bluuebunny/crossref_metadata_2025_split huggingface dataset:
In Situ Defect Engineering Route to Optimize the Cationic Redox Activity of Layered Double Hydroxide Nanosheet via Strong Electronic Coupling with Holey Substrate
Authors: Jin Xiaoyan , Lee Taehun , Tamakloe Wilson , Patil Sharad B. , Soon Aloysius , Kang Yong‐Mook , Hwang Seong‐Ju 
Published: October 2021

AbstractA defect engineering of inorganic solids garners great deal of research activities because of its high efficacy to optimize diverse energy‐related functionalities of nanostructured materials. In this study, a novel in situ defect engineering route to maximize electrocatalytic redox activity of inorganic nanosheet is developed by using holey nanostructured substrate with strong interfacial electronic coupling. Density functional theory calculations and in situ spectroscopic analyses confirm that efficient interfacial charge transfer takes place between holey TiN and Ni−Fe‐layered double hydroxide (LDH), leading to the feedback formation of nitrogen vacancies and a maximization of cation redox activity. The holey TiN−LDH nanohybrid is found to exhibit a superior functionality as an oxygen electrocatalyst and electrode for Li−O2 batteries compared to its non‐holey homologues. The great impact of hybridization‐driven vacancy introduction on the electrochemical performance originates from an efficient electrochemical activation of both Fe and Ni ions during electrocatalytic process, a reinforcement of interfacial electronic coupling, an increase in electrochemical active sites, and an improvement in electrocatalysis/charge‐transfer kinetics.
Polydopamine Nanoparticle‐Mediated Dopaminergic Immunoregulation in Colitis
Authors: Li Juanjuan , Hou Weiliang , Lin Sisi , Wang Lu , Pan Chao , Wu Feng , Liu Jinyao 
Published: October 2021

AbstractDespite immunosuppression is critical for reducing immune overactivation, existing immunosuppressive agents are largely restricted by low inhibition efficiencies and unpredictable off‐target toxicities. Here, the use of the dopaminergic system is reported to suppress hyperactive immune responses in local inflamed tissues. A polydopamine nanoparticular immunosuppressant (PDNI) is synthesized to stimulate regulatory T (Treg) cells and directly inhibit T helper 1 (Th1), Th2, and Th17 cells. Moreover, PDNI can inhibit the activation of dendritic cells to upregulate the ratio of Treg/Th17, which assists the reversion of inflammatory responses. The application of dopaminergic immunoregulation is further disclosed by combining with gut microbiota modulation for treating inflammations. The combination is implemented by coating living beneficial bacteria with PDNI. Following oral delivery, coated bacteria not only suppress the hyperactive immune responses but also positively modulate the gut microbiome in mice characterized with colitis. Strikingly, the combination demonstrates enhanced treatment efficacies in comparison with clinical aminosalicylic acid in two murine models of colitis. The use of the dopaminergic system opens a window to intervene immune responses and provides a versatile platform for the development of new therapeutics for treating inflammatory diseases.
Cardiovascular findings in Williams–Beuren Syndrome: Experience of a single center with 127 cases
Authors: Honjo Rachel Sayuri , Monteleone Vanessa Figueiredo , Aiello Vera Demarchi , Wagenfuhr Jaqueline , Issa Victor Sarli , Pomerantzeff Pablo Maria Alberto , Furusawa Erika Arai , Zanardo Evelin Aline , Kulikowski Leslie Domenici , Bertola Debora Romeo , Kim Chong Ae 
Published: October 2021

