bluuebunny/crossref_metadata_2025 huggingface dataset:
Homoleptic Phosphaalkyne Complexes of Silver(I)
Authors: Rummel Eva‐Maria , Mastrorilli Piero , Todisco Stefano , Latronico Mario , Balázs Gábor , Virovets Alexander V. , Scheer Manfred
Published: September 2016

By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC12F15}3], [Al{OC(CF3)3}4]), two phosphaalkynes could be coordinated side‐on to a bare silver(I) center to form the unprecedented homoleptic complexes [Ag(η2‐P≡CtBu)2][FAl{OC12F15}3] (1) and [Ag(η2‐P≡CtBu)2][Al{OC(CF3)3}4] (2). DFT calculations show that the perpendicular arrangement in 1 is the minimum energy structure of the coordination of the two phosphaalkynes to a silver atom, whereas for 2 a unique square‐planar coordination mode of the phosphaalkynes at Ag+ was found. Reactions with donor molecules yield the trigonally planar coordinated silver salts [((CH3)2CO)Ag(η2‐P≡CtBu)2][FAl{OC12F15}3] (3) and [(C7H8)2Ag(η2‐P≡CtBu)][FAl{OC12F15}3] (4). All of the compounds were comprehensively characterized in solution and in the solid state.
Synthesis of a Ferrolite: A Zeolitic All‐Iron Framework
Authors: Latshaw Allison M. , Chance W. Michael , Morrison Gregory , zur Loye Karl D. , Wilkins Branford O. , Smith Mark D. , Whitfield Pamela S. , Kirkham Melanie J. , Stoian Sebastian A. , zur Loye Hans‐Conrad
Published: September 2016

Crystals of the first sodalite‐type zeolite containing an all‐iron framework, a ferrolite, Ba8(Fe12O24)Nay(OH)6⋅x H2O, were synthesized using the hydroflux method in nearly quantitative yield. Ba8(Fe12O24)Nay(OH)6⋅x H2O crystallizes in the cubic space group
with a=10.0476(1) Å. Slightly distorted FeO4 tetrahedra are linked to form Fe4O4 and Fe6O6 rings, which in turn yield channels and internal cavities that are characteristic of the sodalite structure. Barium, sodium, and hydroxide ions and water molecules are found in the channels and provide charge balance. Magnetic measurements indicate that the ferrolite exhibits magnetic order up to at least 700 K, with the field‐cooled and zero‐field‐cooled curves diverging. Analysis of the 57Fe Mössbauer spectra revealed two spectral components that have equal spectral areas, indicating the presence of two subsets of iron centers in the structure. Dehydrated versions of the ferrolite were also prepared by heating the sample.
Extremely Active Organocatalysts Enable a Highly Enantioselective Addition of Allyltrimethylsilane to Aldehydes
Authors: Kaib Philip S. J. , Schreyer Lucas , Lee Sunggi , Properzi Roberta , List Benjamin
Published: September 2016

The enantioselective allylation of aldehydes to form homoallylic alcohols is one of the most frequently used carbon–carbon bond‐forming reaction in chemical synthesis and, for several decades, has been a testing ground for new asymmetric methodology. However, a general and highly enantioselective catalytic addition of the inexpensive, nontoxic, air‐ and moisture‐stable allyltrimethylsilane to aldehydes, the Hosomi–Sakurai reaction, has remained elusive. Reported herein is the design and synthesis of a highly acidic imidodiphosphorimidate motif (IDPi), which enables this transformation, thus converting various aldehydes with aromatic and aliphatic groups at catalyst loadings ranging from 0.05 to 2.0 mol % with excellent enantioselectivities. Our rationally constructed catalysts feature a highly tunable active site, and selectively process small substrates, thus promising utility in various other challenging chemical reactions.
Chemoselective Reduction of Tertiary Amides to Amines Catalyzed by Triphenylborane
Authors: Mukherjee Debabrata , Shirase Satoru , Mashima Kazushi , Okuda Jun
Published: September 2016

Triphenylborane (BPh3) was found to catalyze the reduction of tertiary amides with hydrosilanes to give amines under mild condition with high chemoselectivity in the presence of ketones, esters, and imines. N,N‐Dimethylacrylamide was reduced to provide the α‐silyl amide. Preliminary studies indicate that the hydrosilylation catalyzed by BPh3 may be mechanistically different from that catalyzed by the more electrophilic B(C6F5)3.
The Mechanical Strength of a Mechanical Bond: Sonochemical Polymer Mechanochemistry of Poly(catenane) Copolymers
Authors: Lee Bobin , Niu Zhenbin , Craig Stephen L.
Published: September 2016

Topological molecular connections and structures, including physical entanglements in polymer networks, knots along polymer chains, and rotaxanes in sliding ring gels, have important consequences for the physical properties of polymeric materials. Often these topologies contribute through their ability to bear mechanical stress, but experimental measures of their relative mechanical strength are rare. Here, we use sonochemical polymer mechanochemistry to assess the relative mechanical strength of a multicatenane copolymer relative to copolymers of cyclic and linear analogs. The relative mechanical strengths are obtained by comparing the limiting molecular weights (Mlim) and contour lengths (Llim) of the polymers under pulsed ultrasound of their dilute solutions. The values of Mlim and Llim, and thus the inferred mechanical strengths of the polymers, are effectively identical. The mechanical bonds of the catenanes are therefore as strong, or stronger, mechanically as the covalent bonds along the polymer backbone.
Uni‐Directional Transportation on Peristome‐Mimetic Surfaces for Completely Wetting Liquids
Authors: Li Chuxin , Li Ning , Zhang Xinshi , Dong Zhichao , Chen Huawei , Jiang Lei
Published: September 2016

