bluuebunny/crossref_metadata_2025 huggingface dataset:
Host‐ and pathogen‐derived adjuvant coatings on protein nanoparticle vaccines
Authors: Chang Timothy Z. , Diambou Ishatou , Kim Jong Rok , Wang Baozhong , Champion Julie A.
Published: December 2016

Nanoparticulate and molecular adjuvants have shown great efficacy in enhancing immune responses, and the immunogenic vaccines of the future will most likely contain both. To investigate the immunostimulatory effects of molecular adjuvants on nanoparticle vaccines, we have designed ovalbumin (OVA) protein nanoparticles coated with two different adjuvants—flagellin (FliC) and immunoglobulin M (IgM). These proteins, derived from Salmonella and mice, respectively, are representatives of pathogen‐ and host‐derived molecules that can enhance immune responses. FliC‐coated OVA nanoparticles, soluble FliC (sFliC) admixed with OVA nanoparticles, IgM‐coated nanoparticles, and OVA‐coated nanoparticles were assessed for immunogenicity in an in vivo mouse immunization study. IgM coatings on nanoparticles significantly enhanced both antibody and T cell responses, and promoted IgG2a class switching but not affinity maturation. FliC‐coated nanoparticles and FliC‐admixed with nanoparticles both triggered IgG2a class switching, but only FliC‐coated nanoparticles enhanced antibody affinity maturation. Our findings that affinity maturation and class switching can be directed independently of one another suggest that adjuvant coatings on nanoparticles can be tailored to generate specific vaccine effector responses against different classes of pathogens.
Behavior of nucleolus in the tobacco male meiocytes involved in cytomixis
Authors: Mursalimov Sergey , Sidorchuk Yuriy , Deineko Elena
Published: December 2016

Behavior of nucleolus during the nuclear migration between plant cells (cytomixis) is studied for the first time in the tobacco male meiosis. As is shown, the nucleolus is located in a nonrandom manner in the migrating nuclei. In the majority of cases, the nucleolus resides on the nuclear pole strictly opposite to the cytomictic channel. Owing to this localization, the nucleolus extremely rare enters the recipient cell, so that the nucleolar material is in most cases undetectable in the micronuclei formed after cytomixis. When a whole nucleus migrates from a donor cell to recipient, the nucleolus can leave the nucleus and remain in the donor cells either alone or with a small amount of chromatin. The causes underlying a nonrandom location of the nucleolus in cytomictic cells are discussed. It is assumed that the nucleolar material contacts the cytoplasmic cytoskeleton, which prevents migration of the nucleolus into another cell within the nucleus. The potential use of cytomixis as a model for studying the nuclear motion is discussed.
Mounier–Kuhn syndrome: a case of tracheal smooth muscle remodeling
Authors: Cook Daniel P. , Adam Ryan J. , Abou Alaiwa Mahmoud H. , Eberlein Michael , Klesney‐Tait Julia A. , Parekh Kalpaj R. , Meyerholz David K. , Stoltz David A.
Published: December 2016

Key Clinical Message

Mounier–Kuhn syndrome is a rare clinical disorder characterized by tracheobronchial dilation and recurrent lower respiratory tract infections. While the etiology of the disease remains unknown, histopathological analysis of Mounier–Kuhn airways demonstrates that the disease is, in part, characterized by cellular changes in airway smooth muscle.
Effects of Extraction Methods on Structure and Valorization of Corn Stover Lignin by a Pd/C Catalyst
Authors: Peng Chang , Chen Qin , Guo Haiwei , Hu Gang , Li Changzhi , Wen Jialong , Wang Haisong , Zhang Tao , Zhao Zongbao Kent , Sun Runcang , Xie Haibo
Published: December 2016

With the significant development of efficient pretreatments of lignocellulosic biomass towards using carbohydrate compositions for biofuel production, the valorization of associated lignin products into valuable chemicals has gained much attention. Four lignins obtained by pretreatment of corn stover with emerging ionic liquid‐based mixed organic electrolytes (ILOE) and alkaline twin‐screw extrusion (ATSE) pretreatment technologies were characterized by gel permeation chromatography (GPC), FTIR, HSQC, 31P NMR spectroscopy, and SEM. These lignins were valorized by using Pd/C under various conditions, followed by an elucidation of the relationship between the lignin structure and valorization efficiency and selectivity. The pretreatment/separation methods have a significant effect on lignin structure and subsequent valorization efficiency. HSQC spectra revealed that corn stover lignin consisted of β‐O‐4, β‐5, β‐1 linkages, and cinnamyl alcohol end groups. The extracted lignins (EL) showed less carbohydrates and β‐O‐4 units than those of enzymatic hydrolytic lignins (EHL). The yields of bio‐oils were 61.7 % and 57.9 % for ATSE‐EL and ILOE‐EL, and 34.2 % and 45.1 % for ATSE‐EHL and ILOE‐EHL under optimal and comparative conditions, respectively. Part of the syringyl (S) units were converted into guaiacyl or p‐hydroxyphenyl (H) units by release of methoxyl groups on the aromatic ring through hydrogenolysis, which led to a decreased proportion of S units and an increased proportion of H units in oil compared with in lignin.
State‐of‐the‐Art Aluminum Porphyrin‐based Heterogeneous Catalysts for the Chemical Fixation of CO2 into Cyclic Carbonates at Ambient Conditions
Authors: Chen Yaju , Luo Rongchang , Xu Qihang , Zhang Wuying , Zhou Xiantai , Ji Hongbing
Published: December 2016