AbstractWilliams–Beuren syndrome (WBS) is a rare, microdeletion syndrome characterized by facial dysmorphisms, intellectual disability, a friendly personality, cardiovascular and other abnormalities. Cardiovascular defects (CVD) are among the most prevalent characteristics in WBS, being supravalvular aortic stenosis (SVAS) the most frequent, followed by peripheral pulmonary stenosis (PPS). A comprehensive retrospective review of medical records of 127 patients with molecular diagnosis of WBS, in a period of 20 years, was done to evaluate the incidence, the natural history of cardiovascular disease, and the need for surgical intervention, including heart transplantation (HT). A total of 94/127 patients presented with CVD. Of these 94 patients, 50% presented with SVAS and 22.3% needed heart surgery and/or cardiac catheterization including one that required HT due to severe SVAS‐related heart failure at 19 years of age. The patient died in the postoperative period due to infectious complications. Cardiovascular problems are the major cause of sudden death in patients with WBS, who have a significantly higher mortality risk associated with surgical interventions. There is a higher risk for anesthesia‐related adverse events and for major adverse cardiac events following surgery. End‐stage heart failure due to myocardial ischemia has been described in WBS patients and it is important to consider that HT can become their only viable option. To our knowledge, the case mentioned here is the first HT reported in an adolescent with WBS. HT can be a viable therapeutic option in WBS patients with adequate evaluation, planning, and a multidisciplinary team to provide the required perioperative care and follow‐up.
Photo‐Induced Polymer Cyclization via Supramolecular Confinement of Cyanostilbenes
Authors: Xue Yuncong , Jiang Sixun , Zhong Hua , Chen Ze , Wang Feng 
Published: October 2021

AbstractEfficient synthesis of cyclic polymers has received much attention in polymer chemistry field. Although photochemical cycloaddition of terminal π‐bonded units provides a plausible way toward cyclic polymerization, it remains challenging to avoid side reactions by manipulating the reaction selectivity. Herein supramolecular confinement has been developed as a promising strategy to address this issue, by introducing highly directional hydrogen bonds to the photo‐reactive cyanostilbenes. The cyanostilbenes units on both ends of a telechelic macromonomer are orientationally aligned with high local concentrations, yielding [2+2] photo‐cycloaddition products upon 430 nm light irradiation. It leads to the formation of cyclic polymers in the self‐assembled state, in stark contrast to Z‐E isomerization of cyanostilbenes in the monomeric state. Overall, supramolecular confinement effect exemplified in the current study provides new avenues toward cyclic topological polymers with high synthetic efficiency.
Precise Spatial‐Designed Metal‐Organic‐Framework Nanosheets for Efficient Energy Transfer and Photocatalysis
Authors: Cai Peiyu , Xu Ming , Meng Sha‐Sha , Lin Zaifeng , Yan Tianhao , Drake Hannah F. , Zhang Peng , Pang Jiandong , Gu Zhi‐Yuan , Zhou Hong‐Cai 
Published: October 2021

AbstractHigh‐efficiency photocatalysis in metal‐organic frameworks (MOF) and MOF nanosheets (NSs) are often limited by their short‐lived charge separation as well as self‐quenching. Here, we propose to use the energy‐transfer process (EnT) to increase charge separation, thus enhancing the catalytic performance of a series of MOF NSs. With the use of NS, the photocatalyst can also be well isolated to reduce self‐quenching. Tetrakis(4‐carboxyphenyl) porphyrin (H4TCPP) and 1,3,6,8‐tetrakis(p‐benzoic acid)pyrene (H4TBAPy) linkers were chosen as the acceptor and donor moieties, respectively. Accounting for the precise spatial design afforded by the MOF NSs, the donor and acceptor moieties could be closely positioned on the NSs, allowing for an efficient EnT process as well as a high degree of site isolation. Two templates, donor‐on‐acceptor NS and acceptor‐on‐donor NS catalysts, were successfully synthesized, and the results show that the second one has much enhanced catalytic performances over the first one due to site‐isolated active photocatalysts.
Rhenium‐Mediated Conversion of Dinitrogen and Nitric Oxide to Nitrous Oxide
Authors: Alig Lukas , Eisenlohr Kim A. , Zelenkova Yaroslava , Rosendahl Sven , Herbst‐Irmer Regine , Demeshko Serhiy , Holthausen Max C. , Schneider Sven 
Published: October 2021

