bluuebunny/crossref_metadata_2025_split huggingface dataset:
Finely Tuned Porous Coordination Polymers To Boost Methane Separation Efficiency
Authors: Wang Yang , Dong Qiubing , Cao Haifei , Ji Wei , Duan Jingui , Jing Su , Jin Wanqin 
Published: April 2019

AbstractAbsorbents with high breakthrough efficiency and weak host–guest interaction are considered to be promising candidates for an energy‐saving process in feasible pressure/volume swing adsorption (PSA/VSA). Herein, two groups of finely designed Fe‐ and Co‐based porous coordination polymers (PCPs) are proposed and validated; these possess hourglass‐shaped nanochannels, through the cooperation of T‐shaped ligands with shifted methyl groups. Featuring optimal nanochannels, high static adsorption, and relatively lower binding energy, one of these polymers, named NTU‐30, enables significant C2H6/CH4 and C2H4/CH4 breakthrough efficiency, with approximately 1.0 or 0.6 g CH4 (100 %) harvested from the corresponding mixtures using 1 g of sample at ambient temperature. Furthermore, the positive effect of aromatic sites within NTU‐30 is detected and investigated through an in situ IR study.
Improving Catalyst Activity in Hydrocarbon Functionalization by Remote Pyrene–Graphene Stacking
Authors: Ballestin Pilar , Ventura‐Espinosa David , Martín Santiago , Caballero Ana , Mata Jose A. , Pérez Pedro J. 
Published: April 2019

AbstractA copper complex bearing an N‐heterocyclic carbene ligand with a pyrene “tail” attached to the backbone has been prepared and supported on reduced graphene oxide (rGO). The free and supported copper materials have been employed as homogeneous and heterogeneous catalysts in the functionalization of hydrocarbons such as n‐hexane, cyclohexane, and benzene through incorporation of the CHCO2Et unit from ethyl diazoacetate. The graphene‐anchored complex displays higher reaction rates and induces higher yields than its soluble counterpart, features that can be rationalized in terms of a decrease in electron density at the metal center due to a remote net electronic flux from the supported copper complex to the graphene surface.
A bis‐Pyrazolate Pincer on Reduced Cr Deoxygenates CO2: Selective Capture of the Derived Oxide by CrII
Authors: Labrum Nicholas S. , Chen Chun‐Hsing , Caulton Kenneth G. 
Published: April 2019

AbstractReduction of the bis‐(pyrazolyl)pyridine complex [LCr]2 with stoichiometric KC8 in THF produces a species that is reactive with CO2 to produce an aggregate composed of paramagnetic K2L2Cr2(CO3) linked by KCl into a product of formula [K2L2Cr2(CO3)]4⋅2KCl. X‐ray diffraction reveals a pincer hydrocarbon exterior and an inorganic interior composed of K+, Cl− and carbonate oxygens. Every Cr is five coordinate and square pyramidal, with the axial N donor weakly bonded to Cr due to the Jahn–Teller effect of a high spin d4 configuration. Reaction with 13CO2 confirms that carbonate here is derived from CO2, that oxide is derived from CO2, and that CO is indeed released, since it is not a competent ligand to CrII. Guiding principles for selectivity in CO2 reduction are deduced from the diverse successful molecular constructs to date.
Hyperpolarizing Concentrated Metronidazole 15NO2 Group over Six Chemical Bonds with More than 15 % Polarization and a 20 Minute Lifetime
Authors: Shchepin Roman V. , Birchall Jonathan R. , Chukanov Nikita V. , Kovtunov Kirill V. , Koptyug Igor V. , Theis Thomas , Warren Warren S. , Gelovani Juri G. , Goodson Boyd M. , Shokouhi Sepideh , Rosen Matthew S. , Yen Yi‐Fen , Pham Wellington , Chekmenev Eduard Y. 
Published: April 2019

AbstractThe NMR hyperpolarization of uniformly 15N‐labeled [15N3]metronidazole is demonstrated by using SABRE‐SHEATH. In this antibiotic, the 15NO2 group is hyperpolarized through spin relays created by 15N spins in [15N3]metronidazole, and the polarization is transferred from parahydrogen‐derived hydrides over six chemical bonds. In less than a minute of parahydrogen bubbling at approximately 0.4 μT, a high level of nuclear spin polarization (P15N) of around 16 % is achieved on all three 15N sites. This product of 15N polarization and concentration of 15N spins is around six‐fold better than any previous value determined for 15N SABRE‐derived hyperpolarization. At 1.4 T, the hyperpolarized state persists for tens of minutes (relaxation time, T1≈10 min). A novel synthesis of uniformly 15N‐enriched metronidazole is reported with a yield of 15 %. This approach can potentially be used for synthesis of a wide variety of in vivo metabolic probes with potential uses ranging from hypoxia sensing to theranostic imaging.
Unprecedented Diastereoselective Arylogous Michael Addition of Unactivated Phthalides
Authors: Sicignano Marina , Schettini Rosaria , Sica Luisa , Pierri Giovanni , De Riccardis Francesco , Izzo Irene , Maity Bholanath , Minenkov Yury , Cavallo Luigi , Della Sala Giorgio 
Published: April 2019

