bluuebunny/crossref_metadata_2025 huggingface dataset:
MnO2‐Modified Persistent Luminescence Nanoparticles for Detection and Imaging of Glutathione in Living Cells and In Vivo
Authors: Li Na , Diao Wei , Han Yaoyao , Pan Wei , Zhang Tingting , Tang Bo
Published: October 2014

Persistent luminescence nanoparticles (PLNPs) hold great promise for the detection and imaging of biomolecules. Herein, we have demonstrated a novel nanoprobe, based on the manganese dioxide (MnO2)‐modified PLNPs, that can detect and image glutathione in living cells and in vivo. The persistent luminescence of the PLNPs can be efficiently quenched by the MnO2 nanosheets. In the presence of glutathione (GSH), MnO2 was reduced to Mn2+ and the luminescence of PLNPs can be restored. The persistent luminescence property can allow detection and imaging without external excitation and avoid the background noise originating from the in situ excitation. This strategy can offer a promising platform for detection and imaging of reactive species in living cells or in vivo.
Alkylation of Pyridines at Their 4‐Positions with Styrenes plus Yttrium Reagent or Benzyl Grignard Reagents
Authors: Mizumori Tomoya , Hata Takeshi , Urabe Hirokazu
Published: October 2014

A new regioselective alkylation of pyridines at their 4‐position was achieved with styrenes in the presence of yttrium trichloride, BuLi, and diisobutylaluminium hydride (DIBAL‐H) in THF. Alternatively, similar products were more simply prepared from pyridines and benzyl Grignard reagents. These reactions are not only a useful preparation of 4‐substituted pyridines but are also complementary to other relevant reactions usually giving 2‐substituted pyridines.
Low‐Temperature Topochemical Transformation of Bi13Pt3I7 into the New Layered Honeycomb Metal Bi12Pt3I5
Authors: Kaiser Martin , Rasche Bertold , Isaeva Anna , Ruck Michael
Published: October 2014

Ordered single‐crystals of the metallic subiodide Bi13Pt3I7 were grown and treated with n‐butyllithium. At 45 °C, complete pseudomorphosis to Bi12Pt3I5 was achieved within two days. The new compound is air‐stable and contains the same ${{{\hfill 2\atop \hfill \infty }}}$[(PtBi8/2)3I]n+ honeycomb nets and iodide layers as the starting material Bi13Pt3I7, but does not include ${{{\hfill 1\atop \hfill \infty }}}$[BiI2I4/2]− iodidobismuthate strands. Electron microscopy and X‐ray diffraction studies of solid intermediates visualize the process of the topochemical crystal‐to‐crystal transformation. In the electronic band structures of Bi13Pt3I7 and Bi12Pt3I5, the vicinities of the Fermi levels are dominated by the intermetallic fragments. Upon the transformation of Bi13Pt3I7 into Bi12Pt3I5, the intermetallic part is oxidized and the Fermi level is lowered by 0.16 eV. Whereas in Bi13Pt3I7 the intermetallic layers do not interact across the iodidobismuthate spacers (two‐dimensional metal), they couple in Bi12Pt3I5 and form a three‐dimensional metal.
Fourfold Diels–Alder Reaction of Tetraethynylsilane
Authors: Geyer Florian L. , Rode Alexander , Bunz Uwe H. F.
Published: October 2014

A series of ethynylated silanes, including tetraethynylsilane, was treated with tetraphenylcyclopentadienone at 300 °C under microwave irradiation to give the aromatized Diels–Alder adducts as sterically encumbered mini‐dendrimers with up to 20 benzene rings. The sterically most congested adducts display red‐shifted emission through intramolecular π–π interactions in the excited state.
Metallogels Derived from Silver Coordination Polymers of C3‐Symmetric Tris(pyridylamide) Tripodal Ligands: Synthesis of Ag Nanoparticles and Catalysis
Authors: Paul Mithun , Sarkar Koushik , Dastidar Parthasarathi
Published: October 2014

By applying a recently developed crystal engineering rationale, four C3 symmetric tris(pyridylamide) ligands namely 1,3,5‐tris(nicotinamidomethyl)‐2,4,6‐triethylbenzene, 1,3,5‐tris(isonicotinamidomethyl)‐2,4,6‐triethylbenzene, 1,3,5‐tris(nicotinamidomethyl)‐2,4,6‐trimethylbenzene, and 1,3,5‐tris(isonicotinamidomethyl)‐2,4,6‐trimethylbenzene, which contain potential hydrogen‐bonding sites, were designed and synthesized for generating AgI coordination polymers and coordination‐polymer‐based gels. The coordination polymers thus obtained were characterized by single‐crystal X‐ray diffraction. The silver metallogels were characterized by transmission electron microscopy (TEM) and dynamic rheology. Upon exposure to visible light, these silver metallogels produced silver nanoparticles (AgNPs), which were characterized by TEM, powder X‐ray diffraction, energy dispersive X‐ray and X‐ray photoelectron spectroscopy. These NPs were found to be effectively catalyzed the reduction of 4‐nitrophenolate to 4‐aminophenolate without the use of any exogenous reducing agent.
Cyclodextrin‐Based Size‐Complementary [3]Rotaxanes: Selective Synthesis and Specific Dissociation
Authors: Akae Yosuke , Koyama Yasuhito , Kuwata Shigeki , Takata Toshikazu
Published: October 2014

