bluuebunny/crossref_metadata_2025 huggingface dataset:
Temporal expression profiles of lncRNA and mRNA in human embryonic stem cell-derived motor neurons during differentiation
Authors: Sun Xue-Jiao , Li Ming-Xing , Gong Chen-Zi , Chen Jing , Nasb Mohammad , Shah Sayed Zulfiqar Ali , Rehan Muhammad , Li Ya-Jie , Chen Hong
Published: November 2020

Background

Human embryonic stem cells (hESC) have been an invaluable research tool to study motor neuron development and disorders. However, transcriptional regulation of multiple temporal stages from ESCs to spinal motor neurons (MNs) has not yet been fully elucidated. Thus, the goals of this study were to profile the time-course expression patterns of lncRNAs during MN differentiation of ESCs and to clarify the potential mechanisms of the lncRNAs that are related to MN differentiation.

Methods

We utilized our previous protocol which can harvest motor neuron in more than 90% purity from hESCs. Then, differentially expressed lncRNAs (DElncRNAs) and mRNAs (DEmRNAs) during MN differentiation were identified through RNA sequencing. Bioinformatic analyses were performed to assess potential biological functions of genes. We also performed qRT-PCR to validate the DElncRNAs and DEmRNAs.

Results

A total of 441 lncRNAs and 1,068 mRNAs at day 6, 443 and 1,175 at day 12, and 338 lncRNAs and 68 mRNAs at day 18 were differentially expressed compared with day 0. Bioinformatic analyses identified that several key regulatory genes including POU5F1, TDGF1, SOX17, LEFTY2 and ZSCAN10, which involved in the regulation of embryonic development. We also predicted 283 target genes of DElncRNAs, in which 6 mRNAs were differentially expressed. Significant fold changes in lncRNAs (NCAM1-AS) and mRNAs (HOXA3) were confirmed by qRT-PCR. Then, through predicted overlapped miRNA verification, we constructed a lncRNA NCAM1-AS-miRNA-HOXA3 network.
Cytokine RT-qPCR and ddPCR for immunological investigations of the endangered Australian sea lion (Neophoca cinerea) and other mammals
Authors: Meza Cerda María-Ignacia , Gray Rachael , Higgins Damien P.
Published: November 2020

Measurement of cytokine gene expression by reverse transcription quantitative polymerase chain reaction (RT-qPCR) is used widely to assess the immune system of animals and to identify biomarkers of disease, but its application is limited in wildlife species due to a lack of species-specific reagents. The free-ranging endangered Australian sea lion (Neophoca cinerea) experiences significant clinical disease and high pup mortality due to intestinal hookworm infection. Developing immunological tools specific to the species will aid in the assessment of drivers of disease and its impact in population demographics. This study describes the development and validation of cross-reactive RT-qPCR assays to measure five important cytokines involved in innate and Th1/Th2 responses (IL-6, TNFα, IFNγ, IL-4 and IL-10) in unstimulated blood samples from a range of different mammalian species including the Australian sea lion. All RT-qPCR assays efficiencies ranged between 87% (Ovis ariesTNFα) and 111% (Bos taurusIL-10) and had strong linearity (R2). IL-4 and IFNγ gene expression forN. cinereafell below the dynamic range (and therefore quantifiable limits) of RT-qPCR assays but were able to be quantified using the novel droplet digital PCR (ddPCR). This study delivers new immunological tools for eco-immunologists studying cytokine gene expression in wildlife species and is to our knowledge, the first cytokine ddPCR approach to be reported in a pinniped species.
Clinical impact of lenvatinib in patients with unresectable hepatocellular carcinoma who received sorafenib
Authors: Chen Yen-Yang , Wang Chih-Chi , Liu Yueh-Wei , Li Wei-Feng , Chen Yen-Hao
Published: November 2020

Background

Lenvatinib has been approved for use in the systemic treatment for unresectable hepatocellular carcinoma (HCC). This study aimed to investigate the efficacy and safety of lenvatinib in patients with unresectable HCC who received sorafenib.

Methods

A total of 40 patients who received lenvatinib after sorafenib were retrospectively identified: as second line in 20 patients, third line in 10 patients, and fourth line and later lines in 10 patients. The treatment response to lenvatinib was determined in accordance with the guidelines of the modified Response Evaluation Criteria in Solid Tumors (mRECIST) every 2–3 months after commencement of lenvatinib.

Results

Median progression-free survival (PFS) and median overall survival (OS) of the whole population were 3.3 and 9.8 months, respectively. The objective response rate was 27.5%. Univariate and multivariate analyses showed that alpha-fetoprotein level >400 ng/mL was an independent prognostic factor of worse PFS and OS. The clinical outcomes of lenvatinib therapy as second-line, third-line, or fourth line and later line treatment were similar, and previous response to sorafenib could predict the response to subsequent lenvatinib. Most adverse events were grades 1–2, and the majority of patients tolerated the side effects. Our study confirms the efficacy and safety of lenvatinib as second-line and later line treatment for patients with unresectable HCC who received sorafenib in clinical practice.
Inverted Power Rama Distribution with Applications to Life Time Data
Authors: Onyekwere Chrisogonus K. , Osuji George A. , Enogwe Samuel U.
Published: November 2020

In this paper, we introduced the Inverted Power Rama distribution as an extension of the Inverted Rama distribution. This new distribution is capable of modeling real life data with upside down bathtub shape and heavy tails. Mathematical and statistical characteristics such as the quantile function, mode, moments and moment generating function, entropy measure, stochastic ordering and distribution of order statistics have been derived. Furthermore, reliability measures like survival function, hazard function and odds function have been derived. The method of maximum likelihood was used for estimating the parameters of the distribution. To demonstrate the applicability of the distribution, a numerical example was given. Based on the results, the proposed distribution performed better than the competing distributions.
Modeling the Impact of Optimal Control Strategies on the Dynamics of Zika Virus Disease Using the Sterile Insect Technology
Authors: William Atokolo , Johnson Akpa , Alih Daniel Musa , Samuel Olayemi Kehinde , Godwin C. E. Mbah
Published: November 2020