AbstractInvited for the cover of this issue are the groups of Giorgio Della Sala at the Università degli Studi di Salerno and Luigi Cavallo at the King Abdullah University of Science and Technology. The image depicts the transition state involved in the crown ether catalyzed arylogous Michael reaction of phthalides. Read the full text of the article at 10.1002/chem.201900168.
A phase 2, randomized trial evaluating the combination of dalantercept plus axitinib in patients with advanced clear cell renal cell carcinoma
Authors: Voss Martin H. , Bhatt Rupal S. , Vogelzang Nicholas J. , Fishman Mayer , Alter Robert S. , Rini Brian I. , Beck J. Thaddeus , Joshi Monika , Hauke Ralph , Atkins Michael B. , Burgess Earle , Logan Theodore F. , Shaffer David , Parikh Rahul , Moazzam Nauman , Zhang Xiaosha , Glasser Chad , Sherman Matthew L. , Plimack Elizabeth R. 
Published: April 2019

BackgroundIn a prior open‐label study, the combination of dalantercept, a novel antiangiogenic targeting activin receptor‐like kinase 1 (ALK1), plus axitinib was deemed safe and tolerable with a promising efficacy signal in patients with advanced renal cell carcinoma (RCC).MethodsIn the current phase 2, randomized, double‐blind, placebo‐controlled study, patients with clear cell RCC previously treated with 1 prior angiogenesis inhibitor were randomized 1:1 to receive axitinib plus dalantercept versus axitinib plus placebo. Randomization was stratified by the type of prior therapy. The primary endpoint was progression‐free survival (PFS). Secondary endpoints were PFS in patients with ≥2 prior lines of anticancer therapy, overall survival, and the objective response rate.ResultsBetween June 10, 2014, and February 23, 2017, a total of 124 patients were randomly assigned to receive axitinib plus dalantercept (59 patients) or placebo (65 patients). The median PFS was not found to be significantly different between the treatment groups (median, 6.8 months vs 5.6 months; hazard ratio, 1.11 [95% CI, 0.71‐1.73; P = .670]). Neither group reached the median overall survival (hazard ratio, 1.39 [95% CI, 0.70‐2.77; P = .349]). The objective response rate was 19.0% (11 of 58 patients; 95% CI, 9.9%‐31.4%) in the dalantercept plus axitinib group and 24.6% (15 of 61 patients; 95% CI, 14.5%‐37.3%) in the placebo plus axitinib group. At least 1 treatment‐emergent adverse event of ≥grade 3 was observed in 59% of patients (34 of 58 patients) in the dalantercept group and 64% of patients (39 of 61 patients) in the placebo group. One treatment‐related death occurred in the placebo plus axitinib group.ConclusionsAlthough well tolerated, the addition of dalantercept to axitinib did not appear to improve treatment‐related outcomes in previously treated patients with advanced RCC.
Multiple myeloma epidemiology and patient geographic distribution in Canada: A population study
Authors: Tsang Matthew , Le Michelle , Ghazawi Feras M. , Cyr Janelle , Alakel Akram , Rahme Elham , Lagacé François , Netchiporouk Elena , Moreau Linda , Zubarev Andrei , Roshdy Osama , Glassman Steven J. , Sasseville Denis , Popradi Gizelle , Litvinov Ivan V. 
Published: April 2019