α‐Cyclodextrin (CD)‐based size‐complementary [3]rotaxanes with alkylene axles were prepared in one‐pot by end‐capping reactions with aryl isocyanates in water. The selective formation of [3]rotaxane with a head‐to‐head regularity was indicated by the X‐ray structural analyses. Thermal degradation of the [3]rotaxanes bearing appropriate end groups proceeded by stepwise dissociation to yield not only the original components but also [2]rotaxanes. From the kinetic profiles of the deslippage, it turned out that the maximum yield of [2]rotaxane was estimated to be 94 %. Thermodynamic studies and NOESY analyses of such rotaxanes revealed that [2]rotaxanes are specially stabilized, and that the dissociation capability of the [3]rotaxanes to the components can be adjusted by controlling the structure of the end groups, direction of the CD groups, and length of the alkylene axle.
Thalamocortical projections of the anteroventral thalamic nucleus in the rabbit
Authors: Shibata Hideshi , Yoshiko Honda
Published: October 2014

The anterior thalamic nuclei are one of the regions that play critical roles in behavioral learning and memory functions. A part of the anterior thalamic nuclei, the anteroventral nucleus (AV) is well developed and differentiated into the parvocellular (AVp) and magnocellular (AVm) division in the rabbit. The AV is crucial for learning discriminative avoidance conditioning. Although communication between the AV and cortex is considered important in learning, little is known about the neural connections of the AV in the rabbit. Thus, this study used anterograde tracer biotinylated dextran amine and the retrograde tracer cholera toxin B subunit to examine the organization of the thalamocortical projections of the AV. Our data show that each division of the AV provides a unique set of projections to restricted regions and layers of the retrosplenial cortex and presubiculum. In addition, the AVp projects to layers I and IV of retrosplenial areas 29 and 30 and to layers I and VI of the presubiculum. The dorsolateral AVm projects to layers I and IV of area 29 and to layers I, III, and V of the presubiculum. However, the ventromedial AVm only projects to layer I of area 29. These projections are generally organized such that the rostral‐to‐caudal axis of the AV corresponds to the caudal‐to‐rostral axis of the retrosplenial cortex and to the temporal‐to‐septal axis of the presubiculum. These findings suggest distinct functional roles played by each division of the AV in the learning and memory functions. J. Comp. Neurol. 523:726–741, 2015. © 2014 Wiley Periodicals, Inc.
Vulnerability of the medial frontal corticospinal projection accompanies combined lateral frontal and parietal cortex injury in rhesus monkey
Authors: Morecraft R.J. , Ge J. , Stilwell‐Morecraft K.S. , McNeal D.W. , Hynes S.M. , Pizzimenti M.A. , Rotella D.L. , Darling W.G.
Published: October 2014

Concurrent damage to the lateral frontal and parietal cortex is common following middle cerebral artery infarction, leading to upper extremity paresis, paresthesia, and sensory loss. Motor recovery is often poor, and the mechanisms that support or impede this process are unclear. Since the medial wall of the cerebral hemisphere is commonly spared following stroke, we investigated the spontaneous long‐term (6 and 12 month) effects of lateral frontoparietal injury (F2P2 lesion) on the terminal distribution of the corticospinal projection (CSP) from intact, ipsilesional supplementary motor cortex (M2) at spinal levels C5 to T1. Isolated injury to the frontoparietal arm/hand region resulted in a significant loss of contralateral corticospinal boutons from M2 compared with controls. Specifically, reductions occurred in the medial and lateral parts of lamina VII and the dorsal quadrants of lamina IX. There were no statistical differences in the ipsilateral CSP. Contrary to isolated lateral frontal motor injury (F2 lesion), which results in substantial increases in contralateral M2 labeling in laminae VII and IX (McNeal et al. [2010] J. Comp. Neurol. 518:586–621), the added effect of adjacent parietal cortex injury to the frontal motor lesion (F2P2 lesion) not only impedes a favorable compensatory neuroplastic response but results in a substantial loss of M2 CSP terminals. This dramatic reversal of the CSP response suggests a critical trophic role for cortical somatosensory influence on spared ipsilesional frontal corticospinal projections, and that restoration of a favorable compensatory response will require therapeutic intervention. J. Comp. Neurol. 523:669–697, 2015. © 2014 Wiley Periodicals, Inc.
Inhibition of Ammonia Poisoning by Addition of Platinum to Ru/α‐Al2O3 for Preferential CO Oxidation in Fuel Cells
Authors: Sato Katsutoshi , Yagi Sho , Zaitsu Shuhei , Kitayama Godai , Kayada Yuto , Teramura Kentaro , Takita Yusaku , Nagaoka Katsutoshi
Published: October 2014

In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α‐Al2O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst’s PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α‐Al2O3 decreased sharply upon addition of NH3, whereas Pt/Ru/α‐Al2O3 exhibited excellent PROX activity even in the presence of NH3. Ruthenium K‐edge X‐ray absorption near‐edge structure (XANES) spectra indicated that in the presence of NH3, some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3, whereas ruthenium oxidation was not observed with Pt/Ru/α‐Al2O3. These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3.
Crosstalk between intestinal microbiota, adipose tissue and skeletal muscle as an early event in systemic low‐grade inflammation and the development of obesity and diabetes
Authors: Bleau Christian , Karelis Antony D. , St‐Pierre David H. , Lamontagne Lucie
Published: October 2014