This work is aimed at formulating a mathematical model for the control of zika virus infection using Sterile Insect Technology (SIT). The model is extended to incorporate optimal control strategy by introducing three control measures. The optimal control is aimed at minimizing the number of Exposed human, Infected human and the total number of Mosquitoes in a population and as such reducing contacts between mosquitoes and human, human to human and above all, eliminates the population of Mosquitoes. The Pontryagin’s maximum principle was used to obtain the necessary conditions, find the optimality system of our model and to obtain solution to the control problem. Numerical simulations result shows that; reduction in the number of Exposed human population, Infected human population and reduction in the entire population of Mosquito population is best achieved using the optimal control strategy.
Traditional Herbal Medicines and their Fertility Potential: A Review
Authors: Kumar Ashwani , Gadhwal Nisha
Published: November 2020

Rapid increase in population growth is causing strain on medical resources world  wide. Traditional folk medicines are region-specific, local resources based indigenous herb based, village based, and in many cases, community-specific. Different systems of medicine developed accordingly, which have been termed as Ayurvedic, Japanese, Chinese, Korean, Malaysian, Yunani and more recently Homoeopathic. Aim of the present review is to study and review role of traditional herbal medicines in regulation of fertility problems including impotency   and female gynaecological problems. The method used was results of our own studies, existing literature, traditional knowledge from gunis vaidyas etc. It has been found that   Chlorophytum borivilianum Santapau & Fernandes (Liliaceae), Asparagus adscendens Roxb and Mucuna  pruriens L (DC) is being used in the indigenous systems of medicine as a galactogogue and aphrodisiac. It can be concluded that traditional medicines have an important role in improving fertility potential in humans.
Comércio mudo: mito e evidência histórica
Authors: Farias Paulo F. de Moraes , Macedo Apresentação de José Rivair
Published: November 2020

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Uma carta de negócios para a Costa da Mina
Authors: Souza Daniele Santos
Published: November 2020

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As muitas Minas de Minas Gerais
Authors: Motta José Flávio
Published: November 2020

Resenha de:
MARTINS, Roberto Borges. Crescendo em silêncio: a incrível economia escravista de Minas Gerais no século XIX. Belo Horizonte: ICAM: ABPHE, 2018. 632p.
Reimaginando pelo afeto o feminismo negro na era da interseccionalidade
Authors: Leite Diana Silveira
Published: November 2020

Resenha de:
NASH, Jennifer C. Black Feminisms Reimagined: After Intersectionality. Durham: Duke University Press, 2019. 170 p.
A grande fraude
Authors: Baldraia Fernando
Published: November 2020

Resenha de:
Graham, Jessica Lynn. Shifting the Meaning of Democracy: Race, Politics, and Culture in the United States and Brazil. Los Angeles: University of California Press, 2019. 365p.
O direito de explorar e o direito de viver
Authors: Filgueiras Vitor
Published: November 2020

Resenha de:
SAKAMOTO, Leonardo (org.). Escravidão contemporânea. São Paulo: Contexto, 2020. 191p.
Schooling age adolescents’ knowledge concerning contraceptive methods: challenges / O conhecimento de adolescentes escolares sobre os métodos contraceptivos: desafios
Authors: Ferreira Ediane de Andrade , Alves Valdecyr Herdy , Pereira Audrey Vidal , Rodrigues Diego Pereira , Brito Vilma Maria da Costa , Tostes Nádia Cecília Barros
Published: November 2020

Objetivo: analisar o conhecimentos de adolescentes escolares sobre os métodos contraceptivos. Método: estudo descritivo e exploratório, de natureza qualitativa, realizado com quarenta e seis adolescentes em três escolas públicas do município de Macapá, capital do Estado do Amapá. A coleta de dados ocorreu através de entrevistas realizadas com a autorização dos respectivos responsáveis, posteriormente transcritos e submetidos à análise de conteúdo na modalidade temática. Resultados: observou a presença de profissionais de saúde no espaço escolar, com a iniciativa de realizar palestra como método educativo, principalmente quanto aos métodos contraceptivos, mostrando as vantagens e desvantagens dos métodos. Conclusão: há uma necessidade de ampliação de ações estratégias para a garantia de um cuidado integral e qualificados com jovens e adolescentes, para a promoção e prevenção de agravos na saúde sexual e reprodutiva.
Emotional and physical exhaustion of family caregivers / Exaustão emocional e física de cuidadores familiares
Authors: Saikai Glaucy Mara Pelicer Nogueira , Nardi Susilene Maria Tonelli , Saikai William , Pereira Diego Dalvan , Millin Rosemeire Cordoba , Paschoal Vânia Del’Arco
Published: November 2020

