bluuebunny/crossref_metadata_2025_split huggingface dataset:
Epigenetic and transcriptomic consequences of excess X‐chromosome material in 47,XXX syndrome—A comparison with Turner syndrome and 46,XX females
Authors: Nielsen Morten Muhlig , Trolle Christian , Vang Søren , Hornshøj Henrik , Skakkebæk Anne , Hedegaard Jakob , Nordentoft Iver , Pedersen Jakob Skou , Gravholt Claus Højbjerg 
Published: June 2020

Abstract47,XXX (triple X) and Turner syndrome (45,X) are sex chromosomal abnormalities with detrimental effects on health with increased mortality and morbidity. In karyotypical normal females, X‐chromosome inactivation balances gene expression between sexes and upregulation of the X chromosome in both sexes maintain stoichiometry with the autosomes. In 47,XXX and Turner syndrome a gene dosage imbalance may ensue from increased or decreased expression from the genes that escape X inactivation, as well as from incomplete X chromosome inactivation in 47,XXX. We aim to study genome‐wide DNA‐methylation and RNA‐expression changes can explain phenotypic traits in 47,XXX syndrome. We compare DNA‐methylation and RNA‐expression data derived from white blood cells of seven women with 47,XXX syndrome, with data from seven female controls, as well as with seven women with Turner syndrome (45,X). To address these questions, we explored genome‐wide DNA‐methylation and transcriptome data in blood from seven females with 47,XXX syndrome, seven females with Turner syndrome, and seven karyotypically normal females (46,XX). Based on promoter methylation, we describe a demethylation of six X‐chromosomal genes (AMOT, HTR2C, IL1RAPL2, STAG2, TCEANC, ZNF673), increased methylation for GEMIN8, and four differentially methylated autosomal regions related to four genes (SPEG, MUC4, SP6, and ZNF492). We illustrate how these changes seem compensated at the transcriptome level although several genes show differential exon usage. In conclusion, our results suggest an impact of the supernumerary X chromosome in 47,XXX syndrome on the methylation status of selected genes despite an overall comparable expression profile.
Atroposelective Synthesis of Axially Chiral N‐Arylpyrroles by Chiral‐at‐Rhodium Catalysis
Authors: Ye Chen‐Xi , Chen Shuming , Han Feng , Xie Xiulan , Ivlev Sergei , Houk K. N. , Meggers Eric 
Published: June 2020

AbstractA transformation of fluxional into configurationally stable axially chiral N‐arylpyrroles was achieved with a highly atroposelective electrophilic aromatic substitution catalyzed by a chiral‐at‐metal rhodium Lewis acid. Specifically, N‐arylpyrroles were alkylated with N‐acryloyl‐1H‐pyrazole electrophiles in up to 93 % yield and with up to >99.5 % ee, and follow‐up conversions reveal the synthetic utility of this new method. DFT calculations elucidate the origins of the observed excellent atroposelectivity.
How To Make Nitroaromatic Compounds Glow: Next‐Generation Large X‐Shaped, Centrosymmetric Diketopyrrolopyrroles
Authors: Skonieczny Kamil , Papadopoulos Ilias , Thiel Dominik , Gutkowski Krzysztof , Haines Philipp , McCosker Patrick M. , Laurent Adèle D. , Keller Paul A. , Clark Timothy , Jacquemin Denis , Guldi Dirk M. , Gryko Daniel T. 
Published: June 2020

AbstractRed‐emissive π‐expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching λ=750 nm can be easily synthesized by a three‐step strategy involving the preparation of diketopyrrolopyrrole followed by N‐arylation and subsequent intramolecular palladium‐catalyzed direct arylation. Comprehensive spectroscopic assays combined with first‐principles calculations corroborated that both N‐arylated and fused DPPs reach a locally excited (S1) state after excitation, followed by internal conversion to states with solvent and structural relaxation, before eventually undergoing intersystem crossing. Only the structurally relaxed state is fluorescent, with lifetimes in the range of several nanoseconds and tens of picoseconds in nonpolar and polar solvents, respectively. The lifetimes correlate with the fluorescence quantum yields, which range from 6 % to 88 % in nonpolar solvents and from 0.4 % and 3.2 % in polar solvents. A very inefficient (T1) population is responsible for fluorescence quantum yields as high as 88 % for the fully fused DPP in polar solvents.
Ineffective OH Pinning of the Flipping Dynamics of a Spherical Guest within a Tight‐Fitting Tube
Authors: Matsuno Taisuke , Someya Maki , Sato Sota , Maeda Satoshi , Isobe Hiroyuki 
Published: June 2020