Obesity is associated with a systemic chronic low‐grade inflammation that contributes to the development of metabolic disorders such as cardiovascular diseases and type 2 diabetes. However, the etiology of this obesity‐related pro‐inflammatory process remains unclear. Most studies have focused on adipose tissue dysfunctions and/or insulin resistance in skeletal muscle cells as well as changes in adipokine profile and macrophage recruitment as potential sources of inflammation. However, low‐grade systemic inflammation probably involves a complex network of signals interconnecting several organs. Recent evidences have suggested that disturbances in the composition of the gut microbial flora and alterations in levels of gut peptides following the ingestion of a high‐fat diet may be a cause of low‐grade systemic inflammation that may even precede and predispose to obesity, metabolic disorders or type 2 diabetes. This hypothesis is appealing because the gastrointestinal system is first exposed to nutrients and may thereby represent the first link in the chain of events leading to the development of obesity‐associated systemic inflammation. Therefore, the present review will summarize the latest advances interconnecting intestinal mucosal bacteria‐mediated inflammation, adipose tissue and skeletal muscle in a coordinated circuitry favouring the onset of a high‐fat diet‐related systemic low‐grade inflammation preceding obesity and predisposing to metabolic disorders and/or type 2 diabetes. A particular emphasis will be given to high‐fat diet‐induced alterations of gut homeostasis as an early initiator event of mucosal inflammation and adverse consequences contributing to the promotion of extended systemic inflammation, especially in adipose and muscular tissues. Copyright © 2014 John Wiley & Sons, Ltd.
Dysglycemia and long‐term mortality: observations from the Israel study of glucose intolerance, obesity and hypertension
Authors: Bergman Michael , Chetrit Angela , Roth Jesse , Dankner Rachel
Published: October 2014

Background

We describe the relationship between dysglycemia and long‐term mortality and elucidate the relationship between blood glucose levels during an oral glucose tolerance test (OGTT) and haemoglobin A1 (HbA1) and mortality.

Methods

A cohort of 1410 individuals was followed for 33 years since 1980. Fasting and post‐OGTT glucose parameters were used to categorize the cohort according to baseline glycemic status.

Results

The mortality rate increased from 43% in normoglycemic individuals to 53.3, 61.7, 72.9 and 88.0% in those with impaired fasting glucose (IFG), impaired glucose tolerance (IGT), IFG/IGT and diabetes, respectively. The highest mortality rate, compared with the normoglycemic category, was observed in individuals with IFG/IGT and diabetes according to a Cox proportional hazard model (HR = 1.38, 95%CI 1.10–1.74 and HR = 2.14, 95%CI 1.70–2.70, respectively), followed by individuals with IGT and IFG, but this did not reach statistical significance. We speculate that the IFG group may represent a mixture of individuals en route from normal to the next two categories as well as another cohort whose glucose levels are stably set at the upper reaches of the normal distribution.

Significant differences were found between 1 and 2 h glucose values (p < 0.001). Fasting, 60 and 120 min glucose values were positively associated with increasing HbA1 quintiles (p < 0.05). The mean HbA1 was significantly higher in those who died (p = 0.01). The highest mortality (58.8%) was observed in the upper HbA1 quintile that was also associated with the highest prevalence of the metabolic syndrome (17.2%).

Conclusions

This study shows a continuous relationship between the severity of dysglycemia and long‐term mortality and should promote the early recognition of prediabetes. The 1 h post‐load glucose level was continuously associated with increasing HbA1 concentrations and may therefore serve as an early marker for abnormalities in glucose tolerance. An elevated 1 h post‐load glucose level may potentially identify at‐risk individuals well before the traditional 2 h glucose value. Copyright © 2014 John Wiley & Sons, Ltd.
Lens defects in Astyanax mexicanus Cavefish: Evolution of crystallins and a role for alphaA‐crystallin
Authors: Hinaux Hélène , Blin Maryline , Fumey Julien , Legendre Laurent , Heuzé Aurélie , Casane Didier , Rétaux Sylvie
Published: October 2014

The fish Astyanax mexicanus presents, within the same species, populations of river‐dwelling surface fish (SF) and blind cave‐living fish. In cavefish (CF), the eyes develop almost normally during embryogenesis. But 40 h after fertilization, the lens enters apoptosis, triggering the progressive degeneration of the entire eye. Before apoptosis, the CF lens expresses early differentiation factors correctly. Here, we searched for possible late differentiation defects that would be causal in CF lens degeneration. We reasoned that crystallins, the major lens structural proteins, could be defective or misregulated. We surveyed the CF and SF transcriptomes and uncovered 14 Astyanax crystallins from the beta, gamma, lambda, mu, and zeta families. These proteins are less polymorphic and accumulate more fixed mutations, some at highly conserved positions, in CF than in SF, suggesting relaxed selection at these loci in CF. In situ hybridizations and qPCR show that crybb1c, crybgx, crygm5 are expressed at much lower levels or are not expressed in the CF lens. For the best crystallin candidates, we tested a potential causal role in CF lens apoptosis. Crybgx, crybb1c (not expressed in CF from very early on), and cryaa (previously shown to be faintly expressed in CF) failed to induce any defect when knocked‐down in zebrafish embryos. However, the anti‐apoptotic cryaa protected lens cells from apoptosis when reexpressed by transgenesis in CF, suggesting a cell‐autonomous effect of cryaa on lens cell survival. Altogether, these data suggest that crystallin sequence evolution and expression defects may contribute to the loss of eyes in CF. © 2014 Wiley Periodicals, Inc. Develop Neurobiol 75: 505–521, 2015
Sexual size dimorphism is not associated with the evolution of parental care in frogs
Authors: Monroe Melanie J. , Alonzo Suzanne H.
Published: October 2014