Liquid uni‐directional transport on solid surface without energy input would advance a variety of applications, such as in bio‐fluidic devices, self‐lubrication, and high‐resolution printing. Inspired by the liquid uni‐directional transportation on the peristome surface of Nepenthes alata, here, we fabricated a peristome‐mimicking surface through high‐resolution stereo‐lithography and demonstrated the detailed uni‐directional transportation mechanism from a micro‐scaled view visualized through X‐ray microscopy. Significantly, an overflow‐controlled liquid uni‐directional transportation mechanism is proposed and demonstrated. Unlike the canonical predictions for completely wetting liquids spreading symmetrically on a high‐energy surface, liquids with varied surface tensions and viscosities can spontaneously propagate in a single preferred direction and pin in all others. The fundamental understanding gained from this robust system enabled us to tailor advanced micro‐computerized tomography scanning and stereo‐lithography fabrication to mimic natural creatures and construct a wide variety of fluidic machines out of traditional materials.
Redox Non‐Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond
Authors: Pearce Adam J. , Cassabaum Alyssa A. , Gast Grace E. , Frontiera Renee R. , Tonks Ian A.
Published: September 2016

The synthesis of the first terminal Group 9 hydrazido(2‐) complex, Cp*IrN(TMP) (6) (TMP=2,2,6,6‐tetramethylpiperidine) is reported. Electronic structure and X‐ray diffraction analysis indicate that this complex contains an Ir−N triple bond, similar to Bergman's seminal Cp*Ir(NtBu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non‐innocent reactivity owing to the presence of the Nβ lone pair. Treatment of 6 with MeI results in electron transfer from Nβ to Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally IrIII metal center through a hydrazido(2−)/isodiazene valence tautomerization.
Synthesis of 1,3‐Cycloalkadienes from Cycloalkenes: Unprecedented Reactivity of Oxoammonium Salts
Authors: Nagasawa Shota , Sasano Yusuke , Iwabuchi Yoshiharu
Published: September 2016

Few methods allow for the direct conversion of cycloalkenes into cycloalkadienes with high chemo‐ and regioselectivity. Herein, we report a convenient one‐pot process for this transformation that involves the unprecedented N‐preferential group transfer of N‐oxoammonium salts to cycloalkenes, followed by Cope elimination, to afford cycloalkadienes at room temperature and pressure.
RNA–DNA Chimeras in the Context of an RNA World Transition to an RNA/DNA World
Authors: Gavette Jesse V. , Stoop Matthias , Hud Nicholas V. , Krishnamurthy Ramanarayanan
Published: September 2016

The RNA world hypothesis posits that DNA and proteins were later inventions of early life, or the chemistry that gave rise to life. Most scenarios put forth for the emergence of DNA assume a clean separation of RNA and DNA polymer, and a smooth transition between RNA and DNA. However, based on the reality of “clutter” and lack of sophisticated separation/discrimination mechanisms in a protobiological (and/or prebiological) world, heterogeneous RNA–DNA backbone containing chimeric sequences could have been common—and have not been fully considered in models transitioning from an RNA world to an RNA–DNA world. Herein we show that there is a significant decrease in Watson–Crick duplex stability of the heterogeneous backbone chimeric duplexes that would impede base‐pair mediated interactions (and functions). These results point to the difficulties for the transition from one homogeneous system (RNA) to another (RNA/DNA) in an RNA world with a heterogeneous mixture of ribo‐ and deoxyribonucleotides and sequences, while suggesting an alternative scenario of prebiological accumulation and co‐evolution of homogeneous systems (RNA and DNA).
Separations: A Personal Account of Bowen Family Systems Theory
Authors: Palombi Martina
Published: September 2016

This paper is a personal account of my own family of origin research. It explores the impact of separations from parents, nuclear family, and extended family through a Bowen family systems theory perspective using concepts pertaining to Bowen theory such as chronic anxiety, differentiation of self, multigenerational family process, and the emotional system. An outline of the process of doing research in ‘vivo’ with my mother as well as conversations with my supervisor are included. Theoretical differences between individual and system models are discussed. A Bowen theoretical approach to the anxiety of separations is investigated. The efficacy of engaging in family of origin work and the effects of thinking systems is examined in light of how it assisted me to view family members, family system disturbances, and clients’ emotional systems more objectively.
Optimal scheduling of inspection times in a production process with a finite planning horizon
Authors: Chipoyera Honest
Published: September 2016

Inspection models applicable to a finite planning horizon are developed for the following lifetime distributions: uniform, exponential, and Weibull distribution. For a given lifetime distribution, maximization of profit is used as the sole optimization criterion for determining an optimal planning horizon over which a system may be operated as well as ideal inspection times. Illustrative examples (focusing on the uniform and Weibull distributions and using Mathematica programs) are given. For some situations, evenly spreading inspections over the entire planning horizon are seen to result in the attainment of desirable profit levels over a shorter planning horizon. Scope for further research is given as well. Copyright © 2016 John Wiley & Sons, Ltd.
Online calibration of an integrated framework for information‐based evacuation operations
Authors: Hsu Yu‐Ting , Peeta Srinivas
Published: September 2016