AbstractA supramolecular/synthetic method has been devised to affix a sterically hindered substituent onto a fullerene guest encapsulated in a tubular host. A two‐wheeled complex of (C59N)‐(C59N) with a tubular host was oxidatively bisected to afford a C59N+ cation captured in the tube. The C59N+ cation in the tube was then trapped by ethanol or water, which led to an oxy substituent pinned on the guest. The guest motions within the tube were modulated by the pinned substituent, and up‐and‐down flipping motions were halted by an ethoxy substituent. A hydroxy substituent, however, was ineffective in halting the flipping motions, despite the tight‐fitting relationship between the tubular host and the spherical guest. Theoretical calculations of the dynamics revealed that the flipping motions were assisted by OH‐π hydrogen bonds between the guest and the carbon‐rich wall and that sliding motions of the OH group were also facilitated by deformations of the tube.
Cation‐Controlled Assembly of Polyoxotungstate‐Based Coordination Networks
Authors: Chen Linfeng , Turo Michael J. , Gembicky Milan , Reinicke Ruth A. , Schimpf Alina M. 
Published: June 2020

AbstractThe Preyssler polyoxoanion, [NaP5W30O110]14− ({P5W30}), is used as a platform for evaluating the role of nonbridging cations in the formation of transition‐metal‐bridged polyoxometalate (POM) coordination frameworks. Specifically, the assembly architecture of Co2+‐bridged frameworks is shown to be dependent on the identity and amount of alkali or alkaline‐earth cations present during crystallization. The inclusion of Li+, Na+, K+, Mg2+, or Ca2+ in the framework synthesis is used to selectively synthesize five different Co2+‐bridged {P5W30} structures. The influence of the competition between K+ and Co2+ for binding to {P5W30} in dictating framework assembly is evaluated. The role of ion pairing on framework assembly structure and available void volume is discussed. Overall, these results provide insight into factors governing the ability to achieve controlled assembly of POM‐based coordination networks.
Chemie freier Radikale von Phosphasilenen
Authors: Samedov Kerim , Heider Yannic , Cai Yuanjing , Willmes Philipp , Mühlhausen Daniel , Huch Volker , West Robert , Scheschkewitz David , Percival Paul W. 
Published: June 2020

AbstractDas Verständnis der Eigenschaften von Radikalen, die ausgehend von Si‐haltigen, schweren Analoga von Alkenen gebildet werden, ist wichtig für ihre Anwendung in der radikalischen Polymerisation. Sterische und elektronische Substituenteneffekte in Phosphasilenen stabilisieren nicht nur die Si=P‐Doppelbindung, sondern beeinflussen auch die Struktur und Natur der gebildeten Radikale. Wir berichten hier über Untersuchungen an Phosphasilen‐abgeleiteten Radikalen mit Mes‐, Tip‐, Dur‐ und NMe2‐Substituenten am P‐Atom mithilfe von Myonenspinspektroskopie und DFT‐Rechnungen. Die Addition von Myonium (einem leichten Isotop von Wasserstoff) an Phosphasilene zeigt, dass a) das Elektronendonor‐NMe2‐ und das sperrigste Tip‐substituierte Phosphasilen mehrere myonierte Radikale mit unterschiedlichen Rotamer‐Konformationen bilden; b) das sperrige Dur‐substituierte Phosphasilen zwei Radikale (Si‐ und P‐zentriert) bildet; und c) Mes‐substituiertes Phosphasilen hauptsächlich eine Radikalspezies am P‐Zentrum bildet. Diese signifikanten Unterschiede rühren von einem intramolekularen Substituenteneffekt her.
Scalable Photoelectrochemical Dehydrogenative Cross‐Coupling of Heteroarenes with Aliphatic C−H Bonds
Authors: Xu Pin , Chen Peng‐Yu , Xu Hai‐Chao 
Published: June 2020