Sex differences in parental care are thought to arise from differential selection on the sexes. Sexual dimorphism, including sexual size dimorphism (SSD), is often used as a proxy for sexual selection on males. Some studies have found an association between male‐biased SSD (i.e., males larger than females) and the loss of paternal care. While the relationship between sexual selection on males and parental care evolution has been studied extensively, the relationship between female‐biased SSD (i.e., females larger than males) and the evolution of parental care has received very little attention. Thus, we have little knowledge of whether female‐biased SSD coevolves with parental care. In species displaying female‐biased SSD, we might expect dimorphism to be associated with the evolution of paternal care or perhaps the loss of maternal care. Here, drawing on data for 99 extant frog species, we use comparative methods to evaluate how parental care and female‐biased SSD have evolved over time. Generally, we find no significant correlation between the evolution of parental care and female‐biased SSD in frogs. This suggests that differential selection on body size between the sexes is unlikely to have driven the evolution of parental care in these clades and questions whether we should expect sexual dimorphism to exhibit a general relationship with the evolution of sex differences in parental care.
Phylogeographic study of Chinese seabuckthorn (Hippophae rhamnoides subsp. sinensis Rousi) reveals two distinct haplotype groups and multiple microrefugia on the Qinghai‐Tibet Plateau
Authors: Wang Hongfang , Liu Han , Yang Mingbo , Bao Lei , Ge Jianping
Published: October 2014

Historical climate change can shape the genetic pattern of a species. Studies on this phenomenon provide great advantage in predicting the response of species to current and future global climate change. Chinese seabuckthorn (Hippophae rhamnoides subsp. sinensis) is one of the most important cultivated plants in Northwest China. However, the subspecies history and the potential genetic resources within the subspecies range remain unclear. In this study, we utilized two intergenic chloroplast regions to characterize the spatial genetic distribution of the species. We found 19 haplotypes in total, 12 of which were unique to the Chinese seabuckthorn. The populations observed on the Qinghai‐Tibet Plateau (QTP) consisted of most of the haplotypes, while in the northeast of the range of the subspecies, an area not on the QTP, only four haplotypes were detected. Our study also revealed two distinct haplotype groups of the subspecies with a sharp transition region located in the south of the Zoige Basin. 89.96% of the genetic variation located between the regions. Mismatch analysis indicated old expansions of these two haplotype groups, approximately around the early stage of Pleistocene. Additional morphological proofs from existing studies and habitat differentiation supported a long independent colonization history among the two regions. Potential adaptation probably occurred but needs more genome and morphology data in future. Chinese seabuckthorn have an older population expansion compared with subspecies in Europe. The lack of large land ice sheets and the heterogeneous landscape of the QTP could have provided extensive microrefugia for Chinese seabuckthorn during the glaciation period. Multiple localities sustaining high‐frequency private haplotypes support this hypothesis. Our study gives clear insight into the distribution of genetic resources and the evolutionary history of Chinese seabuckthorn.
Epigenetic control of thymic Treg‐cell development
Authors: Kitagawa Yohko , Ohkura Naganari , Sakaguchi Shimon
Published: October 2014

Thymus‐derived Treg cells, which express the transcription factor Foxp3, form a functionally stable cell lineage indispensable for the maintenance of immunological self‐tolerance and homeostasis. Foxp3 is critically required for Treg‐cell function, in particular for their suppressive function. Recent studies have implicated the contribution of Treg‐cell‐specific epigenetic modifications as a means to ensure the stable expression of Foxp3 and other molecules associated with Treg‐cell function. Unexpectedly, epigenetic modifications introduced in the course of thymic Treg‐cell development were found to be independent of Foxp3 expression. These findings require reconsideration of the current model of Treg‐cell development based on Foxp3 induction. With reference to other examples of lineage specification, we discuss possible models for thymic Treg‐cell development.
σ2P,O‐Hybrid Ligands: Synthesis of the First 4‐Hydroxy‐1,3‐benzazaphospholes by ortho‐Lithiation of m‐Amidophenyl Diethyl Phosphates
Authors: Aluri Bhaskar R. , Shah Kirti , Gupta Neelima , Fomina Olga S. , Yakhvarov Dmitry G. , Ghalib Mohammed , Jones Peter G. , Schulzke Carola , Heinicke Joachim W.
Published: October 2014

The m‐phosphorylanilides 2 are available from anilides 1 by the Atherton–Todd reaction; the selective ortho‐lithiation of the o′‐methyl‐protected phosphorylpivalanilide 2b with tBuLi proceeded in high yield in the presence of ClSiMe3. The ortho‐lithiation is followed by rapid 1,3‐migration of the PO3Et2 group to yield the phosphonoanilide cis/trans‐3b. This compound mainly reacts with excess LiAlH4 by reductive cyclization to form the 4‐hydroxy‐1H‐1,3‐benzazaphosphole 6. The lithiation of the o′‐unprotected phosphorylpivalanilide 2a with LDA was unselective and led to 3a and 4a in low yields, whereas additional ortho‐lithiation of the benzoyl group occurred for the lithiation of the o′‐protected phosphonobenzanilide 2c with tBuLi/LDA to give 7 in rather low yield. The reduction of crude 7 led to (benzylamino)phenol 8 and the 4‐hydroxy‐1H‐1,3‐benzazaphosphole 9 as a minor product. The properties, NMR spectroscopy data, and crystal structures of 5b, 6, and 8 are reported.
Two Layerlike Supramolecular Assemblies Based on B‐Anderson‐Type Polyanionic Clusters and Their Adsorption Property
Authors: Yan Jinshuang , Gong Kaining , Xue Xiaolong , He Xueli , Zhao Chuan , Han Zhangang , Yu Haitao
Published: October 2014

