bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthetic Approaches for Accessing Pseudaminic Acid (Pse) Bacterial Glycans
Authors: Flack Emily K. P. , Chidwick Harriet S. , Best Matthew , Thomas Gavin H. , Fascione Martin A. 
Published: January 2020

AbstractPseudaminic acids (Pses) are a group of non‐mammalian nonulosonic acids (nulOs) that have been shown to be an important virulence factor for a number of pathogenic bacteria, including emerging multidrug‐resistant ESKAPE pathogens. Despite their discovery over 30 years ago, relatively little is known about the biological significance of Pse glycans compared with their sialic acid analogues, primarily due to a lack of access to the synthetically challenging Pse architecture. Recently, however, the Pse backbone has been subjected to increasing synthetic exploration by carbohydrate (bio)chemists, and the total synthesis of complex Pse glycans achieved with inspiration from the biosynthesis and subsequent detailed study of chemical glycosylation by using Pse donors. Herein, context is provided for these efforts by summarising recent synthetic approaches pioneered for accessing Pse glycans, which are set to open up this underexplored area of glycoscience to the wider scientific community.
Improving the Performance of SiOx/Carbon Materials for High Energy Density Commercial Lithium‐Ion Batteries Based on Montmorillonite
Authors: Feng Lijuan , Song Jimei , Sun Chao , Liu Fangfang , Wang Yuanzhong 
Published: January 2020

AbstractSilicon is recognized as the most promising anode material for the next‐generation battery. In order to improve the processing and electrochemical performances, a silicon‐based anode composite was synthesized using silicon, montmorillonite and carboxymethylcellulose (CMC) as raw materials. The processing parameters, such as particle size and specific surface area, were ameliorated to be consistent with those of commercial lithium‐ion battery (LIB) anode materials. As an anode composite, it perfectly matched with high nickel ternary cathode materials and showed excellent electrochemical properties. The discharge capacities were all above 1000 mAh/g and the coulombic efficiency of each step was over 99 % throughout the 50 cycles at 1 C (1100 mA/g). Its superior performances are attributed to the unique layered structure, which buffers the volume expansion and enhances the stability of the solid electrolyte interface (SEI) film on the anodic electrode, suggesting a perspective future in designing high energy density commercial LIBs.
BaP6N10NH:Eu2+ as a Case Study–An Imidonitridophosphate Showing Luminescence
Authors: Wendl Sebastian , Eisenburger Lucien , Zipkat Mirjam , Günther Daniel , Wright Jonathan P. , Schmidt Peter J. , Oeckler Oliver , Schnick Wolfgang 
Published: January 2020

AbstractBarium imidonitridophosphate BaP6N10NH was synthesized at 5 GPa and 1000 °C with a high‐pressure high‐temperature approach using the multianvil technique. Ba(N3)2, P3N5 and NH4Cl were used as starting materials, applying a combination of azide and mineralizer routes. The structure elucidation of BaP6N10NH (P63, a=7.5633(11), c=8.512(2) Å, Z=2) was performed by a combination of transmission electron microscopy and single‐crystal diffraction with microfocused synchrotron radiation. Phase purity was verified by Rietveld refinement. 1H and 31P solid‐state NMR and FTIR spectroscopy are consistent with the structure model. The chemical composition was confirmed by energy‐dispersive X‐ray spectroscopy and CHNS analyses. Eu2+‐doped samples of BaP6N10NH show blue emission upon excitation with UV to blue light (λem=460 nm, fwhm=2423 cm−1) representing unprecedented Eu2+‐luminescence of an imidonitride.
Is There a Single Ideal Parameter for Halogen‐Bonding‐Based Lewis Acidity?
Authors: Engelage Elric , Reinhard Dominik , Huber Stefan M. 
Published: January 2020