AbstractReductive splitting of N2is an attractive strategy towards nitrogen fixation beyond ammonia at ambient conditions. However, the resulting nitride complexes often suffer from thermodynamic overstabilization hampering functionalization. Furthermore, oxidative nitrogen atom transfer of N2derived nitrides remains unknown. We here report a ReIVpincer platform that mediates N2splitting upon chemical reduction or electrolysis with unprecedented yield. The N2derived ReVnitrides undergo facile nitrogen atom transfer to nitric oxide, giving nitrous oxide nearly quantitatively. Experimental and computational results indicate that outer‐sphere ReN/NO radical coupling is facilitated by the activation of the nitride via initial coordination of NO.
Highly selective and sensitive fluorescent probe possessing AIEE and ICT properties for rapid detection of Pb2+ in aqueous medium and its applications in living cells
Authors: Xue Songsong , Xie Zhengfeng , Chu Yicheng , Shi Wei , Liu Yucheng , Zhao Yunhui 
Published: October 2021

AbstractIn this paper, a novel rapid, highly selective and sensitive Pb2+ fluorescent probe (E)‐N′‐((2‐(4′‐(diphenylamino)‐[1,1′‐biphenyl]‐4‐yl)‐2H‐1,2,3‐triazol‐4‐yl)methylene) (DBTBH) was synthesized. The probe DBTBH not only exhibited more excellent selectivity and sensitivity to Pb2+ detection compared with other analytes (include metal ions and anions) in H2O:THF solution (v:v = 9:1, 10 mM Tris–HCl, 1 mM KI, pH 7.4), but also had excellent optical properties such as aggregation‐induced emission enhancement (AIEE) and intramolecular charge transfer (ICT). Detection limit of the probe DBTBH towards Pb2+ was 4.49 × 10−8 M. The possible mechanism was verified by 1H NMR titration and HR‐MS. Furthermore, the successful detection of Pb2+ by DBTBH in real water samples and HeLa cells indicated that DBTBH has great potential for selective recognition of Pb2+ in the natural environment and biological systems. These findings will provide a promising new idea for designing better Pb2+ fluorescent probes in the future.
Effect of Substituted Styrene‐Butadiene Rubber Binders on the Stability of 4.5 V‐Charged LiCoO2 Electrode
Authors: Tatara Ryoichi , Umezawa Takuma , Kubota Kei , Horiba Tatsuo , Takaishi Rena , Hida Kazuo , Matsuyama Takashi , Yasuno Satoshi , Komaba Shinichi 
Published: October 2021

AbstractThe combination of synthetically modified styrene‐butadiene rubber (SBR) and sodium carboxymethyl cellulose (CMC) was studied as an aqueous binder for LiCoO2 composite electrodes under high‐voltage operation. Methyl methacrylate (MMA) and 2‐vinylpyridine (VP) substituted SBR copolymers were synthesized and examined as functional polymer binders. The electrolyte‐solvent uptake of the binder‐polymer film was increased by the introduction of the MMA units, but the solubility of the polymer in the solvent remained negligibly low. Hard‐X‐ray photoelectron spectroscopy revealed the formation of a relatively thick passivation layer on the LiCoO2 surface with MMA‐substituted SBR and CMC binder, which suppressed the self‐discharge of 4.5 V‐charged LiCoO2. The capacity retention during battery cycling experiments was similar for the LiCoO2 electrodes with MMA‐modified and unmodified SBR binders. While the effect of VP‐substitution was not significant, incorporation of the MMA unit enhanced the stability of the charged LiCoO2 electrode and provided improved self‐discharge performance.
CFPboard anonymous case histories: Ethical themes of compensation disclosure
Authors: Sensenig Derek J. , Lurtz Meghaan , Joseph Mindy , Harris Josh , White Kenneth J. , McCoy Megan 
Published: October 2021