Two layerlike supramolecular assemblies that consist of Ag‐supported B‐Anderson‐type clusters (H2bpp)[Ag{AlMo6(OH)6O18}]·2.5H2O (1) and (H2bpe)[Ag(OH2){AlMo6(OH)6O18}] (2) [bpp = 1,3‐di(4‐pyridyl)propane; bpe = 1,2‐di(4‐pyridyl)ethylene] have been synthesized and characterized. X‐ray diffraction analysis reveals that the supramolecular structures of two compounds are built upon alternative arrangements of inorganic anionic and organic cationic layers. In 1 and 2 the oxophile silver centers have different coordination modes to bridge Anderson‐type clusters into 2D inorganic anionic layers. There are extensive noncovalent forces among inorganic anions and organic cations to construct 3D supramolecular frameworks of compounds 1–2. The preliminary experiments show that the two crystals possess an adsorption–desorption property for methylene blue (MB). Crystal 2 shows a very fast adsorption rate towards MB, and a relatively high value (ca. 90 %) can be reached within 15 min.
Two Supramolecular Inorganic–Organic Hybrids of 12‐Silicotungstic Acid Heteropolyoxometalate and Trinuclear Lanthanide Clusters: Syntheses, Structures, and Magnetic Properties
Authors: Lotfian Nahid , Mirzaei Masoud , Eshtiagh‐Hosseini Hossein , Löffler Marta , Korabik Maria , Salimi Alireza
Published: October 2014

Hydrothermal synthesis of two novel inorganic–organic hybrid assemblies, {Na[Ln(pydc‐OH)(H2O)4]3}[SiW12O40]·15H2O [Ln = Nd (1) and Ln = Sm, (2); pydc‐OH = 4‐hydroxypyridine‐2,6‐dicarboxy], and their characterization is described. Structural characterizations by single‐crystal X‐ray diffraction reveal that these compounds are isostructural, and each consists of [SiW12O40]4– Keggin‐type polyoxometalates (POMs) linked by three lanthanide ions to yield discrete trinuclear lanthanide clusters. These discrete molecules are further packed into 3D supramolecular assemblies by means of hydrogen‐bonding and anion–π interactions. Both compounds exhibit remarkable thermal stability. The temperature variation in the magnetic susceptibility χm and of the χmT product and Bohr magnetons of the NdIII (1)‐ and SmIII (2)‐based compounds are considered. The magnetic data have been interpreted relative to data presented in the literature.
Isolated Uranyl Chromate and Polychromate Units in Crown Ether Templated Compounds
Authors: Siidra Oleg I. , Nazarchuk Evgeny V. , Sysoeva Elena V. , Kayukov Roman A. , Depmeier Wulf
Published: October 2014

Two compounds containing isolated uranyl chromate and polychromate units were synthesized through room‐temperature reactions of uranyl nitrate, chromium(VI) oxide, and 18‐crown‐6/15‐crown‐5 in aqueous solutions. Uranyl chromate with 18‐crown‐6 consists of neutral ∞0[(UO2)(CrO4)(H2O)3] units formed by the bidentate character of the edge sharing UrO5 bipyramid with only CrO4 and organic molecules and no additional crystallization water molecules. Uranyl polychromate with 15‐crown‐5 is the first inorganic compound in which [CrO4]2–, [Cr2O7]2–, and [Cr3O10]2– chromate groups are observed simultaneously.
Electrochemical Conversion of Bicarbonate to Formate Mediated by the Complex RuIII(edta) (edta4– = ethylenediaminetetraacetate)
Authors: Chatterjee Debabrata , Jaiswal Namita , Banerjee Priyabrata
Published: October 2014

In this paper, we present the first example of a ruthenium(III) complex, [RuIII(edta)] (edta = ethylenediaminetetraacetate), that catalyzes the electrochemical conversion of hydrogen carbonate to formate selectively. The formation of an [RuIII(edta)(HCO3)]2– species through the reaction of the [RuIII(edta)(H2O)]– catalyst and hydrogen carbonate (HCO3–) was studied kinetically by using the stopped‐flow technique. The value of the second‐order rate constant for the formation of the [RuIII(edta)(HCO3)]2– complex was 82 ± 7 M–1 s–1 at 25 °C and pH = 6.4. Electrochemical reduction of hydrogen carbonate (HCO3–) was achieved by carrying out constant‐potential bulk electrolysis at –0.4 V (vs. SCE) with a mercury‐pool cathode at pH = 6.4. The formation of formate as the only reduction product was evidenced by a 13C NMR analysis of the reaction mixture obtained after electrolysis.
Iron‐Catalyzed [4C+1N] Cyclization of 4‐Acetylenic Ketones with Primary Amines: Synthesis of 5‐(Aryl)alkylidene‐4,5‐dihydropyrroles
Authors: Sun Bo , Ma Quan , Wang Yeming , Zhao Yuegang , Liao Peiqiu , Bi Xihe
Published: October 2014

An environmentally friendly route to fully substituted 4,5‐dihydropyrroles was developed through the iron‐catalyzed [4C+1N] cyclization of 4‐acetylenic ketones with primary amines in 1,5‐pentanediol.
Simultaneous Voltammetric Determination of Zn(II), Pb(II), Cu(II), and Hg(II) in Ethanol Fuel Using an Organofunctionalized Modified Graphite‐Polyurethane Composite Disposable Screen‐Printed Device
Authors: Saciloto Thalita R. , Cervini Priscila , Cavalheiro Éder T. G.
Published: October 2014

A disposable screen‐printed device containing working, auxiliary, and reference electrodes is proposed for the simultaneous voltammetric determination of Zn(II), Pb(II), Cu(II), and Hg(II) in ethanol fuel. The working electrode was printed using an ink modified with 2‐benzothiazole‐2‐thiol organofunctionalized SBA‐15 silica, in order to increase sensitivity. The performance of this electrode was compared with that of bare and SBA‐15‐modified electrodes. After optimizing the experimental parameters, the device was applied in determination of the analytes in commercial ethanol fuel samples, using 0.10 mol L−1 KCl/ethanol ratios of 30 : 70 (v/v), with [H+]=10−5 mol L−1. After 5 min of preconcentration at − 1.3 V (vs. pseudo‐Ag/AgCl), four well‐resolved signals were obtained, enabling simultaneous determination of the four analytes using a differential pulse anodic stripping voltammetry (DPASV) procedure. The limits of detection were 0.30, 0.065, 0.030, and 0.046 µmol L−1 for Zn(II), Pb(II), Cu(II), and Hg(II), respectively. The results of these analyses were in agreement with those obtained using graphite furnace atomic absorption spectroscopy (GFAAS) for Pb(II), Cu(II), and Hg(II), and high‐resolution continuum source flame atomic absorption spectrometry (HR‐CS‐FAAS) for Zn2+, at a 95 % confidence level. Analytes originally present in the samples could be detected, and the interference of some cations and anions was evaluated.
Rapid screening of aminopeptidase N inhibitors by capillary electrophoresis with electrophoretically mediated microanalysis
Authors: Wang Hairong , Xu Wenfang , Cao Jiangying , Wang Weihong
Published: October 2014