AbstractHalogen‐bond donors (halogen‐based Lewis acids) have now found various applications in diverse fields of chemistry. The goal of this study was to identify a parameter obtainable from a single DFT calculation that reliably describes halogen‐bonding strength (Lewis acidity). First, several DFT methods were benchmarked against the CCSD(T) CBS binding data of complexes of 17 carbon‐based halogen‐bond donors with chloride and ammonia as representative Lewis bases, which revealed M05‐2X with a partially augmented def2‐TZVP(D) basis set as the best model chemistry. The best single parameter to predict halogen‐bonding strengths was the static σ‐hole depth, but it still provided inaccurate predictions for a series of compounds. Thus, a more reliable parameter, Ωσ*, has been developed through the linear combination of the σ‐hole depth and the σ*(C−I) energy, which was further validated against neutral, cationic, halogen‐ and nitrogen‐based halogen‐bond donors with very good performance.
Live Monitoring of Strain‐Promoted Azide Alkyne Cycloadditions in Complex Reaction Environments by Inline ATR‐IR Spectroscopy
Authors: Svatunek Dennis , Eilenberger Gottfried , Denk Christoph , Lumpi Daniel , Hametner Christian , Allmaier Günter , Mikula Hannes 
Published: January 2020

AbstractThe strain‐promoted azide alkyne cycloaddition (SPAAC) is a powerful tool for forming covalent bonds between molecules even under physiological conditions, and therefore found broad application in fields ranging from biological chemistry and biomedical research to materials sciences. For many applications, knowledge about reaction kinetics of these ligations is of utmost importance. Kinetics are commonly assessed and studied by NMR measurements. However, these experiments are limited in terms of temperature and restricted to deuterated solvents. By using an inline ATR‐IR probe we show that the cycloaddition of azides and alkynes can be monitored in aqueous and even complex biological fluids enabling the investigation of reaction kinetics in various solvents and even human blood plasma under controlled conditions in low reaction volumes.
Tuning the Fluorescence Through Reorientation of the Axle in Calix[6]arene‐Based Pseudorotaxanes
Authors: Bazzoni Margherita , Terenziani Francesca , Secchi Andrea , Cera Gianpiero , Jabin Ivan , De Leener Gaël , Luhmer Michel , Arduini Arturo 
Published: January 2020

AbstractThis work describes a calix[6]arene‐based wheel that binds, in non‐polar media, a stilbazolium salt to yield a mixture of pseudorotaxane orientational isomers. The isomer's abundance ratio evolves with time and can be reversibly tuned by adjusting the temperature. The spectroscopic properties, and notably the emission spectrum, of the bound guest depend on its orientation inside the non‐palindromic wheel, suggesting such a system as a switch with spectroscopic readout.
Structural Peculiarities and Thermoelectric Study of Iron Indium Thiospinel
Authors: Wyżga Paweł , Veremchuk Igor , Bobnar Matej , Koželj Primož , Klenner Steffen , Pöttgen Rainer , Leithe‐Jasper Andreas , Gumeniuk Roman 
Published: January 2020

AbstractThe homogeneity range of ternary iron indium thiospinel at 873 K was investigated. A detailed study was focused on two distinct series (y=z): 1) a previously reported charge‐balanced (In0.67+0.33y□0.33−0.33y)tetr[In2−zFez]octS4 (A1‐series; □ stands for vacancy; the abbreviations “tetr” and “oct” indicate atoms occupying tetrahedral 8a and octahedral 16d sites, respectively) and 2) a new charge‐unbalanced (In0.67+y□0.33−y)tetr[In2−zFez]octS4 (A2‐series). Fe atoms were confirmed to exclusively occupy an octahedral position in both series. An unusual reduction of the unit cell parameter with increasing Fe content is explained by differences in the ionic radii between Fe and In, as well as by an additional electrostatic attraction originating from charge imbalance (latter only in A2‐series). The studied compound is an n‐type semiconductor, and its charge carrier concentration increases or decreases for larger Fe content within the A1‐ and A2‐series, respectively. The thermal conductivity κtot is significantly reduced upon increasing vacancy concentration, whereas the change of power factor is insufficient to drastically improve the thermoelectric figure of merit.
Interception of Elusive Cationic Hf–Al and Hf–Zn Heterobimetallic Adducts with Mixed Alkyl Bridges Featuring Multiple Agostic Interactions
Authors: Tensi Leonardo , Froese Robert D. J. , Kuhlman Roger L. , Macchioni Alceo , Zuccaccia Cristiano 
Published: January 2020