This study seeks to online calibrate the parameters of aggregate evacuee behavior models used in a behavior‐consistent information‐based control module for determining information strategies for real‐time evacuation operations. It enables the deployment of an operational framework for mass evacuation that integrates three aspects underlying an evacuation operation: demand (evacuee behavior), supply (network management), and disaster characteristics. To attain behavior‐consistency, the control module factors evacuees' likely responses to the disseminated information in determining information‐based control strategies. Hence, the ability of the behavior models to predict evacuees' likely responses is critical to the effectiveness of traffic routing by information strategies. The mixed logit structure is used for the aggregate behavior models to accommodate the behavioral heterogeneity across the population. An online calibration problem is proposed to calibrate the random parameters in the behavior models by using the least square estimator to minimize the gap between the predicted network flows and unfolding traffic dynamics. Background traffic, an important but rarely studied issue for modeling evacuation traffic, is also accounted for in the proposed problem. Numerical experiments are conducted to illustrate the importance of the calibration problem for addressing the system consistency issues and integrating the demand, supply, and disaster characteristics for more efficient evacuation operations. Copyright © 2016 John Wiley & Sons, Ltd.
Dyspraxia in ASD: Impaired coordination of movement elements
Authors: McAuliffe Danielle , Pillai Ajay S. , Tiedemann Alyssa , Mostofsky Stewart H. , Ewen Joshua B.
Published: September 2016

Children with autism spectrum disorders (ASD) have long been known to have deficits in the performance of praxis gestures; these motor deficits also correlate with social and communicative deficits. To date, the precise nature of the errors involved in praxis has not been clearly mapped out. Based on observations of individuals with ASD performing gestures, we hypothesized that the simultaneous execution of multiple movement elements is especially impaired in affected children. We examined 25 school‐aged participants with ASD and 25 age‐matched controls performing seven simultaneous gestures that required the concurrent performance of movement elements and nine serial gestures, in which all elements were performed serially. There was indeed a group × gesture‐type interaction (P < 0.001). Whereas both groups had greater difficulty performing simultaneous than serial gestures, children with ASD had a 2.6‐times greater performance decrement with simultaneous (vs. serial) gestures than controls. These results point to a potential deficit in the simultaneous processing of multiple inputs and outputs in ASD. Such deficits could relate to models of social interaction that highlight the parallel‐processing nature of social communication. Autism Res 2016,. © 2016 International Society for Autism Research, Wiley Periodicals, Inc. Autism Res 2017, 10: 648–652. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
Survival benefit of gastrectomy for gastric cancer with peritoneal carcinomatosis: a propensity score‐matched analysis
Authors: Geng Xiuwen , Liu Hao , Lin Tian , Hu Yanfeng , Chen Hao , Zhao Liying , Mou Tingyu , Qi Xiaolong , Yu Jiang , Li Guoxin
Published: September 2016

Peritoneal carcinomatosis (PC) is the most frequent pattern of metastasis in stage IV gastric cancer (GC). The study aims to investigate the efficacy of gastrectomy in GC with PC. Clinicopathological data of 518 stage IV GC patients were retrospectively collected in Nanfang Hospital. Among all cases, 312 GC patients with PC (without other site of metastasis) were eligible. Univariate and multivariate analyses were performed to identify the independent prognostic factors. Propensity score matching analysis was performed to balance the characteristics and treatment‐related factors. There was a significantly improved overall survival in gastrectomy group (148 patients) compared with nonresection group (164 patients) (P < 0.001). The 1‐year and 2‐year survival rates were 49.8% and 21.5% in gastrectomy group, whereas 28.8% and 9.7% in nonresection group, respectively. Further analysis showed that gastrectomy had also improved survival in P1 (P = 0.017) and P2 stage patients (P < 0.001), but not P3 stage (P = 0.495). The modality of gastrectomy plus chemotherapy plus hyperthermic intraperitoneal chemotherapy (HIPEC) showed an optimum survival. In addition, P3 disease, nongastrectomy, nonchemotherapy, non‐HIPEC, and age ≥ 60 years were independently associated with poor survival. The gastrectomy plus chemotherapy plus HIPEC modality showed a significant survival benefit for gastric adenocarcinoma patients, particularly in those with P1 and P2 diseases.
Late subannular aortic root rupture following transcatheter aortic valve implantation presenting as ST elevation myocardial infarction
Authors: Harper A.R. , Dawkins S. , Newton J.D.
Published: September 2016

Transcatheter aortic valve implantation (TAVI) has transformed the treatment of severe aortic stenosis. Here, we present a case of late aortic root rupture presenting as ST‐elevation myocardial infarction five weeks following successful TAVI. Aortic root rupture is a rare complication of TAVI, which occurs in ∼1% of procedures and usually arises during or soon after the procedure and is associated with high mortality (∼50%). Early recognition of late‐presenting complications related to TAVI, including aortic root rupture, is essential for specialists and nonspecialists. © 2016 Wiley Periodicals, Inc.
Independent predictors of retrograde failure in CTO‐PCI after successful collateral channel crossing
Authors: Suzuki Yoriyasu , Muto Makoto , Yamane Masahisa , Muramatsu Toshiya , Okamura Atsunori , Igarashi Yasumi , Fujita Tsutomu , Nakamura Shigeru , Oida Akitsugu , Tsuchikane Etsuo
Published: September 2016

Objectives

To evaluate factors for predicting retrograde CTO‐PCI failure after successful collateral channel crossing. Background: Successful guidewire/catheter collateral channel crossing is important for the retrograde approach in percutaneous coronary intervention (PCI) for chronic total occlusion (CTO).

Methods

A total of 5984 CTO‐PCI procedures performed in 45 centers in Japan from 2009 to 2012 were studied. The retrograde approach was used in 1656 CTO‐PCIs (27.7%). We investigated these retrograde procedures to evaluate factors for predicting retrograde CTO‐PCI failure even after successful collateral channel crossing.

Results

Successful guidewire/catheter collateral crossing was achieved in 77.1% (n = 1,276) of 1656 retrograde CTO‐PCI procedures. Retrograde procedural success after successful collateral crossing was achieved in 89.4% (n = 1,141). Univariate analysis showed that the predictors for retrograde CTO‐PCI failure were in‐stent occlusion (OR = 1.9829, 95%CI = 1.1783 – 3.3370 P = 0.0088), calcified lesions (OR = 1.9233, 95%CI = 1.2463 – 2.9679, P = 0.0027), and lesion tortuosity (OR = 1.5244, 95%CI = 1.0618 – 2.1883, P = 0.0216). On multivariate analysis, lesion calcification was an independent predictor of retrograde CTO‐PCI failure after successful collateral channel crossing (OR = 1.3472, 95%CI = 1.0614 – 1.7169, P = 0.0141).

