philippe , Hérold Claire
Published: November 2019

The intercalation of electron donor species into graphite belongs to the class of two‐dimensional topotactic reactions. During the intercalation, which requires an oxido‐reduction between the reagents, the graphene planes, which form the skeleton of the host material, remain indeed quasi unaltered while their spacing is strongly expanded allowing the setting up of the guest reagent layers. Intercalation into graphite is therefore the prototype of the topotactic reaction. The intercalation mechanisms of these electron donors such as metals, metallic alloys and metal combinations (molecules, electronegative elements) have been significantly studied at length. They are especially numerous and greatly diversified. In this paper, we do not aim to depict all the known graphite intercalation compounds but to draw up an inventory of the whole of these mechanisms. The latter are systematically illustrated by means of several characteristic examples for each one. This significant diversity appears as a remarkable distinctive feature of graphite as host lamellar material.
2,6‐Bis(diazaboryl)pyridine – A Ligand with Hemilabile Donor and Lewis Acid Functionalities
Authors: Schröder Jan , Böttcher Tobias
Published: November 2019

The coordination chemistry of 2,6‐bis(diazaboryl)pyridine (dab2py) is studied towards selected halides of aluminum(III), gallium(III) and germanium(II). Addition of dab2py to AlBr3 readily yielded the salt of ligand induced ionization [(dab2py)AlBr2][AlBr4]. The aluminum atom in the cation is coordinated by the pyridine's nitrogen atom and also by one nitrogen atom of each diazaboryl group, resembling the coordination motif found for tridentate pincer ligands, e.g. 2,6‐diiminopyridines. By NMR spectroscopic measurements a rapid exchange reaction between all four Ndab‐atoms was detected, showing that the tridentate coordination motif of dab2py is less rigid compared with 2,6‐diiminopyridines. The adduct formation of dab2py and GaCl3 does not proceed at room temperature in solution. Addition of GeCl2·dioxane to this mixture gave the salt [(dab2py)GeCl][GaCl4]. The germanium atom is coordinated by the pyridine's nitrogen atom and a nitrogen atom of one diazaboryl group. The product of partial hydrolysis of the cation [(dab2py)GeCl]+ was isolated as single crystals. The structure determination revealed the insertion of an oxygen atom between the germanium atom and a boron atom, showing that the diazaboryl groups do not only provide hemilabile Lewis donor but also weak Lewis acid functionalities that are involved in the stabilization of main group cations.
Efficient One‐Pot Reductive Aminations of Carbonyl Compounds with Aquivion‐Fe as a Recyclable Catalyst and Sodium Borohydride
Authors: Airoldi Veronica , Piccolo Oreste , Roda Gabriella , Appiani Rebecca , Bavo Francesco , Tassini Riccardo , Paganelli Stefano , Arnoldi Sebastiano , Pallavicini Marco , Bolchi Cristiano
Published: November 2019

A one‐pot reductive amination of aldehydes and ketones with NaBH4 was developed with a view to providing efficient, economical and greener synthetic conditions. A recyclable iron‐based Lewis catalyst, Aquivion‐Fe, was used to promote imine formation in cyclopentyl methyl ether, followed by the addition of a small amount of methanol to the reaction mixture to enable C=N reduction by NaBH4. The protocol, applied to a wide number of amines and carbonyl compounds, resulted in ever complete conversion of these latter with excellent chemoselectivity towards the expected amination products in the most cases. Isolated yields, determined for a selection of the screened substrates, were found consistent with the previously obtained conversion and selectivity data. Cinacalcet, an important active pharmaceutical ingredient, was efficiently prepared by the title procedure.
Reduced Graphene Oxide/Pt Nanoparticles/Zn‐MOF‐74 Nanomaterial for a Glucose Biosensor Construction
Authors: Uzak Didem , Atiroğlu Atheer , Atiroğlu Vesen , Çakıroğlu Bekir , Özacar Mahmut
Published: November 2019

In this study, a new glucose biosensor was fabricated by immobilizing glucose oxidase (GOx) on platinum nanoparticles (Pt NPs) decorated reduced graphene oxide (rGO)/Zn‐MOF‐74 hybrid nanomaterial. Herein, the biosensor fused the advantages of rGO with those of porous Zn‐MOF and conductive Pt NPs. This has not only enlarged the surface area and porosity for the efficient GOx immobilization and faster mass transport, but also provided favorable electrochemical features such as high current density, remarkable electron mobility through metal nanoparticles, and improved electron transfer between the components. The GOx‐rGO/Pt NPs@Zn‐MOF‐74 coated electrode displayed a linear measurement range for glucose from 0.006 to 6 mM, with a detection limit of 1.8 μM (S/N: 3) and sensitivity of 64.51 μA mM−1 cm−2. The amperometric response of the enzyme biosensor demonstrated the typical behavior of Michaelis‐Menten kinetics. The obtained satisfying sensitivity and measurement range enabled fast and accurate glucose measurement in cherry juice using the fabricated biosensor. The water‐stable Zn‐MOF‐74 demonstrated higher enzyme loading capacity and can be potent supporting material for biosensor construction.
Functional exploration of free and encapsulated probiotic bacteria in yogurt and simulated gastrointestinal conditions
Authors: Afzaal Muhammad , Khan Azmat Ullah , Saeed Farhan , Ahmed Aftab , Ahmad Muhammad Haseeb , Maan Abid Aslam , Tufail Tabussam , Anjum Faqir Muhammad , Hussain Shahzad
Published: November 2019