In this work, an electrophoretically mediated microanalysis (EMMA) method with a partial‐filling technique was setup to evaluate the inhibitory potency of novel compounds toward aminopeptidase N (APN). It was necessary to optimize the electrophoretic conditions with respect to the kinetic constraints and for attaining high sensitivity. In our setup, a part of the capillary was filled with the incubation buffer for the enzyme reaction, whereas the rest was filled with a suitable BGE for the separation of substrates and products. To monitor the performance of the newly developed method, the kinetic constants (Km and Vmax) for the catalyzed dissociation of l‐Leucine‐p‐nitroanilide in the presence of APN as well as the inhibition constant (IC50) of a known competitive inhibitor, that is bestatin, were determined and these results were compared with those obtained by a classical spectrophotometric assay. The developed EMMA method was subsequently applied to the screening of 30 APN inhibitors. Whereas the inhibition potency of these inhibitors (expressed in IC50 values) were significantly underestimated by the EMMA method, the order of the inhibitory potential of these various compounds was found in agreement with the literature.
Effect of oligonucleotide probes substituted by deoxyinosines on the specificity of SNP detection on the DNA microarray
Authors: Qian Xiaoting , Pu Dan , Liu Bicheng , Xiao Pengfeng
Published: October 2014

One of the main factors that can affect the quality of microarray results is the microarray hybridization specificity. The key factor that affects hybridization specificity is the design of the probes. In this paper, we described a novel oligonucleotide probe containing deoxyinosines aimed at improving DNA hybridization specificity. We compared different probes to determine the distance between deoxyinosine base and SNPs site and the number of deoxyinosine bases. The new probe sequences contained two set of deoxyinosines (each set had two deoxyinosines), in which the interval between SNP site and each set of deoxyinosines was two bases. The new probes could obtain the highest hybridization specificity. The experimental results showed that probes containing deoxyinosines hybridized effectively to the perfectly matched target and improved the hybridization specificity of DNA microarray. By including a simple washing step after hybridization, these probes could distinguish matched targets from single‐base‐mismatched sequences perfectly. For the probes containing deoxyinosines, the fluorescence intensity of a match sequence was more than eight times stronger than that of a mismatch. However, the intensity ratio was only 1.3 times or less for the probes without deoxyinosines. Finally, using hybridization of the PCR product microarrays, we successfully genotyped SNP of 140 samples using these new labeled probes. Our results show that this is a useful new strategy for modifying oligonucleotide probes for use in DNA microarray analysis.
Capillary isoelectric focusing immunoassay as a new nanoscale approach for the detection of oligoclonal bands
Authors: Halbgebauer Steffen , Haußmann Ute , Klafki Hans , Tumani Hayrettin , Wiltfang Jens , Otto Markus
Published: October 2014

The detection of oligoclonal bands (OCBs) in cerebrospinal fluid is an indicator of intrathecal synthesis of immunoglobulins which is a neurochemical sign of chronic inflammatory brain diseases. Intrathecally synthesized IgGs are typically observed in patients with multiple sclerosis. The current standard protocol for the detection of OCBs is IEF on agarose or polyacrylamide gels followed by immunoblotting or silver staining. These methods are time consuming, show substantial interlaboratory variation and cannot be used in a high throughput‐approach. We have developed a new nanoscale method for the detection of OCBs based on automated capillary IEF followed by immunological detection. Evidence for intrathecal IgG synthesis was found in all tested patients (n = 27) with multiple sclerosis, even in two subjects who did not have oligoclonal bands according to standard methods. The test specificity was at 97.5% (n = 19). Our findings indicate that the novel OCB‐CIEF‐immunoassay is suitable for the rapid and highly sensitive detection of OCBs in clinical samples. Furthermore, the method allows for a higher sample throughput than the current standard methods.
Asenapine in the treatment of older adults with bipolar disorder
Authors: Sajatovic Martha , Dines Philipp , Fuentes‐Casiano Edna , Athey Melanie , Cassidy Kristin A. , Sams Johnny , Clegg Kathleen , Locala Joseph , Stagno Susan , Tatsuoka Curtis
Published: October 2014

Objective

In spite of growing numbers of older people, there are few treatment studies on late‐life bipolar disorder (BD). This was a 12‐week prospective, open‐label trial to assess efficacy and tolerability of adjunct asenapine in non‐demented older adults (≥60 years) with sub‐optimal previous response to BD treatments.

Methods

Asenapine was initiated at 5 mg/day and titrated as tolerated. Effects on global psychopathology were measured with Clinical Global Impression, bipolar version (CGI‐BP), and the Brief Psychiatric Rating Scale (BPRS). Mood polarity severity was measured with the Hamilton Depression Rating Scale, Montgomery Asberg Depression Rating Scale, and Young Mania Rating Scale. Other outcomes included the World Health Organization Disability Assessment Schedule II.

