bluuebunny/crossref_metadata_2025 huggingface dataset:
Effect of melt composition on crustal carbonate assimilation: Implications for the transition from calcite consumption to skarnification and associated CO2 degassing
Authors: Carter Laura B. , Dasgupta Rajdeep
Published: September 2016

Skarns are residue of relatively low‐temperature magma‐induced decarbonation in the crust largely associated with silicic plutons. Mafic magmatic intrusions are also capable of releasing excess CO2 due to carbonate assimilation. However, the effect of mafic to silicic melt evolution on the decarbonation processes, in addition to temperature controls on carbonate‐intrusive magmatic systems, particularly at continental arcs, remains unclear. In this study, experiments performed in a piston cylinder apparatus at midcrustal depth (0.5 GPa) at supersolidus temperatures (900–1200°C) document calcite interaction with andesite and dacite melts at equilibrium under closed‐system conditions at calcite saturation in a 1:1 melt‐calcite ratio by weight. With increasing silica content in the starting melt, at similar melt fractions and identical pressure, assimilation decreases drastically (≤65% andesite‐calcite to ≤18% dacite‐calcite). In conjunction, the CaO/SiO2 ratio in melts resulting from calcite assimilation in andesitic starting material is >1, but ≤0.3 in those formed from dacite‐calcite interaction. With increasing silica‐content in the starting melt skarn mineralogy, particularly wollastonite, increases in modal abundance while diopsidic clinopyroxene decreases slightly. More CO2 is released with andesite‐calcite reaction (≤2.9 × 1011 g/y) than with more skarn‐like dacite‐calcite interaction (≤8.1 × 1010 g/y, at one volcano assuming respective calcite‐free‐superliquidus conditions and a magma flux of 1012 g/y). Our experimental results thus suggest that calcite assimilation in more mafic magmas may have first degassed a significant amount of crustal carbon before the melt evolves to more silicic compositions, producing skarn. Crustal decarbonation in long‐lived magmatic systems may hence deliver significant albeit diminishing amounts of carbon to the atmosphere and contribute to long‐term climate change.
Contribution of viscoelastic flow in earthquake cycles within the lithosphere‐asthenosphere system
Authors: Lambert Valère , Barbot Sylvain
Published: September 2016

Faults slip relaxes lithospheric stress imposed by mantle flow and in turn transfers stress to the ductile regions. The interplay of these systems governs the style of deformation at plate boundaries including the recurrence of seismic events. However, such deep processes remain challenging to incorporate in numerical simulations of earthquake cycles. Here we propose a model that couples fault slip and viscoelastic deformation to simulate fault dynamics in the lithosphere‐asthenosphere system. Our method resolves all phases of the earthquake cycle, including dynamic rupture propagation, afterslip, slow‐slip events, and the modulation of strain rate incurred in the ductile regions. Transient strain accelerations in the asthenosphere may follow both earthquakes and slow‐slip events shortly after the rupture, depending on the rheology of the upper mantle and the magnitude of the event. This study opens the door to greater insight into the variability of earthquake cycles by incorporating the dynamics of distributed deformation.
Precipitation variation over eastern China and arid central Asia during the past millennium and its possible mechanism: Perspectives from PMIP3 experiments
Authors: Shi Jian , Yan Qing , Jiang Dabang , Min Jinzhong , Jiang Ying
Published: September 2016

Multiproxies suggest a tripole humidity pattern in Asia in the Medieval Climate Anomaly (MCA, 950–1250 A.D.) and Little Ice Age (LIA, 1500–1800 A.D.), with drier (wetter) conditions in arid central Asia (ACA), wetter (drier) conditions in North China, and drier (wetter) conditions in South China. However, the mechanisms behind this reconstructed humidity variation remain unclear. In this study, we investigate Asian humidity changes by using the last millennium simulations of the Paleoclimate Modelling Intercomparison Project Phase III (PMIP3). The results indicate that only one out of nine PMIP3 models (Meteorological Research Institute Coupled ocean‐atmosphere General Circulation Model version 3) can well reproduce the reconstructed humidity pattern. This model indicates that the tripole humidity pattern is mainly caused by precipitation changes in spring and summer and is prominent in the past millennium on a multidecadal time scale. In spring, the reduction (increase) of precipitation in ACA and South China is attributed to the northward (southward) shift of the westerlies and a weakened (strengthened) western Pacific subtropical high in the MCA (LIA). In summer, precipitation over ACA decreases (increases) due to a local descending (ascending) motion, while abundant (deficient) precipitation over eastern China results from the enhanced (depressed) summer monsoon. Moreover, we suggest that a La Niña (El Niño)‐like condition may be the primary reason the tripole precipitation pattern was maintained in the MCA (LIA), although a warmer (colder) North Pacific and North Atlantic also play a role. The mechanisms must be further validated since most simulations fail to reproduce the reconstructed humidity condition in the MCA/LIA, making model‐model comparisons difficult.
PolymerizationCatalysis by Metal Phenolates
Authors: Dagorne Samuel , Romain Charles
Published: September 2016

The present contribution provides a broad overview on the latest significant developments on metal phenolate complexes for use in polymerization catalysis of olefins, cyclic esters, and cyclic carbonates. Systems mediating the CO
2
/epoxide polymerization are also especially emphasized.
Artificial Metalloenzyme‐Based Enzyme Replacement Therapy for the Treatment of Hyperuricemia
Authors: Liu Xinping , Zhang Zhijun , Zhang Yan , Guan Yijia , Liu Zhen , Ren Jinsong , Qu Xiaogang
Published: September 2016