AbstractHeteroarenes are structural motifs found in many bioactive compounds and functional materials. Dehydrogenative cross‐coupling of heteroarenes with aliphatic C−H bonds provides straightforward access to functionalized heteroarenes from readily available materials. Established methods employ stoichiometric chemical oxidants under conditions of heating or light irradiation. By merging electrochemistry and photochemistry, we have achieved efficient photoelectrochemical dehydrogenative cross‐coupling of heteroarenes and C(sp3)−H donors through H2 evolution, without the addition of metal catalysts or chemical oxidants. Mechanistically, the C(sp3)−H donor is converted to a nucleophilic carbon radical through H‐atom transfer with chlorine atom, which is produced by light irradiation of anodically generated Cl2 from Cl−. The carbon radical then undergoes radical substitution to the heteroarene to afford alkylated heteroarene products.
Feasibility of foam forming technology for producing wood plastic composites
Authors: Immonen Kirsi , Jetsu Petri , Keränen Janne , Torvinen Katariina 
Published: June 2020

AbstractCellulose fiber‐containing thermoplastic composite materials are being used in an increasing number of applications produced typically by injection molding and extrusion processing methods. One potential way to manufacture thermoplastic cellulosic fiber composites is foam forming technology developed originally for paper manufacturing. This article compares the low‐density polyethylene (LDPE) and unrefined northern bleached softwood kraft pulp (NBSKP) composite materials prepared with foam forming, extrusion, and injection molding. The results show that the foam forming enabled three times higher Charpy impact strength properties and 68% higher tensile modulus compared to injection molded 30% NBSKP fiber‐containing LDPE composites without changes in composite color. Foam forming is a potential large‐scale manufacturing method for thermoplastic composite sheets used, for example, in compression molding or thermoforming.
Synthesis of amino‐cosubstituted polyorganophosphazenes and fabrication of their nanoparticles for anticancer drug delivery
Authors: Khan Rizwan Ullah , Yu Haojie , Wang Li , Teng Lisong , Zain‐ul‐Abdin  , Nazir Ahsan , Fahad Shah , Elshaarani Tarig , Haq Fazal , Shen Di 
Published: June 2020

AbstractThe development of safe drug carriers is cardinal in cancer therapy, which can target the cancer cells and release the loaded drug on‐demand without damaging the healthy cells of the body. In our work, we synthesized three different biodegradable polymers, poly[(ethyl aminobezoate) (ethyl glycinato) phosphazenes] (PABGPs), in different mole ratio of side groups. The successful synthesis of these PABGPs was confirmed by 1H NMR, 31P NMR, FT‐IR, and gel permeation chromatography. These PABGPs were fabricated into drug (camptothecin, CPT, a hydrophobic anticancer drug) loaded nanoparticles. These drug‐loaded nanoparticles showed good drug release behaviors under normal physiological conditions (pH 7.4 and temperature 37°C). These PABGPs‐based nanoparticles may find their application as effective drug carriers for cancer therapy.
Tribological characterization of graphene nanoplatelets/alumina particles filled epoxy hybrid nanocomposites
Authors: Kesavulu A. , Mohanty Akash 
Published: June 2020