Results

Fifteen individuals were enrolled (mean age 68.6, SD 6.12; 53% female; 73% Caucasian, 13% African American, and 7% Asian). There were 4/15 (27%) individuals who prematurely terminated the study, whereas 11/15 (73%) completed the study. There were significant improvements from baseline on the BPRS (p < 0.05), on CGI‐BP overall (p < 0.01), and on CGI‐BP mania (p < 0.05) and depression (p < 0.01) subscales. The mean dose of asenapine was 11.2 (SD 6.2) mg/day. The most common reported side effects were gastrointestinal discomfort (n = 5, 33%), restlessness (n = 2, 13%), tremors (n = 2, 13%), cognitive difficulties (n = 2, 13%), and sluggishness (n = 2, 13%).

Conclusions

Older people with BD had global improvements on asenapine. Most reported adverse effects were mild and transient, but adverse effects prompted drug discontinuation in just over one quarter of patients. Although risks versus benefits in older people must always be carefully considered, asenapine may be a treatment consideration for some non‐demented geriatric BD patients. Copyright © 2014 John Wiley & Sons, Ltd.
How does ageing affect the impact of medically unexplained symptoms and medically explained symptoms on health‐related quality of life?
Authors: Hilderink Peter H. , Collard Rose , Rosmalen Judith G. M. , Oude Voshaar Richard C.
Published: October 2014

Background

Physical symptoms significantly impair health‐related quality of life (HRQoL), but age effects and differential effects of medically unexplained symptoms (MUS) and medically explained symptoms (MES) have hardly been examined. Our objective was to determine the effect of age on the impact of MUS and MES on HRQoL.

Methods

In a population‐based cohort (n = 946, aged 28–75 years), MUS and MES were measured using the Composite International Diagnostic Interview and HRQoL using the EuroQol‐5 dimensions (EQ‐5D). Using multiple linear regression, we regressed MUS, MES and their interaction with age on HRQoL, adjusted for socio‐demographic variables and the presence of depressive and anxiety disorders. In case of significant interaction terms, age‐stratified results will be presented.

Results

In the whole study population, the association between MUS and HRQoL was stronger (β = −0.35; p < 0.001) than between MES and HRQoL (β = −0.26; p < 0.001). Adjusted for depressive and anxiety disorders, differences between these associations decline (MUS: β = −0.28, p < 0.001; MES: β = −0.25, p < 0.001). Age significantly interacted with number of MUS in explaining variance in HRQoL but not with the number of MES. The impact of MUS on HRQoL is much larger in people aged below 65 years (β = −0.39, p < 0.001) versus those aged 65 years and over (β = −0.21, p = 0.002). In the older group, the association between MUS and HRQoL lost significance when adjusted for depressive and anxiety disorders (β = −0.12 p = 0.062).

Conclusion

Our results show that age affects the association between MUS and HRQoL, which suggest that older persons cope better with MUS than younger persons. Copyright © 2014 John Wiley & Sons, Ltd.
Endoscope‐assisted extracapsular dissection of benign parotid tumors using hairline incision
Authors: Woo Seung Hoon , Kim Jin Pyeong , Baek Chung‐Hwan
Published: October 2014

Background

This study evaluated the feasibility of endoscopic‐assisted extracapsular dissection of benign parotid tumors using only hairline incision.

Methods

Endoscope‐assisted extracapsular dissection via only hairline incision was performed in 18 cases (5 men and 13 women) of benign parotid gland tumor (pleomorphic adenoma in 4 cases, Warthin's tumor in 14 cases).

Results

All 18 operations were successfully performed and no conversions to conventional open resection were necessary. One patient had transient facial paresis and recovered within 1 month. The duration of the procedure was 82.5 ± 18.5 minutes.

Conclusion

Endoscope‐assisted extracapsular dissection using only hairline incision is a feasible method for treatment of benign parotid tumors. The main advantage of this procedure is that the operative scar is concealed in the hairline area. © 2015 Wiley Periodicals, Inc. Head Neck 38: 375–379, 2016
Transoral robotic approach for laryngeal schwannoma
Authors: Millas Teresa , Granell Jose , Garrido Laura , Mendez‐Benegassi Ivan , Gutierrez‐Fonseca Raimundo
Published: October 2014

Background

The laryngeal schwannoma is a rare benign tumor of the larynx, most frequently found in the aryepiglottic fold, which can be rather bulky when diagnosed.

Methods

We present a primary transoral robotic surgery (TORS) for a laryngeal schwannoma and highlight the advantages of the robotic assistance.

Results

Thanks to the high‐definition 3D dynamic vision and an improved freedom of movement, it is possible to accurately accomplish surgical tasks that previously were much more complex or even unfeasible through a minimally invasive approach, potentially minimizing the surgical damage.

Conclusion

Robotic‐assisted surgery eased excision, supporting that it can expand the indications for transoral approaches. © 2015 Wiley Periodicals, Inc. Head Neck 37: E70–E73, 2015
Carbon ion radiotherapy for locally advanced squamous cell carcinoma of the external auditory canal and middle ear
Authors: Koto Masashi , Hasegawa Azusa , Takagi Ryo , Sasahara Go , Ikawa Hiroaki , Mizoe Jun‐etsu , Jingu Keiichi , Tsujii Hirohiko , Kamada Tadashi , Okamoto Yoshitaka ,   Organizing Committee for the Working Group for Head and Neck Cancer
Published: October 2014

Background

The prognosis of advanced squamous cell carcinoma (SCC) of the external auditory canal and middle ear remains poor. Carbon ion radiotherapy (C‐ion RT) has shown promise for locally advanced head and neck cancer. Therefore, we evaluated the safety and efficacy of C‐ion RT for locally advanced SCC of the external auditory canal and middle ear.

Methods

The cases of 13 patients with advanced (T3 and T4) SCC of the external auditory canal and middle ear who received C‐ion RT as the primary treatment were reviewed.