Enzyme replacement therapy (ERT) holds great potential for treating enzyme deficiency related diseases. However, the enzymic vulnerability and the undesirable toxic side effects have strongly limited its clinical applications. Here a novel artificial metalloenzyme‐based ERT with significant self‐protection and toxic self‐cleaning ability is developed for the treatment of hyperuricemia. The uricase and platinum nanoparticles (PtNPs) are closely confined in the pores of mesoporous silica nanoparticles and encapsulated within a silica defense layer to form a tandem catalytic system. This artificial metalloenzyme keeps a high uric acid (UA) degradation activity, as well as a strong resistance capability toward various insults, such as pH, high temperature, and protease. Besides, the H2O2 produced by UA can be simultaneously eliminated by the PtNPs, resulting in significant improvement on the mammalian cell viability. In vivo studies display prominent therapy effect and no obvious side effects during the treatment of hyperuricemia mice using this artificial metalloenzyme. These results provide new insights into development of efficient and friendly enzyme replacement therapy.
Plasmonic Nanowire‐Enhanced Upconversion Luminescence for Anticounterfeit Devices
Authors: Park Kisun , Jung Kinam , Kwon Seok Joon , Jang Ho Seong , Byun Dongjin , Han Il Ki , Ko Hyungduk
Published: September 2016

A novel, efficient, cost‐effective, and high‐level security performance anticounterfeit device achieved by plasmonic‐enhanced upconversion luminescence (UCL) is demonstrated. The plasmonic architecture consists of the randomly dispersed Ag nanowires (AgNWs) network, upconversion nanoparticles (UCNPs) monolayer, and metal film, in which the UCL is enhanced by a few tens, compared to reference sample, becuase the plasmonic modes lead to the concentration of the incident near infrared (NIR) light in the UCNPs monolayer. In the configuration, both the localized surface plasmons (LSPs) around the metallic nanostructures and gap plasmon polaritons (GPPs) confined in the UCNPs monolayer, significantly contribute to the UCL enhancement. The UCL enhancement mechanism resulting from enhanced NIR absorption, boosted internal quantum process, and formation of strong plasmonic hot spots in the plasmonic architecture is analyzed theoretically and numerically. More interestingly, a proof‐of‐concept anticounterfeit device using the plasmonic‐enhanced UCL is proposed, through which a nonreusable and high‐level cost‐effective security device protecting the genuine products is realized.
Nitrogen‐Doped Graphene Ribbon Assembled Core–Sheath MnO@Graphene Scrolls as Hierarchically Ordered 3D Porous Electrodes for Fast and Durable Lithium Storage
Authors: Zhang Yun , Chen Penghui , Gao Xu , Wang Bo , Liu Heng , Wu Hao , Liu Huakun , Dou Shixue
Published: September 2016

Graphene scroll is an emerging 1D tubular form of graphitic carbon that has potential applications in electrochemical energy storage. However, it still remains a challenge to composite graphene scrolls with other nanomaterials for building advanced electrode configuration with fast and durable lithium storage properties. Here, a transition‐metal‐oxide‐based hierarchically ordered 3D porous electrode is designed based on assembling 1D core–sheath MnO@N‐doped graphene scrolls with 2D N‐doped graphene ribbons. In the resulting architecture, porous MnO nanowires confined in tubular graphene scrolls are mechanically isolated but electronically well‐connected, while the interwoven graphene ribbons offer continuous conductive paths for electron transfer in all directions. Moreover, the elastic graphene scrolls together with enough internal voids are able to accommodate the volume expansion of the enclosed MnO. Because of these merits, the as‐built electrode manifests ultrahigh rate capability (349 mAh g−1 at 8.0 A g−1; 205 mAh g−1 at 15.0 A g−1) and robust cycling stability (812 mAh g−1 remaining after 1000 cycles at 2.0 A g−1) and is the most efficient MnO‐based anode ever reported for lithium‐ion batteries. This unique multidimensional and hierarchically ordered structure design is believed to hold great potential in generalizable synthesis of graphene scrolls composited with oxide nanowires for mutifuctional energy storage.
Iodide/tert‐Butyl Hydroperoxide‐Mediated Benzylic C–H Sulfonylation and Peroxidation of Phenol Derivatives
Authors: Yang Wen‐Chao , Dai Peng , Luo Kai , Wu Lei
Published: September 2016

We disclose here the first iodine/tert‐butyl hydroperoxide (I2/TBHP)‐mediated benzylic C–H sulfonylation of phenol derivatives. This new methodology provides an economic, operationally simple and metal‐free approach toward C(sp3)–S bond formation with medium to excellent yields at room temperature. Moreover, a novel sulfonylative and peroxidative bifunctionalization of phenol derivatives was also achieved by changing the amount of the oxidant. The reaction mechanism is exemplified via a radical pathway.

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Iron(III)‐Catalyzed Peroxide‐Mediated C‐3 Functionalization of Flavones
Authors: Mir Bilal Ahmad , Banerjee Arghya , Santra Sourav Kumar , Rajamanickam Suresh , Patel Bhisma K.
Published: September 2016

An iron(III)‐catalyzed C‐3 functionalization of flavones has been achieved using tert‐butyl peroxybenzoate (TBPB)/potassium persulphate (K2S2O8) oxidant combinations with a suitable solvent. In the presence of iron(III)/tert‐butyl peroxybenzoate/potassium persulphate, the reaction of flavones in cycloalkanes afforded exclusive C‐3 cycloalkylation via C
–C
coupling, whereas the solvent N,N‐dialkylformamide provided C‐3 amidation via C
–C
coupling. Under identical reaction conditions just by switching the solvent to chlorobenzene, C‐3 methylated flavones were obtained where tert‐butyl peroxybenzoate (TBPB) served as the source of the methyl group.