AbstractHeterobimetallic complexes with inequivalent bridging alkyl chains are very often invoked as key intermediates in many catalytic processes, yet their interception and structural characterization are lacking. Such complexes have been prepared from reactions of the cationic cyclometalated hafnocene [CpPrCpHf][B(C6F5)4] (1) with main group metal alkyls to afford the corresponding hetero‐bridged cationic products, [CpPrCpHf(μ‐R)E(R)n][B(C6F5)4] (E=Al or Zn; R=Me, Et, oriBu). NMR and DFT studies demonstrate that both bridging alkyls establish agostic interactions with Hf, which are appreciably stronger for ethyl rather than methyl groups. Hf–Al and Hf–Zn distances are surprisingly short and only slightly longer than computed Hf–Al or Hf–Zn single bond lengths (2.80 Å). Finally, a reaction of [CpPrCpHf(μ‐Me)Zn(Me)][B(C6F5)4] with excess ZnMe2yields an unprecedented heterotrimetallic species, [(CpPr)2Hf(μ‐Me)(ZnMe)(μ3‐CH2)ZnMe][B(C6F5)4], the detailed structure of which is elucidated by a combination of NMR spectroscopic methods and molecular calculations.
Photoinduced Heterogeneous C−H Arylation by a Reusable Hybrid Copper Catalyst
Authors: Choi Isaac , Müller Valentin , Lole Gaurav , Köhler Robert , Karius Volker , Viöl Wolfgang , Jooss Christian , Ackermann Lutz 
Published: January 2020

AbstractHeterogeneous copper catalysis enabled photoinduced C−H arylations under exceedingly mild conditions at room temperature. The versatile hybrid copper catalyst provided step‐economical access to arylated heteroarenes, terpenes and alkaloid natural products with various aryl halides. The hybrid copper catalyst could be reused without significant loss of catalytic efficacy. Detailed studies in terms of TEM, HRTEM and XPS analysis of the hybrid copper catalyst, among others, supported its outstanding stability and reusability.
Industrial Application Aspects of the Electrochemical Reduction of CO2 to CO in Aqueous Electrolyte
Authors: Krause Ralf , Reinisch David , Reller Christian , Eckert Helmut , Hartmann David , Taroata Dan , Wiesner‐Fleischer Kerstin , Bulan Andreas , Lueken Alexander , Schmid Guenter 
Published: January 2020

AbstractThe industrialization of the electrochemical reduction of CO2 toward CO in aqueous electrolytes has recently been started using silver‐based gas diffusion electrodes. The performance of a CO2‐to‐CO electrolyzer model on a 10‐cm2 cell size is assessed with respect to operating pressure, achievable current density at faradaic efficiency of CO above 90 %, composition of gas streams and operational lifetime. Operational lifetime has exceeded 1500 h. The first scaling step to 300 cm2 has been accomplished. The rated power of such a cell is around 300 W.
Chemoenzymatic Synthesis of 5‐Hydroxymethylfurfural (HMF)‐Derived Plasticizers by Coupling HMF Reduction with Enzymatic Esterification
Authors: Arias Karen S. , Carceller Jose M. , Climent Maria J. , Corma Avelino , Iborra Sara 
Published: January 2020