A series of metalloporphyrin‐based hyper‐crosslinked polymers (M‐HCPs: M=Al, Co, Fe, Mn) has been directly synthesized through Friedel–Crafts alkylation reactions. The M‐HCPs afforded abundant permanent nanopores, high Brunauer–Emmett–Teller (BET) surface area, and exceptional CO2/N2 adsorptive selectivity. The experimental results suggested that the hollow tubular Al‐HCP exhibited extraordinary catalytic performance in the solvent‐free synthesis of cyclic carbonates from epoxides and CO2 by using tetrabutylammonium bromide as a cocatalyst under mild conditions, which was clearly superior to the corresponding homogeneous analogue. Surprisingly, a high turnover frequency (TOF) value of 14 880 h−1 was achieved with propylene oxide at 100 °C and 3.0 MPa, which was a promising result for industrial production compared with previously reported heterogeneous catalysts. More interestingly, Al‐HCP could smoothly catalyze the cycloaddition reaction, producing the corresponding cyclic carbonates by using simulated flue gas (15 % CO2 and 85 % N2 in volume) as the raw material under ambient conditions. Moreover, Al‐HCP could be readily recycled and efficiently reused more than ten times, exhibiting excellent stability.
Can Biogas Plants Contribute to Lower the Demand for Power Grid Expansion?
Authors: Trommler Marcus , Barchmann Tino , Dotzauer Martin , Cieleit Antje
Published: December 2016

For a stable power grid operation, the appropriateness of several technical parameters is required like voltage bands, transformer and cable loading, losses during operation, and back‐feeding of power into higher voltage level grids. Biogas plants can operate in a flexible mode and in this way influence the above‐mentioned parameters. By using real grid data, different scenarios of flexible biogas plants and their effects on grid related technical parameters are analyzed. Results show that the flexible operation of biogas plants can achieve improvements on such parameters compared to their operation solely orientated at an optimum at the European Power Exchange (EPEX Spot SE). In this way, flexibly operated biogas plants can reduce the need for grid expansion.
Luminescent Metal–Organic Framework Sensor: Exceptional Cd2+ Turn‐On Detection and First In Situ Visualization of Cd2+ Ion Diffusion into a Crystal
Authors: Lim Kwang Soo , Jeong So Yeon , Kang Dong Won , Song Jeong Hwa , Jo Hyuna , Lee Woo Ram , Phang Won Ju , Moon Dohyun , Hong Chang Seop
Published: December 2016

With regard to fluorescence quenching commonly observed during metal‐ion detection, “turn‐on” chemical sensing has been rarely reported, but could be extremely important because it facilitates the selective recognition of target objects of interest against a dark background. A metal–organic framework (MOF) chemosensor has been prepared that serves as an efficient platform for the selective detection of Cu2+ and Cd2+ ions over other metal ions. In particular, this framework shows the highest fluorescence enhancement (≈60‐fold relative to Cd‐free MOF) for the hazardous metal ion Cd2+ among luminescent MOFs and displays excellent reusability in repeated cycles. The direct diffusion of Cd2+ into the crystal pores has also been visualized for the first time.
“On the Dot”—The Timing of Self‐Assembled Growth to the Quantum Scale
Authors: Sonkaria Sanjiv , Ahn Sung‐Hoon , Lee Caroline S. , Khare Varsha
Published: December 2016

Understanding the complex world of material growth and tunability has mystified the minds of material scientists and has been met with increasing efforts to close the gap between controllability and applicability. The reality of this journey is frustratingly tortuous but is being eased through better conceptual appreciation of metal crystalline frameworks that originate from shape and size dependent solvent responsive growth patterns. The quantum confinement of TiO2 in the range of 0.8–2 nm has been synthetically challenging to achieve but lessons from biomineralization processes have enabled alternative routes to be explored via self‐induced pre‐nucleation events. In driving this concept, we have incorporated many of these key features integrating aspects of low temperature annealing at the interface of complex heterogeneous nucleation between hard and soft materials to arrest the biomimetic amorphous phase of TiO2 to a tunable crystalline quantumized state. The stabilization of metastable states of quantum sized TiO2 driven by kinetic and thermodynamic processes show hallmarks of biomineralized controlled events that suggest the inter‐play between new pathways and interfacial energies that preferentially favor low dimensionality at the quantum scale. This provides the potential to re‐direct synthetic assemblies under tightly controlled parameters to generate a host of new materials with size, shape and anisotropic properties as smart stimuli responsive materials. These new stabilities leading to the growth arrest of TiO2 are discussed in terms of molecular interactions and structural frameworks that were previously inaccessible via conventional routes. There exists an undiscovered parallel between synthetic and biomineralized routes enabling unprecedented access to the availability and tunability of novel quantum confined materials. The parametrics of complex material design at the crossroads of synthetically and biologically driven processes is only now surfacing.
Synthesis and Olfactory Properties of a 6′‐Silasubstituted “Spiro[4.5]‐δ‐Damascone”
Authors: Lovchik Martin A. , Kraft Philip
Published: December 2016

The silicon analogue of the potent spirocyclic δ‐damascone odorant 6 was synthesized from allyltrichlorosilane (15) and but‐2‐en‐1‐ol (16). The latter was transformed to 3‐methylpen‐4‐enenitrile (11) by Saucy–Marbet reaction with ethoxyethane and subsequent treatment with HONH2⋅HCl. The resulting γ,δ‐unsaturated nitrile 11 was silylated with 1‐allyl‐1‐chlorosilolane (14), which was prepared from allyltrichlorosilane (15) and the bis‐Grignard reagent of 1,4‐dichlorobutane. Metathetic ring closure employing the Grubbs I catalyst, followed by DIBAL reduction with non‐aqueous work up, Grignard reaction with prop‐1‐en‐1‐ylmagnesium bromide, and Attenburrow MnO2 oxidation concluded the synthesis. The target compound was found to be olfactorily related to the spiro[4.5]‐δ‐damascone lead, but approximately 900 times weaker. In a type of enol Brook rearrangement, it thermally decomposes however to 3,6‐dihydro‐2H‐1,2‐oxasilocine (20), which surprisingly is a damascone odorant as well; although, 12 000 times weaker.
Double Reduction of 4,4′‐Bipyridine and Reductive Coupling of Pyridine by Two Thorium(III) Single‐Electron Transfers
Authors: Formanuik Alasdair , Ortu Fabrizio , Liu Jingjing , Nodaraki Lydia E. , Tuna Floriana , Kerridge Andrew , Mills David P.
Published: December 2016

