bluuebunny/crossref_metadata_2025_split huggingface dataset:
Oxidative Esterification of Methacrolein to Methyl Methacrylate over Supported Gold Catalysts Prepared by Colloid Deposition
Authors: Li Yuchao , Zheng Yanxia , Wang Lei , Fu Zhongjun 
Published: February 2017

AbstractEsterification is one of the most pivotal organic transformations. Au catalysts were prepared by using a colloid deposition method with poly(vinyl alcohol) (PVA) as a protective agent. The catalyst was used for the oxidative esterification of methacrylate (MAL) to methyl methacrylate (MMA). Three pre‐treatments were used to remove the PVA, which is unfavorable for catalytic activity. It is found that the catalyst pre‐treated at 300 °C showed substantially improved activity owing to the lower PVA loading compared with catalysts treated with hot water washing and water reflux. Surprisingly, it is also found that the distribution and loading content of Au particles was closely related to the pH of the colloid solution. We demonstrate that the deposition process is controlled by the different charge of the support surface at different colloid solution pH. Further, the catalysts with similar size Au particles loaded on TiO2, SiO2, Al2O3, CeO2, ZrO2, and ZnO were successfully prepared by controlling the colloid solution pH. The Au/ZnO catalyst presented the best performance, which may be a result of the strong basic surface sites that improved the formation of the intermediate and the strong interaction between Au and ZnO. This interaction caused an anchoring effect and changed the geometries of Au particles, which could enhance the stability of catalysts and promote the mobility of oxygen, respectively.
Catalysis 4.0
Authors: Schlögl Robert 
Published: February 2017

AbstractIndustry 4.0 processes including digitalization of industry are game‐changing developments in economic evolution. In the chemical industry the prevailing concepts of economy of scale and continuous operation inhibit the exploitation of the potential benefits of industry 4.0 in the production of large and intermediate chemicals and create interface problems to other industries. Under aspects of systemic rather than local efficiency, novel forms of decentralized chemical production may be realized. Advanced catalysis science today can help to meet the challenges of possible future structures of chemical industries.
Catalytic Hydrogenation of Arenes in Water Over In Situ Generated Ruthenium Nanoparticles Immobilized on Carbon
Authors: Dwivedi Ambikesh Dhar , Rai Rohit Kumar , Gupta Kavita , Singh Sanjay Kumar 
Published: February 2017

AbstractWe describe a tandem process to generate active Ru nanoparticles (≈7 nm) immobilised in situ on carbon from an organometallic precursor and formic acid to afford the hydrogenation of a wide range of arenes and heteroarenes in yields up to 72 % with high conversions and selectivities for the desired products. The hydrogenation of several substrates analogous to lignin‐derived fragments to the corresponding alicyclic products was also achieved. Our experimental investigations evidenced that the observed enhanced activity for arene hydrogenation was driven by the unique structural advantages of the organometallic precursor to activate formic acid, in which the presence of a nitrogen ligand is crucial to achieve a high catalytic activity. TEM analysis revealed the formation of Ru0 nanoparticles, and Hg0 poisoning experiments support the heterogeneous nature of the active catalyst.
Electrochemical Stability of Diphenylanthracene and Its Effect on Alternating‐Current‐Driven Blue‐Light Electrochemiluminescence Properties
Authors: Tsuneyasu Shota , Ichikawa Takuya , Nakamura Kazuki , Kobayashi Norihisa 
Published: February 2017

AbstractElectrochemiluminescence (ECL) is a phenomenon in which light is emitted from excited species generated by electrochemical reactions at electrodes. Alternating‐current‐driven ECL (AC‐ECL) devices show good brightness and fast ECL response in comparison to direct‐current‐driven ECL devices. In this report, we focus on the ECL intensity and long‐term stability of blue‐light‐emitting AC‐ECL systems. We used a mixed solvent of propylene carbonate and toluene (volume ratio=1 : 1) to achieve stable blue ECL from 9,10‐diphenylanthracene (DPA) molecules. We analyzed the electrochemical, optical, and AC‐ECL properties of DPA in this mixed solvent to investigate the effect of the stabilities of redox species on AC‐ECL properties. We found that the composition of the electrolyte solution affects the stability of these species. We conclude that stability of generated active species is required to achieve good performance in blue AC‐ECL devices.
Thermodynamic Stability of Heterodimetallic [LnLn′] Complexes: Synthesis and DFT Studies
Authors: Gónzalez‐Fabra Joan , Bandeira Nuno A. G. , Velasco Verónica , Barrios Leoní A. , Aguilà David , Teat Simon J. , Roubeau Olivier , Bo Carles , Aromí Guillem 
Published: February 2017