AbstractIn this work, graphene nanoplatelets have been synthesized using liquid phase exfoliation of graphite flake powder. The exfoliated graphene nanoplatelets were identified and characterized by using UV–Visible–NIR spectroscopy, High resolution transmission electron microscopy, electron diffraction, scanning electron microscopy and X‐ray diffraction. The obtained graphene nanoplatelets and nano alumina at various weight ratios were dispersed in an epoxy matrix to enhance the surface roughness (Ra), micro hardness (Hv) and coefficient of friction (CoF) of epoxy hybrid nanocomposites. The results showed that the Ra and CoF value for the combined loading of 0.2 wt% of graphene nanoplatelets and 0.8 wt% of alumina into the epoxy was decreased to 41.02 and 20.01% whereas, the Hv value was increased to 10.04% when compared with the neat epoxy. The improved mechanical and tribological behaviors are suitable for the applications bearing and coating.
Production of Substituted Styrene Bioproducts from Lignin and Lignocellulose Using Engineered Pseudomonas putida KT2440
Authors: Williamson James J. , Bahrin Nurfariza , Hardiman Elizabeth M. , Bugg Timothy D. H. 
Published: June 2020

AbstractFerulic acid is a renewable chemical found in lignocellulose from grasses such as wheat straw and sugarcane. Pseudomonas putida is able to liberate and metabolize ferulic acid from plant biomass. Deletion of the hydroxycinnamoyl‐CoA hydratase‐lyase gene (ech) produced a strain of P. putida unable to utilize ferulic and p‐coumaric acid, which is able to accumulate ferulic acid and p‐coumaric acid from wheat straw or sugar cane bagasse. Further engineering of this strain saw the replacement of ech with the phenolic acid decarboxylase padC, which converts p‐coumaric and ferulic acid into 4‐vinylphenol and the flavor agent 4‐vinylguaiacol, respectively. The engineered strain containing padC is able to generate 4‐vinylguaiacol and 4‐vinylphenol from media containing lignocellulose or Green Value Protobind lignin as feedstock, and does not require the addition of an exogenous inducer molecule. Biopolymerization of 4‐vinylguaiacol and 4‐vinylcatechol styrene products is also carried out, using Trametes versicolor laccase, to generate “biopolystyrene” materials on small scale.
Breast cancer surgery in older women: outcomes of the Bridging Age Gap in Breast Cancer study
Authors: Morgan J L , George J , Holmes G , Martin C , Reed M W R , Ward S , Walters S J , Cheung K Leung , Audisio R A , Wyld L 
Published: June 2020

Abstract

Background
Breast cancer surgery in older women is variable and sometimes non-standard owing to concerns about morbidity. Bridging the Age Gap in Breast Cancer is a prospective multicentre cohort study aiming to determine factors influencing treatment selection and outcomes from surgery for older patients with breast cancer.

Methods
Women aged at least 70 years with operable breast cancer were recruited from 57 UK breast units between 2013 and 2018. Associations between patient and tumour characteristics and type of surgery in the breast and axilla were evaluated using univariable and multivariable analyses. Oncological outcomes, adverse events and quality-of-life (QoL) outcomes were monitored for 2 years.

Results
Among 3375 women recruited, surgery was performed in 2816 patients, of whom 24 with inadequate data were excluded. Sixty-two women had bilateral tumours, giving a total of 2854 surgical events. Median age was 76 (range 70–95) years. Breast surgery comprised mastectomy in 1138 and breast-conserving surgery in 1716 procedures. Axillary surgery comprised axillary lymph node dissection in 575 and sentinel node biopsy in 2203; 76 had no axillary surgery. Age, frailty, dementia and co-morbidities were predictors of mastectomy (multivariable odds ratio (OR) for age 1·06, 95 per cent c.i. 1·05 to 1·08). Age, frailty and co-morbidity were significant predictors of no axillary surgery (OR for age 0·91, 0·87 to 0·96). The rate of adverse events was moderate (551 of 2854, 19·3 per cent), with no 30-day mortality. Long-term QoL and functional independence were adversely affected by surgery.

Conclusion
Breast cancer surgery is safe in women aged 70 years or more, with serious adverse events being rare and no mortality. Age, ill health and frailty all influence surgical decision-making. Surgery has a negative impact on QoL and independence, which must be considered when counselling patients about choices.
Proof of surgical publication prowess: prospective observational study of factors associated with surrogate markers of academic reach
Authors: Robinson D B T , Powell A G M T , Hopkins L , James O P , Abdelrahman T , Egan R , Lewis W G 
Published: June 2020

Abstract

Background
In the UK, general surgery higher surgical trainees (HSTs) must publish at least three peer-reviewed scientific articles (as first, second or corresponding author) to qualify for certification of completion of training (CCT). This study aimed to identify the factors associated with success in this arena.