The redox chemistry of uranium is burgeoning and uranium(III) complexes have been shown to promote many interesting synthetic transformations. However, their utility is limited by their reduction potentials, which are smaller than many non‐traditional lanthanide(II) complexes. Thorium(III) has a greater redox potential so it should present unprecedented opportunities for actinide reactivity but as with uranium(II) and thorium(II) chemistry, these have not yet been fully realized. Herein we present reactivity studies of two equivalents of [Th(Cp′′)3] (1, Cp′′={C5H3(SiMe3)2‐1,3}) with 4,4′‐bipyridine or two equivalents of pyridine to give [{Th(Cp′′)3}2{μ‐(NC5H4)2}] (2) and [{Th(Cp′′)3}2{μ‐(NC5H5)2}] (3), respectively. As relatively large reduction potentials are required to effect these transformations we have shown that thorium(III) can promote reactions that uranium(III) cannot, opening up promising new reductive chemistry for the actinides.
Distribution of enantiomers of volatile organic compounds in selected fruit distillates
Authors: Vyviurska Olga , Zvrškovcová Helena , Špánik Ivan
Published: December 2016

The enantiomer ratios of chiral volatile organic compounds in fruit distillates were determined by multidimensional gas chromatography using solid‐phase microextraction (SPME) as a sample treatment procedure. Linalool and its oxides, limonene, α‐terpineol, and nerolidol, were present at the highest concentration levels, while significantly lower amounts of β‐citronellol and lactones were found in the studied samples. However, almost all terpenoids mainly occur as a racemic or near‐racemic mixture; enantiomer distribution of some chiral organic compounds in fruit distillates correlated to a botanical origin. In particular, a significant enantiomeric excess of (R)‐linalool and (S)‐α‐terpineol was found only for pear brandy, and likewise the dominance (R)‐limonene and the second eluted enantiomer of nerolidol for Sorbus domestica and strawberry, respectively. The distribution of γ‐lactones stereoisomers was more nonspecific, with a general excess of the R‐enantiomer.
Kölliker–Fuse GABAergic and glutamatergic neurons project to distinct targets
Authors: Geerling Joel C. , Yokota Shigefumi , Rukhadze Irma , Roe Dan , Chamberlin Nancy L.
Published: December 2016

The Kölliker‐Fuse nucleus (KF) is known primarily for its respiratory function as the “pneumotaxic center” or “pontine respiratory group.” Considered part of the parabrachial (PB) complex, KF contains glutamatergic neurons that project to respiratory‐related targets in the medulla and spinal cord (Yokota, Oka, Tsumori, Nakamura, & Yasui, 2007). Here we describe an unexpected population of neurons in the caudal KF and adjacent lateral crescent subnucleus (PBlc), which are γ‐aminobutyric acid (GABA)ergic and have an entirely different pattern of projections than glutamatergic KF neurons. First, immunofluorescence, in situ hybridization, and Cre‐reporter labeling revealed that many of these GABAergic neurons express FoxP2 in both rats and mice. Next, using Cre‐dependent axonal tracing in Vgat‐IRES‐Cre and Vglut2‐IRES‐Cre mice, we identified different projection patterns from GABAergic and glutamatergic neurons in this region. GABAergic neurons in KF and PBlc project heavily and almost exclusively to trigeminal sensory nuclei, with minimal projections to cardiorespiratory nuclei in the brainstem, and none to the spinal cord. In contrast, glutamatergic KF neurons project heavily to the autonomic, respiratory, and motor regions of the medulla and spinal cord previously identified as efferent targets mediating KF cardiorespiratory effects. These findings identify a novel, GABAergic subpopulation of KF/PB neurons with a distinct efferent projection pattern targeting the brainstem trigeminal sensory system. Rather than regulating breathing, we propose that these neurons influence vibrissal sensorimotor function.
Increase in the β‐Sheet Character of an Amyloidogenic Peptide upon Adsorption onto Gold and Silver Surfaces
Authors: Soltani Nima , Gholami Mohammad Reza
Published: December 2016

Fibrillation of amyloid beta (Aβ) peptide is the hallmark of Alzheimer's disease. Given that interactions at the bio–nano interface affect the fibrillation tendency of this peptide, an understanding of the interactions at Aβ peptide–inorganic surfaces on the microscopic level can help to determine the possible neurotoxicity of nanoparticles. Here, the interactions between a fibril‐forming peptide, Aβ25–35, and (111) and (100) facets of gold and silver surfaces have been studied by conducting atomistic molecular dynamics simulations. The obtained results indicate that the adsorption onto gold and silver surfaces force the peptide into the β‐sheet‐rich conformations, which is prone to aggregation, suggesting a new mechanism for the acceleration of fibril formation upon interaction with nanoparticles. To quantify the β‐sheet content for a single peptide, a new metrics based on the Ramachandran probability distribution is introduced.
Ultrasmall Yttrium Iron Garnet Nanoparticles with High Coercivity at Low Temperature Synthesized by Laser Ablation and Fragmentation of Pressed Powders
Authors: Schmitz Tim , Wiedwald Ulf , Dubs Carsten , Gökce Bilal
Published: December 2016