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Phenotype and genotype in 52 patients with Rubinstein–Taybi syndrome caused by EP300 mutations
Authors: Fergelot Patricia , Van Belzen Martine , Van Gils Julien , Afenjar Alexandra , Armour Christine M. , Arveiler Benoit , Beets Lex , Burglen Lydie , Busa Tiffany , Collet Marie , Deforges Julie , de Vries Bert B. A. , Dominguez Garrido Elena , Dorison Nathalie , Dupont Juliette , Francannet Christine , Garciá‐Minaúr Sixto , Gabau Vila Elisabeth , Gebre‐Medhin Samuel , Gener Querol Blanca , Geneviève David , Gérard Marion , Gervasini Cristina Giovanna , Goldenberg Alice , Josifova Dragana , Lachlan Katherine , Maas Saskia , Maranda Bruno , Moilanen Jukka S. , Nordgren Ann , Parent Philippe , Rankin Julia , Reardon Willie , Rio Marlène , Roume Joëlle , Shaw Adam , Smigiel Robert , Sojo Amaia , Solomon Benjamin , Stembalska Agnieszka , Stumpel Constance , Suarez Francisco , Terhal Paulien , Thomas Simon , Touraine Renaud , Verloes Alain , Vincent‐Delorme Catherine , Wincent Josephine , Peters Dorien J. M. , Bartsch Oliver , Larizza Lidia , Lacombe Didier , Hennekam Raoul C.
Published: September 2016

Rubinstein–Taybi syndrome (RSTS) is a developmental disorder characterized by a typical face and distal limbs abnormalities, intellectual disability, and a vast number of other features. Two genes are known to cause RSTS, CREBBP in 60% and EP300 in 8–10% of clinically diagnosed cases. Both paralogs act in chromatin remodeling and encode for transcriptional co‐activators interacting with >400 proteins. Up to now 26 individuals with an EP300 mutation have been published. Here, we describe the phenotype and genotype of 42 unpublished RSTS patients carrying EP300 mutations and intragenic deletions and offer an update on another 10 patients. We compare the data to 308 individuals with CREBBP mutations. We demonstrate that EP300 mutations cause a phenotype that typically resembles the classical RSTS phenotype due to CREBBP mutations to a great extent, although most facial signs are less marked with the exception of a low‐hanging columella. The limb anomalies are more similar to those in CREBBP mutated individuals except for angulation of thumbs and halluces which is very uncommon in EP300 mutated individuals. The intellectual disability is variable but typically less marked whereas the microcephaly is more common. All types of mutations occur but truncating mutations and small rearrangements are most common (86%). Missense mutations in the HAT domain are associated with a classical RSTS phenotype but otherwise no genotype–phenotype correlation is detected. Pre‐eclampsia occurs in 12/52 mothers of EP300 mutated individuals versus in 2/59 mothers of CREBBP mutated individuals, making pregnancy with an EP300 mutated fetus the strongest known predictor for pre‐eclampsia. © 2016 Wiley Periodicals, Inc.
The Construction of Anhydro Monosaccharides
Authors: Xie Weijia , Lin Aijun , Xu Jinyi , Wu Xiaoming
Published: September 2016

Anhydro monosaccharide is a specific and distinctive category of carbohydrates, which is found in many naturally derived and artificial bioactive substrates. In the field of organic chemistry, some anhydro sugars can be used as common synthons to construct different carbohydrate structures. The development of efficient methodologies for the construction of various anhydro sugar fragments is very important in carbohydrate chemistry, which has attracted considerable attention in the past few years. This review mainly covers the development of new synthetic methods since 2000 and gives an overview of the development in the formation of anhydro monosaccharide structures. It systematically summarizes all methods to establish an intramolecular ether bridge in furanose and pyranose structures, which are the most commonly used monosaccharide fragments in carbohydrate chemistry.
Organocatalyzed Assembly of Chlorinated Quaternary Stereogenic Centers
Authors: Gómez‐Martínez Melania , Alonso Diego A. , Pastor Isidro M. , Guillena Gabriela , Baeza Alejandro
Published: September 2016

The catalytic asymmetric construction of chiral quaternary stereocenters is a continual area of research for organic chemists. In this sense, when a chlorine atom is introduced to a quaternary stereocenter, the synthetic difficulty of the resulting molecule increases along with its significance. This is true not only because of the intrinsic interest in such chlorinated molecules but also because they are highly valuable chiral building blocks in organic synthesis, as they can be converted into more complex molecules by a SN2 displacement reaction. Among the different strategies to create chlorinated quaternary stereogenic centers, organocatalysis has played a pivotal role over the past decade. In this review, a comprehensive analysis of such organocatalyzed transformations with a focus on the α‐chlorination of carbonyl compounds is presented.
Physiology of freezing of gait
Authors: Snijders Anke H. , Takakusaki Kaoru , Debu Bettina , Lozano Andres M. , Krishna Vibhor , Fasano Alfonso , Aziz Tipu Z. , Papa Stella M. , Factor Stewart A. , Hallett Mark
Published: September 2016

Freezing of gait (FOG) is a common and debilitating, but largely mysterious, symptom of Parkinson disease. In this review, we will discuss the cerebral substrate of FOG focusing on brain physiology and animal models. Walking is a combination of automatic movement processes, afferent information processing, and intentional adjustments. Thus, normal gait requires a delicate balance between various interacting neuronal systems. To further understand gait control and specifically FOG, we will discuss the basic physiology of gait, animal models of gait disturbance including FOG, alternative etiologies of FOG, and functional magnetic resonance studies investigating FOG. The outcomes of these studies point to a dynamic network of cortical areas such as the supplementary motor area, as well as subcortical areas such as the striatum and the mesencephalic locomotor region including the pedunculopontine nucleus (PPN). Additionally, we will review PPN (area) stimulation as a possible treatment for FOG, and ponder whether PPN stimulation truly is the right step forward. Ann Neurol 2016;80:644–659
An Integrated Chemical Cytometry Method: Shining a Light on Akt Activity in Single Cells
Authors: Mainz Emilie R. , Wang Qunzhao , Lawrence David S. , Allbritton Nancy L.
Published: September 2016

