bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bridging the Gap between Structurally Distinct 2D Lamellar Zeolitic Precursors through a 3D Germanosilicate Intermediate
Authors: Xu Le , Choudhary Madhuresh K. , Muraoka Koki , Chaikittisilp Watcharop , Wakihara Toru , Rimer Jeffrey D. , Okubo Tatsuya 
Published: August 2019

AbstractThere is broad scientific interest in lamellar zeolitic materials for a large variety of technological applications. The traditional synthetic methods towards two‐dimensional (2D) zeolitic precursors have made a great impact in the construction of families of related zeolites; however, the connection between structurally distinct 2D zeolitic precursors is much less investigated in comparison, thereby resulting in a synthetic obstacle that theoretically limits the types of zeolites that can be constructed from each layer. Herein, we report a Ge‐recycling strategy for the topotactic conversion between different 2D zeolitic precursors through a three‐dimensional (3D) germanosilicate. Specifically, the intermediate germanosilicate can be constructed within 150 min by taking advantage of its structural similarity with the parent lamellar precursor. This process enables the conversion of one 2D zeolite structure into another distinct structure, thus overcoming the synthetic obstacle between two families of zeolitic materials.
A Dual Killing Strategy: Photocatalytic Generation of Singlet Oxygen with Concomitant PtIV Prodrug Activation
Authors: Norman Daniel J. , Gambardella Alessia , Mount Andrew R. , Murray Alan F. , Bradley Mark 
Published: August 2019

AbstractA ruthenium‐based mitochondrial‐targeting photosensitiser that undergoes efficient cell uptake, enables the rapid catalytic conversion of PtIV prodrugs into their active PtII counterparts, and drives the generation of singlet oxygen was designed. This dual mode of action drives two orthogonal cancer‐cell killing mechanisms with temporal and spatial control. The designed photosensitiser was shown to elicit cell death of a panel of cancer cell lines including those showing oxaliplatin‐resistance.
Synthesis of A Pincer‐IrVComplex with A Base‐Free Alumanyl Ligand and Its Application toward the Dehydrogenation of Alkanes
Authors: Morisako Shogo , Watanabe Seiya , Ikemoto Satoru , Muratsugu Satoshi , Tada Mizuki , Yamashita Makoto 
Published: August 2019

AbstractA pincer‐iridium complex bearing a Lewis‐base‐free X‐type alumanyl ligand has been synthesized. X‐ray diffraction, NMR and IR spectroscopy, as well as XANES analysis confirmed its tetrahydrido‐IrVstructure and Lewis acidity at the Al center as supported by DFT calculations. The resulting complex was applied as a catalyst for the transfer dehydrogenation of cyclooctane.
Potent Lymphatic Translocation and Spatial Control Over Innate Immune Activation by Polymer–Lipid Amphiphile Conjugates of Small‐Molecule TLR7/8 Agonists
Authors: De Vrieze Jana , Louage Benoit , Deswarte Kim , Zhong Zifu , De Coen Ruben , Van Herck Simon , Nuhn Lutz , Kaas Frich Camilla , Zelikin Alexander N. , Lienenklaus Stefan , Sanders Niek N. , Lambrecht Bart N. , David Sunil A. , De Geest Bruno G. 
Published: August 2019

AbstractUncontrolled systemic inflammatory immune triggering has hampered the clinical translation of several classes of small‐molecule immunomodulators, such as imidazoquinoline TLR7/8 agonists for vaccine design and cancer immunotherapy. By taking advantage of the inherent serum‐protein‐binding property of lipid motifs and their tendency to accumulate in lymphoid tissue, we designed amphiphilic lipid–polymer conjugates that suppress systemic inflammation but provoke potent lymph‐node immune activation. This work provides a rational basis for the design of lipid–polymer amphiphiles for optimized lymphoid targeting.
Synthesis, spectroscopic characterization, biological screening and in vitro cytotoxic studies of 4‐methyl‐3‐thiosemicarbazone derived Schiff bases and their Co (II), Ni (II), Cu (II) and Zn (II) complexes
Authors: Devi J. , Yadav M. , Jindal D.K. , Kumar D. , Poornachandra Y. 
Published: August 2019