AbstractThe solid‐state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL)3(NO3)(py)(H2O)] (1), (Hpy)[CeEr(HL)3(NO3)(py)(H2O)] (2), (Hpy)[CeGd(HL)3(NO3)(py)(H2O)] (3), (Hpy)[PrSm(HL)3(NO3)(py)(H2O)] (4), and (Hpy)2[LaYb(HL)3(NO3)(H2O)](NO3) (5), in which H3L is 6‐(3‐oxo‐3‐(2‐hydroxyphenyl)propionyl)pyridine‐2‐carboxylic acid and py is pyridine, were analyzed experimentally and by using DFT calculations. Complexes 3, 4, and 5 are described here for the first time, and were analyzed by using single‐crystal X‐ray diffraction and mass spectrometry. The theoretical study was also extended to the [LaCe] and [LaLu] analogues. The results are consistent with a remarkable selectivity of the metal distribution within the molecule in the solid state, enhanced by the size difference between the different ions. This selectivity was reduced in solution, particularly for ions with the most similar radii. This unique entry into 4f–4f′′ heterometallic chemistry establishes for the first time the difference between the selectivity in solution and that in the solid state, as a result of changes to the coordination that follow the dissociation of terminal ligands upon dissolution of the complexes.
From Coordination Cages to a Stable Crystalline Porous Hydrogen‐Bonded Framework
Authors: Ju Zhanfeng , Liu Guoliang , Chen Yu‐Sheng , Yuan Daqiang , Chen Banglin 
Published: February 2017

AbstractA stable framework has been constructed through multiple charge‐assisted H‐bonds between cationic coordination cages and chloride ions. The framework maintained its original structure upon desolvation, which has been established by single‐crystal structure analysis. This is the first fully characterized stable porous framework based on coordination cages after desolvation, with a moderately high Brunauer–Emmett–Teller (BET) surface area of 1201 m2 g−1. This work will not only give a light to construct stable porous frameworks based on coordination cages and thus broaden their applications, but will also provide a new avenue to the assembly of other porous materials such as porous organic cages and hydrogen‐bonded organic frameworks (HOFs) through non covalent bonds.
Synthesis and Antiproliferative Effect of Ethyl 4‐[4‐(4‐Substituted Piperidin‐1‐yl)]benzylpyrrolo[1,2‐a]quinoxalinecarboxylate Derivatives on Human Leukemia Cells
Authors: Desplat Vanessa , Vincenzi Marian , Lucas Romain , Moreau Stéphane , Savrimoutou Solène , Rubio Sandra , Pinaud Noël , Bigat David , Enriquez Elodie , Marchivie Mathieu , Routier Sylvain , Sonnet Pascal , Rossi Filomena , Ronga Luisa , Guillon Jean 
Published: February 2017

AbstractAcute leukemia is a hematological malignancy with high incidence and recurrence rates and is characterized by an accumulation of blasts in bone marrow due to proliferation of immature lymphoid or myeloid cells associated with a blockade of differentiation. The heterogeneity of leukemia led us to look for new specific molecules for leukemia subtypes or for therapy‐resistant cases. Among heterocyclic derivatives that attracted attention due to their wide range of biological activities, we focused our interest on the pyrrolo[1,2‐a]quinoxaline heterocyclic framework that has been previously identified as an interesting scaffold for antiproliferative activities against various human cancer cell lines. In this work, new ethyl 4‐[4‐(4‐substituted piperidin‐1‐yl)]benzylpyrrolo[1,2‐a]quinoxalinecarboxylate derivatives (1 a–o) were designed, synthesized, and evaluated against five different leukemia cell lines, including Jurkat and U266 (lymphoid cell lines) and K562, U937, and HL60 (myeloid cell lines), as well as on normal human peripheral blood mononuclear cells (PBMCs). This new pyrrolo[1,2‐a]quinoxaline series showed interesting cytotoxic potential against all tested leukemia cell lines. In particular, pyrroloquinoxalines 1 a and 1 m,n seem to be interesting due to their high activity against leukemia and their low activity against normal hematopoietic cells, leading to a high index of selectivity.
Epstein‐Barr virus‐specific adoptive immunotherapy for recurrent, metastatic nasopharyngeal carcinoma
Authors: Huang Julian , Fogg Mark , Wirth Lori J. , Daley Heather , Ritz Jerome , Posner Marshall R. , Wang Fred C. , Lorch Jochen H. 
Published: February 2017