AbstractThis study analyzed the CFP® Board's anonymous case histories (ACH) for the ethical use and misuse of compensation disclosures on the CFP Board's “Find A CFP Professional” tool. More specifically we explored the research question: what are the characteristics of CFP professionals who have violated established ethical standards regarding fee‐only, fee‐based, and commission fee structures from 2009 to 2020 according to the theory of fraudulent ethical behavior? A thematic analysis was used to compare cases in which CFP certificants incorrectly characterized their compensation structure (n = 23). Four themes emerged: practitioner characteristics, firm characteristics, payment characteristics, and culpability. Each theme was examined under the fraud pentagon's theoretical framework (Crowe, 2011). Several interesting findings emerged from the study, including tenured professionals representing a larger proportion of planners who committed ethics violations than previous research would suggest. In addition, there appeared to be difficulties understanding the fee‐only structure when working under certain licenses or firm structures. These findings support the need to maintain public disclosure of fee‐structure for consumers, highlights the importance of educating consumers on the differences between compensation types, and reinforces the need for continued education for CFP professionals to stay abreast of compliance matters.
Cobaloxime Complex Salts: Synthesis, Patterning on Carbon Nanomembranes and Heterogeneous Hydrogen Evolution Studies
Authors: Oswald Eva , Gaus Anna‐Laurine , Kund Julian , Küllmer Maria , Romer Jan , Weizenegger Simon , Ullrich Tobias , Mengele Alexander K. , Petermann Lydia , Leiter Robert , Unwin Patrick R. , Kaiser Ute , Rau Sven , Kahnt Axel , Turchanin Andrey , von Delius Max , Kranz Christine 
Published: October 2021

AbstractCobaloximes are promising, earth‐abundant catalysts for the light‐driven hydrogen evolution reaction (HER). Typically, these cobalt(III) complexes are prepared in situ or employed in their neutral form, for example, [Co(dmgH)2(py)Cl], even though related complex salts have been reported previously and could, in principle, offer improved catalytic activity as well as more efficient immobilization on solid support. Herein, we report an interdisciplinary investigation into complex salts [Co(dmgH)2(py)2]+[Co(dmgBPh2)2Cl2]−,
and [Co(dmgH)2(py)2]+BArF−. We describe their strategic syntheses from the commercially available complex [Co(dmgH)2(py)Cl] and demonstrate that these double and single complex salts are potent catalysts for the light‐driven HER. We also show that scanning electrochemical cell microscopy can be used to deposit arrays of catalysts [Co(dmgH)2(py)2]+[Co(dmgBPh2)2Cl2]−,
and [Co(dmgH)2(py)Cl] on supported and free‐standing amino‐terminated ∼1‐nm‐thick carbon nanomembranes (CNMs). Photocatalytic H2 evolution at such arrays was quantified with Pd microsensors by scanning electrochemical microscopy, thus providing a new approach for catalytic evaluation and opening up novel routes for the creation and analysis of “designer catalyst arrays”, nanoprinted in a desired pattern on a solid support.
Development of an Enzyme‐Inhibitor Reaction Using Cellular Retinoic Acid Binding Protein II for One‐Pot Megamolecule Assembly
Authors: Kimmel Blaise R. , Mrksich Milan 
Published: October 2021

AbstractThis paper presents an enzyme building block for the assembly of megamolecules. The system is based on the inhibition of the human‐derived cellular retinoic acid binding protein II (CRABP2) domain. We synthesized a synthetic retinoid bearing an arylfluorosulfate group, which uses sulfur fluoride exchange click chemistry to covalently inhibit CRABP2. We conjugated both the inhibitor and a fluorescein tag to an oligo(ethylene glycol) backbone and measured a second‐order rate constant for the protein inhibition reaction of approximately 3,600 M−1s−1. We used this new enzyme‐inhibitor pair to assemble multi‐protein structures in one‐pot reactions using three orthogonal assembly chemistries to demonstrate exact control over the placement of protein domains within a single, homogeneous molecule. This work enables a new dimension of control over specificity, orientation, and stoichiometry of protein domains within atomically precise nanostructures.
Negishi Cross‐Coupling Provides Alkylated Tryptophans and Tryptophan Regioisomers
Authors: Dachwitz Steffen , Scharkowski Bjarne , Sewald Norbert 
Published: October 2021

