bluuebunny/crossref_metadata_2025 huggingface dataset:
The role of liquid‐based cytology and ancillary techniques in pleural and pericardic effusions: An institutional experience
Authors: Rossi Esther Diana , Bizzarro Tommaso , Schmitt Fernando , Longatto‐Filho Adhemar
Published: January 2015

BACKGROUND

Fine‐needle aspiration cytology (FNAC) of serous membrane effusions may fulfil a challenging role in the diagnostic analysis of both primary and metastatic disease. From this perspective, liquid‐based cytology (LBC) represents a feasible and reliable method for empowering the performance of ancillary techniques (ie, immunocytochemistry and molecular testing) with high diagnostic accuracy.

METHODS

In total, 3171 LBC pleural and pericardic effusions were appraised between January 2000 and December 2013. They were classified as negative for malignancy (NM), suspicious for malignancy (SM), or positive for malignancy (PM).

RESULTS

The cytologic diagnoses included 2721 NM effusions (2505 pleural and 216 pericardic), 104 SM effusions (93 pleural and 11 pericardic), and 346 PM effusions (321 pleural and 25 pericardic). The malignant pleural series included 76 unknown malignancies (36 SM and 40 PM effusions), 174 metastatic lesions (85 SM and 89 PM effusions), 14 lymphomas (3 SM and 11 PM effusions), 16 mesotheliomas (5 SM and 11 SM effusions), and 3 myelomas (all SM effusions). The malignant pericardic category included 20 unknown malignancies (5 SM and 15 PM effusions), 15 metastatic lesions (1 SM and 14 PM effusions), and 1 lymphoma (1 PM effusion). There were 411 conclusive immunocytochemical analyses and 47 molecular analyses, and the authors documented 88% sensitivity, 100% specificity, 98% diagnostic accuracy, 98% negative predictive value, and 100% positive predictive value for FNAC.

CONCLUSIONS

FNAC represents a primary diagnostic tool for effusions and a reliable approach with which to determine the correct follow‐up. Furthermore, LBC is useful for ancillary techniques, such as immunocytochemistry and molecular analysis, with feasible diagnostic and predictive utility. Cancer (Cancer Cytopathol) 2015;123:258–266. © 2015 American Cancer Society.
Difluorinated 6,13‐Bis(triisopropylsilylethynyl)pentacene: Synthesis, Crystallinity, and Charge‐Transport Properties
Authors: Kim Chang‐Hyun , Hlaing Htay , Payne Marcia M. , Parkin Sean R. , Anthony John E. , Kymissis Ioannis
Published: January 2015

Fluorination has been demonstrated to improve stability and processing in thiophene‐containing small‐molecule semiconductors. Here, the impact of partial fluorination on these parameters in a pentacene derivative is examined. Although the improvement in photostability is not as dramatic, there is a clear improvement in the stability of the chromophore upon fluorination. The improvement in processability is more dramatic; devices formed by spin‐coating with the fluorinated derivative perform substantially better than those formed from the nonfluorinated compound.
Cubic Perovskite ZnTiO3 Nanopowder as a Recyclable Heterogeneous Catalyst for the Synthesis of 1,6‐Naphthyridines in Water
Authors: Ray Suman , Das Paramita , Banerjee Biplab , Bhaumik Asim , Mukhopadhyay Chhanda
Published: January 2015

Cubic perovskite ZnTiO3 nanopowder has been prepared by means of a sustainable sol–gel method. The nanopowder (12–20 nm) has been thoroughly characterized by N2 sorption analysis, high‐resolution (HR) TEM, X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), SEM, and FTIR analyses. The environmentally benign synthesis of highly substituted 1,6‐naphthyridines catalyzed by ZnTiO3 nanopowder in aqueous media has been demonstrated. It requires two different catalytic functions, that is, an acid one, which is provided by TiIV ions, and a basic one, which is provided by the oxide ion incorporated within the ZnTiO3 metal oxide framework. 1,6‐Naphthyridines are of tremendous biological importance, and this method is simple and environmentally friendly. The greenness of the process was satisfactorily established as water was exploited as the reaction medium and there was very high atom economy.
How a [CoIV${^{\underline{.....}}}$O]2+ Fragment Oxidizes Water: Involvement of a Biradicaloid [CoII–(⋅O⋅)]2+ Species in Forming the OO Bond
Authors: Crandell Douglas W. , Ghosh Soumya , Berlinguette Curtis P. , Baik Mu‐Hyun
Published: January 2015