Objetivo: verificar o perfil de distúrbios osteomusculares, a sobrecarga emocional e a saúde de cuidadores de pessoas com sequelas de lesão no Sistema Nervoso Central. Método: estudo descritivo com 23 cuidadores. Foram aplicados testes de lesão osteomusculares (Nórdico), de sobrecarga (Carregiver Burden Scale) e a Escala de Avaliação do Risco na Movimentação e Transferência. Resultados: os cuidadores tinham idade média de 52,9, mulheres, cônjuges, ensino fundamental e com função de cuidar do paciente e residência sem renumeração, média de 15,8h/dia de trabalho. 47,8% receberam poucas orientações sobre como cuidar. Os de maior idade sofrem mais com dor (coluna e membros superiores) e se afastam mais das atividades comparados aos mais jovens (valor-p=0,01). A tensão geral, o isolamento e a sobrecarga emocional foram impactantes (valor-p=0,03). Conclusão: as cuidadoras são familiares, de baixa renda, apresentam dores osteomusculares, considerável sobrecarga emocional e dor física e necessitam de cuidados da equipe de saúde.
A Novel Strategy for Constructing 3D Dislocated Chiral Metamaterial with Negative Poisson's Ratio
Authors: Zhong Rongchang , Zheng Binbin , Fu Minghui
Published: November 2020

Metamaterials with negative Poisson's ratio (NPR) have a broad range of application background, such as aerospace engineering, automotive engineering, medical instrument engineering, and wearable engineering. Herein, a novel strategy for constructing 3D dislocated chiral metamaterial is proposed that can achieve NPR effect in three directions. According to this strategy, a new dislocated chiral metamaterial composed of dislocated tetrachiral honeycombs and inclined rods is designed and selected as an example to investigate the effectiveness of the strategy. Experiments and numerical simulations are carried out to study the mechanical properties of the new metamaterial, confirming that this metamaterial exhibits NPR effect. The influence of geometric parameters on the elastic constants of the metamaterial is discussed based on experimental and numerical results. Meanwhile, the local loading performances of this dislocated chiral metamaterial and the previous aligned chiral metamaterial are studied and compared. Results show that this dislocated metamaterial possesses a stronger damage resistance capacity than the aligned one. By adjusting the rotational direction of ligaments in honeycombs and the arrangement of inclined rods, more special 3D dislocated chiral metamaterials with advanced properties are available, such as metamaterial with both positive and NPRs, metamaterial with compression–torsion effect.
Integrating Low‐Cost Earth‐Abundant Co‐Catalysts with Encapsulated Perovskite Solar Cells for Efficient and Stable Overall Solar Water Splitting
Authors: Chen Hongjun , Zhang Meng , Tran‐Phu Thanh , Bo Renheng , Shi Lei , Di Bernardo Iolanda , Bing Jueming , Pan Jian , Singh Simrjit , Lipton‐Duffin Josh , Wu Tom , Amal Rose , Huang Shujuan , Ho‐Baillie Anita W. Y. , Tricoli Antonio
Published: November 2020

Metal halide perovskite solar cells have an appropriate bandgap (1.5–1.6 eV), and thus output voltage (>1 V), to directly drive solar water splitting. Despite significant progress, their moisture sensitivity still hampers their application for integrated monolithic devices. Furthermore, the prevalence of the use of noble metals as co‐catalysts for existing perovskite‐based devices undermines their use for low‐cost H2 production. Here, a monolithic architecture for stable perovskite‐based devices with earth‐abundant co‐catalysts is reported, demonstrating an unassisted overall solar‐to‐hydrogen efficiency of 8.54%. The device layout consists of two monolithically encapsulated perovskite (FA0.80MA0.15Cs0.05PbI2.55Br0.45) solar cells with low‐cost earth‐abundant CoP and FeNi(OH)x co‐catalysts as the photocathode and photoanode, respectively. The CoP‐based photocathode demonstrates more than 17 h of continuous operation, with a photocurrent density of 12.4 mA cm−2 at 0 V and an onset potential as positive as ≈1 V versus reversible hydrogen electrode (RHE). The FeNi(OH)x‐based photoanode achieves a photocurrent of 11 mA cm−2 at 1.23 V versus RHE for more than 13 h continuous operation. These excellent stability and performance demonstrate the potential for monolithic integration of perovskite solar cells and low‐cost earth‐abundant co‐catalysts for efficient direct solar H2 production.
Bifunctional CoFeVOx Catalyst for Solar Water Splitting by using Multijunction and Heterojunction Silicon Solar Cells
Authors: Lee Minoh , Ding Xinyu , Banerjee Swarnendu , Krause Florian , Smirnov Vladimir , Astakhov Oleksandr , Merdzhanova Tsvetelina , Klingebiel Benjamin , Kirchartz Thomas , Finger Friedhelm , Rau Uwe , Haas Stefan
Published: November 2020

Photovoltaic driven electrochemical (PV‐EC) water splitting technology is considered as one of the solutions for an environmental‐friendly hydrogen supply. In a PV‐EC system, efficient catalysts are required to increase the rate of both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Here, the development of a CoFeVOx bifunctional catalyst produced by a simple electrodeposition method is presented. It is found that after the water splitting reaction, vanadium is almost completely depleted in the mixture of elements for OER, while its concentration at the HER catalyst is similar or even higher after the reaction. For the OER catalyst, the depletion of vanadium might lead to the formation of pores, which could be correlated with the activity enhancement. The developed catalyst is integrated into PV‐EC devices, coupled with different types of silicon PV. An average solar to hydrogen efficiency of 13.3% (9.6 cm2 PV aperture area) is achieved with a shingled module consisting of three laterally series‐connected silicon heterojunction solar cells.
Soft Magnetic Pillars to Secure an Upper Airway for the Relief of Obstructive Sleep Apnea
Authors: Kim Hyunjong , Sung Chung Man , Ju Hunpyo , Park Hyeongoh , Jeong Jinmo , Nam Kwang Il , Yang Hyung Chae , Lee Jongho
Published: November 2020