Results

The median follow‐up for all patients and the 7 surviving patients was 12 and 32 months, respectively. The 1‐year and 3‐year local control and overall survival (OS) rates were 72% and 54% and 70% and 40%, respectively. Severe temporal bone necrosis was observed in 2 patients.

Conclusion

C‐ion RT is effective and generally safe for locally advanced SCC of the external auditory canal and middle ear. © 2015 Wiley Periodicals, Inc. Head Neck 38: 512–516, 2016
Patterns of care and perioperative outcomes in transoral endoscopic surgery for oropharyngeal squamous cell carcinoma
Authors: Zevallos Jose P. , Mitra Nandita , Swisher–McClure Samuel
Published: October 2014

Background

Transoral endoscopic surgery is a promising new treatment for oropharyngeal squamous cell carcinoma (SCC).

Methods

We examined care patterns and outcomes in 514 patients with oropharyngeal SCC undergoing transoral endoscopic surgery within the 2010 to 2011 National Cancer Database (NCDB).

Results

Most patients had T1 to T2 tumors (88.5%), and were treated in academic facilities (64.2%). Mean length of hospitalization was 5.1 days and perioperative mortality was 0.8%. Final surgical margins were positive in 20% of patients, and were more common with T2 (odds ratio [OR] = 2.35; p < .05) or N2 disease (OR = 4.18; p < .001), treatment in community cancer centers (OR = 1.81; p < .05), and low volume centers (OR = 2.43; p < .05).

Conclusion

Early adoption of transoral surgery for oropharyngeal SCC had an excellent safety profile. We observed higher rates of positive surgical margins than previously reported. These findings highlight the importance of surgeon experience and patient selection, and suggest that transoral endoscopic surgery for oropharyngeal SCC be performed by highly trained surgeons in the context of multidisciplinary care. © 2015 Wiley Periodicals, Inc. Head Neck 38: 402–409, 2016
Co‐targeting of multiple microRNAs on factor‐Inhibiting hypoxia‐Inducible factor gene for the pathogenesis of head and neck carcinomas
Authors: Kao Shou‐Yen , Tsai Meng‐Miao , Wu Cheng‐Hsieh , Chen Jing‐Jung , Tseng Ssu‐Hsueh , Lin Shu‐Chun , Chang Kuo‐Wei
Published: October 2014

Background

MicroRNAs (miRNAs) are short, noncoding RNAs that inhibit the expression of target genes that play roles in tumorigenesis. MiR‐21, miR‐31, and miR‐184 are oncogenic miRNAs for head and neck squamous cell carcinoma (HNSCC). Factor‐inhibiting hypoxia (FIH)‐inducible factor is known to inactivate hypoxia‐induced downstream effectors and is involved in HNSCC suppression. This study investigates whether miR‐21, miR‐31, and miR‐184 target FIH in HNSCC.

Methods

Reporter assays, Western blot analysis, quantitative reverse transcriptase‐polymerase chain reaction (PCR) analysis, and phenotypic assays were used to prove that miR‐21, miR‐31, and miR‐184 directly target FIH. Clinicopathological implications of the gene expression were also analyzed.

Results

MiR‐21, miR‐31, and miR‐184 directly bind to various sites in the 3′ untranslated region (UTR) of FIH transcript, and this binding is associated with decreased FIH protein expression in HNSCC cells. Treatment with the precursors of these miRNAs increases the proliferation and migration of HNSCC cells. Concomitant treatment with precursors repressed FIH and enhanced oncogenicity most profoundly. Upregulation of miR‐21, miR‐31, and miR‐184 expression is found in more than 80% of HNSCC tumors and 72% of tumors have concordant upregulation of these 3 oncogenic miRNAs. The highest expression of these miRNAs is present in T4b and stage IVB tumors. Downregulation of FIH mRNA expression is noted in 69% of HNSCC tumors, and in tumors exhibiting high expression of these miRNAs, the FIH mRNA expression is consistently downregulated.

Conclusion

This study provides novel clues indicating that miR‐21, miR‐31, and miR‐184 co‐target FIH tumor suppressor during pathogenesis in the vast majority of HNSCC. © 2015 Wiley Periodicals, Inc. Head Neck 38: 522–528, 2016
Significant preservation of swallowing function in chemoradiotherapy for advanced head and neck cancer by prophylactic swallowing exercise
Authors: Ohba Shinichi , Yokoyama Junkichi , Kojima Masataka , Fujimaki Mitsuhisa , Anzai Takashi , Komatsu Hiroaki , Ikeda Katsuhisa
Published: October 2014

Background

Dysphagia is a serious complication of chemoradiotherapy (CRT) in patients with head and neck cancer. Approximately 20% to 30% of patients who have dysphagia require feeding tubes. The purpose of this study was to evaluate the impact of prophylactic swallowing exercises on swallowing function.

Methods

Fifty‐one patients with advanced oropharyngeal, hypopharyngeal, and laryngeal cancers were included in this study. Twenty‐one patients performed the Shaker exercise and 30 practiced traditional Mendelsohn maneuvers (control group). Before and after treatment, videofluoroscopy and swallowing motion were analyzed to establish movement of the hyoid bone, larynx, and aspiration scores.

Results

Average movement of the hyoid bone, thyrohyoid shortening, and upper esophageal sphincter opening were significantly better maintained in the Shaker group. Aspiration score of the Shaker exercise was significantly lower than control group. Feeding tube rates for the Shaker and control groups were 14% and 40% (p < .05).

Conclusion

Shaker exercises as a prophylactic exercise contributed to preservation of swallowing function in patients with head and neck cancer. © 2015 Wiley Periodicals, Inc. Head Neck 38: 517–521, 2016