BackgroundMultiple myeloma (MM) is a malignancy of mature plasma cells. Environmental risk factors identified for this malignancy, among others, include farming and exposure to pesticides.MethodsUsing 3 independent population‐based databases (the Canadian Cancer Registry, le Registre Québécois du Cancer, and Canadian Vital Statistics), this study analyzed patients’ clinical characteristics and the incidence, mortality, and geographic distribution of MM cases in Canada during 1992‐2015.ResultsIn total, ~32,065 patients were identified, and 53.7% were male. The mean age at the time of diagnosis was 70 ± 12.1 years. The average incidence rate in Canada was 54.29 cases per million individuals per year, and linear regression modeling showed a steady rise in the annual rate of 0.96 cases per million individuals per year. At the provincial level, Quebec and Ontario had significantly higher incidence rates than the rest of Canada. An analysis of individual municipalities and postal codes showed lower incidence rates in large metropolitan areas and in high‐latitude regions of the country, whereas high incidence rates were observed in smaller municipalities and rural areas. Land use analysis demonstrated increased density of crop farms and agricultural industries in high‐incidence areas. A comparison with the available data from 2011‐2015 showed several consistent trends at provincial, municipal, and regional levels.ConclusionsThese results provide a comprehensive analysis of the MM burden in Canada. Large metropolitan cities as well as high‐latitude regions were associated with lower MM incidence. Higher incidence rates were noted in smaller cities and rural areas and were associated with increased density of agricultural facilities.
Pretectal projections to the oculomotor cerebellum in hummingbirds (Calypte anna), zebra finches (Taeniopygia guttata), and pigeons (Columba livia)
Authors: Gaede Andrea H. , Gutierrez‐Ibanez Cristian , Armstrong Melissa S. , Altshuler Douglas L. , Wylie Douglas R. 
Published: April 2019

AbstractIn birds, optic flow is processed by a retinal‐recipient nucleus in the pretectum, the nucleus lentiformis mesencephali (LM), which then projects to the cerebellum, a key site for sensorimotor integration. Previous studies have shown that the LM is hypertrophied in hummingbirds, and that LM cell response properties differ between hummingbirds and other birds. Given these differences in anatomy and physiology, we ask here if there are also species differences in the connectivity of the LM. The LM is separated into lateral and medial subdivisions, which project to the oculomotor cerebellum and the vestibulocerebellum. In pigeons, the projection to the vestibulocerebellum largely arises from the lateral LM; the projection to the oculomotor cerebellum largely arises from the medial LM. Here, using retrograde tracing, we demonstrate differences in the distribution of projections in these pathways between Anna's hummingbirds (Calypte anna), zebra finches (Taeniopygia guttata), and pigeons (Columba livia). In all three species, the projections to the vestibulocerebellum were largely from lateral LM. In contrast, projections to the oculomotor cerebellum in hummingbirds and zebra finches do not originate in the medial LM (as in pigeons) but instead largely arise from pretectal structures just medial, the nucleus laminaris precommissuralis and nucleus principalis precommissuralis. These species differences in projection patterns provide further evidence that optic flow circuits differ among bird species with distinct modes of flight.
Size Fractionation of Graphene Oxide via Solvent‐Mediated Consecutive Charge Manipulation and Investigation of the Size Effect as Hole Transporting Layer in Perovskite Solar Cells
Authors: Kim Ungsoo , Choi Keunsu , Park Kwang Hyun , Lee Junghyun , Choi Yunseong , Seo Jihyung , Oh Nam Khen , Jung Seungon , Yang Hyemi , Lee Jun Hee , Yang Changduk , Park Hyesung 
Published: April 2019

AbstractAlthough intensive research for graphene oxide (GO) has been conducted, the broad size distribution of as‐synthesized GO flakes still remains a challenging issue since flake size has a direct impact on the material properties and related applications. Herein, we propose a facile and scalable approach for the size fractionation of GO flakes by manipulating the surface charge of GO with an organic solvent‐mediated aqueous solution. Both the experimental and simulation results confirm that the dispersion of GO flakes is notably influenced by the bond strength with solvent, which is attributed by the charge amount of oxygen in solvent molecule. From the understanding of the dispersion mechanism, an optimal solvent for the size fractionation of GO flakes was determined and GO flakes were successfully sorted into various size groups with a narrow distribution. The effect of size fractionation on the material property and related application was confirmed through various analyses. Our results could bring significant advances in producing two‐dimensional materials with reliable and reproducible material properties toward practical applications.
First‐in‐Human Pharmacokinetics and Safety Study of GSK3008356, a Selective DGAT1 Inhibitor, in Healthy Volunteers
Authors: Okour Malek , Gress Angela , Zhu Xinyi , Rieman David , Lickliter Jason D. , Brigandi Richard A. 
Published: April 2019