Methods
Deanery rosters supplemented with data from the Intercollegiate Surgical Curriculum Programme, PubMed and ResearchGate were used to identify the profiles of consecutive HSTs. Primary outcomes were publication numbers at defined points in higher training (speciality training year (ST) 3–8); secondary outcomes were the Hirsch index and ResearchGate scores.

Results
Fifty-nine consecutive HSTs (24 women, 35 men) were studied. The median publication number was 3 (range 0–30). At least three published articles were obtained by 30 HSTs (51 per cent), with 19 (38 per cent) of 50 HSTs achieving this by ST4 (of whom 15 (79 per cent) had undertaken out of programme for research (OOPR) time) and 24 (80 per cent) by ST6. Thirteen HSTs (22 per cent) (ST3, 6; ST4, 4; ST5, 2; ST8, 1) had yet to publish at the time of writing. OOPR was associated with achieving three publications (24 of 35 (69 per cent) versus 6 of 24 (25 per cent) with no formal research time; P = 0·001), higher overall number of publications (median 6 versus 1 respectively; P &lt; 0·001), higher ResearchGate score (median 23·37 versus 5·27; P &lt; 0·001) and higher Hirsch index (median 3 versus 1; P &lt; 0·001). In multivariable analysis, training grade (odds ratio (OR) 1·89, 95 per cent c.i. 0·01 to 3·52; P = 0·045) and OOPR (OR 6·55, 2·04 to 21·04; P = 0·002) were associated with achieving three publications.

Conclusion
If CCT credentials are to include publication profiles, HST programmes should incorporate research training in workforce planning.
Towards an integrated model for the transference of environmental responsibility
Authors: Gilal Faheem Gul , Gilal Naeem Gul , Channa Nisar Ahmed , Gilal Rehman Gul , Gilal Rukhsana Gul , Tunio Muhammad Nawaz 
Published: June 2020

AbstractThis research explores how environmental responsibility transfers to others. Although environmental responsibility is one of the most debated topics in environmental management literature, a framework describing how a teacher's environmental responsibility shapes the student's environmental responsibility is still lacking. Adopting emotional contagion theory as a lens, the paper addresses this issue via the mediation of emotional contagion and the moderation of a teacher's environmental concern. Based on a survey of teachers and students (N = 283) conducted in Pakistan, our findings provide evidence that a teacher's environmental responsibility can better transfer to students via emotional contagion. Additionally, our data establish that the transference of environmental responsibility from teachers to students via emotional contagion is more effective when the teacher has a high level of environmental concern than when he or she has a low level of environmental concern. Finally, the authors discuss the implications for policy in detail.
Nostalgia prompts sustainable product disposal
Authors: Wang Yan , Tian Hong , Sarigöllü Emine , Xu Wei 
Published: June 2020

AbstractConsumers' product‐disposal behaviors impact the environment, businesses, society, and consumer well‐being. This research explores if and how consumers' disposal behaviors are influenced by sentiments of nostalgia. Four experimental studies are conducted, two on student samples and two on general population, to test our hypotheses. Study 1 shows that compared with collective nostalgia, personal nostalgia elicits higher intention to keep and reuse products. In contrast, collective nostalgia elicits higher intention to donate and recycle products. Both personal nostalgia and collective nostalgia reduce intention to throw away. Study 2 further corroborates the negative impact of personal nostalgia and collective nostalgia on throw away intention. Study 3 finds that the positive effect of personal nostalgia on keep and reuse intention is mediated by self‐continuity. Finally, study 4 demonstrates that collective efficacy mediates the positive effect of collective nostalgia on donate and recycle intention. This study has theoretical contributions and practical implications for scholars and policy makers.
Ansavaricin J, a New Heterocyclic Ring‐Fused Streptovaricin from Gene stvP5‐Deleted Mutant of Streptomyces spectabilis CCTCC M2017417
Authors: Liu Yuan‐Zhen , Chen Xu , Li Zheng‐Yuan , Huang Li–Xia , Sun Yu‐Hui 
Published: June 2020