AbstractBiobased plasticizers, as substitutes for phthalates, have been synthesized from 5‐hydroxymethylfurfural (HMF) and carboxylic acids (or esters) through a chemoenzymatic cascade process that involves as its first step the reduction of 5‐hydroxymethylfurfural into 2,5‐bis(hydroxymethyl)furan (BHMF), followed by the esterification of BHMF with carboxylic acids (or esters) by using a supported lipase (Novozym 435). The reduction of HMF into BHMF is performed by using monodisperse metallic Co nanoparticles with a thin carbon shell (Co@C) with high activity and selectivity. After optimization of reaction conditions (temperature, hydrogen pressure, and solvent), it is possible to achieve 97 % conversion of HMF with 99 % selectivity to BHMF after 2 h reaction time. The reduction of HMF and esterification of BHMF using carboxylic acids or vinyl esters as acyl donors by lipase are optimized separately in batch and in fixed‐bed continuous reactors. The coupling of two flow reactors (for reduction and subsequent esterification) working under optimized reaction conditions affords the diesters of BHMF in roughly 90 % yield with no loss of activity during 60 h of operation.
Cell Cycle Analysis and Relevance for Single‐Cell Gating in Mass Cytometry
Authors: Rein Idun D. , Notø Heidi Ø. , Bostad Monica , Huse Kanutte , Stokke Trond 
Published: January 2020

AbstractCell cycle analysis by mass cytometry (MC) is hampered by the poor resolution of the Iridium‐labeled DNA intercalator compared to DNA‐specific fluorescent dyes. We report here a minimum cell cycle panel for MC consisting of Ir‐intercalator (DNA content), IdU (S phase), anti‐pS28HistoneH3 (mitosis), anti‐CDT1 (G1 phase) and anti‐Geminin (non‐G1 phases). Cell cycle distributions obtained by MC were not significantly different from fluorescence flow cytometry results (r2 = 0.98, P < 0.001). Further subdivision of the G1 and G2 phases could be done with anti‐pS780RB1 (late G1) and anti‐PLK1 (late G2), respectively. A disadvantage of MC is that aggregates of cells cannot easily be removed while retaining all single cells. We have developed an analysis pipeline including unsupervised clustering by FlowSOM and subsequent single‐cell gating. When performed on cells stained with the cell cycle panel, this analysis pipeline successfully identified debris, dead/apoptotic cells, nonsingle‐cell populations and the major cell cycle phases. The presented cell cycle panel and analysis pipeline thus achieves true single‐cell analysis at the same time as any additional channels in the panel are open for phenotyping and cell cycle‐resolved expression or modification analysis. © 2020 The Authors. Cytometry Part A published by Wiley Periodicals LLC. on behalf of International Society for Advancement of Cytometry.
C−H Activation and Olefin Insertion in d8 and d0 Complexes: Same Elementary Steps, Different Electronics
Authors: Bumberger Andreas E. , Gordon Christopher P. , Trummer David , Copéret Christophe 
Published: January 2020