Tools to evaluate oncogenic kinase activity in small clinical samples have the power to guide precision medicine in oncology. Existing platforms have demonstrated impressive insights into the activity of protein kinases, but these technologies are unsuitable for the study of kinase behavior in large numbers of primary human cells. To address these limitations, we developed an integrated analysis system that utilizes a light‐programmable, cell‐permeable reporter deliverable simultaneously to many cells. The reporter's ability to act as a substrate for Akt, a key oncogenic kinase, was masked by a 2‐4,5‐dimethoxy 2‐nitrobenzyl (DMNB) moiety. Upon exposure to ultraviolet light and release of the masking moiety, the substrate sequence enabled programmable reaction times within the cell cytoplasm. When coupled to automated single‐cell capillary electrophoresis, statistically significant numbers of primary human cells were readily evaluated for Akt activity.
Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin‐Catalyzed Doyle–Kirmse Reaction
Authors: Tyagi Vikas , Sreenilayam Gopeekrishnan , Bajaj Priyanka , Tinoco Antonio , Fasan Rudi
Published: September 2016

The first example of a biocatalytic [2,3]‐sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle–Kirmse reaction) is reported. Engineered variants of sperm whale myoglobin catalyze this synthetically valuable C−C bond‐forming transformation with high efficiency and product conversions across a variety of sulfide substrates (e.g., aryl‐, benzyl‐, and alkyl‐substituted allylic sulfides) and α‐diazo esters. Moreover, the scope of this myoglobin‐mediated transformation could be extended to the conversion of propargylic sulfides to give substituted allenes. Active‐site mutations proved effective in enhancing the catalytic efficiency of the hemoprotein in these reactions as well as modulating the enantioselectivity, resulting in the identification of the myoglobin variant Mb(L29S,H64V,V68F), which is capable of mediating asymmetric Doyle–Kirmse reactions with an enantiomeric excess up to 71 %. This work extends the toolbox of currently available biocatalytic strategies for the asymmetric formation of carbon–carbon bonds.
Transforming LiTMP Lithiation of Challenging Diazines through Gallium Alkyl Trans‐Metal‐Trapping
Authors: Uzelac Marina , Kennedy Alan R. , Hevia Eva , Mulvey Robert E.
Published: September 2016

This study establishes a new trans‐metal‐trapping (TMT) procedure based on a mixture of LiTMP (the base) and tris(trimethylsilylmethyl)gallium [Ga(CH2SiMe3)3, GaR3] (the trap) that, operating in a tandem manner, is effective for the regioselective deprotonation of sensitive diazines in hydrocarbon solution, as illustrated through reactions of pyrazine, pyridazine, and pyrimidine, as well as through the N‐S heterocycle benzothiazole. The metallo‐activated complexes of all of these compounds were isolated and structurally defined.
Hidden Hydride Transfer as a Decisive Mechanistic Step in the Reactions of the Unligated Gold Carbide [AuC]+ with Methane under Ambient Conditions
Authors: Li Jilai , Zhou Shaodong , Schlangen Maria , Weiske Thomas , Schwarz Helmut
Published: September 2016

The reactivity of the cationic gold carbide [AuC]+ (bearing an electrophilic carbon atom) towards methane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR‐MS). The product pairs generated, that is, Au+/C2H4, [Au(C2H2)]+/H2, and [C2H3]+/AuH, point to the breaking and making of C−H, C−C, and H−H bonds under single‐collision conditions. The mechanisms of these rather efficient reactions have been elucidated by high‐level quantum‐chemical calculations. As a major result, based on molecular orbital and NBO‐based charge analysis, an unprecedented hydride transfer from methane to the carbon atom of [AuC]+ has been identified as a key step. Also, the origin of this novel mechanistic scenario has been addressed. The mechanistic insights derived from this study may provide guidance for the rational design of carbon‐based catalysts.
BOIMPYs: Rapid Access to a Family of Red‐Emissive Fluorophores and NIR Dyes
Authors: Patalag Lukas J. , Jones Peter G. , Werz Daniel B.
Published: September 2016

A fundamental, highly fluorescent, and easily accessible scaffold derived from the BODIPY core is reported. The use of benzimidazole as a bridging ligand at the meso position enables the binding of two BF2 units to provide sufficient rigidity and enhanced electron‐withdrawing strength. Absorption and emission events thus take place in the red (λ≈600 nm); the fluorescence quantum yields can reach unity (0.96) and show little dependence on solvent polarity. The synthetic route was shortened to two steps starting from commercially available precursors while the preparation is modular and tolerates various pyrrole and benzimidazole moieties. Fluoride replacement by propynyl groups, various halogenations, as well as Knoevenagel‐type condensations were applied to extend the versatility of these new photostable fluorophores, which we termed BOIMPYs.
Understanding the Central Location of a Hexagonal Hole in a B36 Cluster
Authors: Liu Lei , Osorio Edison , Heine Thomas
Published: September 2016