A series of twenty compounds inclusive of bidentate Schiff bases derived from condensation of 4‐methyl‐3‐thiosemicarbazide with substituted derivatives of napthaldehyde/benzaldehyde/salicylaldehyde and their mononuclear Co (II), Ni (II), Cu (II) and Zn (II) complexes in molar ratio (1:1) were synthesized and characterized. The coordination behavior, modes of bonding and overall geometry of the compounds was known from the elemental analysis, spectral techniques (IR, UV–Vis, 1H NMR, 13C NMR, ESR and ESI‐mass), magnetic moment measurements, molar conductance, thermal and powder XRD studies. The studies revealed octahedral geometry for all the complexes where ligands coordinated in a neutral bidentate manner (NS) via nitrogen atom of azomethine group and sulphur atom of thione group with the metal centre. In vitro biological effects of the compounds were tested against four bacterial species and two fungal strains. The results indicated that the metal complexes showed a marked enhancement in biocidal activity in comparable with the parent Schiff bases. In vitro anticancer activity against the malignant tumor cell lines; human alveolar adenocarcinoma epithelial cell line (A549), human breast adenocarcinoma cell line (MCF7), human prostate cancer cell line (DU145) and human normal lung cell line (MRC‐5) using MTT assay, exposed compound 16 as a leading member with lowest IC50 value of 10.6 ± 0.14 μM against (A549) cell line.
Integrated pest management in the academic small greenhouse setting: A case study using Solanum spp. (Solanaceae)
Authors: Hayes Daniel S. , Jordon‐Thaden Ingrid E. , Cantley Jason T. , McDonnell Angela J. , Martine Christopher T. 
Published: August 2019

PremiseBotanical faculty and staff at academic institutions are often tasked with establishing and/or caring for plant collections held in small greenhouse facilities. Once plants are in place, an especially acute challenge is managing plant pest/pathogen populations. Integrated pest management (IPM) approaches are an excellent option, but few examples exist in the literature of successful programs that have been developed in academic small greenhouse settings.Methods and ResultsOver several years, we developed an IPM program for two small research greenhouses on the campus of a primarily undergraduate institution where hundreds of plants have been grown for studies in the genus Solanum. We here present a synopsis of the cultural, mechanical, physical, and biological controls used as part of our successful IPM strategy—including details on the efficacy of multiple predatory insects—with the hope of providing a model for sustainable pest management in the higher education environment.ConclusionsIPM can be an effective strategy for maintaining healthy plant populations in small research greenhouses, but it requires a consistent investment of time and funding. A well‐cared‐for plant collection might help support numerous positive outcomes, including advances in faculty scholarship and opportunities for student learning and/or training.
Click chemistry based regioselective one‐pot synthesis of coumarin‐3‐yl‐methyl‐1,2,3‐triazolyl‐1,2,4‐triazol‐3(4H)‐ones as newer potent antitubercular agents
Authors: Somagond Shilpa M. , Kamble Ravindra R. , Bayannavar Praveen K. , Shaikh Saba Kauser J. , Joshi Shrinivas D. , Kumbar Vijay M. , Nesaragi Aravind R. , Kariduraganavar Mahadevappa Y. 
Published: August 2019

AbstractCoumarin‐3‐yl‐methyl‐1,2,3‐triazolyl‐1,2,4‐triazol‐3(4H)‐ones (8k‐z) were synthesized via copper(I)‐catalyzed azide‐alkyne cycloaddition click chemistry. The synthesized hybrid molecules were characterized by spectral studies. Compounds 8k‐z were screened for their in vitro anti‐TB activity by using the Microplate Alamar Blue assay and for cytotoxicity using the MTT assay. Some of the compounds were found to be most potent against the tested Mycobacterium tuberculosis H37Rv strain with a MIC of 1.60 µg/ml. Further, docking the compounds into the InhA binding pocket showed strong binding interactions and effective overall docking scores were recorded. The drug‐likeness and toxicity studies were computed using Molinspiration and Protox, respectively.
Quantile forecasting based on a bivariate hysteretic autoregressive model with GARCH errors and time ‐varying correlations
Authors: Chen Cathy W.S. , Than‐Thi Hong , So Mike K.P. , Sriboonchitta Songsak 
Published: August 2019