Conclusions

The success rate of retrograde CTO‐PCI following successful guidewire/catheter collateral channel crossing was high in this registry. Lesion calcification was an independent predictor of retrograde CTO‐PCI failure after successful collateral channel crossing. Devices and techniques to overcome complex CTO lesion morphology, such as lesion calcification, are required to further improve the retrograde CTO‐PCI success rate. © 2016 Wiley Periodicals, Inc.
Palladium Supported on Metformin‐Functionalized Magnetic Polymer Nanocomposites: A Highly Efficient and Reusable Catalyst for the Suzuki–Miyaura Coupling Reaction
Authors: Yang Pengbo , Ma Rong , Bian Fengling
Published: September 2016

In this paper, a novel magnetically responsive nanocatalyst, Pd/Fe3O4@PMAA‐Met (PMAA=poly(methacrylic acid), Met=metformin), has been successfully prepared by immobilizing palladium on the surface of metformin‐functionalized magnetic polymer nanocomposites. This novel nanocatalyst was characterized by FTIR, XRD, TEM, X‐ray photoelectron spectroscopy (XPS), and vibrating sample magnetometry (VSM). The prepared nanocatalyst showed excellent catalytic activity for Suzuki–Miyaura coupling reactions of aryl halides (I, Br, Cl) with arylboronic acids even at palladium loadings of 0.01–0.0007 mol % and the turnover frequency (TOF) reached up to 125 714 h−1. The excellent activity of this Pd/Fe3O4@PMAA‐Met catalyst could be attributed to a “release and catch” catalytic mechanism as well as its nanometer size. This nanocatalyst could be simply separated with an external magnet and reused at least twelve times with excellent yields achieved.
Simulation of a Palm Fatty Acid Distillate‐Based Biodiesel Plant Using Homogeneous and Heterogeneous Catalysts
Authors: Heer Parminder K. K. S. , Gaikar Vilas G.
Published: September 2016

A continuous biodiesel production process from palm fatty acid distillate (PFAD) is simulated in Aspen Plus for process engineering aspects emphasizing the critical points in the entire process. The production process involves acid‐catalyzed hydrolysis of residual glycerides of PFAD to additional free fatty acids (FFAs), followed by esterification of the FFAs with methanol for methyl ester production, biodiesel purification, and finally methanol recovery. A two‐phase kinetic model was employed with detailed operating conditions for both, homogeneous and heterogeneous catalysts to design the reactors and critical process units. The operating costs of the process using both catalysts are evaluated.
Continuous and Intensified Laboratory Process Development at Clariant
Authors: Heitmann Dennis
Published: September 2016

The conversion of batch processes into continuous operating regimes offers various advantages in terms of safety, efficiency, product quality, and production costs. The industrial process development also has to be adapted for this purpose. In this essay, the focus will be drawn to the general approach of a process transfer from a batch process towards an intensified continuous process on laboratory scale at Clariant. In this context, process intensification means a holistic approach leading to substantially smaller, cleaner, and more efficient processes, which also result in better products.
Ultrasound‐Assisted Synthesis of Cu and Cu/Ni Nanoparticles on NaP Zeolite Support as Antibacterial Agents
Authors: Behin Jamshid , Shahryarifar Ali , Kazemian Hossein
Published: September 2016

Synthesis, characterization, and antibacterial properties of Cu and Cu/Ni nanoparticles loaded on NaP zeolite against Bacillus subtilis and Escherichia coli were investigated. Synthesis of Cu and Ni nanoparticles of the NaP substrate was carried out by conventional and sonochemical methods in ethylene glycol medium. A Box‐Behnken design of experiment was employed to analyze the influence of nanoparticle loading, Cu content of nanoparticles, and concentration of metallic salts solution on the antibacterial activity of the synthesized product. The synthesized samples provided an about one‐third higher activity against B. subtilis compared to E. coli. Ultrasonic irradiation significantly improved the antibacterial activity against E. coli and B. subtilis. Time‐ and concentration‐dependent bacterial tests of the synthesized sample under optimum conditions were performed with a central composite design of experiment.
Structure and diversity of retinal ganglion cells in steller's sculpin Myoxocephalus stelleri tilesius, 1811
Authors: Pushchin Igor
Published: September 2016

We studied the morphology and diversity of retinal ganglion cells in Steller's sculpin Myoxocephalus stelleri. The cells were retrogradely labeled with horseradish peroxidase and examined in retinal wholemounts. A sample of 123 cells were camera lucida‐drawn and digitized. A total of 18 structural parameters were estimated for each cell. The cells were classified using 10 clustering algorithms. The optimum solution was determined using silhouette analysis. It contained eight clusters and was based on three variables: dendritic field area, vitread stratification boundary, and stratification range. Kruskal–Wallis analysis of variance (ANOVA)‐on‐Ranks with post‐hoc Mann–Whitney U‐tests showed significant pairwise between‐cluster differences in two or more of the original variables. The present classification is compared with those proposed for other teleosts. J. Comp. Neurol. 525:1122–1138, 2017. © 2016 Wiley Periodicals, Inc.
HOXA5 localization in postnatal and adult mouse brain is suggestive of regulatory roles in postmitotic neurons
Authors: Lizen Benoit , Hutlet Bertrand , Bissen Diane , Sauvegarde Deborah , Hermant Maryse , Ahn Marie‐Thérèse , Gofflot Françoise
Published: September 2016