AbstractMetallocene alkyl complexes with d0 electron configuration and d8‐configured square planar α‐diimine late transition metal alkyl complexes show activity in both C−H activation through σ‐bond metathesis and olefin insertion. Herein, we show by analysis of their M−CH3 13C chemical shift tensors that these reactions involve a π(M−C) interaction in the horizontal plane of the complex for both d0 and d8 systems. While in the case of d0 systems the interaction of an empty metal d‐orbital and a filled carbon p‐orbital causes partial alkylidene character of the M−C bond, the corresponding metal d‐orbital is filled in d8 systems, thus generating a filled π*(M−C) orbital that increases the anionic character of the methyl group. This entails fundamentally different reaction mechanisms for d0 and d8 systems, which are reflected in the structures of the transition states: While d0 olefin insertion can be viewed as a [2+2] cycloaddition reaction, d8 olefin insertion rather resembles methyl group migration onto a positively polarized olefin, thus explaining the observed differences in regioselectivity. These findings are translated to σ‐bond metathesis, a reaction which is isolobal to olefin insertion for both early and late transition metals.
Impact of BMI on HER2+ metastatic breast cancer patients treated with pertuzumab and/or trastuzumab emtansine. Real‐world evidence
Authors: Krasniqi Eriseld , Pizzuti Laura , Barchiesi Giacomo , Sergi Domenico , Carpano Silvia , Botti Claudio , Kayal Ramy , Sanguineti Giuseppe , Marchetti Paolo , Botticelli Andrea , Marinelli Daniele , Gamucci Teresa , Natoli Clara , Grassadonia Antonino , Tinari Nicola , Tomao Silverio , Tonini Giuseppe , Santini Daniele , Michelotti Aandrea , Mentuccia Lucia , Vaccaro Aangela , Magnolfi Emanuela , Gelibter Alain , Magri Valentina , Cortesi Enrico , D’Onofrio Loretta , Cassano Alessandra , Cazzaniga Marina , Moscetti Luca , Fabbri Agnese , Scinto Angelo Fedele , Corsi Domenico , Carbognin Luisa , Bria Emilio , La Verde Nicla , Garufi Carlo , Di Stefano Pia , Mirabelli Rossana , Veltri Enzo , Paris Ida , Giotta Francesco , Lorusso Vito , Landucci Elisa , Ficorella Corrado , Roselli Mario , Adamo Vincenzo , Ricciardi Giuseppina , Russo Antonio , Valerio Maria Rosaria , Berardi Rossana , Pistelli Mirco , Cannita Katia , Zamagni Claudio , Garrone Ornella , Baldini Editta , Livi Lorenzo , Meattini Icro , Del Medico Pietro , Generali Daniele , De Maria Ruggero , Risi Emanuela , Ciliberto Gennaro , Villa Alice , Sperduti Isabella , Mazzotta Marco , Barba Maddalena , Giordano Antonio , Vici Patrizia 
Published: January 2020

AbstractBody mass index (BMI) is a main indicator of obesity and its association with breast cancer is well established. However, little is known in the metastatic setting, especially in HER2‐positive patients. We assessed the influence of BMI on clinical outcomes of patients treated with pertuzumab and/or trastuzumab emtansine (T‐DM1) for HER2+ metastatic breast cancer (mBC). BMI was addressed as a categorical variable, being classified on the basis of the following ranges, that is, 18.5–24.9, 25–29.9, and 30.0–34.9, namely, normal weight, overweight, and Class I obesity. The outcomes chosen were progression‐free survival to first‐line chemotherapy (PFS1) and overall survival (OS). Overall (N = 709), no impact of BMI was observed on PFS1 (p = .15), while BMI ≥ 30 was associated with worse OS (p = .003). In subjects who progressed to first line (N = 575), analyzing data across PFS1 quartiles and strata of disease burden, BMI predicted lower PFS1 in patients within the I PFS1 quartile and with the lowest disease burden (p = .001). Univariate analysis showed a detrimental effect of BMI ≥ 30 on OS for women within the I PFS1 quartile (p = .03). Results were confirmed in multivariate analysis. According to PFS1 quartiles a higher percentage of patients with high BMI and low disease burden progressed within 6 months of therapy. The effect of BMI on prognosis was also confirmed in multivariate analysis of OS for overall population. In our cohort, a BMI ≥ 30 correlated with worse OS in patients with HER2+ mBC who received pertuzumab and/or T‐DM1 but had no impact on PFS to first line. BMI predicted worse I PFS1 quartile.
Long noncoding RNA SNHG12 modulated by human papillomavirus 16 E6/E7 promotes cervical cancer progression via ERK/Slug pathway
Authors: Lai Shu‐Yu , Guan Hong‐Mei , Liu Jie , Huang Li‐Jun , Hu Xiao‐Lin , Chen Yi‐Hong , Wu Yi‐Hua , Wang Ying , Yang Qi , Zhou Jue‐Yu 
Published: January 2020