AbstractTo understand and predict chronological dependence in the second‐order moments of asset returns, this paper considers a multivariate hysteretic autoregressive (HAR) model with generalized autoregressive conditional heteroskedasticity (GARCH) specification and time‐varying correlations, by providing a new method to describe a nonlinear dynamic structure of the target time series. The hysteresis variable governs the nonlinear dynamics of the proposed model in which the regime switch can be delayed if the hysteresis variable lies in a hysteresis zone. The proposed setup combines three useful model components for modeling economic and financial data: (1) the multivariate HAR model, (2) the multivariate hysteretic volatility models, and (3) a dynamic conditional correlation structure. This research further incorporates an adapted multivariate Studenttinnovation based on a scale mixture normal presentation in the HAR model to tolerate for dependence and different shaped innovation components. This study carries out bivariate volatilities, Value at Risk, and marginal expected shortfall based on a Bayesian sampling scheme through adaptive Markov chain Monte Carlo (MCMC) methods, thus allowing to statistically estimate all unknown model parameters and forecasts simultaneously. Lastly, the proposed methods herein employ both simulated and real examples that help to jointly measure for industry downside tail risk.
Process research in early intensive intervention in autism spectrum disorder: Sensitivity to change of the autism behavior coding system
Authors: Herbrecht Evelyn , Lazari Olga , Notter Marianne , Schmeck Klaus , Spiegel René 
Published: August 2019

The development of sensitive measures to capture changes in core autism symptoms is crucial in early intervention research. The study examines the sensitivity to change of the Autism Behavior Coding System (ABCS), a video‐based instrument to assess core autism symptoms during therapist‐child interaction. Video sequences of 40 young children treated in the Frühintervention bei Autistischen Störungen center were analyzed with regard to the question of whether short‐term changes during an 18 day period of early intervention could be captured, and whether these results are reflected in an independent clinical assessment (Developmental Disorders‐Child‐Global Assessment Scale [DD‐C‐GAS]). ABCS results showed statistically significant improvements on behavioral domains such as “expression of wishes” and “social cooperative behavior” (P < 0.01), less pronounced on “eye contact.” Improvements on the DD‐C‐GAS were highly significant on all subdomains. Both scales showed high correlations within their subdomains, yet no significant correlations between the changes in both instruments' scores were found. An additional analysis between the DD‐C‐GAS scores at day 18 and the changes in the ABCS scores showed statistically significant associations in the expected direction between the changes in the variable “eye contact” and all DD‐C‐GAS subdomains. The correspondence of the two levels of assessment is low, but the specifics of this relationship deserve further study. The ABCS may prove useful in addition to standard assessment tools, especially in early intervention research settings, as it allows reliable analysis of core behavioral elements in young children with autism. Autism Res 2019, 12: 1817–1828. © 2019 The Authors. Autism Research published by International Society for Autism Research published by Wiley Periodicals, Inc.Lay SummaryThe study examined the sensitivity of an autism‐specific video coding system (ABCS) in assessing changes after an 18 day period of intensive early intervention. Video sequences of therapist‐child‐interaction of 40 young children with autism spectrum disorder (ASD) were analyzed. Children's behavior improved in expression of wishes, social cooperativity and eye contact. A therapist‐based global assessment scale also showed important improvement after 18 days, yet both assessment instruments showed weak correlations between their respective changes. We showed that the ABCS may prove useful in capturing short‐term changes in autism‐related behaviors, especially in early intervention research.
Hyperthermophilic flavin reductase from Sulfolobus solfataricus P2: Production and biochemical characterization
Authors: Gun Gokhan , Imamoglu Rahmi , Tatli Ozge , Yurum Yuda , Tarik Baykal Ahmet , Dinler‐Doganay Gizem 
Published: August 2019

AbstractNicotinamide adenine dinucleotide phosphate (NAD(P)H)‐flavin oxidoreductases (flavin reductases) catalyze the reduction of flavin by NAD(P)H and provide the reduced form of flavin mononucleotide (FMN) to flavin‐dependent monooxygenases. Based on bioinformatics analysis, we identified a putative flavin reductase gene, sso2055, in the genome of hyperthermophilic archaeon Sulfolobus solfataricus P2, and further cloned this target sequence into an expression vector. The cloned flavin reductase (EC. 1.5.1.30) was purified to homogeneity and characterized further. The purified enzyme exists as a monomer of 17.8 kDa, free of chromogenic cofactors. Homology modeling revealed this enzyme as a TIM barrel, which is also supported by circular dichroism measurements revealing a beta‐sheet rich content. The optimal pH for SSO2055 activity was pH 6.5 in phosphate buffer and the highest activity observed was at 120 °C within the measurable temperature. We showed that this enzyme can use FMN and flavin adenine dinucleotide (FAD) as a substrate to generate their reduced forms. The purified enzyme is predicted to be a potential flavin reductase of flavin‐dependent monooxygenases that could be involved in the biodesulfurization process of S. solfataricus P2.
Knockdown of SP1/Syncytin1 axis inhibits the proliferation and metastasis through the AKT and ERK1/2 signaling pathways in non‐small cell lung cancer
Authors: Li Xiaohui , Fu Yang , Xia Xiyan , Zhang Xin , Xiao Ke , Zhuang Xuewei , Zhang Yi 
Published: August 2019