The core objective of the current study was to evaluate the effect of microencapsulation on the viability and stability of probiotic bacteria in yogurt and simulated gastrointestinal conditions. For this purpose, probiotic bacteria were encapsulated with sodium alginate and carrageenan by encapsulator. Yogurt was prepared with the incorporation of free and encapsulated probiotic bacteria and was analyzed for physicochemical, microbiological, and sensorial attributes. Encapsulation and storage exhibited a significant (p < .05) effect on different parameters of yogurt. An increasing trend in syneresis and acidity while a decreasing trend in viscosity, pH, viability, and stability were observed. The value of syneresis increased from 2.27 ± 0.17 to 2.9 ± 0.14 and acidity from 0.48 ± 0.04 to 0.64 ± 0.01 during 4 weeks of storage. The value of viscosity decreased from 3.68 ± 0.21 to 2.42 ± 0.09 and pH from 4.88 ± 0.31to 4.43 ± 0.36 during 28 days of storage. Unencapsulated (free) cells exhibited poor survival. The viable cell count of probiotic bacteria in the free‐state in yogurt was 9.97 logs CFU/ml at zero‐day that decreased to 6.12 log CFU/ml after 28 days. However, encapsulation improved the viability of the probiotics in the prepared yogurt and GIT. The cell count of probiotics encapsulated with sodium alginate and carrageenan was 9.91 logs CFU/ml and 9.89 logs CFU/ml, respectively, at zero‐day that decreased to 8.74 logs CFU/ml and 8.39 log CFU/ml, respectively. Free cells (unencapsulated) showed very poor survival. Similarly, during in vitro gastrointestinal assay, the survival rate of encapsulated probiotic bacteria in simulated gastric solution and intestinal solutions was higher than that of free cells. In the case of encapsulated bacteria, only 3 logs while for free cells, 7 log reduction was recorded. Sodium alginate microcapsules exhibited better release profile than carrageenan. Conclusively, microencapsulation improved the survival of probiotic bacteria in carrier food as well as in simulated gastrointestinal condition.
Computer‐aided diagnosis of retinal diseases using multidomain feature fusion
Authors: Keerthiveena B. , Esakkirajan S. , Selvakumar K. , Yogesh T.
Published: November 2019

In this article, an attempt is made to combine both transform and spatial domain features to increase the accuracy, sensitivity, and specificity for the classification of retinal diseases. Papilloedema, macular edema, glaucoma, diabetic retinopathy (DR), and central retinal vein occlusion (CRVO) are the leading cause of blindness in humans. To identify these diseases in a mass screening process, it consumes intense labor and time. In this proposed work, an automated computer aided algorithm is developed to classify the normal from the abnormal (Papilledema, macular edema, glaucoma, DR, and CRVO) images. For any classification task, an increase in data size, number of classes, and dimension of the feature space affect the performance of any classifier. A single classifier is generally unable to handle the wide variability and scalability of the data in any problem. In the proposed algorithm, the feature fusion technique is employed to reduce the input data to the classifier. The features are extracted from wavelet packet transform (WPT) and intensity hue saturation (IHS). A support vector machine (SVM)‐based learning algorithm is used to train the classifier using the extracted features. The proposed method yields better results than the existing classifier fusion method with an overall accuracy, sensitivity, specificity, positive prediction value (PPV), negative prediction value (NPV), and area under ROC curve (AUC) of 96.3%, 95.8%, 97.8%, 96.4%,98.1%, and 0.971 respectively.
Phase‐sensitive fluorescence detector for parathyroid glands during thyroidectomy: A preliminary report
Authors: Kim Yikeun , Kim Sung Won , Lee Kang Dae , Ahn Yeh‐Chan
Published: November 2019

Despite advances in medical technology, the parathyroid glands are still damaged during thyroid surgery. Our previous studies exploring methods for locating the parathyroid glands using autofluorescence have limitations, such as turning off the surgical light or requiring additional matching between the autofluorescence image and real‐surgical field‐of‐view. We developed a probe‐type parathyroid autofluorescence detector using a phase‐sensitive process and optical filtering to overcome these limitations. A preliminary clinical trial was performed on eight parathyroid glands in four patients. The normalized mean signal of the normal parathyroid glands was 332% stronger than that of the thyroid, and 384%, 459% and 286% stronger than the signal of the muscle, trachea and fat, respectively. Additionally, the device also detected fluorescence from indocyanine green.
Integrated transcriptomic and proteomic analyses of the tissues from the digestive gland of Chlamys farreri following cadmium exposure
Authors: Zhang Hui , Zhai Yuxiu
Published: November 2019

Objectives

Cadmium causes the pollution of marine habitat and Chlamys farreri is an effective concentrator of heavy metals, the aim of this study was to study the response mechanism of C. farreri to cadmium stress at transcriptomic and proteomic levels.