The inherent mechanical properties of soft structures allow fragile objects to be safely manipulated without the need for precise force control. Soft structures and driving mechanisms are employed in applications ranging from gripping and locomotion to biomedical devices. Such soft structures can be especially beneficial for manipulating excessively relaxed live soft human tissue, to relieve discomfort or medical conditions. An example is obstructive sleep apnea (OSA), where soft tissue narrows or blocks the upper airway while sleeping, causing difficulty breathing. In this paper, an approach to relieve OSA using injectable soft magnetic pillars paired with a removable magnet holder that can be worn while sleeping to secure the upper airway is reported. The approach provides an alternative to currently available treatments that may cause inconveniences such as difficulty swallowing, protrusion through soft tissue, repetitive surgeries, or sleep disruption. Experimental results and computational studies are used to determine the necessary degree of pulling force and distance, which can be adjusted by controlling the number of implanted soft magnetic pillars and external magnetic field strength. Further experiments using cadavers demonstrate the opening of the upper airway confirming the feasibility of the approach.
Temperature Effect of Plasmonic Circular Dichroism in Dynamic Oligomers of AuNR@Ag Nanorods Driven by Cysteine: The Role of Surface Atom Migration
Authors: Meng Dejing , Chen Yuandong , Ji Yinglu , Shi Xinghua , Wang Hui , Wu Xiaochun
Published: November 2020

Achieving huge chiroptical responses is one of the driving forces for the applications of plasmonic metamaterials. Heat‐assisted symmetry breaking can amplify plasmonic circular dichroism (PCD) signals in Au nanorod (AuNR) oligomers; however, the PCD responses disappear on Ag‐exposed surface (AuNR@Ag core‐shell nanorods) at high temperature. Thus, the inherent reason of different chiral response between Au‐ and Ag‐surface nanorods oligomers is explored, and the chiral mechanism is further cognized. The enhanced mobility of surface Ag atoms at elevated temperatures leads to the damage of cysteine chiral networks on Ag surface. It therefore causes great reduction of chiral drive forces, thus restricting the PCD temperature amplification effect to a lower annealing temperature, compared to their Au‐exposed counterparts. In addition, the PCD signals of the AuNR@Ag oligomers show a pH‐dependent on‐off behavior, substantiating the dominant role of chiral network. In addition, density functional theory simulation and relevant experiments reveal facet‐dependent chiral response of Ag and Au oligomers. Then, Au–Ag alloy shells can suppress Ag atoms migration; the chiral network and PCD temperature amplification effect can exist in high temperature. The findings reveal the importance of understanding interface ligands, plasmonic nanoparticles, and their interactions in the rational design of chiral assemblies composed of plasmonic nano‐units.
Planarized and Compact Light Scattering Layers Based on Disordered Titania Nanopillars for Light Extraction in Organic Light Emitting Diodes
Authors: Donie Yidenekachew J. , Theobald Dominik , Moghadamzadeh Somayeh , Mertens Adrian , Hossain Ihteaz M. , Paetzold Ulrich W. , Lemmer Uli , Gomard Guillaume
Published: November 2020

In this work, the extraction of waveguided and substrate modes in organic light emitting diodes (OLEDs) is improved by using compact light scattering layers composed of a disordered 2D array of TiO2 nanopillars. The TiO2 nanopillars are fabricated by combining a self‐assembly and a solvent‐assisted lift‐off process, and are further planarized by a 250 nm thin epoxy‐based photoresist layer to facilitate their anode deposition and integration within the OLED stack. This fabrication route allows engineering internal light outcoupling elements with a limited amount of parasitic absorption and with easily tunable light scattering properties that are effective over a broad spectral and angular range. Taking the example of a monochromatic bottom emitting OLED ( = 520 nm), the authors demonstrate an efficiency enhancement of +22%rel upon the incorporation of the planarized light extraction layer as well as ameliorated angular emission characteristics. This approach can be integrated in a high‐throughput fabrication routine and straightforwardly extended to other OLED layouts.
Exploiting Complementary Terahertz Ellipsometry Configurations to Probe the Hydration and Cellular Structure of Skin In Vivo
Authors: Chen Xuequan , Sun Qiushuo , Wang Jiarui , Lindley-Hatcher Hannah , Pickwell-MacPherson Emma
Published: November 2020

The noninvasive and water‐sensitive characteristics of terahertz (THz) light make it highly attractive for in vivo studies, especially for skin applications. However, THz instrumentation has not been developed sufficiently to fully explore all the potential applications arising: current systems cannot obtain uncorrelated reflections from multiple configurations to determine the complicated structure of living tissues. Herein, this bottleneck is overcome by implementing a novel ellipsometry configuration able to efficiently provide four complementary sets of spectral ratios, significantly enhancing characterization capabilities. An accurate model of the skin is established and validated. The anisotropy of the stratum corneum (SC) caused by its cellular structure is verified both theoretically and experimentally. The in vivo response of skin on the volar forearm to occlusion is observed by the dynamic changes in the SC and the epidermis. In addition, the THz dispersion and birefringence sensitively probe the level of hydration and the cellular inhomogeneity, producing results in good agreement with microscope images and the biological processes of the SC. The presented technique offers a brand‐new functionality in extracting insightful structural information from complex systems, significantly extending the versatility of THz spectroscopy.
Recent Achievements in the Rhodium‐Catalyzed Concise Construction of Medium N‐Heterocycles, Azepines and Azocines
Authors: Ouyang Wensen , Rao Jianhang , Li Yibiao , Liu Xiaohang , Huo Yanping , Chen Qian , Li Xianwei
Published: November 2020

Medium N‐heterocycles, azepines and azocines, serve as important skeletons that occurred widely in natural products, however, due to the lack of efficient synthetic methodologies, their application potential in biologically active molecules, pharmaceuticals and agrochemicals remained to be explored. In this context, rhodium catalysis in this field featured good reactivity and functional group tolerance, with readily available starting materials, and enabled rapid access to the azepines and azocines. Delightfully, great achievements in the concise construction of these 7 and 8‐membered N‐heterocycles under rhodium catalysis have been made, which mainly included cycloisomerization of unsaturated C−X bonds (which might also combine the ring‐opening strategy on strained rings), metal carbenoid or nitrene insertion involved transformations and direct C−H activation reactions. Considering the great performance of rhodium catalyst in the synthesis of azepines and azocines, herein, we summarized the recent results in this field, and wish to give further insight and inspired more encouraging methodologies and new drug discovery based on these 7 and 8‐membered N‐heterocycles.