Hoxa5 is a member of the Hox gene family, which plays critical roles in successive steps of the central nervous system formation during embryonic and fetal development. Hoxa5 expression in the adult mouse brain has been reported, suggesting that this gene may be functionally required in the brain after birth. To provide further insight into the Hoxa5 expression pattern and potential functions in the brain, we have characterized its neuroanatomical profile from embryonic stages to adulthood. While most Hox mapping studies have been based solely on transcript analysis, we extended our analysis to HOXA5 protein localization in adulthood using specific antibodies. Our results show that Hoxa5 expression appears in the most caudal part of the hindbrain at fetal stages, where it is maintained until adulthood. In the medulla oblongata and pons, we detected Hoxa5 expression in many precerebellar neurons and in several nuclei implicated in the control of autonomic functions. In these territories, the HOXA5 protein is present solely in neurons, specifically in γ‐aminobutyric acid (GABA)ergic, glutamatergic, and catecholaminergic neurons. Finally, we also detected Hoxa5 transcripts, but not the HOXA5 protein, in the thalamus and the cortex, from postnatal stages to adult stages, and in the cerebellum at adulthood. We provide evidence that some larger variants of Hoxa5 transcripts are present in these territories. Our mapping analysis allowed us to build hypotheses regarding HOXA5 functions in the nervous system after birth, such as a potential role in the establishment and refinement/plasticity of precerebellar circuits during postnatal and adult life. J. Comp. Neurol. 525:1155–1175, 2017. © 2016 Wiley Periodicals, Inc.
Central neural alterations predominate in an insect model of nociceptive sensitization
Authors: Tabuena Dennis R. , Solis Allan , Geraldi Ken , Moffatt Christopher A. , Fuse Megumi
Published: September 2016

Many organisms respond to noxious stimuli with defensive maneuvers. This is noted in the hornworm, Manduca sexta, as a defensive strike response. After tissue damage, organisms typically display sensitized responses to both noxious or normally innocuous stimuli. To further understand this phenomenon, we used novel in situ and in vitro preparations based on paired extracellular nerve recordings and videography to identify central and peripheral nerves responsible for nociception and sensitization of the defensive behavior in M. sexta. In addition, we used the in vivo defensive strike response threshold assayed with von Frey filaments to examine the roles that N‐methyl‐D‐aspartate receptor (NMDAR) and hyperpolarization‐activated, cyclic nucleotide‐gated (HCN) channels play in this nociceptive sensitization using the inhibitors MK‐801 and AP5 (NMDAR), and ivabradine and ZD7288 (HCN). Using our new preparations, we found that afferent activity evoked by noxious pinch in these preparations was conveyed to central ganglia by axons in the anterior‐ and lateral‐dorsal nerve branches, and that sensitization induced by tissue damage was mediated centrally. Furthermore, sensitization was blocked by all inhibitors tested except the inactive isomer L‐AP5, and reversed by ivabradine both in vivo and in vitro. Our findings suggest that M. sexta's sensitization occurs through central signal amplification. Due to the relatively natural sensitization method and conserved molecular actions, we suggest that M. sexta may be a valuable model for studying the electrophysiological properties of nociceptive sensitization and potentially related conditions such as allodynia and hyperalgesia in a comparative setting that offers unique experimental advantages. J. Comp. Neurol. 525:1176–1191, 2017. © 2016 Wiley Periodicals, Inc.
A methodology for constraining power in finite element modeling of radiofrequency ablation
Authors: Jiang Yansheng , Possebon Ricardo , Mulier Stefaan , Wang Chong , Chen Feng , Feng Yuanbo , Xia Qian , Liu Yewei , Yin Ting , Oyen Raymond , Ni Yicheng
Published: September 2016

Radiofrequency ablation (RFA) is a minimally invasive thermal therapy for the treatment of cancer, hyperopia, and cardiac tachyarrhythmia. In RFA, the power delivered to the tissue is a key parameter. The objective of this study was to establish a methodology for the finite element modeling of RFA with constant power. Because of changes in the electric conductivity of tissue with temperature, a nonconventional boundary value problem arises in the mathematic modeling of RFA: neither the voltage (Dirichlet condition) nor the current (Neumann condition), but the power, that is, the product of voltage and current was prescribed on part of boundary. We solved the problem using Lagrange multiplier: the product of the voltage and current on the electrode surface is constrained to be equal to the Joule heating. We theoretically proved the equality between the product of the voltage and current on the surface of the electrode and the Joule heating in the domain. We also proved the well‐posedness of the problem of solving the Laplace equation for the electric potential under a constant power constraint prescribed on the electrode surface. The Pennes bioheat transfer equation and the Laplace equation for electric potential augmented with the constraint of constant power were solved simultaneously using the Newton‐Raphson algorithm. Three problems for validation were solved. Numerical results were compared either with an analytical solution deduced in this study or with results obtained by ANSYS or experiments. This work provides the finite element modeling of constant power RFA with a firm mathematical basis and opens pathway for achieving the optimal RFA power.
Arginine‐Assisted Formation of Hierarchical TiO2 Microspheres for Lithium‐Ion and Sodium‐Ion Battery Applications
Authors: Chang Yi‐Chun , Wang Yu‐Xuan , Lee Chi‐Young , Chiu Hsin‐Tien
Published: September 2016