The most stable form of a B36 cluster has a central hexagonal hole. Such an interesting finding has led to the possible synthesis of a 2D boron sheet by employing the B36 cluster as the building unit. Herein, a DFT study to investigate the reason for the central location of the hexagonal hole in the B36 cluster is presented. The results show that the B36 cluster with a central hexagonal hole is highly thermodynamically and kinetically stable. More importantly, such high stability is further understood through chemical bonding analysis.
Detecting the structure of marine atmospheric boundary layer over the Northern South China Sea by shipboard GPS sondes
Authors: Peng Shiqiu , Zhu Yuhang , Huang Ke , Ding Xuanru , Shi Rui , Wu Dongmei , Feng Yerong , Wang Dongxiao
Published: September 2016

Global Positioning System (GPS) sondes has been launched over the Northern South China Sea (NSCS) during the marine survey cruise each summer since 2006. These GPS‐sounding data provide a great opportunity to monitor the vertical structure of marine atmospheric boundary layer (MABL) which is very important to the high‐impact weather systems influencing the coastal regions. Our analysis on these GPS soundings reveals that the vertical structure of MABL over the NSCS is apparently correlated with the surface atmospheric stability. These MABL observations collected by GPS sondes are quite valuable for the forecasting of high‐impact weather systems in the coastal regions of the southern China.
From lignocellulosic metagenomes to lignocellulolytic genes: trends, challenges and future prospects
Authors: Batista‐García Ramón A. , del Rayo Sánchez‐Carbente María , Talia Paola , Jackson Stephen A. , O'Leary Niall D. , Dobson Alan D. W. , Folch‐Mallol Jorge Luis
Published: September 2016

Lignocellulose is the most abundant biomass on Earth with immense potential to act as a primary resource for the production of a range of compounds currently obtained from fossil fuel sources. However, lignocellulosic feedstocks remain largely underexploited due to the complex mixture of recalcitrant polymers present, whose structural features hinder access to the utilizable monosaccharide reservoir within cellulose. Various fungi and bacteria have been identified that can enzymatically decompose lignocellulose to its monomeric compounds for use as carbon sources. The investigation of such lignocellulolytic organisms has proven very useful in gaining primary insights into degradation processes and key microbial enzymes, but the established limitations of culture‐based approaches suggest that we have yet to understand the full range of lignocellulolytic mechanisms, likely expressed within natural systems. In this review, we focus on metagenomic approaches to study lignocellulose degradation from structural and functional perspectives, which may provide novel insights into this process in order to rationally design methods for the extraction of compounds from biomass that could enhance biorefinery efficiencies. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd
Biodiesel program in Brazil: learning curve over ten years (2005–2015)
Authors: Nogueira Luiz A.H. , Capaz Rafael S. , Souza Simone P. , Seabra Joaquim E.A.
Published: September 2016

The biodiesel blending mandate was launched at 2005 in Brazil, by a governmental program based mainly on sustainability concerns, especially toward social and environmental aspects. Since 2007, B7, i.e., 7% biodiesel in diesel, in volume terms, has been mandatory, and B10 is the next target. In this context, this paper aims to evaluate the biodiesel program along the ten years from 2005 to 2015 in Brazil, considering the evolution of the estimated costs and the auction prices intending to verify some tendency in a learning curve perspective. A decreasing tendency of the biodiesel production costs and prices was observed, with a reduction of the profit margin in recent years, suggesting a learning trend. The Progress Ratio (PR) of the whole period was 101.7%, but in the 2011–2015, it was estimated at 59.3%. Relevant technology changes in biodiesel production process were not verified, but the increased competitiveness in the market, the gains of scale of plant profiles, and mainly the decrease of soybean oil prices explain this evolution. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd
Evaluating side effects of nanoparticle‐mediated siRNA delivery to mesenchymal stem cells using next generation sequencing and enrichment analysis
Authors: Malcolm Dominic W. , Sorrells Janet E. , Van Twisk Daniel , Thakar Juilee , Benoit Danielle S. W.
Published: September 2016

RNA interference has immense potential to modulate cell functions. However, effective delivery of small interfering RNA (siRNA) while avoiding deleterious side effects has proven challenging. This study investigates both intended and unintended effects of diblock copolymer nanoparticle (NP) delivery of siRNA delivery to human mesenchymal stem cells (hMSC). Specifically, siRNA delivery was investigated at a range of NP‐siRNA:hMSC ratios with a focus on the effects of NP‐siRNA treatment on hMSC functions. Additionally, next generation RNA sequencing (RNAseq) was used with enrichment analysis to observe side effects in hMSC gene expression. Results show NP‐siRNA delivery is negatively correlated with hMSC density. However, higher NP‐siRNA:hMSC ratios increased cytotoxicity and decreased metabolic activity. hMSC proliferation was largely unaffected by NP‐siRNA treatment, except for a threefold reduction in hMSCs seeded at 4,000 cells/cm2. Flow cytometry reveals that apoptosis is a function of NP‐siRNA treatment time and seeding density; ∼14% of the treated hMSCs seeded at 8,000 cells/cm2 were annexin V+‐siRNA+ 24 hr after treatment, while 11% of the treated population was annexin V+‐siRNA−. RNAseq shows that NP‐siRNA treatment results in transcriptomic changes in hMSCs, while pathway analysis shows upregulation of apoptosis signaling and downregulation of metabolism, cell cycle, and DNA replication pathways, as corroborated by apoptosis, metabolism, and proliferation assays. Additionally, multiple innate immune signaling pathways such as toll‐like receptor, RIG‐I‐like receptor, and nuclear factor‐κB signaling pathways are upregulated. Furthermore, and consistent with traditional siRNA immune activation, cytokine–cytokine receptor signaling was also upregulated. Overall, this study provides insight into NP‐siRNA:hMSC ratios that are favorable for siRNA delivery. Moreover, NP‐siRNA delivery results in side effects across the hMSC transcriptome that suggest activation of the innate immunity that could alter MSC functions associated with their therapeutic potential.
Forensic clinical anatomy: A new field of study with application to medicolegal issues
Authors: Porzionato Andrea , Macchi Veronica , Stecco Carla , Loukas Marios , Tubbs R. Shane , De Caro Raffaele
Published: September 2016