AbstractRecently, long noncoding RNA SNHG12 has been reported to be dysregulated in various types of cancer. This study investigated its biological function and the underlying molecular mechanism in cervical squamous cell carcinoma (CSCC). We found that SNHG12 was significantly overexpressed in CSCC tissues. Further evidence showed that human papillomavirus (HPV) type 16 E6 and E7 might regulate the expression level of SNHG12 by modulating transcription factor c‐Myc. Functional experiments suggested that SNHG12 knockdown dramatically repressed CSCC cells proliferation, migration, and invasion while induced apoptosis in vitro as well as suppressed tumor growth in vivo. In addition, SNHG12 could facilitate epithelial–mesenchymal transition through ERK/Slug/E‐cadherin pathway at least in part. Our findings highlight SNHG12 functions as an oncogenic long noncoding RNA in malignant phenotype and tumorigenesis of CSCC, which implicate it may be a potential target for CSCC treatment.
Network‐based integration method for potential breast cancer gene identification
Authors: Zhang Yue , Li Wan , Zhang Yihua , Hu Erqiang , Rong Zherou , Ge Luanfeng , Deng Gui , He Yuehan , Lv Junjie , Chen Lina , He Weiming 
Published: January 2020

AbstractBreast cancer is the most common female death‐causing cancer worldwide. A network‐based integration method was proposed to identify potential breast cancer genes. First, genes were prioritized using a gene prioritization algorithm by the strategy of disease risks transferred between genes in a network with weighted vertexes and edges. Our prioritization algorithm was effectives and robust for top‐ranked seed gene number and higher area under the curve values compared to ToppGene and ToppNet. Then, 20 potential breast cancer genes were identified as common genes of the top 50 candidate genes for their robustness in multiple prioritizations. These genes could accurately classify tumor and normal samples of all and paired sample sets and three independent datasets. Of potential breast cancer genes, 18 were verified by literature and 2 were novel genes that need further study. This study would contribute to the understanding of the genetic architecture for the diagnosis and treatment of breast cancer.
Local‐regional recurrence risk after autologous fat grafting in breast cancer patients: A systematic review and meta‐analysis
Authors: Wang Ke , Dai Yuechu , Pan Yin , Cheng Pu , Jin Xiaoyan 
Published: January 2020

AbstractThis meta‐analysis aims to determine whether autologous fat grafting (AFG) affects the risk of local‐regional recurrence (LRR) in breast cancer patients. In pooled analyses of 11 eligible studies, AFG was not associated with increased LRR. Subgroup analyses showed that AFG did not increase the risk of LRR in patients undergoing breast‐conserving surgery or mastectomy, in patients with in situ carcinomas or invasive carcinomas, or in patients undergoing postoperative radiotherapy.
Impact of neoadjuvant chemotherapy on surgical and pathological results of gastric cancer patients: A case‐control study
Authors: Charruf Amir Zeide , Ramos Marcus Fernando Kodama Pertille , Pereira Marina Alessandra , Dias Andre Roncon , de Castria Tiago Biachi , Zilberstein Bruno , Cecconelo Ivan , Ribeiro Ulysses 
Published: January 2020

AbstractBackground and ObjectiveNeoadjuvant chemotherapy (NACT) followed by radical surgery represents a treatment option for patients with advanced gastric cancer (GC). This case‐control study aimed to evaluate the clinicopathological characteristics and surgical outcomes of GC patients who received NACT, and its impact on survival.MethodsWe retrospectively reviewed all patients with GC who underwent gastrectomy. A total of 45 cases with NACT were matched with consecutive 45 patients who underwent upfront gastrectomy for the following characteristics: gender, age, gastrectomy type, lymphadenectomy extent, American Society of Anesthesiologists class, histological type, cT and cN.ResultsNACT group had smaller tumors (4.9 vs 6.8 cm P = .006), lower lymphatic invasion rate (40% vs 73.3%, P = .001), lower venous invasion rate (18% vs 46.7%, P = .003) and lower perineural invasion rate (35% vs 77.8%, P < .0001). The ypTNM stage was lower in patients treated with NACT (P < .001). The major postoperative complication (POC) rate was lower in NACT patients (6.7% vs 24.4%, P = .02), as was hospital length of stay (10.8 vs 17 days, P = .005).ConclusionsNACT allowed nodal and tumor downstaging. In addition, patients who underwent NACT had fewer POC and shorter length of hospital stay.