AbstractDiacylglycerol acyltransferase (DGAT) enzymes are involved in triglyceride (TG) biosynthesis. GSK3008356 is a potent and selective DGAT1 inhibitor that was administered orally in a 2‐part study as double‐blind, randomized, placebo‐controlled single doses (SDs) and repeat doses (RDs) in healthy subjects to investigate its pharmacokinetics, pharmacodynamics, and safety/tolerability. Gastrointestinal adverse events were considered drug related and increased with dose and when given as multiple doses. In the SD part (n = 80), GSK3008356 was dosed from 5 to 200 mg as single or multiple doses per day. In the RD part (n = 24), GSK3008356 was dosed twice daily at 1, 3, and 10 mg for 14 days. GSK3008356 was generally well tolerated in the SD and RD parts. With single doses, absorption was rapid (median tmax, 0.5–1.5 hours), whereas single‐day divided dosing resulted in higher tmax. Following 14‐day RD oral administration, GSK3008356 was also rapidly absorbed, with median tmax ranging from 0.5 to 0.75 hours on days 1 and 14. Estimated mean half‐life ranged from 1.5 to 4.6 hours with SDs and 1.3 to 2.1 hours with RDs. Exposure of GSK3008356 was largely dose proportional after RDs. At higher doses, there was a trend toward lower absolute postprandial TG level in some subjects.
Design of a blind quantization‐based audio watermarking scheme using singular value decomposition
Authors: Bhat K Vivekananda , Das Ashok Kumar , Lee Jong‐Hyouk 
Published: April 2019

SummaryWatermarking is a mechanism in which owner of the audio file hides the watermark information into a audio for various applications. The identity of the owner of the audio file is hidden in the audio, which is known as watermark. In this article, a quantization‐based audio watermarking using singular value decomposition (SVD) is proposed. The original audio signal is converted into non overlapping two dimensional matrix blocks. The SVD is applied to each block. The watermark is embedded into audio signal by quantization of largest singular value of the block. The watermark is extracted blindly without using original audio signal. Experimental results show the watermark's high imperceptibility in the audio signal and good performance against Stirmark as well as traditional signal processing attacks. Compared with other audio watermarking methods, our method has higher embedding capacity and robust against various traditional signal processing attacks.
Efficient Building Blocks for Solid‐Phase Peptide Synthesis of Spin Labeled Peptides for Electron Paramagnetic Resonance and Dynamic Nuclear Polarization Applications
Authors: Brodrecht Martin , Herr Kevin , Bothe Sarah , de Oliveira Marcos , Gutmann Torsten , Buntkowsky Gerd 
Published: April 2019

AbstractSpecific spin labeling allows the site‐selective investigation of biomolecules by EPR and DNP enhanced NMR spectroscopy. A novel spin labeling strategy for commercially available Fmoc‐amino acids is developed. In this approach, the PROXYL spin label is covalently attached to the hydroxyl side chain of three amino acids hydroxyproline (Hyp), serine (Ser) and tyrosine (Tyr) by a simple three‐step synthesis route. The obtained PROXYL containing building‐blocks are N‐terminally protected by the Fmoc‐protection group, which makes them applicable for the use in solid‐phase peptide synthesis (SPPS). This approach allows the insertion of the spin label at any desired position during SPPS, which makes it more versatile than the widely used post synthetic spin labeling strategies. For the final building‐blocks, the radical activity is proven by EPR. DNP enhanced solid‐state NMR experiments employing these building‐blocks in a TCE solution show enhancement factors of up to 26 for 1H and 13C (1H→13C cross‐polarization). To proof the viability of the presented building‐blocks for insertion of the spin label during SPPS the penta‐peptide Acetyl‐Gly‐Ser(PROXYL)‐Gly‐Gly‐Gly was synthesized employing the spin labeled Ser building‐block. This peptide could successfully be isolated and the spin label activity proved by EPR and DNP NMR measurements, showing enhancement factors of 12.1±0.1 for 1H and 13.9±0.5 for 13C (direct polarization).
Processes and Their Limitations in Oxygen Depolarized Cathodes: A Dynamic Model‐Based Analysis
Authors: Röhe Maximilian , Kubannek Fabian , Krewer Ulrike 
Published: April 2019