AbstractSyncytin 1 is considered as an oncogene in various malignant tumors, but its effect on non‐small cell lung cancer (NSCLC) has not been reported. We investigated the specific role of Syncytin 1 on NSCLC through the transfection of Syncytin 1 knockdown or overexpression plamids in A549 cells. Our results proved that knockdown of Syncytin 1 inhibited the proliferation, and blocked the cell cycle on G1 phase by inhibiting the expression of Nusap1, Cyclin D1, CDK6, and CDK4. Cell cycle arrest also leaded to increased apoptosis in Syncytin 1 knockdown cells. Suppression of Syncytin 1 inhibited the migration and invasion, as well as the expressions of epithelial‐mesenchymal transition (EMT) makers, N‐cadherin, β‐catenin, and Vimentin, indicating that Syncytin 1 knockdown inhibited the metastasis via reversing the EMT process in A549 cells. The phosphorylation levels of Akt, mTOR, and Erk1/2 were all decreased in Syncytin 1 knockdown cells, suggesting the signaling pathways by which Syncytin 1 operated as an oncogene in NSCLC. Moreover, the underexpression of transcription factor SP1 downregulated the Syncytin 1 expression in A549 cells. The rescue experiment of Syncytin 1 in SP1 knockdown cells further proved that Syncytin 1 could block the inhibition of cell growth induced by SP1 knockdown. In conclusion, knockdown of SP1/Syncytin1 axis inhibited the progression of NSCLC by the reversion of tumor epithelial‐mesenchymal transition process and suppression of Akt and Erk signaling pathways, suggesting that they are potential targets for targeted therapy of NSCLC.
Prognostic role of diastolic dysfunction in patients undergoing transcatheter aortic valve replacement
Authors: Kampaktsis Polydoros N. , Vavuranakis Manolis , Choi Daniel Y. , Sherifi Ines , Christofi Angela , Triantafyllou Dionysis , Siasos Gerasimos , Salemi Arash , Tousoulis Dimitrios , Wong S. Chiu , Devereux Richard B. 
Published: August 2019

AbstractObjectivesPrior studies have shown that left ventricular diastolic dysfunction (DD) is associated with increased mortality after surgical aortic valve replacement but studies on transcatheter aortic valve replacement (TAVR) are limited and have not taken into account mitral annular calcification (MAC), which limits the use of mitral valve annular tissue Doppler imaging. We performed a single‐center retrospective analysis to better evaluate the role of baseline DD on outcomes after TAVR.MethodsAfter excluding patients with atrial fibrillation, mitral valve prostheses and significant mitral stenosis, 359 consecutive TAVR patients were included in the study. Moderate‐to‐severe MAC was present in 58% of the patients. We classified patients into severe versus nonsevere DD based on the evaluation of elevated left ventricular filling pressure. The outcome measure was all‐cause mortality or heart failure hospitalization.ResultsOver a mean follow‐up time of 13 months, severe DD was associated with an increased risk for the outcome measure (HR 2.02 [1.23–3.30], p = .005). However, this association was lost in a propensity‐matched cohort. In multivariate analysis, STS score was the only independent predictor of all cause mortality of heart failure hospitalization (HR 1.1 [1.05–1.15], p < .001).ConclusionsWe evaluated the role of baseline DD on outcomes after TAVR by taking into account the presence of MAC. Severe DD was associated with increased all‐cause mortality or heart failure hospitalization but not independently of other structural parameters and known predictors of the outcome measure.
Anemia and leukopenia following intravenous colloidal silver infusions—Clinical and hematological features, unique peripheral blood film appearance and effective therapy with supplemental oral copper and apheresis
Authors: Natelson Ethan A. , Baker Kelty R. , Pyatt David W. 
Published: August 2019

AbstractAlternative medical therapy with multiple intravenous colloidal silver infusions may cause severe illness, including profound copper deficiency‐induced anemia and hepatic toxicity. No chelating agent for silver poisoning exists and effective therapy requires apheresis in combination with continuous administration of oral copper.
Role of Iron on the Structure and Stability of Ni3.2Fe/Al2O3 during Dynamic CO2 Methanation for P2X Applications
Authors: Serrer Marc‐André , Kalz Kai F. , Saraҫi Erisa , Lichtenberg Henning , Grunwaldt Jan‐Dierk 
Published: August 2019