BACKGROUNDEarly‐stage and intermediate‐stage nasopharyngeal cancer (NPC) generally carry a good prognosis, but for patients with recurrent, metastatic disease, options are limited. In the current study, the authors present a phase 1/2 study to evaluate the efficacy of Epstein‐Barr virus (EBV)‐stimulated cytotoxic T‐lymphocyte (EBV‐CTL) immunotherapy in this patient population.METHODSScreening for patients with active, recurrent, metastatic EBV‐associated NPC began in February 2007, and the study was closed to accrual in January 2012. After informed consent was obtained, patients had their blood drawn to initiate manufacturing of the EBV‐CTL product. During product manufacturing, patients were placed on interim standard‐of‐care chemotherapy, and only after disease progression on the interim chemotherapy did patients receive investigational immunotherapy. Patients were restaged every 2 months until disease progression and then followed for survival.RESULTSA total of 28 patients were enrolled, and 21 patients were treated. There was 1 complete response achieved, and at the time of last follow‐up, the patient had been in remission for >8 years since treatment. The median progression‐free survival was 2.2 months, and the median overall survival was 16.7 months. Two other patients, after failing EBV‐CTL immunotherapy, unexpectedly demonstrated strong responses to the chemotherapy regimens they had previously failed. Patient EBV viral load and EBV‐CTL specificity for tumor‐associated viral antigens did not appear to correlate with clinical response.CONCLUSIONSA durable response was observed with EBV‐CTL immunotherapy, but the overall response rate for patients with recurrent, metastatic NPC was low. Further research is necessary to increase the efficacy of EBV‐specific immunotherapy in patients with incurable NPC, and to characterize mechanisms for refacilitation to chemotherapy. Cancer 2017;123:2642‐50. © 2017 American Cancer Society.
Meaningful endpoints for therapies approved for hematologic malignancies
Authors: Smith B. Douglas , DeZern Amy E. , Bastian Alex W. , Durie Brian G. M. 
Published: February 2017

BACKGROUNDOverall survival (OS) is considered the gold standard for determining treatment efficacy in oncology trials, but the relation between treatment and OS can be challenging to assess because of long study durations and the impact of subsequent therapies on outcome. Using OS can be particularly difficult for new therapies in hematologic malignancies (HMs).METHODSThis retrospective analysis was conducted to characterize the primary endpoints used to support US Food and Drug Administration (FDA) approvals for new drug or novel HM indications between January 2002 and July 2015. Data on approvals were retrieved from the FDA and CenterWatch websites, and from the FDA prescribing information on respective products at the time of approval.RESULTSSixty‐three FDA approvals involving 35 drugs and 16 HMs were identified. Of the 63 approvals, 45 (71.4%) included response rate (RR), and 17 (27%) included progression‐free survival (PFS; n = 14) or time to progression (n = 3), and 1 approval included OS. Twenty‐three approvals (36.5%) included trials with an active comparator arm. The median relative magnitude of benefit versus comparator was 71% improvement (range, 26%‐127%), with a median hazard ratio of 0.55 (range, 0.16‐0.72).CONCLUSIONSFDA approvals for new drug or novel HM indications are often based on endpoints other than OS, such as RR and PFS. Tools for determining the magnitude of clinical benefit and treatment value in HMs should take into account the importance of RR, PFS, and other non‐OS endpoints. Cancer 2017;123:1689–1694. © 2017 American Cancer Society.
Precursor‐Directed Nucleation and Self‐Assembly Growth: From Hollow Microprisms to Nanoplatelets
Authors: Li Zhaojin , Hu Tao , Peng Zhenzhen , Hu Minmin , Zhu Kongjun , Wang Xiaohui 
Published: February 2017