A facile route was established to synthesize hierarchically structured high specific surface area (122 m2 g−1) TiO2 microspheres (diameter: 0.5–1 μm). In a heated Teflon‐coated stainless‐steel autoclave, titanium tetrabutoxide Ti(OBu)4, arginine, and absolute ethanol were reacted via the solvothermal reaction to generate the TiO2 precursor. The as‐formed precursor solid was further processed at 673 K under air to generate the TiO2 microspheres of nanosheets (thickness: 18 nm). The products were examined as potential anode materials for Li‐ion and Na‐ion batteries. After 100 cycles at 0.1 C (1C=335 mA h g−1), the assembled batteries showed respectable specific capacity 241 mA h g−1 and 145 mA h g−1 for Li‐ion and Na‐ion batteries, respectively.
Utilization of Diurnal Rodents in the Research of Depression
Authors: Bilu Carmel , Einat Haim , Kronfeld‐Schor Noga
Published: September 2016

Preclinical Research

Most neuropsychiatric research, including that related to the circadian system, is performed using nocturnal animals, mainly laboratory mice and rats. Mood disorders are known to be associated with circadian rhythm abnormalities, but the mechanisms by which circadian rhythm disruptions interact with depression remain unclear. As the circadian system of diurnal and nocturnal mammals differs, we previously suggested that the utilization of diurnal animal models may be advantageous for understanding these relations. During the last 10 years, we and others established the validity of several diurnal rodent species as a model for the interactions between circadian rhythms and depression. Diurnal rodents respond to photoperiod manipulation in a similar way to humans, the behavioral outcome is directly related to the circadian system, and treatment that is effective in patients is also effective in the model. Moreover, less effective treatments in patients are also less effective in the model. We, therefore, suggest that using diurnal animal models to study circadian rhythms‐related affective disorders, such as depression, will provide new insights that will hopefully lead to the development of more effective treatments. Drug Dev Res 77 : 347–356, 2016. © 2016 Wiley Periodicals, Inc.
Quality versus quantity: Foraging decisions in the honeybee (Apis mellifera scutellata) feeding on wildflower nectar and fruit juice
Authors: Shackleton Kyle , Balfour Nicholas J. , Al Toufailia Hasan , Gaioski Roberto , de Matos Barbosa Marcela , Silva Carina A. de S. , Bento José M. S. , Alves Denise A. , Ratnieks Francis L. W.
Published: September 2016

Foraging animals must often decide among resources which vary in quality and quantity. Nectar is a resource that exists along a continuum of quality in terms of sugar concentration and is the primary energy source for bees. Alternative sugar sources exist, including fruit juice, which generally has lower energetic value than nectar. We observed many honeybees (Apis mellifera scutellata) foraging on juice from fallen guava (Psidium guajava) fruit near others foraging on nectar. To investigate whether fruit and nectar offered contrasting benefits of quality and quantity, we compared honeybee foraging performance on P. guajava fruit versus two wildflowers growing within 50 m, Richardia brasiliensis and Tridax procumbens. Bees gained weight significantly faster on fruit, 2.72 mg/min, than on either flower (0.17 and 0.12 mg/min, respectively). However, the crop sugar concentration of fruit foragers was significantly lower than for either flower (12.4% vs. 37.0% and 22.7%, respectively). Fruit foragers also spent the most time handling and the least time flying, suggesting that fruit juice was energetically inexpensive to collect. We interpret honeybee foraging decisions in the context of existing foraging models and consider how nest‐patch distance may be a key factor for central place foragers choosing between resources of contrasting quality and quantity. We also discuss how dilute solutions, such as fruit juice, can help maintain colony sugar–water balance. These results show the benefits of feeding on resources with contrasting quality and quantity and that even low‐quality resources have value.
Right ventricular dysfunction in heart failure with preserved ejection fraction: a systematic review and meta‐analysis
Authors: Gorter Thomas M. , Hoendermis Elke S. , van Veldhuisen Dirk J. , Voors Adriaan A. , Lam Carolyn S.P. , Geelhoed Bastiaan , Willems Tineke P. , van Melle Joost P.
Published: September 2016

Aims

Right ventricular (RV) dysfunction and pulmonary hypertension (PH) are increasingly recognized in heart failure with preserved ejection fraction (HFpEF). The prevalence and prognostic value of RV dysfunction in HFpEF have been widely but variably reported. We therefore conducted a systematic review and meta‐analysis according to Preferred Reporting Items for Systematic Reviews and Meta‐Analyses.

Methods and results

English literature until May 2016 was evaluated for prevalence of RV dysfunction [i.e. tricuspid annular plane systolic excursion (TAPSE) <16 mm, fractional area change (FAC) <35%, or tricuspid annular systolic velocity (RV S') <9.5 cm/s)] and PH [i.e. mean pulmonary artery pressure (MPAP) ≥25 mmHg or pulmonary artery systolic pressure (PASP) ≥35 mmHg]. Combined hazard ratios (HRs) for outcomes were calculated. A total of 38 studies was included. In studies with stringent HFpEF criteria, prevalence of RV dysfunction was 28% for TAPSE, 18% for FAC, and 21% for RV S'. Prevalence of PH was 68% for both increased MPAP and PASP. TAPSE (HR 1.26/5 mm decrease; P < 0.0001), FAC (HR 1.15/5% decrease; P < 0.0001), MPAP (HR 1.26/5 mmHg increase; P < 0.0001), and PASP (1.16/5 mmHg increase; P < 0.0001) were all univariably associated with mortality. HRs for RV S' were not reported.