AbstractAn energy scenario, mainly based on renewables, requires efficient and flexible Power‐to‐X (P2X) storage technologies, including the methanation of CO2. As active Ni0 surface sites of monometallic nickel‐based catalysts are prone to surface oxidation under hydrogen‐deficient conditions, we investigated iron as “protective” dopant. A combined operando X‐ray absorption spectroscopy and X‐ray diffraction setup with quantitative on‐line product analysis was used to unravel the structure of Ni and Fe in an alloyed Ni−Fe/Al2O3 catalyst during dynamically driven methanation of CO2. We observed that Fe protects Ni from oxidation and is itself more dynamic in the oxidation and reduction process. Hence, such “sacrificial” or “protective” dopants added in order to preserve the catalytic activity under dynamic reaction conditions may not only be of high relevance with respect to fine‐tuning of catalysts for future industrial P2X applications but certainly also of general interest.
Central (S) to Central (M=Ir, Rh) to Planar (Metallocene, M=Fe, Ru) Chirality Transfer Using Sulfoxide‐Substituted Mesoionic Carbene Ligands: Synthesis of Bimetallic Planar Chiral Metallocenes
Authors: Avello Marta G. , de la Torre María C. , Sierra Miguel A. , Gornitzka Heinz , Hemmert Catherine 
Published: August 2019

AbstractEnantiopure bimetallic systems containing three different elements of chirality, namely a main‐group‐based chiral center (sulfur), a transition‐metal chiral center (rhodium or iridium), and a planar chiral element (ferrocene or ruthenocene), have been prepared by a sequence of diastereoselective reactions. The chirality of the chiral sulfur center attached to C‐5 of a 1,2,3‐triazolylidene mesoionic carbene (MIC) ligand coordinated to a metal (Ir, Rh) was transferred through the formation of bimetallic complexes having a chiral‐at‐metal center and a planar chiral metallocene by C−H activation of the sandwich moiety (M=Fe, Ru). The sense of the planar chirality formed in this sequence of reactions depended on the nature of the ligands at the metal center of the starting complex. The configurations of these species were assigned on the basis of a combination of X‐ray diffraction and CD measurements. An electrochemical study of these bimetallic complexes in coordinating solvents showed an equilibrium between the cationic complexes and the neutral species. The effect of the half‐sandwich moiety on the oxidation potentials of the system is remarkable, producing notable cathodic displacements. DFT calculations support these findings.
Twining Poly(polyoxometalate) Chains into Nanoropes
Authors: Zhang Lan‐Lan , Miao Wen‐Ke , Ren Li‐Jun , Yan Yu‐Kun , Lin Yue , Wang Wei 
Published: August 2019

AbstractOrganic polymers and inorganic clusters belong to two different disciplines and have completely different properties and structures. When a cluster is attached to the backbone of a polymer as a pendant, the resultant hybrid polymers (polyclusters) exhibit unique behaviours totally different from those of conventional polymers owing to the nanoscale size of the cluster and its particular interactions. Herein, the aggregation of a poly(polyoxometalate)—a polynorbornene backbone with inorganic polyoxometalate cluster pendants—upon addition of a non‐solvent to its dilute solution is reported. A three‐dimensional network of tangled and snake‐like nanothreads was observed. Direct visualisation of individual nanoscale clusters enabled identification of single chains within the nanothreads. These observations suggest that during the process of aggregation, the hybrid polymer forms curved or extended chains as a consequence of an armouring effect in which the collapsed cluster pendants wrap around the backbone. The collapse occurs because they become less soluble in the solvent/non‐solvent mixture. The extended chains then become entwined and form nanoropes consisting of multiple chains wound around each other. This study provides a deeper understanding of the nature of polyclusters and should also prove useful for their future development and application.
Carbene‐Catalyzed Direct Functionalization of the β‐sp3‐Carbon Atoms of α‐Chloroaldehydes
Authors: Liu Bin , Luo Guoyong , Wang Hongling , Hao Lin , Yang Song , Jin Zhichao , Chi Yonggui Robin 
Published: August 2019

AbstractA direct functionalization of the β‐sp3 carbon atom of α‐chloro aldehyde has been developed. The reaction starts with the addition of a carbene catalyst to α‐chloroaldehyde to eventually form the homoenolate intermediate. This overall redox‐neutral process successfully converts the otherwise inert β‐sp3‐carbon atom of the aldehyde substrate to a nucleophilic carbon atom for asymmetric reactions. This study constitutes the first success in activating α‐chloroaldehydes to generate homoenolate intermediates by carbene organic catalysis and shall encourage further explorations in using organic catalysis for transforming inert chemical bonds.