AbstractDirectly controlling the morphology and orientation of nanocrystals is a key step for their tailored applications. Achieving such controlled synthesis requires insight into the formation mechanism. Using Li3PO4 microprisms as a solid precursor sealed in capillary tube, we unravel the structural and morphological evolution from the precursor to the resultant LiFePO4 nanoplatelets by means of in situ temperature monitoring, ex situ Raman spectroscopy and TEM/STEM. Under water‐deficient conditions, the precursor dissolves in a sluggish manner, facilitating simultaneous heterogeneous nucleation of LiFePO4 on undissolved Li3PO4 and homogeneous nucleation in solution. Vertically aligned nanoribbons consisting of primary LiFePO4 particles on the Li3PO4 surface undergo self‐assembly growth though oriented attachment. The [100]‐orientation is explained by the fact that H3O+ preferably adsorbed on the LiFePO4 (100) facet and suppressed the crystal growth more along the [100] direction than the others.
Time‐Resolved X‐Ray Powder Diffraction Study of Photoinduced Phase Transitions in Ti3O5 Nanoparticles
Authors: Tasca Kelin R. , Esposito Vincent , Lantz Gabriel , Beaud Paul , Kubli Martin , Savoini Matteo , Giles Carlos , Johnson Steven L. 
Published: February 2017

AbstractNanoparticles of Ti3O5 have been reported to show a permanent photoinduced phase transition at room temperature. This suggests that light‐induced phase transformations of Ti3O5 nanoparticles may be promising for technological applications. Here, we report a photoinduced semiconductor‐to‐metal phase transition from β‐Ti3O5 to λ‐Ti3O5 nanoparticles at room temperature observed directly by time‐resolved X‐ray powder diffraction in a pump‐probe setup. The results show a partial structural change, limited by differences between pumped and probed volumes, which persists a few microseconds after excitation. The first step in the relaxation back to the ground state can be described by a single exponential decay with time constant within microsecond timescales. Analysis of the change in lattice constants enables us to estimate an average temperature increase across the phase transition, consistent with a thermally driven process.
Fast‐transient DC‐DC converter using a high‐performance error amplifier with a rapid output‐voltage control technique
Authors: Javed Khurram , Yeo Jaejin , Lee Jaeseong , Roh Jeongjin 
Published: February 2017

SummaryThis letter presents a method for improving the transient response of DC‐DC converters. The proposed technique replaces the conventional error amplifier with a combination of two different amplifiers to achieve a high loop gain and high slew rate. In addition, a rapid output‐voltage control circuit is employed to further reduce the recovery time. The proposed technique was applied to a four‐phase buck converter, and the chip was implemented using a 0.18‐μm CMOS process. The switching frequency of each phase was set at 2 MHz. Using a supply voltage of 2.7–5.5 V and an output voltage of 0.6–1.5 V, the regulator provided up to 2‐A load current with maximum measured recovery time of only 6.2 and 6.5 μs for increasing and decreasing load current, respectively. Copyright © 2017 John Wiley & Sons, Ltd.
Detecting spatial ontogenetic niche shifts in complex dendritic ecological networks
Authors: Fields William R. , Grant Evan H. Campbell , Lowe Winsor H. 
Published: February 2017

AbstractOntogenetic niche shifts (ONS) are important drivers of population and community dynamics, but they can be difficult to identify for species with prolonged larval or juvenile stages, or for species that inhabit continuous habitats. Most studies of ONS focus on single transitions among discrete habitat patches at local scales. However, for species with long larval or juvenile periods, affinity for particular locations within connected habitat networks may differ among cohorts. The resulting spatial patterns of distribution can result from a combination of landscape‐scale habitat structure, position of a habitat patch within a network, and local habitat characteristics—all of which may interact and change as individuals grow. We estimated such spatialONSfor spring salamanders (Gyrinophilus porphyriticus), which have a larval period that can last 4 years or more. Using mixture models to identify larval cohorts from size frequency data, we fit occupancy models for each age class using two measures of the branching structure of stream networks and three measures of stream network position. Larval salamander cohorts showed different preferences for the position of a site within the stream network, and the strength of these responses depended on the basin‐wide spatial structure of the stream network. The isolation of a site had a stronger effect on occupancy in watersheds with more isolated headwater streams, while the catchment area, which is associated with gradients in stream habitat, had a stronger effect on occupancy in watersheds with more paired headwater streams. Our results show that considering the spatial structure of habitat networks can provide new insights on ONS in long‐lived species.
Climate and density dependence cause changes in adult sex ratio in a large Arctic herbivore
Authors: Peeters Bart , Veiberg Vebjørn , Pedersen Åshild Ønvik , Stien Audun , Irvine Robert Justin , Aanes Ronny , Sæther Bernt‐Erik , Strand Olav , Hansen Brage Bremset 
Published: February 2017