Forensic clinical anatomy is a new practical application of the discipline of Clinical Anatomy for ascertaining and evaluating medicolegal questions. In particular, individual anatomy (normal anatomy, anatomical variations, age‐, disease‐, or surgery‐related modifications) can acquire significant relevance in various fields of legal medicine such as child abuse, sudden death, medical responsibility and/or liability, personal injury and damage. Anatomical data of forensic interest frequently arise from the correct application of methods of ascertainment; anatomical methods may then be required for further comprehensive analysis. The rigorous interpretation of anatomical data, derived from the ascertainment phase and analyzed on the basis of pertinent literature, can be pivotal for the correct application of evaluation criteria in various forensic contexts. Clin. Anat. 30:2–5, 2017. © 2016 Wiley Periodicals, Inc.
Electrochemical Monitoring of Hydrogen Sulfide Release from Single Cells
Authors: Hu Xue‐Bo , Liu Yan‐Ling , Zhang Hai‐Wei , Xiao Chong , Qin Yu , Duo Huan‐Huan , Xu Jia‐Quan , Guo Shan , Pang Dai‐Wen , Huang Wei‐Hua
Published: September 2016

Real‐time and in situ monitoring of H2S in biological systems has become crucial, but faces big challenges as H2S has been identified as an important endogenous gas signaling molecule. Herein, we prepare a poly(3,4‐ethylenedioxythiophene) (PEDOT)‐modified nanoporous gold (NPG) microelectrode for the electrochemical detection of H2S. The NPG framework possesses excellent conductivity, a 3D porous structure, and a large specific area. The PEDOT sensing film effectively retards electrode fouling during the detection, which ensures a stable response towards H2S over the range of interest. The synergetic properties of the NPG scaffold and the PEDOT sensing films endow the microelectrode with high sensitivity and a fast response, thus allowing H2S release from single cells to be monitored. This work represents the first step toward real‐time electrochemical monitoring of H2S from single cells, thereby potentially facilitating future studies to better understand the function of H2S in biological and pathological processes.
Kinetics of VIII and VII Sulfate Precipitation Processes in Negative Half‐Cell Electrolyte of the Vanadium Redox Flow Battery
Authors: Mousa Asem , Skyllas‐Kazacos Maria
Published: September 2016

The low‐temperature stability and precipitation behaviour of VIII and VII sulfate solutions are critical for the optimal operation of vanadium redox flow batteries. In this study, the kinetics of the VIII and VII sulfate precipitation processes have been studied at different temperatures and sulfate concentrations. Kinetic studies of the precipitation of stagnant vanadium(III) sulfate solutions followed a first‐order rate law with rate constants on the order of 0.007 h−1 and an activation energy of about 14.6 kJ mol−1. Stirring the solutions at low supersaturation causes a ten‐fold increase in the rate of precipitation and also resulted in a change in the precipitation mechanism from diffusion controlled to a surface reaction controlled mechanism with an activation energy of 37.0 kJ mol−1. Stagnant solutions at high supersaturation followed a second‐order rate law with an activation energy of 27.0 kJ mol−1 for the first 30 % of the precipitation process. The process becomes first order in the last 70 % with an activation energy of 14.3 kJ mol−1, indicating a change in the reaction mechanism to a diffusion‐controlled mechanism. Kinetic studies of the precipitation of vanadium(II) sulfate solutions showed that both stagnant and stirred solutions follow a first‐order rate law with a low activation energy (10.7 and 14.5 kJ mol−1, respectively). This indicates a diffusion‐controlled precipitation mechanism under both conditions.
An approach for simultaneous estimation of reaction kinetics and curve resolution from process and spectral data
Authors: Chen Weifeng , Biegler Lorenz T. , Muñoz Salvador García
Published: September 2016

Parameter estimation of reaction kinetics from spectroscopic data remains an important and challenging problem. This study describes a unified framework to address this challenge. The presented framework is based on maximum likelihood principles, nonlinear optimization techniques, and the use of collocation methods to solve the differential equations involved. To solve the overall parameter estimation problem, we first develop an iterative optimization‐based procedure to estimate the variances of the noise in system variables (eg, concentrations) and spectral measurements. Once these variances are estimated, we then determine the concentration profiles and kinetic parameters simultaneously. From the properties of the nonlinear programming solver and solution sensitivity, we also obtain the covariance matrix and standard deviations for the estimated kinetic parameters. Our proposed approach is demonstrated on 7 case studies that include simulated data as well as actual experimental data. Moreover, our numerical results compare well with the multivariate curve resolution alternating least squares approach.
The Uncommon Channel‐Based Ln‐MOFs for Highly Selective Fe3+ Detection and Superior Rhodamine B Adsorption
Authors: Xing Shanghua , Bing Qiming , Song Lifei , Li Guanghua , Liu Jingyao , Shi Zhan , Feng Shouhua , Xu Ruren
Published: September 2016