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Gold‐Catalyzed Bicyclic and [3+2]‐Annulations of Internal Propargyl Alcohols with Nitrones and Imines To Yield to Two Distinct Heterocycles
Authors: More Sayaji Arjun , Chao Tzu‐Hsuan , Cheng Mu‐Jeng , Liu Rai‐Shung
Published: November 2020

A gold‐catalyzed synthesis of 1,3‐dihydrooxazolo[3,4‐a]indoles from 1‐oxo‐3‐yn‐4‐ols and nitrones is described; this new bicyclic annulation presents the first examples that internal alkynes can react with nitrones to undergo an oxoarylation route. DFT calculations indicate a [3,3]‐sigmatropic shift of initial alkenylgold intermediates to elude the intermediacy of gold carbenes. We also developed new [3+2]‐annulations of the same 1‐oxo‐3‐yn‐4‐ols with imines, yielding oxazolidin‐4‐ylidene derivatives efficiently. The tethered alcohols of these 1‐oxo‐3‐ynes allow trapping of their metastable 2‐azadienium intermediates to enable a novel annulation. Our mechanistic analysis indicates that the two products, despite their structural relevance, are produced from two independent systems.

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Metal–Organic Framework‐Derived Anode and Polyaniline Chain Networked Cathode with Mesoporous and Conductive Pathways for High Energy Density, Ultrafast Rechargeable, and Long‐Life Hybrid Capacitors
Authors: Ock Il Woo , Lee Jiyoung , Kang Jeung Ku
Published: November 2020

Hybrid lithium‐ion energy storage devices are promising for future applications, but their anodes and cathodes still have structural limitations, for example, accommodating rich cationic/anionic reactions, rapid charge movement, and long cycle life. Herein, high‐capacity/high‐rate anode and cathode structures are developed to overcome these challenges. Molybdenum oxide (MoO2)‐implanted carbon frameworks making conductive carbon bonds with reduced graphene oxide (rGO) shells are developed as anode structures by forming mesoporous channels for fast lithium‐ion transport, carbon‐rGO pathways for facile electron conduction, and ultrafine MoO2 units for high capacity. The operando X‐ray diffraction and kinetics analyses reveal that lithium‐ion insertion and extraction occur via capacitive and diffusion‐controlled reactions. Also, polyaniline (PANI) chains are elongated on rGO sheets through in situ polymerization to form crosslinked polyaniline chain‐integrated rGO as cathode structures. These display multiporosity for rapid anion transport, N‐doping sites for high capacity, and π–π bonding between PANI and rGO for electron conduction and cycle stability. Moreover, hybrid capacitors configured by this anode and cathode allow for the exploitation of battery‐type and pseudocapacitive reactions, as demonstrated by their extremely high energy density (up to 242 Wh kg−1), ultrafast chargeable power density (up to 28 750 W kg−1), and long‐life stability over 10 000 cycles.
Nitrogen partitioning traits and expression patterns of N metabolism‐associated genes in maize hybrids with contrasting N utilization efficiencies
Authors: Li Xiangling , Ji Pengtao , Zhou Baoyuan , Dong Weixin , Zhang Lei , Xiao Kai , Yin Baozhong , Zhang Yuechen
Published: November 2020

The nitrogen (N) uptake and utilization in maize (Zea mays L.) plants are accomplished through a series of biochemical reactions and transformations involving the N assimilation enzymes. Nitrate reductase (NR) and glutamine synthetase (GS) exert important functions in the N assimilation and remobilization processes. The mechanisms underlying plant N partitioning and the associated expression patterns of NR and GS genes in maize hybrids with different N utilization efficiencies were still not clear. In this study, the expression of ZmNR and ZmGS genes that are related to N partitioning were analyzed in two maize hybrids (XY335 and HN138). Results showed that XY335 displayed higher grain yield, kernel numbers, shoot N uptake, and physiological N utilization efficiency (NUtE) than those shown in HN138 under low‐N conditions. The higher post‐silking N uptake and N remobilization in vegetative organs in XY335 were associated with the enhanced net photosynthetic rate (Pn), the NR and GS activities in ear‐leaf. Additionally, the expression levels of ZmGS1.3 and ZmGS1.4 were up‐regulated when exposed to low‐N stress, showing higher values in XY335 than those in HN138. Correlation analysis showed that the expression levels of ZmNR, ZmGS1.3, and ZmGS1.4 are correlated with leaf NR and GS activities, N remobilization, and grain yield. Our investigation suggested the critical roles of the N metabolism‐associated genes in the modulation of internal N translocation and plant productivity in maize. Future transgene analysis on ZmNR and ZmGS can provide insights into the molecular mechanisms underlying plant tolerance to low N stress in maize.
Conformational Modulation of Iduronic Acid‐Containing Sulfated Glycosaminoglycans by a Polynuclear Platinum Compound and Implications for Development of Antimetastatic Platinum Drugs
Authors: Gorle Anil K. , Haselhorst Thomas , Katner Samantha J. , Everest‐Dass Arun V. , Hampton James D. , Peterson Erica J. , Koblinski Jennifer E. , Katsuta Eriko , Takabe Kazuaki , von Itzstein Mark , Berners‐Price Susan J. , Farrell Nicholas P.
Published: November 2020