Pulsed laser ablation of pressed yttrium iron garnet powders in water is studied and compared to the ablation of a single‐crystal target. We find that target porosity is a crucial factor, which has far‐reaching implications on nanoparticle productivity. Although nanoparticle size distributions obtained by analytical disc centrifugation and transmission electron microscopy (TEM) are in agreement, X‐ray diffraction and energy dispersive X‐ray analysis show that only nanoparticles obtained from targets with densities close to that of a bulk target lead to comparable properties. Our findings also show why the gravimetrical measurement of nanoparticle productivity is often flawed and needs to be complemented by colloidal productivity measurements. The synthesized YIG nanoparticles are further reduced in size by laser fragmentation to obtain sizes smaller than 3 nm. Since the particle diameters are close to the YIG lattice constant, these ultrasmall nanoparticles reveal an immense change of the magnetic properties, exhibiting huge coercivity (0.11 T) and irreversibility fields (8 T) at low temperatures.
Cancer Prevention in the Era of Precision Oncology
Authors: Brahme NN , Szabo E
Published: December 2016

Cancer is a highly heterogeneous disease, both between and within different target organs. Precision cancer prevention requires understanding the molecular pathways leading to cancer on a “per‐person” level, identification of individuals most at risk for developing cancer, and tailoring interventions to accommodate pathogenesis, risk, and individual responses to interventions. This commentary will discuss how an investment in precision prevention research can accelerate cancer prevention agent development—the key to reducing cancer incidence and mortality.
A Hydrazone‐Based Covalent Organic Framework as an Efficient and Reusable Photocatalyst for the Cross‐Dehydrogenative Coupling Reaction of N‐Aryltetrahydroisoquinolines
Authors: Liu Wanting , Su Qing , Ju Pengyao , Guo Bixuan , Zhou Hui , Li Guanghua , Wu Qiaolin
Published: December 2016

A hydrazone‐based covalent organic framework (COF) was synthesized by condensation of 2,5‐dimethoxyterephthalohydrazide with 1,3,5‐triformylbenzene under solvothermal conditions. The COF material exhibits excellent porosity with a BET surface area of up to 1501 m2 g−1, high crystallinity, and good thermal and chemical stability. Moreover, it showed efficient photocatalytic activity towards cross‐dehydrogenative coupling (CDC) reactions between tetrahydroisoquinolines and nucleophiles such as nitromethane, acetone, and phenylethyl ketone. The metal‐free catalytic system also offers attractive advantages including simplicity of operation, wide substrate adaptability, ambient reaction conditions, and robust recycling capability of the catalyst, thus providing a promising platform for highly efficient and reusable photocatalysts.
The impact of early environmental interventions on structural plasticity of the axon initial segment in neocortex
Authors: Nozari Masoumeh , Suzuki Toshimitsu , Rosa Marcello G. P. , Yamakawa Kazuhiro , Atapour Nafiseh
Published: December 2016

Plasticity of the axon initial segment (AIS) is a newly discovered type of structural plasticity that regulates cell excitability. AIS plasticity has been reported to happen during normal development of neocortex and also in a few pathological conditions involving disruption of the inhibition/excitation balance. Here we report on the impact of early environmental interventions on structural plasticity of AIS in the mouse neocortex. C57BL/6 mice were raised in standard or enriched environment (EE) from birth up to the time of experiments and were injected with saline or MK‐801 [N‐Methyl‐D‐Aspartate (NMDA) receptor antagonist, 1 mg/kg] on postnatal days (P) 6–10. We used Ankyrin G immunoreactivity to mark the AIS of cortical neurons in two sub‐regions of frontal cortex (frontal association area, FrA and secondary motor cortex, M2) and in the secondary visual cortex (V2). In 1‐month‐old mice, the mean AIS length differed between three areas, with the shortest AISs being observed in V2. Postnatal MK‐801 or EE led to shortening of AIS only in the frontal areas. However, exposure to EE restored AIS shortening induced by MK‐801. Chronic postnatal MK‐801 results in structural plasticity of AIS exclusive to the frontal cortex. EE may modify underlying neuronal mechanisms resulting in restoration of AIS length.
Magnetic resonance imaging of intra‐pancreatic ductal nanoparticle delivery to islet cells
Authors: Wang Ping , Ross Alana , Yoo Byunghee , Yang Jingsheng , Farrar Christian , Ran Chongzhao , Pantazopoulos Pamela , Medarova Zdravka , Moore Anna
Published: December 2016

Background

The absence of reliable drug delivery systems to pancreatic islet cells hampers efficient treatment of type 1 diabetes. Nanoparticle delivery systems equipped with imaging capabilities could enable selective delivery to pancreatic islet cells. Biodistribution of nanoparticles is defined by several factors including the mode of administration, which determines accumulation in various organs.

Methods

In this study, we tested whether intrapancreatic ductal injection of magnetic nanoparticles would result in efficient cellular uptake by pancreatic islet cells. Dextran‐coated iron oxide nanoparticles labeled with the near infrared fluorescent dye Cy5.5 were injected into the intrapancreatic ducts of streptozotocin‐induced diabetic and healthy mice. To monitor the distribution of the nanoparticles, we performed in vivo magnetic resonance imaging followed by optical imaging and histology.

Results

Both imaging modalities demonstrated accumulation of the nanoparticles in the pancreas. However, histology revealed a high accumulation of nanoparticles in the insulin‐producing cells in the pancreata of diabetic animals. By contrast, in nondiabetic controls, nanoparticles were mainly restricted to nonendocrine tissues.