Two new isostructural 3D lanthanide–organic frameworks [H2N(Me)2] [Ln3(OH)(bpt)3(H2O)3] (DMF)2⋅(H2O)4 (1‐Ln; Ln=Sm and Eu) with a 1D channel (25 Å) have been successfully assembled from the rare trinuclear [Ln3(OH)(COO)9] clusters and biphenyl‐3,4′,5‐tricarboxylic acid (H3bpt) and exhibit high stability towards water in the pH range 3–10. MOF 1‐Eu is a promising luminescent probe for sensing Fe3+ in aqueous solution and is also selective towards rhodamine B (RhB) with a superior adsorption capacity of 735 mg g−1, which is the highest among the reported Ln‐MOFs for RhB removal so far. Periodic DFT calculations further confirmed the selective adsorption of rhodamine B over other dyes.
A phase 2 study of dalantercept, an activin receptor‐like kinase‐1 ligand trap, in patients with recurrent or metastatic squamous cell carcinoma of the head and neck
Authors: Jimeno Antonio , Posner Marshall R. , Wirth Lori J. , Saba Nabil F. , Cohen Roger B. , Popa Elizabeta C. , Argiris Athanassios , Grossmann Kenneth F. , Sukari Ammar , Wilson Dawn , Zhang Xiaosha , Sun Jade , Glasser Chad , Attie Kenneth M. , Sherman Matthew L. , Pandya Susan S. , Weiss Jared
Published: September 2016

BACKGROUND

Patients with platinum‐refractory, recurrent or metastatic squamous cell carcinoma of the head and neck (RM‐SCCHN) have limited options. Activin receptor‐like kinase 1 (ALK1) is a type I receptor of the transforming growth factor β superfamily expressed on activated endothelial cells. Dalantercept is an ALK1 receptor fusion protein that acts as a ligand trap to block signaling through ALK1 and inhibits stages of angiogenesis involved in blood vessel maturation and stabilization. In a phase 1 study, dalantercept demonstrated clinical activity in patients with RM‐SCCHN. The objective of the current study was to evaluate the activity of dalantercept in RM‐SCCHN.

METHODS

Forty‐six patients received dalantercept at doses of 80 mg (n = 2), 0.6 mg/kg (n = 13), or 1.2 mg/kg (n = 31) subcutaneously every 3 weeks. The primary endpoint was the overall response rate according to Response Evaluation Criteria in Solid Tumors (RECIST version 1.1). Secondary endpoints included progression‐free survival and overall survival, safety and tolerability, and pharmacokinetic and pharmacodynamic assessments.

RESULTS

Forty patients were evaluable for response (13 who received dalantercept 0.6 mg/kg and 27 who received dalantercept 1.2 mg/kg). The overall response rate was 5% (n = 2), and 35% of patients had stable disease; 44% of patients who received 1.2 mg/kg and 30.8% of those who received 0.6 mg/kg achieved disease control (partial response or stable disease). The median progression‐fee survival was 1.4 months (95% confidence interval, 1.3‐2.2 months), and the median overall survival was 7.1 months (95% confidence interval, 5.5‐11.1 months). Drug‐related adverse events (>15%) were anemia, fatigue, peripheral edema, headache, and hyponatremia.

CONCLUSIONS

In an unselected, heavily pretreated population of patients with RM‐SCCHN, dalantercept monotherapy resulted in a favorable safety profile but only modest dose‐dependent activity, and it did not meet the primary efficacy objective of the study. Cancer 2016;122:3641‐9. © 2016 American Cancer Society.
Current management and future directions in metastatic pancreatic adenocarcinoma
Authors: Varghese Anna M. , Lowery Maeve A. , Yu Kenneth H. , O'Reilly Eileen M.
Published: September 2016

Of the anticipated 50,000 individuals expected to be diagnosed with pancreatic cancer in 2016, the majority will have metastatic disease. Given the noncurative nature of advanced pancreatic adenocarcinoma, treatment is aimed at inducing disease regression, controlling symptom, and extending life. The last 5 years have been marked by advances in the treatment of metastatic pancreatic cancer, specifically the approval by the US Food and Drug Administration of 2 combination chemotherapy regimens and the widespread use of a third, which have reproducibly been shown to improve survival. Ongoing studies are building on these regimens along with targeted and immunotherapeutic agents. This article will review the current treatment standards and emerging targets for metastatic pancreatic cancer. Cancer 2016;122:3765–3775. © 2016 American Cancer Society.
On the Two‐Dimensional Muskat Problem with Monotone Large Initial Data
Authors: Deng Fan , Lei Zhen , Lin Fanghua
Published: September 2016

We consider the evolution of two incompressible, immiscible fluids with different densities in porous media, known as the Muskat problem [21], which in two dimensions is analogous to the Hele‐Shaw cell [24]. We establish, for a class of large and monotone initial data, the global existence of weak solutions. The proof is based on a local well‐posedness result for the initial data with certain specific asymptotics at spatial infinity and a new maximum principle for the first derivative of the graph function.© 2016 Wiley Periodicals, Inc.
Fast Water Relaxation through One‐Dimensional Channels by Rapid Energy Transfer
Authors: Ohba Tomonori , Ideta Keiko , Hata Koichiro , Yoon Seong‐Ho , Miyawaki Jin , Hata Kenji
Published: September 2016

Water in carbon nanotubes is surrounded by hydrophobic carbon surfaces and shows anomalous structural and fast transport properties. However, the dynamics of water in hydrophobic nanospaces is only phenomenologically understood. In this study, water dynamics in hydrophobic carbon nanotubes is evaluated based on water relaxation using nuclear magnetic resonance spectroscopy and molecular dynamics simulations. Extremely fast relaxation (0.001 s) of water confined in carbon nanotubes of 1 nm in diameter on average is observed; the relaxation times of water confined in carbon nanotubes with an average diameter of 2 nm (0.40 s) is similar to that of bulk water (0.44 s). The extremely fast relaxation time of water confined in carbon nanotubes with an average diameter of 1 nm is a result of frequent energy transfer between water and carbon surfaces. Water relaxation in carbon nanotubes of average diameter 2 nm is slow because of the limited number of collisions between water molecules. The dynamics of interfacial water can therefore be controlled by varying the size of the hydrophobic nanospace.
Phase formation in molten system (Na/K)2O‐TiO2‐P2O5. Crystal structures of NASICON and langbeinite‐related phosphates (K/Na)1+xTi2(PO4)3 (x = 0 and 0.357)
Authors: Strutynska Nataliia , Bondarenko Marina , Slobodyanik Nikolay , Baumer Vyacheslav , Zatovsky Igor , Bychkov Kostyantin , Puzan Anna
Published: September 2016