1H NMR spectroscopic studies on the 1:1 adduct of the pentasaccharide Fondaparinux (FPX) and the substitution‐inert polynuclear platinum complex TriplatinNC show significant modulation of geometry around the glycosidic linkages of the FPX constituent monosaccharides. FPX is a valid model for the highly sulfated cell signalling molecule heparan sulfate (HS). The conformational ratio of the 1C4:2S0 forms of the FPX residue IdoA(2S) is altered from ca. 35:65 (free FPX) to ca. 75:25 in the adduct; the first demonstration of a small molecule affecting conformational changes on a HS oligosaccharide. Functional consequences of such binding are suggested to be inhibition of HS cleavage in MDA‐MB‐231 triple‐negative breast cancer (TNBC) cells. We further describe inhibition of metastasis by TriplatinNC in the TNBC 4T1 syngeneic tumour model. Our work provides insight into a novel approach for design of platinum drugs (and coordination compounds in general) with intrinsic anti‐metastatic potential.
Role of Pyridinic Nitrogen in the Mechanism of the Oxygen Reduction Reaction on Carbon Electrocatalysts
Authors: Takeyasu Kotaro , Furukawa Moeko , Shimoyama Yuto , Singh Santosh K. , Nakamura Junji
Published: November 2020

The introduction of pyridinic nitrogen (pyri‐N) into carbon‐based electrocatalysts for the oxygen reduction reaction is considered to create new active sites. Herein, the role of pyri‐N in such catalysts was investigated from a mechanistic viewpoint using carbon black (CB)‐supported pyri‐N‐containing molecules as model catalysts; the highest activity was observed for 1,10‐phenanthroline/CB. X‐ray photoemission spectroscopy showed that in acidic electrolytes, both pyri‐N atoms of 1,10‐phenanthroline could be protonated to form pyridinium ions (pyri‐NH+). In O2‐saturated electrolytes, one of the pyri‐NH+ species was reduced to pyri‐NH upon the application of a potential; no such reduction was observed in N2‐saturated electrolytes. This behavior was ascribed to electrochemical reduction of pyri‐NH+ occurring simultaneously with the thermal adsorption of O2, as supported by DFT calculations. According to these calculations, the coupled reduction was promoted by hydrophobic environments.
Chemical Tagging of Protein Lipoylation
Authors: Tang Qi , Guo Yilan , Meng Liying , Chen Xing
Published: November 2020

Protein lipoylation is a post‐translational modification of emerging importance in both prokaryotes and eukaryotes. However, labeling and large‐scale profiling of protein lipoylation remain challenging. Here, we report the development of iLCL (iodoacetamide‐assisted lipoate‐cyclooctyne ligation), a chemoselective reaction that enables chemical tagging of protein lipoylation. We demonstrate that the cyclic disulfide of lipoamide but not linear disulfides can selectively react with iodoacetamide to produce sulfenic acid, which can be conjugated with cyclooctyne probes. iLCL enables tagging of lipoylated proteins for gel‐based detection and cellular imaging. Furthermore, we apply iLCL for proteomic profiling of lipoylated proteins in both bacteria and mammalian cells. In addition to all of the eight known lipoylated proteins, we identified seven candidates for novel lipoylated proteins. The iLCL strategy should facilitate uncovering the biological function of protein lipoylation.
Face‐to‐Face Orientation of Quasiplanar Donor and Acceptor Enables Highly Efficient Intramolecular Exciplex Fluorescence
Authors: Wu Chao , Liu Weiqiang , Li Kai , Cheng Gang , Xiong Jinfan , Teng Teng , Che Chi‐Ming , Yang Chuluo
Published: November 2020

Intramolecular through‐space charge‐transfer (TSCT) excited states have been exploited for developing thermally activated delayed fluorescence (TADF) emitters, but the tuning of excited state dynamics by conformational engineering remains sparse. Designed here is a series of TSCT emitters with precisely controlled alignment of the donor and acceptor segments. With increasing intramolecular π–π interactions, the radiative decay rate of the lowest singlet excited state (S1) progressively increased together with a suppression of nonradiative decay, leading to significantly enhanced photoluminescence quantum yields of up to 0.99 in doped thin films. A high‐efficiency electroluminescence device, with a maximum external quantum efficiency (EQE) of 23.96 %, was achieved and maintains >20 % at a brightness of 1000 cd m−2. This work sheds light on the importance of conformation control for achieving high‐efficiency intramolecular exciplex emitters.
Supramolecular Assembly of An Organoplatinum(II) Complex with Ratiometric Dual Emission for Two‐Photon Bioimaging
Authors: Ouyang Cheng , Li Yongguang , Rees Thomas W. , Liao Xinxing , Jia Jianhua , Chen Yu , Zhang Xiting , Ji Liangnian , Chao Hui
Published: November 2020

The organoplatinum(II) complex [Pt(C^N^N)(Cl)] (C^N^N=5,6‐diphenyl‐2,2′‐bipyridine, Pt1) can assemble into nanoaggregates via π–π stacking and complementary hydrogen bonds, rather than Pt–Pt interactions. Pt1 exhibits ratiometric dual emission, including rare blue emission (λem=445 nm) and assembly‐induced yellow emission (λem=573 nm), under one‐ and two‐photon excitation. Pt1 displays blue emission in cells with an intact membrane due to its low cellular uptake. In cells where the membrane is disrupted, uptake of the complex is increased and at higher concentrations yellow emission is observed. The ratio of yellow to blue emission shows a linear relationship to the loss of cell membrane integrity. Pt1 is, to our knowledge, the first example of an assembly‐induced two‐photon ratiometric dual emission organoplatinum complex. The excellent and unique characteristics of the complex enabled its use for the tracking of cell apoptosis, necrosis, and the inflammation process in zebrafish.
A Multilayer Ceramic Electrolyte for All‐Solid‐State Li Batteries
Authors: Zhu Jianxun , Li XiaoLei , Wu Changwei , Gao Jian , Xu Henghui , Li Yutao , Guo Xiangxin , Li Hong , Zhou Weidong
Published: November 2020