The mechanism of water oxidation performed by a recently discovered cobalt complex [Co(Py5)(OH2)](ClO4)2 (1; Py5=2,6‐(bis(bis‐2‐pyridyl)‐methoxymethane)pyridine) was examined using quantum chemical models based on density functional theory. The computer models were first benchmarked against the experimental cyclic voltammetry data to identify the catalytically competent resting state of the catalyst, which was thought to contain a CoIV–oxyl complex. The electronic structure calculations suggest that the low‐spin doublet state is energetically most favorable, but the catalytically most active species is the intermediate‐spin quartet complex that is almost isoenergetic with the doublet state. The electronic structure of the quartet state shows significant spin polarization on the terminal oxygen atom, which is consistent with an intramolecular electron transfer from the oxygen to the metal. Based on the calculated spin densities, the formally [CoIV${^{\underline{.....}}}$O] can be viewed as a biradicaloid [CoII(⋅O⋅)]2+, that is, a cobalt–oxene moiety. This electronic structure is reminiscent of many other systems where similar electronic patterns were proposed to be responsible for the oxidative reactivity. In this context, this first‐row transition‐metal system constitutes a logical extension, because the oxyl‐radical character is maximized by using the more easily accessible high‐spin configurations in which two half‐filled Codπ orbitals can work in concert to maximize the oxyl‐radical character to ultimately afford a new reactive intermediate that can be characterized as carrying a biradicaloid oxene moiety with a formal oxidation state of zero. This conceptual proposal for the catalytically active species provides a plausible rationale for the remarkable oxidative reactivity.
Titania‐Supported Catalysts for Levulinic Acid Hydrogenation: Influence of Support and its Impact on γ‐Valerolactone Yield
Authors: Ruppert A. M. , Grams J. , Jędrzejczyk M. , Matras‐Michalska J. , Keller N. , Ostojska K. , Sautet P.
Published: January 2015

A series of titania‐supported ruthenium and platinum catalysts was investigated in the levulinic acid hydrogenation towards γ‐valerolactone, a key reaction for the catalytic transformation of biomass. It was shown that various morphologies and phases of titania strongly influence the physicochemical and catalytic properties of supported Ru and Pt catalysts in different ways. In the case of the catalyst supported on mixed TiO2 phases, Ru particles are exclusively located on the minority rutile crystallites, whereas such an effect was not observed for platinum. The platinum catalyst activity could be increased when the metal was dispersed on the large surface‐area anatase, which was not the case for ruthenium as a result of its agglomeration on this support. The activity of ruthenium on anatase could be increased in two ways: a) when RuO2 formation during catalyst preparation was avoided; b) when pure anatase support material was modified so that it exhibited no microporosity. The obtained results allow a better understanding of the role of the support for Ru and Pt catalysts.
A hierarchical Bayesian model to estimate the unobservable predation rate on sawfly cocoons by small mammals
Authors: Pinkantayong Panisara , Suzuki Satoshi , Kubo Mamoru , Muramoto Ken‐ichiro , Kamata Naoto
Published: January 2015

Predation by small mammals has been reported as an important mortality factor for the cocoons of sawfly species. However, it is difficult to provide an accurate estimate of newly spun cocoons and subsequent predation rates by small mammals for several reasons. First, all larvae do not spin cocoons at the same time. Second, cocoons are exposed to small mammal predation immediately after being spun. Third, the cocoons of the current generation are indistinguishable from those of the previous generation. We developed a hierarchical Bayesian model to estimate these values from annual one‐time soil sampling datasets. To apply this model to an actual data set, field surveys were conducted in eight stands of larch plantations in central Hokkaido (Japan) from 2009 to 2012. Ten 0.04‐m2 soil samples were annually collected from each site in mid‐October. The abundance of unopened cocoons (I), cocoons emptied by small‐mammal predation (M), and empty cocoons caused by something other than small‐mammal predation (H) were determined. The abundance of newly spun cocoons, the predation rate by small mammals before and after cocoon sampling, and the annual rate of empty cocoons that remained were estimated. A posterior predictive check yielded Bayesian P‐values of 0.54, 0.48, and 0.07 for I, M, and H, respectively. Estimated predation rates showed a significant positive correlation with the number of trap captures of small mammals. Estimates of the number of newly spun cocoons had a significant positive correlation with defoliation intensity. These results indicate that our model showed an acceptable fit, with reasonable estimates. Our model is expected to be widely applicable to all hymenopteran and lepidopteran insects that spin cocoons in soil.
Trends in the Synthesis and Functionalization of Guaianolides
Authors: Santana Alejandro , Molinillo José M. G. , Macías Francisco A.
Published: January 2015