AbstractMild transition‐metal catalysed cross‐couplings enable direct functionalisation of biocatalytically halogenated tryptophans with alkyl iodides, representing a new alternative for late‐stage derivatisations of halogenated aromatic amino acids. Moreover, this strategy enables preparation of (homo)tryptophan regioisomers in a simple two‐step synthesis using a Pd‐catalysed Negishi cross coupling. This method provides access to non‐canonical constitutional surrogates of tryptophan, ready for use in peptide synthesis.
Synthesis of Fluorinated Imidazole[4,5f][1,10]phenanthroline Derivatives as Potential Inhibitors of Liver Cancer Cell Proliferation by Inducing Apoptosis via DNA Damage
Authors: Bai Ming‐Jun , Liu Ning‐Zhi , Zhou Yu‐Ling , Liu Jie , Zou Jun , Tan Wei‐Jun , Huang Xiao‐Ting , Mei Wen‐Jie 
Published: October 2021

AbstractPhenanthroline derivatives containing fluorinated imidazole ring are effective anti‐neoplastic agents. Herein, a series of four fluorinated imidazole[4,5f][1,10]phenanthroline derivatives were synthesized and investigated as potential inhibitors to fight against the growth of liver cancer cells. The in vitro antitumor activity of targeted compounds have been evaluated by using MTT assay, and results showed that compound 4 (2‐(2,3‐difluorophenyl)‐1H‐imidazo[4,5‐f][1,10]phenanthroline) exhibited excellent inhibitory effect against the growth of various tumor cells, particularly for HepG2 cells, with IC50 value of approximately 0.29 μM. This result has been further confirmed by colony formation assay, showing that compound 4 suppressed the proliferation of HepG2 cells. Moreover, cell apoptosis (AO/PI dual staining and flow cytometry) analyses as well as comet assay showed that compound 4 may induce apoptosis of HepG2 cells through triggering DNA damage. Furthermore, the in vivo anti‐tumor activity were evaluated on zebrafish bearing HepG2 cells showed that compound 4 can observably block the growth of liver cancer cells. All in together, these compounds, particularly compound 4, may be developed as a potential agent to treat liver cancer in the future.
Identification of equine in vitro metabolites of seven non‐steroidal selective androgen receptor modulators for doping control purposes
Authors: Cutler Charlotte , Viljanto Marjaana , Taylor Polly , Hincks Pamela , Biddle Simon , Van Eenoo Peter 
Published: October 2021

AbstractSelective androgen receptor modulators, SARMs, are a large class of compounds developed to provide therapeutic anabolic effects with minimal androgenic side effects. A wide range of these compounds are available to purchase online and thus provide the potential for abuse in sports. Knowledge of the metabolism of these compounds is essential to aid their detection in doping control samples. In vitro models allow a quick, cost‐effective response where administration studies are yet to be carried out. In this study, the equine phase I metabolism of the non‐steroidal SARMs GSK2881078, LGD‐2226, LGD‐3303, PF‐06260414, ACP‐105, RAD‐140 and S‐23 was investigated using equine liver microsomes. Liquid chromatography coupled to a QExactive Orbitrap mass spectrometer allowed identification of metabolites with high resolution and mass accuracy. Three metabolites were identified for both GSK2881078 and LGD‐2226, four for LGD‐3303 and RAD‐140, five for PF‐06260414, twelve for ACP‐105 and ten for S‐23. The equine metabolism of GSK‐2881078, LGD‐2226, LGD‐3303 and PF‐06260414 is reported for the first time. Although the equine metabolism of ACP‐105, RAD‐140 and S‐23 has previously been reported, the results obtained in this study have been compared with published data.
Historical Maps provide insight into a century and a half of habitat change in Fijian coasts
Authors: Lawson Katherine N. , Letendre Haleigh , Drew Joshua A. 
Published: October 2021

Abstract

Meaningful conservation goals require setting baselines derived from long‐term ecological records and information that is rare in many regions of the world. Historical data allow us to shift baselines back in time in order to strengthen conservation outcomes in the future.