Despite of the good stability with Li‐metal, Li6.75La3Zr1.75Ta0.25O12(LLZTO) suffers from large interfacial resistance and severe Li‐metal penetration. Herein, a dual layer ceramic electrolyte of Ti‐doped LLZTO(Ti‐LLZTO)/LLZTO was developed, with the reducible Ti‐LLZTO layer contacting Li‐metal and the LLZTO layer contacting cathode. The identical crystal structures of Ti‐LLZTO and LLZTO enables a seamless contact and a barrierless Li+ transport between them. The densities of Ti‐LLZTO pellets are higher than that of LLZTO. With an in situ reduction of Ti‐LLZTO by Li‐metal, the interfacial wettability was improved and a mixed ion‐electron conducting layer was created. Both features help to reduce defects/pores on interface and homogenize the interfacial ionic/electronic flux, facilitating the reduction of interfacial resistance and suppression of dendrites. With the help of Ti‐LLZTO layer, long‐term stable lithium plating/stripping was reached in an areal capacity of 3.0 mAh cm−2.
Artificial Solid‐Electrolyte Interphase for Lithium Metal Batteries
Authors: Kang Danmiao , Xiao Muye , Lemmon John P.
Published: November 2020

Li metal has attracted intense attention due to its high specific capacity, but the dendrite growth during cycling impedes its practical application as a rechargeable anode. To improve the stability of the solid‐electrolyte interphase (SEI) on Li metal is the key to develop Li anode with high safety. In native SEI, inorganics act as fast ion channels and organics play the role of soft base with high flexibility to buffer volume change. However, the SEI with inorganics close to Li surface and organics close to electrolyte always leads to a fragile structure, resulting in repeatedly breaking and growing of the surface layer. Artificial SEI is one of the most effective ways to improve interphase stability and extend the cycle life of Li anode. Inorganics such as Li fluoride, Li nitride, Li phosphate and Li alloys have been widely applied in Li protection. In situ chemical reactions, spin coating and doctor blade coating of organics were also conducted to obtain SEI with high lithiophilic functional groups and high elasticity. To fabricate an ideal artificial SEI, organic and inorganic components should be rearranged as a rational structure to possess synergetic effects with both high flexibility and ionic conductivity. This Minireview summarizes the most recent works on artificial SEI and discusses the electrochemical performance of different components as interphase, aiming to inspire the study on designing and fabricating stable Li anode with robust interphase structure.
Volition to behave sustainably: An examination of the role of self‐control
Authors: Gómez‐Olmedo Ana M. , Carrero Bosch Isabel , Martínez Carmen Valor
Published: November 2020

To address the current socioenvironmental crisis, the individual adoption of pro‐environmental lifestyles has been recognized as being of paramount importance. Past research has largely assumed that motivation will drive pro‐environmental behaviour. In contrast, this study argues that, in addition to motivation, volitional abilities are fundamental since these abilities facilitate circumventing internal and external barriers, disrupting unsustainable habits and foregoing short‐term personal gratification for long‐term societal benefits. More specifically, this study examines the direct influence of self‐control (SC) on the adoption of pro‐environmental behaviour (PEB). We theorize that SC is more predictive of behaviour than perceived behavioural control (PBC), and we suggest a direct association between SC and the adoption of PEB. Moreover, we hypothesize that the magnitude of the effect is even greater for actions with fewer external barriers, which require more volitional control. These hypotheses are supported by a study of 412 individuals. Our study contributes to the literature on environmental behaviour by showing the importance of volitional skills in explaining PEB. Furthermore, given the malleability of SC, this study proposes strategies for its development to promote pro‐environmental lifestyles as mainstream.
Efficient Editing of Silver Nanoclusters by Changing Simply One Cytosine in a DNA Template
Authors: Ma Jinliang , Li Kexin , Gu Shaobin
Published: November 2020

DNA with genetic information was edited to regulate and repair the structure and function of a protein. In DNA nanotechnology, DNA with programmable information can be designed to edit the fluorescence intensity and emissive colors of DNA‐stabilized silver nanoclusters (DNA/AgNCs). By introducing and moving one cytosine in the spacer of the emitter domain, we have built up a simple strategy to regulate the excitation and emission wavelengths of AgNCs. When replacing thymine in the spacer of the emitter with one cytosine, the expected excitation and emission change do not occur. However, after moving the introduced cytosine, DNA templates produce AgNCs with extremely different excitation and emission wavelengths from those of the initial template, leading to a template for near‐infrared (NIR) emissive species with the highest fluorescence intensity. The formation of AgNCs induces the DNA template into condensed secondary structure based on an altered migration rate in PAGE. The simple strategy of moving one cytosine in a spacer in the emitter domain can enrich the library of templates for synthesizing diverse DNA/AgNCs and has great potential in bioimaging and probe design.
In Situ Growth of Hollow Trimetallic Nanocubes on Nickel Foam for the Electrocatalytic Oxygen Evolution Reaction
Authors: Li Zhuzhu , Deng Puhui , Zhang Xue , Zhang Linping , Hou Yu
Published: November 2020