Conclusions

Our results demonstrate that pancreatic ductal injection accompanied by image guidance could serve as an alternative pathway for nanoparticle delivery. We expect to utilize this intraductal delivery method for theranostic applications in type 1 diabetes.
Might genetics play a role in understanding and treating diabetic polyneuropathy?
Authors: Spallone Vincenza
Published: December 2016

Despite the high prevalence and impact on quality of life, costs, and survival, there are still unresolved issues regarding diabetic polyneuropathy (DPN): the lack of definite knowledge of its pathogenesis; the limited preventive action of glycaemic control in type 2 diabetes; and the unavailability of evidence‐based effective disease‐modifying treatment.

How can genetics provide the tools to address these gaps? Ziegler et al for the GDS Group explore the novel hypothesis that genetic variability in transketolase (TKT) might contribute to susceptibility to DPN in patients with newly diagnosed type 1 and type 2 diabetes (well characterised for DPN). Transketolase diverts excess glycolytic metabolites from the hexosamine, protein kinase C, and advanced glycation endproduct pathways to the pentose phosphate pathway, with a protective effect against hyperglycaemia‐induced damage. Moreover, thiamine and its derivative benfotiamine are among the few disease‐modifying agents still under consideration as DPN treatment. The authors find significant associations of single‐nucleotide polymorphisms of the TKT gene with the Total Symptom Score and thermal thresholds, in particular in male participants with type 2 diabetes. Moreover, they measure plasma methylglyoxal (a glycating agent, whose availability is hindered by TKT) without however finding a relation with TKT single‐nucleotide polymorphisms. The link found between TKT genetic variability and nerve function measures is considered here in the context of DPN genetic studies and of experimental and clinical findings regarding thiamine and benfotiamine. The conclusion is that available data supports the decision to maintain focus on both the search for DPN genetic biomarkers and the therapeutic attempts to target thiamine, TKT, and methylglyoxal.
Therapeutic and pathological roles of fibroblast growth factors in pulmonary diseases
Authors: El Agha Elie , Seeger Werner , Bellusci Saverio
Published: December 2016

Fibroblast growth factors (FGFs) constitute a large family of polypeptides that are involved in many biological processes, ranging from prenatal cell‐fate specification and organogenesis to hormonal and metabolic regulation in postnatal life. During embryonic development, these growth factors are important mediators of the crosstalk among ectoderm‐, mesoderm‐, and endoderm‐derived cells, and they instruct the spatial and temporal growth of organs and tissues such as the brain, bone, lung, gut, and others. The involvement of FGFs in postnatal lung homeostasis is a growing field, and there is emerging literature about their roles in lung pathophysiology. In this review, the involvement of FGF signaling in a wide array of lung diseases will be summarized. Developmental Dynamics 246:235–244, 2017. © 2016 Wiley Periodicals, Inc.
Preferentially expanding Vγ1+ γδ T cells are associated with protective immunity against Plasmodium infection in mice
Authors: Inoue Shin‐Ichi , Niikura Mamoru , Asahi Hiroko , Iwakura Yoichiro , Kawakami Yasushi , Kobayashi Fumie
Published: December 2016

γδ T cells play a crucial role in controlling malaria parasites. Dendritic cell (DC) activation via CD40 ligand (CD40L)‐CD40 signaling by γδ T cells induces protective immunity against the blood‐stage Plasmodium berghei XAT (PbXAT) parasites in mice. However, it is unknown which γδ T‐cell subset has an effector role and is required to control the Plasmodium infection. Here, using antibodies to deplete TCR Vγ1+ cells, we saw that Vγ1+ γδ T cells were important for the control of PbXAT infection. Splenic Vγ1+ γδ T cells preferentially expand and express CD40L, and both Vγ1+ and Vγ4+ γδ T cells produce IFN‐γ during infection. Although expression of CD40L on Vγ1+ γδ T cells is maintained during infection, the IFN‐γ positivity of Vγ1+ γδ T cells is reduced in late‐phase infection due to γδ T‐cell dysfunction. In Plasmodium‐infected IFN‐γ signaling‐deficient mice, DC activation is reduced, resulting in the suppression of γδ T‐cell dysfunction and the dampening of γδ T‐cell expansion in the late phase of infection. Our data suggest that Vγ1+ γδ T cells represent a major subset responding to PbXAT infection and that the Vγ1+ γδ T‐cell response is dependent on IFN‐γ‐activated DCs.
Concomitant Formation of Compositionally Distinct Coordination Polymers Based on a Triacid Linker: Solvent‐Mediated Metamorphosis
Authors: Chandrasekhar Pujari , Bajpai Alankriti , Savitha Govardhan , Moorthy Jarugu Narasimha
Published: December 2016

The solvothermal reaction of the semirigid tritopic ligand 1,3,5‐tris[2,6‐dimethyl‐4‐(α‐carboxy)methoxyphenyl]benzene (H3BTA) with Zn(NO3)2 in a DEF/EtOH/H2O (4:2:1 v/v/v, DEF = N,N‐diethylformamide) mixture leads to the formation of three compositionally distinct coordination polymers (CPs) with different morphologies, that is, rods (Zn‐R), needles (Zn‐N), and blocks (Zn‐B), in the same pot at different concentrations and temperatures. Two sets of compositionally distinct CPs are formed concomitantly at two different reactant concentrations, and one of them is common to the two sets. Attempts to interconvert the three CPs at different temperatures in the same solvent system revealed that the acentric crystals of Zn‐N and Zn‐R convert to the chiral crystals of Zn‐B irreversibly, and the latter remain intact. The crystal‐packing analysis reveals that the three CPs have different Zn2+ coordination geometries, secondary building units (SBUs), framework structures, and solvent‐accessible volumes; therefore, an interplay of kinetic and thermodynamic factors determines the energetics of the metal‐mediated self‐assembly. The formation of two sets of concomitant compositionally distinct CPs from different concentrations of reactants and the conversion of the achiral crystals to the chiral ones are in agreement with the coordination preferences of the metal ions and the structural flexibility of the semirigid linker, and the solvent system plays a pivotal role.
The Multifaceted Chemistry of Ferrocene
Authors: Štěpnička Petr
Published: December 2016