To explore how different histories of land use and development influenced coastal ecosystems in two Fijian cities (Suva and Savusavu), we compared a series of historical navigational charts. These charts recorded change in coral reef area and coastal mangrove forests, as well as expansions of hardened shorelines. We used geographic information systems (GIS) to georeference and make quantitative comparisons starting in 1,840 in Suva and 1876 in Savusavu.

Our findings show that, despite increasing urbanization in the capital Suva, available coral reef habitat has not significantly changed in over 150 years, but development has hastened a nearly 50% loss of mangroves. Meanwhile, in the smaller city of Savusavu, coral habitats suffered significant loss in area and an increase in patchiness. As in Suva, shoreline hardening increased in Savusavu, but this change was not accompanied by a loss of mangroves.

Nautical charts provided hitherto unavailable information on the long‐term loss and alteration of coastal habitats in Fiji. Historical ecology allows scientists to combat shifting baseline syndrome and set measured standards for conservation objectives.
Intraseasonal predictability of natural phytoplankton population dynamics
Authors: Agarwal Vitul , James Chase C. , Widdicombe Claire E. , Barton Andrew D. 
Published: October 2021

AbstractIt is difficult to make skillful predictions about the future dynamics of marine phytoplankton populations. Here, we use a 22‐year time series of monthly average abundances for 198 phytoplankton taxa from Station L4 in the Western English Channel (1992–2014) to test whether and how aggregating phytoplankton into multi‐species assemblages can improve predictability of their temporal dynamics. Using a non‐parametric framework to assess predictability, we demonstrate that the prediction skill is significantly affected by how species data are grouped into assemblages, the presence of noise, and stochastic behavior within species. Overall, we find that predictability one month into the future increases when species are aggregated together into assemblages with more species, compared with the predictability of individual taxa. However, predictability within dinoflagellates and larger phytoplankton (>12 μm cell radius) is low overall and does not increase by aggregating similar species together. High variability in the data, due to observational error (noise) or stochasticity in population growth rates, reduces the predictability of individual species more than the predictability of assemblages. These findings show that there is greater potential for univariate prediction of species assemblages or whole‐community metrics, such as total chlorophyll or biomass, than for the individual dynamics of phytoplankton species.
Structural and Magnetic Studies on Lanthanide Bis(benzoxazol‐2‐yl)methanides
Authors: Lüert Daniel , Herbst‐Irmer Regine , Stalke Dietmar 
Published: October 2021

AbstractWe describe the syntheses, solid‐state structures, and magnetic properties of lanthanide(III)‐tris(bis(heterocyclo)methanides) [(THF)M{(NCOC6H4)2CH}3], with M=Tb (1), Dy (2), Ho (3), and Er (4), respectively. The corresponding lanthanide bis(trimethylsilyl)amides have been prepared as starting materials to deprotonate the neutral bis(benzoxazol‐2‐yl)methane ({NCOC6H4}2CH2) at the central methylene bridge to generate the monoanionic ligand. In the course of this investigations the hitherto unknown holmium tris(bis(trimethylsilyl)amide) is communicated in here. X‐ray diffraction data of 1–4 demonstrate an almost planar ligand with metal coordination in an N,N'‐chelating fashion. Different to their d‐metal analogous the magnetic data of the f‐metal complexes presented here show no single‐molecule magnet (SMM) properties.