Methods

Transcriptomic analysis based on RNA‐sequencing and proteomic analysis based on isobaric tags for relative and absolute quantitation were performed to reveal the molecular response of C. farreri to different concentrations of cadmium (0.1, 0.3, and 1 mg/L). In addition, a protein‐protein interaction (PPI) network was constructed based on the Cytoscape tool to identify hub proteins related to the response of C. farreri to cadmium stress.

Results

A total of 24 190 unigenes from 58 683 candidates were annotated in known databases. The numbers of the differentially expressed unigenes (DEGs) was different among the three cadmium‐treated groups compared with the control group. DEGs were involved in many pathways such as ABC transporters, protein processing in endoplasmic reticulum and endocytosis. A total of 660 proteins were identified, and differentially expressed proteins (DEPs) among different groups were determined. The overlapping DEGs and DEPs were associated with cadmium response. The upregulated unigene0002618 and downregulated unigene0000904 may be more important for the response of C. farreri to cadmium stress. Unigene0009750 was the hub protein in the PPI network with the highest degree of 20.

Conclusions

Our transcriptomic and proteomic analyses elucidated the molecular response of C. farreri to cadmium stress.
Mining TCGA database for screening and identification of hub genes in kidney renal clear cell carcinoma microenvironment
Authors: Li Song , Xu Weibo
Published: November 2019

To evaluate the diagnosis and prognosis of the tumor microenvironment (immunization and stromal cells) in kidney renal clear cell carcinoma (KIRC), KIRC cases selected from The Cancer Genome Atlas database were divided into two groups according to the ESTIMATE algorithm‐derived immune scores. Our data suggested that the Von Hippel‐Lindau mutations and pathologic grades are associated with immune scores. Importat ntly, we identified 173 differential expression genes (DEGs) associated with prognosis in patients with KIRC. Consequently, Gene Ontology functional enrichment and Kyoto Encyclopedia of Genes and Genomes pathway analyses were performed on these DEGs, which included immune response, defense response, intrinsic to the plasma membrane, positive regulation of immune system process, and cytokine binding. Next, the protein‐protein interaction network of DEGs and the most significant module was constructed. Five hub genes were identified and analyzed using biological analysis. The survival analysis of the hub genes showed that KIRC patients with high gene expression of C2, MXRA8, TNFSF13B, and X‐linked inhibitor of apoptosis protein‐associated factor 1 (XAF1) had worse overall survival, and MXRA8, TNFSF13B, and XAF1 alteration were significantly associated with disease‐free survival (DFS). In addition, high gene expression of XAF1 alteration showed better DFS. Conclusion: we identified a list of microenvironment‐related genes that are useful for understanding the molecular mechanisms and prognosis of KIRC.
Association of single‐nucleotide polymorphisms in TLR4 gene and gene–environment interaction with primary open angle glaucoma in a Chinese northern population
Authors: Liu Huijuan , Qi Shixin , He Wei , Chang Cuirong , Chen Yanhui , Yu Jianguo
Published: November 2019

Background

The present study aimed to investigate the association of several single nucleotide polymorphisms (SNPs) within the Toll‐like receptor 4 (TLR4) gene and additional gene–environment interaction with primary open angle glaucoma (POAG) risk.

Methods

Tests for Hardy–Weinberg equilibrium in controls and haplotype analysis were performed using SNPstats (https://www.snpstats.net). Generalized multifactor dimensionality reduction (GMDR) was performed to test the interaction effects among four SNPs within the TLR4 gene and environmental factors. Logistic regression was performed to calculate the odds ratios (ORs) (95% confidence interval [CI]) for association between four SNPs within the TLR4 gene and POAG risk.

Results

The POAG risk was significantly higher in carriers with the T allele of rs4986791 and the T allele of rs2149356 within the TLR4 gene than in those with the wild‐type genotype, adjusted ORs (95% CI) were 1.65 (1.23–2.12) and 1.70 (1.16–2.31). The GMDR model suggested a significant two‐locus model (p = 0.0010) involving rs2149356 and alcohol drinking. Alcohol drinkers with the rs2149356‐GT+TT genotype within the TLR4 gene have the highest POAG risk compared to never alcohol drinkers with the rs2149356‐GG genotype (OR = 2.62; 95% CI = 1.48–3.78) after covariates adjustment. However, the study did not find a significant any‐locus model involving SNP and smoking. In all samples, the haplotype rs2149356‐G‐rs7873784‐C was observed most frequently in two groups (47.47% and 48.21% for the POAG patients and controls, respectively). The results also indicated that no significant haplotype was associated with POAG risk.

Conclusions

The minor alleles of rs4986791 and rs2149356 within the TLR4 gene, as well as interaction between rs2149356 and alcohol drinking, were associated with an increased POAG risk.