Guest editor Petr Štěpnička explains the role of the discovery of ferrocene in establishing organometallic chemistry as an independent discipline and mentions the prolific research in the field of ferrocene chemistry over 65 years, leading to a wealth of applications.
Made in Europe for the World
Authors: Hindson Karen
Published: December 2016

Editor Karen Hindson highlights the exciting new features that readers can look forward to and introduces new board members that will advise the journal in its 20th volume.
Synthesis of Chiral Heterocyclic N‐Haloamides and ‐imides and Their Applications as Halogenating Agents and Mechanistic Probes
Authors: Hennecke Ulrich , Müller Christian H. , Daniliuc Constantin G.
Published: December 2016

N‐Haloamides and ‐imides are standard halogenating agents and have been used in radical as well as electrophilic halogenation reactions. Despite their many applications, there are only few reports of chiral derivatives of the most common of these reagents such as N‐halosuccinimides. Herein, we report the synthesis of new chiral N‐halogenated amides and imide derivatives, which are easily accessible from inexpensive starting materials of the chiral pool. These new chiral halogenating agents were then applied as stoichiometric reagents in haloetherification reactions and as mechanistic probes in organocatalytic halocyclization reactions.
Decarboxylative Giese‐Type Reaction of Carboxylic Acids Promoted by Visible Light: A Sustainable and Photoredox‐Neutral Protocol
Authors: Ramirez Nieves P. , Gonzalez‐Gomez Jose C.
Published: December 2016

We describe herein a transition‐metal‐free method for the decarboxylative generation of radicals from carboxylic acids and their 1,4‐addition to Michael acceptors. The Fukuzumi catalyst (9‐mesitylene‐10‐methylacridinium perchlorate, [Acr‐Mes]ClO4) enabled this transformation under visible‐light irradiation at room temperature with CO2as the only byproduct. The scope and limitations of this protocol were examined by using a range of Michael acceptors (15 examples) and carboxylic acids (18 examples). The use of 3‐hydroxypivalic acid in this protocol allowed the straightforward formation of a diastereomerically pureδ‐lactone. Moreover, when a homoallylic acid was used, a radical cascade reaction took place with the formation of three C–C bonds.
Stereoselective 11C Labeling of a “Native” Tetrapeptide by Using Asymmetric Phase‐Transfer Catalyzed Alkylation Reactions
Authors: Pekošak Aleksandra , Rotstein Benjamin H. , Collier Thomas L. , Windhorst Albert D. , Vasdev Neil , Poot Alex J.
Published: December 2016

The first 11C‐labeled unmodified (“native”) peptide is described by alkylation of a tetrapeptide Schiff base, which was achieved by an automated five‐step radiochemical reaction. In a proof‐of‐concept study, [11C]Phe‐d‐Trp‐Lys‐Thr was synthesized. This tetrapeptide is the essential pharmacophore of octreotide, an antagonist of somatostatin receptors. The asymmetric alkylation with chiral phase‐transfer catalysts enabled direct labeling of a variety of isolated 11C‐peptides in a highly stereoselective manner (94 % de) with acceptable radiochemical yields (9–10 %) and practical specific activities (15–35 GBq µmol–1 or 405–945 mCi µmol–1) at the end of synthesis. This novel methodology provides a powerful new radiosynthetic method to access novel, stereochemically pure carbon‐11‐labeled native small peptides ready for in vivo studies.
Over‐Oxidized Poly (Phenol Red) Film Modified Glassy Carbon Electrode for Anodic Stripping Voltammetric Determination of Ultra‐Trace Antimony (III)
Authors: Karabiberoğlu Şükriye Ulubay , Dursun Zekerya
Published: December 2016

In this study, we introduce a very sensitive and selective method for the differential pulse anodic stripping determination of Sb(III) ion on the over‐oxidized poly(phenol red) modified glassy carbon electrode (PPhRedox/GCE) in 0.1 mol L‐1 HCl medium. The formation of both poly(phenol red) and over‐oxidized poly(phenol red) film on the electrode surfaces were characterized by electrochemical impedance spectroscopy, X‐ray photoelectron spectroscopy and scanning electron microscopy techniques. An anodic stripping peak of Sb(III) was observed at 0.015 V on the PPhRedox/GCE. Higher anodic stripping peak current of Sb(III) was obtained at PPhRedox/GCE compared with both bare GCE and poly(phenol red) film modified GCE (PPhRed/GCE). The calibration graph consisted of two linear segments of 0.044 ‐ 1.218 μg L−1 and 3.40 – 18.26 μg L−1 with a detection limit of 0.0075 μg L−1. The proposed over‐oxidized polymer film modified electrode was applied successfully for the analysis of antimony in different spiked water samples. Spiked recoveries for water samples were obtained in the range of 93.0–103.0%. The accuracy of the method was also verified through the analysis of standard reference materials (SCP SCIENCE‐EnviroMAT™ EP−L‐2).
Development of an Electrochemical Sensor to Detect Dopamine and Ascorbic Acid Based on Neodymium (III) Oxide and Chitosan
Authors: Nagles Edgar , Calderón Jorge A. , García‐Beltrán Olimpo
Published: December 2016