Nanomaterials derived from Prussian blue (PB) and its analogues (PBAs) possess uniform active centers and large surface areas, which can be applied in the field of electrocatalysis. In this study, nickel‐iron‐cobalt trimetallic PBAs, that is, NiFeCo(4 : 1)PBA nanocubes, were grown in situ on nickel foam (NF), which was subsequently calcined in air to obtain a composite electrode, NiO/FeOX/Co3O4@NF, with a loose porous hollow nanocube morphology. This structure remarkably enlarged the contact area between the electrolyte and the catalyst. In addition, a synergistic effect among these metallic oxides expedited oxygen evolution reaction (OER) kinetics. The Tafel slope (71.25 mV dec−1) toward OER of the constructed electrode is fairly small, much lower than that of our prepared bimetallic oxides@NF electrodes. The enduring stability is more than 22 h. This work indicates that, through morphology and composition control, the electrocatalytic performance of the designed electrode can be effectively improved.
Binding Motifs in the Naked Complexes of Target Amino Acids with an Excerpt of Antitumor Active Biomolecule: An Ion Vibrational Spectroscopy Assay
Authors: Chiavarino Barbara , Sinha Rajeev K. , Crestoni Maria Elisa , Corinti Davide , Filippi Antonello , Fraschetti Caterina , Scuderi Debora , Maitre Philippe , Fornarini Simonetta
Published: November 2020

The structures of proton‐bound complexes of 5,7‐dimethoxy‐4H‐chromen‐4‐one (1) and basic amino acids (AAs), namely, histidine (His) and lysine (Lys), have been examined by means of mass spectrometry coupled with IR ion spectroscopy and quantum chemical calculations. This selection of systems is based on the fact that 1 represents a portion of glabrescione B, a natural small molecule of promising antitumor activity, while His and Lys are protein residues lining the cavity of the alleged receptor binding site. These species are thus a model of the bioactive adduct, although clearly the isolated state of the present study bears little resemblance to the complex biological environment. A common feature of [1+AA+H]+ complexes is the presence of a protonated AA bound to neutral 1, in spite of the fact that the gas‐phase basicity of 1 is comparable to those of Lys and His. The carbonyl group of 1 acts as a powerful hydrogen‐bond acceptor. Within [1+AA+H]+ the side‐chain substituents (imidazole group for His and terminal amino group for Lys) present comparable basic properties to those of the α‐amino group, taking part to a cooperative hydrogen‐bond network. Structural assignment, relying on the comparative analysis of the infrared multiple photon dissociation (IRMPD) spectrum and calculated IR spectra for the candidate geometries, derives from an examination over two frequency ranges: 900–1800 and 2900–3700 cm−1. Information gained from the latter one proved especially valuable, for example, pointing to the contribution of species characterized by an unperturbed carboxylic OH or imidazole NH stretching mode.
Electrophilic and Nucleophilic Aromatic Substitutions are Mechanistically Similar with Opposite Polarity
Authors: Mąkosza Mieczysław
Published: November 2020

Confrontation of the recently formulated general mechanism of nucleophilic substitution in electron‐deficient arenes with the well‐known mechanism of electrophilic substitution revealed that these fundamental processes are mechanistically identical but proceed according to opposite polarity—an Umpolung relation. In this viewpoint this apparently controversial concept is supported by discussion of a variety of experimental results.
Tuning the Organogelating and Spectroscopic Properties of a C3‐Symmetric Pyrene‐Based Gelator through Charge Transfer
Authors: Gainar Adrian , Lai Thanh‐Loan , Oliveras‐González Cristina , Pop Flavia , Raynal Matthieu , Isare Benjamin , Bouteiller Laurent , Linares Mathieu , Canevet David , Avarvari Narcis , Sallé Marc
Published: November 2020

Two‐component organogels and xerogels based on a C3‐symmetric pyrene‐containing gelator have been deeply characterized through a wide range of techniques. Based on the formation of charge transfer complexes, the gelation phenomenon proved to be highly dependent on the nature of the electron poor dopant. This parameter significantly influenced the corresponding gelation domains, the critical gelation concentrations of acceptor dopants, the gel‐to‐sol transition temperatures, the microstructures formed in the xerogel state and their spectroscopic properties. In particular, titrations and variable‐temperature UV–visible absorption spectroscopy demonstrated the key role of donor–acceptor interactions with a remarkable correlation between the phase transition temperatures and the disappearance of the characteristic charge transfer bands. The assignment of these electronic transitions was confirmed through time‐dependent density functional theory (TD‐DFT) calculations. Eventually, it was shown that the luminescent properties of these materials can be tuned with the temperature, either in intensity or emission wavelength.
The Photosensitizing Efficacy of Micelles Containing a Porphyrinic Photosensitizer and KI against Resistant Melanoma Cells
Authors: Castro Kelly A. D. F. , Costa Letícia D. , Prandini Juliana A. , Biazzotto Juliana C. , Tomé Augusto C. , Hamblin Michael R. , da Graça P. M. S. Neves Maria , Faustino M. Amparo F. , da Silva Roberto S.
Published: November 2020

Photodynamic therapy (PDT) is a promising alternative to overcome the resistance of melanoma to conventional therapies. Currently applied photosensitizers (PS) are often based on tetrapyrrolic macrocycles like porphyrins. Unfortunately, in some cases the use of this type of derivative is limited due to their poor solubility in the biological environment. Feasible approaches to surpass this drawback are based on lipid formulations. Besides that, and inspired in the efficacy of potassium iodide (KI) for antimicrobial photodynamic therapy (aPDT), the combined effect of singlet oxygen (1O2) with KI was assessed in this work, as an alternative strategy to potentiate the effect of PDT against resistant melanoma cells.