AbstractVariation in adult sex ratio (ASR) affects population demography and dynamics of large mammals. The mechanisms behind this variation are largely unclear, but may be partly related to climatic drivers and density dependence operating differently on the adult male and female segments of the population. Here, we examine such drivers of annual changes in ASR in the predator‐free wild Svalbard reindeer (Rangifer tarandus platyrhynchus), a high Arctic subspecies whose population dynamics are shaped by climate. Using up to 35 year long time‐series of population count data from two populations, we disentangle drivers of fluctuations in ASR by first analyzing how climate and density dependence affect sex‐specific adult population growth rates through effects on mortality. There were a positive population size trend and an overall female bias in ASR throughout the study period. Increased winter precipitation, a proxy for the harshness of winter feeding conditions, was found to significantly reduce adult population growth rates through reduced survival in males, but not in females. However, increased population size tended to cause a stronger immediate decline in female than in male adult population growth rates. As a consequence, the female bias in ASR increased with harsher winter conditions and declined with higher population size. As expected from the increased frequency of rainy and icy winters due to climate warming, a recent trend toward increased female bias in ASR was evident. This demonstrates that climatic drivers of both short‐term fluctuations and long‐term trends in demography need to be accounted for in the management and population dynamic predictions of Arctic ungulates.
Using Social Network Analysis to Monitor and Assess the Effectiveness of Knowledge Brokers at Connecting Scientists and Decision‐Makers: An Australian case study
Authors: Cvitanovic C. , Cunningham R. , Dowd A‐M. , Howden S.M. , van Putten E.I. 
Published: February 2017

AbstractDespite growing rhetoric regarding the potential benefits of using knowledge brokers in relation to environmental challenges and decision‐making processes, the evidence in support of such claims is mostly anecdotal. This is, in part, due to the lack of established methods to evaluate the effectiveness and efficiency of knowledge brokers. To address this gap we assess the utility of social network analysis (SNA) to evaluate the effectiveness of knowledge brokers in connecting scientists and decision‐makers. Specifically, using a case‐study approach, we undertake longitudinal SNA over a 12‐month period to evaluate the extent to which the knowledge broker developed networks between producers and users of knowledge across different organizations. We also undertook a qualitative survey of scientists (n = 29) who worked in the same organization as the knowledge broker to understand the extent to which the knowledge broker increased the impact of scientific research for decision‐making purposes. Results show that the knowledge broker developed an extensive stakeholder network of 192 individuals spanning over 30 organizations. The results of the SNA found that over time this network increased in density and became more cohesive, both key elements underpinning successful knowledge exchange. Furthermore, the qualitative survey found that the knowledge broker also had a positive impact in other ways, including helping researchers understand the operating environments within decision‐making agencies and the best approaches for engaging with specific decision‐makers. Thus, this study demonstrates the value of SNA for evaluating knowledge brokers and provides empirical support for the use of knowledge brokers in the environmental sector. Copyright © 2017 John Wiley & Sons, Ltd and ERP Environment
Opuntia ficus‐indica seed oil: Biorefinery and bioeconomy aspects
Authors: Ciriminna Rosaria , Delisi Riccardo , Albanese Lorenzo , Meneguzzo Francesco , Pagliaro Mario 
Published: February 2017

In this study, we offer a perspective written from a biorefinery viewpoint aimed at expanding the cactus peer seed oil market and utilizations. Besides antioxidant and skin and hair hydrating action which make it suitable as a valued cosmetic ingredient, the oil contained in the seeds of Opuntia ficus‐indica and Opuntia dillenii, rich in unsaturated fatty acids, also shows anti‐inflammatory properties which offer significant potential as functional ingredient of nutraceutical and food supplement products.Practical applications: The outcomes of the study will be useful in progressing the expansion of the emerging bioeconomy, especially in Opuntia producing countries.The oil contained in the seeds of prickly pear cactus is rich in unsaturated fatty acids and shows significant anti‐inflammatory properties which offer significant potential as functional ingredient of nutraceutical and food supplement products. We offer a perspective written from a biorefinery viewpoint aimed at expanding the utilization of this valued bio‐derived oil.