Conclusion

RV dysfunction and PH are highly prevalent and are both associated with poor outcome in patients with HFpEF.
ZnII and CdII Ferrocenechalcogenolate Complexes
Authors: Wallbank Andrew I. , Lebold Terry P. , Borecki Aneta , Polgar Alexander M. , Waters Blake M. , Workentin Mark S. , Corrigan John F.
Published: September 2016

The preparation of the ferrocene‐based reagents FcSSiMe3 (1) and fc(SSiMe3)2 (2) [Fc = (η5‐C5H5)Fe(η5‐C5H4)–; fc = Fe(η5‐C5H4)2–] is reported together with their use in the formation of the tetrahedral zinc complexes [(N,N′‐tmeda)Zn(SFc)2] (3a) and [(N,N′‐tmeda)Zn(S2fc)] (4a), respectively (tmeda = tetramethylethylenediamine). The structures of these coordination complexes are compared to the new ferroceneselenolates [(N,N′‐tmeda)Zn(SeFc)2] (3b) and [(N,N′‐tmeda)Zn(Se2fc)] (4b), themselves prepared using FcSeSiMe3 and fc(SeSiMe3)2, respectively. The synthesis and characterization of dimeric [Cd2(µ‐EFc)2(EFc)2(PPr3)2] (5a, E = S; 5b, E = Se) are also described.
Heterobimetallic Oxalate‐Bridged MIIReIV (M = Zn, Cu, Ni, Co and Mn) Complexes Incorporating Bis(3,5‐dimethylpyrazol‐1‐yl)methane: Synthesis and Magneto‐Structural Studies
Authors: Gryca Izabela , Palion‐Gazda Joanna , Machura Barbara , Penkala Mateusz , Lloret Francesc , Julve Miguel
Published: September 2016

Five oxalato‐bridged heterobimetallic compounds of general formula [ReCl4(ox)M(bdmpzm)2]·2MeCN [ox = oxalate, bdmpzm = bis(3,5‐dimethylpyrazol‐1‐yl)methane, M = Zn (1), Cu (2), Ni (3), Co (4) and Mn (5)] have been successfully synthesized in the self‐assembly reactions of the [ReCl4(ox)]2– metalloligand with the coordinatively unsaturated [M(bdmpzm)2]2+ complex generated in situ by the reaction of the appropriate metal(II) salt with the bdmpzm ligand. Complexes 1–5 are isostructural compounds the crystal structures of which consist of neutral heterodinuclear [ReCl4(ox)M(bdmpzm)2] units and free acetonitrile molecules. The magnetic properties of 1–5 were investigated in the temperature range 2.0–300 K. Compound 1 behaves as a magnetically isolated ReIV complex with a large zero‐field splitting (zfs) of this metal ion [DRe = 54.7(8) cm–1]. Important ferromagnetic interactions between the ReIV and either CuII in 2 [J = +6.60(2) cm–1, ground spin state S = 2] or NiII in 3 [J = +13.7(1) cm–1, ground spin state S = 5/2] occur through the oxalate bridge, the orthogonality between the magnetic orbitals involved accounting for these ferromagnetic couplings. A thorough analysis of the magnetic data of 4, in which spin–orbit coupling and zfs effects coexist with the magnetic coupling, also reveals the occurrence of a ferromagnetic interaction between ReIV and the high‐spin CoII [J = +3.79(2) cm–1, ground spin state S = 3]. Finally, a relatively weak intramolecular antiferromagnetic interaction is observed in 5 [J = –0.995(5) cm–1, ground spin state S = 1]. The nature and trend of the magnetic interactions in 2–4 are discussed in the light of the number and symmetry of the magnetic orbitals involved and compared with those reported in previous magneto‐structural studies in which [ReCl4(ox)]2– was used as a metalloligand for first‐row transition‐metal ions.
Synthesis and Investigation of Solid‐ and Solution‐State Structures of Nickel(II) Complexes with 1,3‐Dimethyl‐5‐(arylazo)‐6‐aminouracil
Authors: Purkayastha Atanu , Debnath Diptanu , Roy Subhadip , Bauzá Antonio , Choudhury Rupasree , Frontera Antonio , Misra Tarun Kumar
Published: September 2016

The (arylazo‐6‐aminouracil)nickel(II) derivatives [NiII(DMA3U)2] [HDMA3U = 1,3‐dimethyl‐5‐(arylazo)‐6‐aminouracil; arylazo = phenylazo (1), p‐Me‐phenylazo (2), p‐Cl‐phenylazo (3)] have been synthesized and isolated in crystalline form. Single‐crystal X‐ray diffraction study of [Ni(1)2] reveals that, in the complex, the metal center has a square‐planar environment. The intramolecular N–H/π and C–H/π interactions hold in the solid state as well as in poor hydrogen‐bond acceptor (HBA) solvents, but are disrupted in good HBA solvents. Crystal‐structure analysis further shows that the NH groups of the coordinated ligands are not available for hydrogen‐bonding interactions in the solid state, and this conclusion is corroborated by DFT calculations. Complexes exhibit multiple absorption bands in the UV/Vis region and TDDFT studies were performed to understand the origin of the ground‐state electronic absorptions. The complexes exhibit intense emission spectra in poor HBA solvents rather than in good HBA solvents. The association constant (Kasso) values for complex HBA solvents, which were determined UV/Vis spectrophotometrically, range from 1.18 to 2.51 m–1.
Synthesis of Diferrocenyl Hydrazone–Enone Receptor Molecules – Electronic Communication, Metal Binding, and DFT Study
Authors: Mishra Sasmita , Dewangan Smriti , Giri Santanab , Mobin Shaikh M. , Chatterjee Saurav
Published: September 2016