Neodymium (III) oxide (NdOx) was dispersed in chitosan dissolution and deposited on a glassy carbon electrode (chitosan‐NdOx/GCE). The surface properties of the chitosan‐NdOx/GCE were evaluated with FeCN6−3 solution using cyclic voltammetry and electrochemical impedance spectroscopy. The modified electrode was used in the determination of individual dopamine (DP) and ascorbic acid (AA) with square wave adsorptive voltammetry. Under optimal parameters (pH 4.0; accumulation time; tACC 60s and accumulation potential; EACC 0.10 V) for DP and (pH 3,0; tACC 60s and; EACC −0.20 V) for AA, anodic peak currents were proportional to the concentration of DP and AA between 0.90 and 17.0 μmolL−1, with detection limit of 0.079 μmolL−1 for DP and 0.12 μmolL−1 for AA. The sensor was used in the determination of DP and AA in human urine samples and vitamin C tablets with consistent results. The new sensor is easy to develop. In addition, the sensitivity in particular for AA was improved compared with previous work.
Photocharge‐Enhanced Capacitive Response of a Supercapacitor
Authors: Boruah Buddha Deka , Misra Abha
Published: December 2016

A radiation‐sensitive, binder‐free, solid‐state supercapacitor (SC) has been fabricated based on spinel nickel cobaltite (NiCo2O4)/zinc oxide nanorods (ZnO NRs) as the electrode material. The enhanced surface area of the electrochemical electrode not only provides a noteworthy enhancement in electrochemical activity, but also the generated photoinduced excitons significantly contribute to achieving outstanding electrode conductivity. This finding reveals that the generated photocharges during UV irradiation participate largely in converting radiation energy into electrochemical energy through redox reactions that allow the specific capacitance to double when compared to an absence of UV radiation. Moreover, the novel SC demonstrates an outstanding cyclic stability of 98.5 and 97 % capacitance retention after 2000 cycles of charge–discharge in the absence and presence of UV irradiation, respectively. Thus, this study opens up an avenue for the direct utilization of radiation‐sensitive nanomaterials for electrochemical energy storage and demonstrates a strong potential for the fabrication of advanced SCs.
Carbon‐Assisted Technique to Modify the Surface of Recycled Silicon/Silicon Carbide Composite for Lithium‐Ion Batteries
Authors: Chen Bing‐Hong , Chang Chun‐Chi , Duh Jenq‐Gong
Published: December 2016

A green source of microsized silicon/silicon carbide (Si/SiC) composite represent the wastes of solar cell industries that are created during ingot cutting process; the composite can be used as a Si‐based anode for lithium ion batteries. In contrast to Si nanoparticles with a particular morphology design, the microsized Si/SiC composite from the wastes show severe capacity degradation due to the formation of a solid electrolyte interface (SEI) that affects the conductivity and stability of the electrode. In this study, an external treatment of the electrode (a carbon‐assisted technique (CAT)) was adopted to modify the surface of the electrode and compared with an internal treatment of electrode between particles (namely a pitch‐wrapping technique (PWT)). The external and internal carbon treatments of the electrodes were analyzed individually by cyclic voltammetry and ac impedance spectroscopy. The electrochemical behavior reveals that the characteristic peak of SEI formation and the resistance of SEI of CAT was improved with more efficiency than PWT. Furthermore, based on the cycling performance and irreversibility, the charge retention of the microsized composite could be boosted. Therefore, CAT could replace PWT in the case of microsized Si particles. Conclusively, a method was developed to stabilize SEI formation, which could not only enhance the cyclability but also provide an alternative approach to solve the issue related to SEI formation of a Si‐based anode.
Meaningful Memory in Acute Anorexia Nervosa Patients—Comparing Recall, Learning, and Recognition of Semantically Related and Semantically Unrelated Word Stimuli
Authors: Terhoeven Valentin , Kallen Ursula , Ingenerf Katrin , Aschenbrenner Steffen , Weisbrod Matthias , Herzog Wolfgang , Brockmeyer Timo , Friederich Hans‐Christoph , Nikendei Christoph
Published: December 2016

Objective

It is unclear whether observed memory impairment in anorexia nervosa (AN) depends on the semantic structure (categorized words) of material to be encoded. We aimed to investigate the processing of semantically related information in AN.

Method

Memory performance was assessed in a recall, learning, and recognition test in 27 adult women with AN (19 restricting, 8 binge‐eating/purging subtype; average disease duration: 9.32 years) and 30 healthy controls using an extended version of the Rey Auditory Verbal Learning Test, applying semantically related and unrelated word stimuli.

Results

Short‐term memory (immediate recall, learning), regardless of semantics of the words, was significantly worse in AN patients, whereas long‐term memory (delayed recall, recognition) did not differ between AN patients and controls.

Discussion

Semantics of stimuli do not have a better effect on memory recall in AN compared to CO. Impaired short‐term versus long‐term memory is discussed in relation to dysfunctional working memory in AN. Copyright © 2016 John Wiley & Sons, Ltd and Eating Disorders Association.
A critical review of polycyclic aromatic hydrocarbon phototoxicity models
Authors: Marzooghi Solmaz , Di Toro Dominic M.
Published: December 2016