Guaianolides constitute a large and diverse group of biologically active sesquiterpenes. Guaianolide and seco‐guaianolides can also be used as, for example, scaffolds for the development of new active molecules that are readily accessible by synthetic methods. Nevertheless, these lactones often have complex structures that make their synthesis difficult. The aim of this microreview is to provide an overview of the developments in guaianolide synthesis by the two major synthetic strategies: semi‐synthesis and total synthesis. Partial and total syntheses of guaianolides are described, with particular emphasis placed on the methods reported in the last decade. The methods discussed include rearrangements, cycloadditions, ring‐closing metathesis, the use of transition‐metal catalysts, photochemical reactions, and other recently developed techniques as key steps.
Pericyclic Reactions of Azafulvenium Methides Bearing Internal Dipolarophiles – Synthesis of Chromene and Chromane Derivatives
Authors: Ribeiro Laia Fernanda M. , Soares Maria I. L. , Gomes Clara S. B. , Pinho e Melo Teresa M. V. D.
Published: January 2015

The reactivity of azafulvenium methides with internal dipolarophiles was explored as an approach to new chromene derivatives. 4,5‐Dimethoxycarbonyl‐ and 5‐ethoxycarbonyl‐4‐phenylazafulvenium methides with a prop‐2‐ynyloxyphenyl substituent are converted into 2‐[2‐(2H‐chromen‐8‐yl)vinyl]‐1H‐pyrroles through a sequence of rearrangements. 4,5‐Dimethoxycarbonylazafulvenium methide with a more‐activated dipolarophile as well as the more‐activated 5‐(trifluoromethyl)azafulvenium methide with an unactivated alkyne could be trapped by [8π+2π] cycloadditions to afford 8,12a‐dihydro‐6H‐chromeno[4,3‐e]indolizines. 5‐(Trifluoromethyl)azafulvenium methide with a 2‐(3‐methoxycarbonylprop‐2‐enyloxy)phenyl substituent at C‐1 participated in both intramolecular [8π+2π] and [4π+2π] cycloadditions to afford heterocycle‐fused chromanes. The microwave‐induced rearrangements of 3‐[2‐(prop‐2‐ynyloxy)phenyl]‐1H,3H‐pyrrolo[1,2‐c]thiazoles afforded chiral 3‐(2H‐chromen‐8‐yl)‐1H,3H‐pyrrolo[1,2‐c]thiazoles.
Solvent‐Induced Reversal of Enantioselectivity in the Synthesis of Succinimides by the Addition of Aldehydes to Maleimides Catalysed by Carbamate‐Monoprotected 1,2‐Diamines
Authors: Flores‐Ferrándiz Jesús , Fiser Béla , Gómez‐Bengoa Enrique , Chinchilla Rafael
Published: January 2015

A simple change in the polarity of the solvent allows both enantiomers of substituted succinimides to be obtained in the enantioselective conjugate addition reaction of aldehydes, mainly α,α‐disubstituted, to maleimides catalysed by chiral carbamate‐monoprotected trans‐cyclohexane‐1,2‐diamines. Using a single enantiomer of the organocatalyst, both enantiomers of the resulting Michael adducts are obtained in high yields by simply changing the reaction solvent from aqueous DMF (up to 84 % ee) to chloroform (up to 86 % ee). Theoretical calculations are used to explain this uncommon reversal of the enantioselectivity; two transition state orientations of different polarities are differently favoured in polar or nonpolar solvents.
A Route to Benzo‐Annelated δ‐Sultams through Michael Cyclization
Authors: Grosheva Daria S. , Rassadin Valentin A. , Sokolov Victor V.
Published: January 2015

A new approach to benzo‐annelated δ‐sultams containing an aryl–nitrogen bond is described. The method, which involves the intramolecular Michael cyclization of tert‐butyl ortho‐[N‐(methoxycarbonylmethyl)sulfonylamino]cinnamates, allows the synthesis of secondary sultams as well as their tertiary analogues and bridged tricyclic derivatives efficiently and diastereoselectively.
Tailor‐Made Synthesis of N,N,2,6‐Tetrasubstituted 4‐Nitroanilines by Three‐Component Ring Transformation of Dinitropyridone
Authors: Le Song Thi , Asahara Haruyasu , Nishiwaki Nagatoshi
Published: January 2015