AbstractA new ring‐fused streptovaricin analogue, named ansavaricin J, was unprecedently isolated from the culture of the genetically modified strains ΔstvP5 which derived from Streptomyces spectabilis CCTCC M2017417. Its structure was elucidated via comprehensive spectroscopic analyses, including 1D‐ and 2D‐NMR tests, and HR‐ESI‐MS data analysis. Notably, ansavaricin J and E represent the only two reported examples of heterocyclic ring‐fused streptovaricins thus far, however, it only showed insignificant antibacterial activities against Staphylococcus aureus.
Resolution of bone, cutaneous, and muscular involvement after haploidentical hematopoietic stem cell transplantation followed by post‐transplant cyclophosphamide in adult T‐cell leukemia/lymphoma
Authors: Iioka Futoshi , Tanabe Hiroshi , Honjo Gen , Misaki Takashi , Ohno Hitoshi 
Published: June 2020

AbstractHaploidentical hematopoietic stem cell transplantation followed by post‐transplant cyclophosphamide provides a well‐tolerated and potentially curable treatment for chemorefractory acute‐type adult T‐cell leukemia/lymphoma.
High Performance Hydrogen Evolution Reaction Catalyst Based on Single‐Walled Carbon Nanotubes Decorated by RuOx Nanoparticles
Authors: Fedorov Fedor S. , Settipani Daniel , Melandsø Buan Marthe Emelie , Sainio Jani , Ali Farhan S. M. , Ilatovskii Daniil , Kallio Tanja , Nasibulin Albert G. 
Published: June 2020

AbstractWe report a cathode material based on plasma‐treated single‐walled carbon nanotubes decorated by RuOx nanoparticles using atomic layer deposition. We have examined cathode performance towards hydrogen evolution reaction by tailoring material wettability, conductivity yielded by plasma treatment, and the catalyst loading. We discuss that nucleation of particles is facilitated by the appearance of carboxylic and hydroxyl groups triggered by oxygen plasma action. The best performance is associated with samples containing RuOx particles of 4–5 nm, which show hydrogen evolution onset potential to be about −5 mV (vs. RHE) in 0.5 M H2SO4 measured at a current density of −1 mA cm−2 and Tafel slope of 47.5 mV/dec. The material possesses stable performance at −10 mA cm−2 with a potential of about −160 mV.
The Weak 3D Topological Insulator Bi12Rh3Sn3I9
Authors: Lê Anh Mai , Kaiser Martin , Ghimire Madhav Prasad , Richter Manuel , Koepernik Klaus , Gruschwitz Markus , Tegenkamp Christoph , Doert Thomas , Ruck Michael 
Published: June 2020

AbstractTopological insulators (TIs) gained high interest due to their protected electronic surface states that allow dissipation‐free electron and information transport. In consequence, TIs are recommended as materials for spintronics and quantum computing. Yet, the number of well‐characterized TIs is rather limited. To contribute to this field of research, we focused on new bismuth‐based subiodides and recently succeeded in synthesizing a new compound Bi12Rh3Sn3I9, which is structurally closely related to Bi14Rh3I9 – a stable, layered material. In fact, Bi14Rh3I9 is the first experimentally supported weak 3D TI. Both structures are composed of well‐defined intermetallic layers of ∞2[(Bi4Rh)3I]2+ with topologically protected electronic edge‐states. The fundamental difference between Bi14Rh3I9 and Bi12Rh3Sn3I9 lies in the composition and the arrangement of the anionic spacer. While the intermetallic 2D TI layers in Bi14Rh3I9 are isolated by ∞1[Bi2I8]2− chains, the isoelectronic substitution of bismuth(III) with tin(II) leads to ∞2[Sn3I8]2− layers as anionic spacers. First transport experiments support the 2D character of this material class and revealed metallic conductivity.