Polycyclic aromatic hydrocarbons (PAHs) are known to exhibit photo-induced toxicity. Hundreds to thousands of PAH parent and substituted compounds are found in the environment, and developing a predictive model applicable to a wide variety of PAHs and organisms is a necessary precursor to environmental risk assessments. There has been evolutionary progress in phototoxicity modeling since 1977. In the present study, a comprehensive review of the models developed to predict phototoxicity of PAHs is presented. The contributions of each of the models to the state of the art are discussed. The models are compared in terms of their scope of applicability to different organisms, PAHs, endpoints (median lethal time and median lethal concentration), and light conditions. The current state of the science that accounts for the key elements of phototoxicity modeling, including the differences in species sensitivity, the partitioning of PAHs into the target lipid of the organisms, and light absorption by the chemicals, as well as light exposure time and conditions, is discussed. In addition, the remaining issues that need to be addressed are explored: the effect of time-varying exposures to light and PAH concentrations, and the lack of a mechanistic understanding that can explain the failure of the Bunsen–Roscoe law of reciprocity. Environ Toxicol Chem 2017;36:1138–1148. © 2016 SETAC
A finite volume shock‐capturing solver of the fully coupled shallow water‐sediment equations
Authors: Creed Maggie J. , Apostolidou Ilektra‐Georgia , Taylor Paul H. , Borthwick Alistair G.L.
Published: December 2016

This paper describes a numerical solver of well‐balanced, 2D depth‐averaged shallow water‐sediment equations. The equations permit variable horizontal fluid density and are designed to model water‐sediment flow over a mobile bed. A Godunov‐type, Harten–Lax–van Leer contact (HLLC) finite volume scheme is used to solve the fully coupled system of hyperbolic conservation laws that describe flow hydrodynamics, suspended sediment transport, bedload transport and bed morphological change. Dependent variables are specially selected to handle the presence of the variable density property in the mathematical formulation. The model is verified against analytical and semi‐analytical solutions for bedload transport and suspended sediment transport, respectively. The well‐balanced property of the equations is verified for a variable‐density dam break flow over discontinuous bathymetry. Simulations of an idealised dam‐break flow over an erodible bed are in excellent agreement with previously published results, validating the ability of the model to capture the complex interaction between rapidly varying flow and an erodible bed and validating the eigenstructure of the system of variable‐density governing equations. Flow hydrodynamics and final bed topography of a laboratory‐based 2D partial dam breach over a mobile bed are satisfactorily reproduced by the numerical model. Comparison of the final bed topographies, computed for two distinct sediment transport methods, highlights the sensitivity of shallow water‐sediment models to the choice of closure relationships. Copyright © 2016 John Wiley & Sons, Ltd.
End‐of‐life treatment decisions in nursing home residents dying with dementia in the Netherlands
Authors: Hendriks Simone A. , Smalbrugge Martin , Deliens Luc , Koopmans Raymond T. C. M. , Onwuteaka‐Philipsen Bregje D. , Hertogh Cees M. P. M. , van der Steen Jenny T.
Published: December 2016

Objective

The objective was to describe end‐of‐life treatment decisions for patients dying with dementia in various stages of dementia in long‐term care facilities in the Netherlands with elderly care physicians responsible for treatment and care.

Methods

We present data collected in the nationally representative Dutch End of Life in Dementia study (2007–2011). Within 2 weeks after death, 103 physicians completed questionnaires about the last phase of life in 330 residents with dementia who resided in 1 of 34 participating long‐term care facilities. We used descriptive statistics.

Results

Advance directives were rare (4.9%). A minority was hospitalized (8.0%) in the last month (mainly for fractures) or received antibiotics (24.2%) in the last week (mainly for pneumonia). Four residents received tube feeding or rehydration therapy in the last week. In almost half of the residents (42.3%), decisions were made not to start potentially life‐prolonging treatment such as hospital transfer and artificial nutrition and hydration. In more than half of the residents (53.7%), decisions were made to withdraw potentially life‐prolonging treatment such as artificial nutrition and hydration and medication. Antibiotics were more frequently prescribed for residents with less advanced dementia, but otherwise there were no differences in treatment decisions between residents with advanced and less advanced dementia.

Conclusions

Physicians often withhold potentially burdensome life‐prolonging treatment in nursing home residents in all stages of dementia in the Netherlands. This suggests that the physicians feel that a palliative care approach is appropriate at the end of life in dementia in long‐term care. Copyright © 2016 John Wiley & Sons, Ltd. StartCopTextCopyright © 2016 John Wiley & Sons, Ltd.
Disruptions in the left frontoparietal network underlie resting state endophenotypic markers in schizophrenia
Authors: Chahine George , Richter Anja , Wolter Sarah , Goya‐Maldonado Roberto , Gruber Oliver
Published: December 2016

Advances in functional brain imaging have improved the search for potential endophenotypic markers in schizophrenia. Here, we employed independent component analysis (ICA) and dynamic causal modeling (DCM) in resting state fMRI on a sample of 35 schizophrenia patients, 20 first‐degree relatives and 35 control subjects. Analysis on ICA‐derived networks revealed increased functional connectivity between the left frontoparietal network (FPN) and left temporal and parietal regions in schizophrenia patients (P < 0.001). First‐degree relatives shared this hyperconnectivity, in particular in the supramarginal gyrus (SMG; P = 0.008). DCM analysis was employed to further explore underlying effective connectivity. Results showed increased inhibitory connections to the left angular gyrus (AG) in schizophrenia patients from all other nodes of the left FPN (P < 0.001), and in particular from the left SMG (P = 0.001). Relatives also showed a pattern of increased inhibitory connections to the left AG (P = 0.008). Furthermore, the patient group showed increased excitatory connectivity between the left fusiform gyrus and the left SMG (P = 0.002). This connection was negatively correlated to inhibitory afferents to the left AG (P = 0.005) and to the negative symptom score on the PANSS scale (P = 0.001, r = −0.51). Left frontoparietotemporal dysfunction in schizophrenia has been previously associated with a range of abnormalities, including formal thought disorder, working memory dysfunction and sensory hallucinations. Our analysis uncovered new potential endophenotypic markers of schizophrenia and shed light on the organization of the left FPN in patients and their first‐degree relatives. Hum Brain Mapp 38:1741–1750, 2017. © 2017 Wiley Periodicals, Inc.