Crystallization of high temperature self‐flux of system Na2O‐K2O‐TiO2‐P2O5 was investigated at different molar ratios (Na+K)/P = 0.9; 1.0 or 1.2 and Na/K = 1.0 or 2.0 over the temperature range 1000–650°C. The conditions of formation of complex phosphates K0.10Na0.90Ti2(PO4)3 (NASICON‐related) and K0.877Na0.48TiІІІ0.357TiІV1.643(PO4)3 (langbeinite‐related) have been established. The new obtained compounds were investigated using FTIR‐spectroscopy, powder and single crystal X‐ray diffraction and optical microscopy methods. The influence of alkaline metal nature on the structure formation of complex phosphates in the high temperature self‐fluxes is discussed.
Recent experimental and theoretical studies on protein crystallization
Authors: Nanev Christo N.
Published: September 2016

Crystals are required to determine three‐dimensional structures of proteins and other bio‐molecules via X‐ray diffraction. This is the prime cause for the keen interest in protein crystallization. Recently published experimental and theoretical studies on protein crystal nucleation and growth are reviewed, and the prospects of protein‐based crystalline pharmaceuticals mass‐production are considered. A new insight into protein crystal nucleation is presented from a physical perspective. It refers to modeling nuclei number density as a definite (curved) surface where each point has two coordinates, supersaturation and time. In doing so, theoretical S‐shaped dependences of nuclei number densities on both supersaturation and time are found. These dependences are confirmed experimentally by plotting insulin crystal nucleation data. Growth of protein crystals of narrow size distribution is monitored to establish crystal polydispersity cause. Ostwald ripening is considered as a post‐growth stage of the crystallization process.
Amplitude and phase dynamics of noisy oscillators
Authors: Bonnin Michele
Published: September 2016

A description in terms of phase and amplitude variables is given for nonlinear oscillators subject to white Gaussian noise described by Itô stochastic differential equations. The stochastic differential equations derived for the amplitude and the phase are rigorous, and their validity is not limited to the weak noise limit. It is shown that if Floquet vectors are used, then in the neighborhood of a limit cycle the phase variable coincides with the asymptotic phase defined through isochrons. Two techniques for the analysis of the phase and amplitude equations are discussed, that is, asymptotic expansion method and a phase reduction procedure based on projection operators technique. Formulas for the expected angular frequency, expected oscillation amplitude, and amplitude variance are derived using Itô calculus. Copyright © 2016 John Wiley & Sons, Ltd.
Extraction‐spectrophotometric determination of tris(2‐chloroethyl)amine using phthaleins
Authors: Rozsypal Tomas , Halamek Emil
Published: September 2016

Procedures for the extraction‐spectrophotometric determination of tris(2‐chloroethyl)amine, an alkylating agent known as a drug as well as a chemical warfare agent (nitrogen mustard HN‐3), with 7 acid‐base indicators of a triphenylmethane lactone type, phthaleins, were developed. Representatives of phthaleins without an oxygen bridge (thymolphthalein, o‐cresolphthalein, naphtholphthalein) and with an oxygen bridge (fluorescein, 2',7'‐dichlorofluorescein, eosin B and eosin Y) were used. The methods were based on the formation of ion pair complexes. Chloroform was used as a non‐polar solvent for an extraction. The conditions to determine were optimized for the optimal pH of the buffer and the concentration of a phthalein as a reagent. The dependence on the reaction time in a water phase and the stoichiometry of extraction products were studied. The detection limits and the limits of the determination of separate procedures and conditional extraction constants were determined. Comparison with the spectrophotometric method of the group determination of alkyl halides and acyl halides using alkaline ethanol‐water solution of thymolphthalein, the so‐called T‐135 agent, was conducted. While studying the selectivity, the possible interference of bis(2‐chloroethyl)sulphide and 3 nitrogen mustards in the proposed procedures were verified. Copyright © 2016 John Wiley & Sons, Ltd.
Xanthine oxidase inhibition for the treatment of cardiovascular disease: an updated systematic review and meta‐analysis
Authors: Zhang Jufen , Dierckx Riet , Mohee Kevin , Clark Andrew L. , Cleland John G.
Published: September 2016

Background

Previous studies have shown that xanthine oxidase inhibitors (XOI) might improve outcome for patients with cardiovascular disease. However, more evidence is required.

Methods and results

We published a meta‐analysis of trials conducted before 2014 examining the effects of XOI on mortality in patients with cardiovascular disease. At least two further trials (N = 323 patients) have since been published. Accordingly, we repeated our analysis after a further search for randomized controlled trials of XOI in PubMed/MEDLINE, EMBASE, and Cochrane Databases. We identified eight relevant trials with 1031 patients. The average age of the patients was 61 years and 68% were men (one study did not report gender). There were 57 deaths in these eight trials, 26 in those assigned to XOI, and 31 in those assigned to the control. The updated meta‐analysis could not confirm a reduction in mortality for patients assigned to XOI compared with placebo (odds ratio 0.84) but 95% confidence intervals were wide (0.48–1.47).

Conclusions

This updated meta‐analysis does not suggest that XOI exert a large reduction in mortality but also cannot exclude the possibility of substantial harm or benefit.