AbstractOxygen depolarized cathodes (ODCs) are key components of alkaline fuel cells and metal–air batteries or of chlor‐alkaline electrolysis, but suffer from limited oxygen availability at the reaction zone. Dynamic analysis is a highly suitable approach to identify the underlying causes, especially the limiting steps and process interactions in such gas diffusion electrodes. Herein, a one‐dimensional, dynamic, three‐phase model for analyzing the oxygen reduction reaction in silver‐based ODCs is presented. It allows for a detailed evaluation of the electrochemical reaction, the mass transport processes, and their interaction. The model also reveals that the depletion of reactant oxygen in the liquid electrolyte is caused by the current‐dependent change of the gas–liquid equilibrium as the limiting subprocess. The phase equilibrium, in turn, depends on the slow mass transport of water and hydroxide ions in the liquid phase. Key parameters are the location or size of the gas–liquid interface within the electrode. Profiles of local concentrations and partial pressures of different species reveal a steep gradient of oxygen in the liquid phase, but no limitation in oxygen mass transport in the gas phase. Dynamic simulations with potential steps allowed the identification of different time constants to separate overlapping processes. Accordingly, the mass transport of water and hydroxide ions was identified as the slowest process that strongly influenced the dynamic response of all species, including oxygen, and of the current. The characteristic time constant of the mass transport of water and hydroxide ions across the liquid phase within the ODC is determined to be τ
≈0.176 s, whereas the time constant of oxygen mass transport into the reaction zone is several magnitudes smaller: τ
≈1.70×10−6 s. Finally, a sensitivity analysis confirms that the overall performance is best improved by adjusting mass transport properties in the liquid phase.
Microfluidic chip technology applied to fine‐needle aspiration cytology samples for IGH clonality assessment
Authors: Vigliar Elena , Pepe Francesco , Migliatico Ilaria , Nacchio Mariantonia , Cesaro Sonia , Della Pepa Roberta , Bellevicine Claudio , Malapelle Umberto , Fassan Matteo , Pane Fabrizio , Picardi Marco , Troncone Giancarlo 
Published: April 2019

AbstractBackgroundMost cases of non‐Hodgkin lymphoma (NHL) can be diagnosed using a combination of fine‐needle cytology (FNC) and flow cytometry together with immunoglobulin light chain restriction and/or specific phenotypic profiles. However, 5%‐15% of B‐cell NHLs lack these specific diagnostic features. In such cases, the diagnosis of NHL may be supported by molecular clonality testing based on the immunoglobulin heavy chain (IGH) assay of clonality by polyacrylamide heteroduplex analysis or by automated capillary electrophoresis via GeneScan analysis. Chip‐based microfluidic technology (MT), based on miniaturized parallel capillary electrophoresis structures, is a viable alternative to capillary electrophoresis analysis, being less costly and cumbersome. In this study, we evaluated the performance of MT platform in IGH clonality assessment in a series of lymph node FNC samples.MethodsThirty‐five consecutive lymph node FNCs were evaluated. In all cases, the first and the second passes were used to prepare a conventional smear and to collect material for flow cytometry analysis; residual material was collected for molecular clonality assessment, and PCR products were analyzed both by MT and GeneScan platforms.ResultsMolecular clonality assessment by MT had a sensitivity of 84.2% and a specificity of 76.9%; GeneScan analysis had a sensitivity of 88.8% and a specificity of 92.8%. The overall agreement between the two platforms was 85.7% (30/35).ConclusionsMT analysis proved to be a viable technique for IGH clonality assessment on FNC samples. Should our data be confirmed in larger studies, the MT procedure may be suitable for routine diagnostic practice, even on cytological samples.
Sexual conflict in action: An antagonistic relationship between maternal and paternal sex allocation in the tammar wallaby, Notamacropus eugenii
Authors: Edwards Amy M. , Cameron Elissa Z. , Deakin Janine E. , Ezaz Tariq , Pereira Jorge C. , Ferguson‐Smith Malcolm A. , Robert Kylie A. 
Published: April 2019

AbstractSex ratio biases are often inconsistent, both among and within species and populations. While some of these inconsistencies may be due to experimental design, much of the variation remains inexplicable. Recent research suggests that an exclusive focus on mothers may account for some of the inconsistency, with an increasing number of studies showing variation in sperm sex ratios and seminal fluids. Using fluorescent in‐situ hybridization, we show a significant population‐level Y‐chromosome bias in the spermatozoa of wild tammar wallabies, but with significant intraindividual variation between males. We also show a population‐level birth sex ratio trend in the same direction toward male offspring, but a weaning sex ratio that is significantly female‐biased, indicating that males are disproportionately lost during lactation. We hypothesize that sexual conflict between parents may cause mothers to adjust offspring sex ratios after birth, through abandonment of male pouch young and reactivation of diapaused embryos. Further research is required in a captive, controlled setting to understand what is driving and mechanistically controlling sperm sex ratio and offspring sex ratio biases and to understand the sexually antagonistic relationship between mothers and fathers over offspring sex. These results extend beyond sex allocation, as they question studies of population processes that assume equal input of sex chromosomes from fathers, and will also assist with future reproduction studies for management and conservation of marsupials.