Four new diferrocenyl hydrazone–enone compounds were obtained through a two‐step reaction process involving 1,1′‐diacetylferrocene, hydrazides, and ferrocenecarboxaldehyde. The structural characterization of two compounds, 6 and 7, through single‐crystal X‐ray diffraction showed the presence of a stable eclipsed conformation with the two ferrocenyl moieties oriented in trans geometries. The electrochemical and metal‐ion sensing properties of the diferrocenyl‐bifunctionalized compounds were explored to understand their potential in electronic communication and as receptor molecules. Compounds 1,1′‐[(η5‐C5H5)Fe(η5‐C5H4)CH=CHC(O)(η5‐C5H4)Fe{(η5‐C5H4)C(CH3)=N–N(H)C(O)–R}] [R = C6H4OH (6), C6H4N‐p (7)], showed selective interactions with Pb2+ cations and distinct binding interactions with bovine serum albumin (BSA) protein. The mode of the metal–receptor interaction was established through DFT studies. The redox properties of the diferrocenyl compounds with variable end groups revealed distinct electronic communication between the two electroactive groups.
Relationship between chocolate microstructure, oil migration, and fat bloom in filled chocolates
Authors: Delbaere Claudia , Van de Walle Davy , Depypere Frédéric , Gellynck Xavier , Dewettinck Koen
Published: September 2016

Fat bloom is one of the main quality problems in the chocolate industry. A bloomed chocolate product is characterized by the loss of its initial gloss and the formation of a gray‐whitish haze, which makes the product unappealing from a consumer point of view. In the industry, most of the fat bloom related problems arise in filled chocolate products, like pralines and chocolate‐coated biscuits. In these products, oil migration is considered the main cause of fat bloom development. It leads to the dissolution of solid cocoa butter crystals in the chocolate shell which may recrystallize with the formation of undesired crystals. These give rise, upon growth, to visual fat bloom. When looking at the available literature, most of the studies elucidate the possible mechanisms of oil migration and the subsequent fat bloom formation using model systems. These model systems are sometimes too distant from the real industrial applications and the important role of the microstructure of the products are often neglected, although it plays a crucial role in migration‐induced fat bloom development. The main objective of this review is to describe the relationships between chocolate microstructure, oil migration, and fat bloom.

Practical applications: This review can be used as a base for the development of microstructural strategies to retard oil migration and fat bloom development in filled chocolates. An important strategy to retard oil migration and migration‐induced fat bloom is the creation of more dense structures. By creating denser structures, the overall mobility is reduced leading to a decrease in the rate and extent of oil migration. Also, more dense structures hinder recrystallization and Ostwald ripening, thereby delaying the migration‐induced fat bloom development. As fillings are less standardized and not bound by legislation, modification of the filling composition and microstructure offers more opportunities in delaying fat bloom.

The main objective of the review is to describe the relationships between chocolate microstructure, oil migration, and fat bloom, as illustrated in this scheme. The numbers indicate the four parts that are discussed in this review.
Magnetic Supported Copper Nanoparticles: An Efficient Heterogeneous Catalyst for the Synthesis of 1,2‐Diketones by Cross‐Coupling Reaction of Imidazo[1,2‐a]pyridines with Methyl Ketones
Authors: Liu Yi , Zhan Haiying , Yao Kefan , Mai Yingying , Wang Enmin , He Juan , Guo Pengfeng
Published: September 2016

A convenient and new copper nanoparticles‐catalyzed cross‐coupling reaction of imidazo[1,2‐a]pyridines with methyl ketones has been developed to synthesize 1,2‐diketones that have an imidazo[1,2‐a]pyridine core. Highly active magnetic copper nanoparticles [i.e., Cu4O3@Fe3O4_C(II)] were prepared and characterized by standard materials characterization techniques, which included transmission electron microscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy (XPS) and X‐ray diffraction. These methods were also used to acquire information about the size, oxidation state, and crystallinity of the nanoparticle catalyst. With this method, a variety of pharmaceutically important 1,2‐dicarbonyl imidazo[1,2‐a]pyridines were readily synthesized in moderate to good yields. The catalyst was easily separated from the reaction mixture by using an external magnetic field and could be recycled 6 times with only a negligible change in the catalytic performance.
Antagonistic Effect of Acetates in C–N Bond Formation with In Situ Generated Diazonium Salts: A Combined Theoretical and Experimental Study
Authors: Fabre Indira , Perego Luca Alessandro , Bergès Julien , Ciofini Ilaria , Grimaud Laurence , Taillefer Marc
Published: September 2016

The mechanism of the copper‐catalyzed arylation of nitrogen heterocycles using anilines via diazonium salts has been studied by combining DFT and experimental data. A CuI/CuIII redox mechanism is proposed. Our study has revealed the multiple roles of the acid/base couple AcOH/AcO–. An in situ formed triazene species maintains a low concentration of diazonium salts in the reaction medium, which ensures limited formation of decomposition products. The results of DFT calculations have explained the lower reactivity of imidazole nucleophiles as compared with pyrazole in the arylation reaction.
Total Synthesis of the Depsipeptide FR901375 and Preliminary Evaluation of Its Biological Activity
Authors: Narita Koichi , Katoh Yuya , Ojima Ken‐ichi , Dan Singo , Yamori Takao , Ito Akihiro , Yoshida Minoru , Katoh Tadashi
Published: September 2016

The bicyclic depsipeptide FR901375 was efficiently synthesized in a highly convergent manner. The synthesis involved the condensation of a d‐valine–d‐valine–d‐cysteine‐containing segment with a (3S,4E)‐3‐hydroxy‐7‐mercapto‐4‐heptenoic acid–l‐threonine‐containing segment to directly assemble the corresponding seco‐amino acid, followed by cyclization to construct the desired 16‐membered macrocyclic ring. The potency of the synthesized FR901375 was determined in assays for histone deacetylase (HDAC) inhibition and cell‐growth inhibition, and the results were compared to those obtained for the clinically approved depsipeptide FK228 (romidepsin). It was found that FR901375 shows extremely high selectivity (957‐fold) for a class I HDAC 1 (GI50 = 1.7 nm) over a class II HDAC 6 (GI50 = 1627 nm), and shows cell‐growth inhibition GI50 values in the low nanomolar region. Furthermore, new aspects of the structure–activity relationship of bicyclic depsipeptide HDAC inhibitors were revealed.