The ring transformation of dinitropyridone afforded various kinds of 2,6‐disubstituted‐4‐nitroanilines upon treatment with aliphatic ketones in the presence of ammonium acetate as a nitrogen source, wherein dinitropyridone behaved as the synthetic equivalent of unstable nitromalonaldehyde. The benzene ring, as well as the amino group of the nitroaniline framework, was easily modified by only changing a ketone and the nitrogen source, which afforded N,N,2,6‐tetrasubstituted 4‐nitroanilines in good to excellent yields.
La0.6Sr0.4FeO3‐δ and La0.6Sr0.4Co0.2Fe0.8O3‐δ Perovskite Materials for H2O2 and Glucose Electrochemical Sensors
Authors: Liotta L. F. , Puleo F. , La Parola V. , Leonardi S. G. , Donato N. , Aloisio D. , Neri G.
Published: January 2015

LaxSr1‐xCoyFe1‐yO3‐δ perovskites were investigated as electro‐catalytic materials for H2O2 and glucose electrochemical sensors. La0.6Sr0.4FeO3‐δ and La0.6Sr0.4Co0.2Fe0.8O3‐δ formulations have been synthesized by citrate method and characterized by XRD and SEM. TPR and XPS analyses were performed to evaluate the oxidation states of metal ions and surface composition. The electrochemical performances of H2O2 and glucose sensors fabricated by modifying commercial screen printed carbon electrodes with perovskites, were evaluated by cyclic voltammetry and amperometry in alkaline medium. Results demonstrated that the substitution of Fe with Co ions in the ferrite structure enhance the electrocatalytical activity towards the oxidation of H2O2 and glucose.
Green bioprinting: Fabrication of photosynthetic algae‐laden hydrogel scaffolds for biotechnological and medical applications
Authors: Lode Anja , Krujatz Felix , Brüggemeier Sophie , Quade Mandy , Schütz Kathleen , Knaack Sven , Weber Jost , Bley Thomas , Gelinsky Michael
Published: January 2015

Embedding of mammalian cells into hydrogel scaffolds of predesigned architecture by rapid prototyping technologies has been intensively investigated with focus on tissue engineering and organ printing. The study demonstrates that such methods can be extended to cells originating from the plant kingdom. By using 3D plotting, microalgae of the species Chlamydomonas reinhardtii were embedded in 3D alginate‐based scaffolds. The algae survived the plotting process and were able to grow within the hydrogel matrix. Under illumination, the cell number increased as indicated by microscopic analyses and determination of the chlorophyll content which increased 16‐fold within 12 days of cultivation. Photosynthetic activity was evidenced by measurement of oxygen release: within the first 24 h, an oxygen production rate of 0.05 mg L−1 h−1 was detected which rapidly increased during further cultivation (0.25 mg L−1 h−1 between 24 and 48 h). Furthermore, multichannel plotting was applied to combine human cells and microalgae within one scaffold in a spatially organized manner and hence, to establish a patterned coculture system in which the algae are cultivated in close vicinity to human cells. This might encourage the development of new therapeutic concepts based on the delivery of oxygen or secondary metabolites as therapeutic agents by microalgae.
Effect of human‐controlled hydrological regime on the source, transport, and flux of particulate organic carbon from the lower Huanghe (Yellow River)
Authors: Hu Bangqi , Li Jun , Bi Naishuang , Wang Houjie , Wei Helong , Zhao Jingtao , Xie Luhua , Zou Liang , Cui Ruyong , Li Song , Liu Ming , Li Guogang
Published: January 2015

Evaluating the role of fluvial transfer of terrestrial organic carbon (OC) and subsequent burial in the global carbon cycle requires the sources and fluxes of fluvial OC to be assessed, which remains poorly constrained in the Huanghe (Yellow River). Here, we report the elemental, stable isotopic, and radiocarbon activity of particulate organic carbon (POC) sampled at the outlet of Huanghe in 2012–2013. We show that the Huanghe riverine POC can be explained by binary mixing of fossil (POCfossil) and non‐fossil (POCnon‐fossil) components, the former may reach ~40% of the total POC. The Huanghe POCnon‐fossil is mostly sourced from C3 plants, with a mean residence time of c. 2200 years. The current human‐controlled hydrological regime strongly influenced the POC sources, transport modes, and fluxes. In 2012–2013, the Huanghe delivered 0.73 Tg (1 Tg = 1012 g) of POC to the sea, and about 28% of the annual POC flux occurred within a short human induced flood event. Globally, the Huanghe should be one of the largest rivers in the transfer and re‐burial of fossil OC. However, the fate of Huanghe fossil OC is still unconstrained and needs to be further investigated. Copyright © 2015 John Wiley & Sons, Ltd.
Two New Triterpene Saponins from the Seed Residue of Hippophae rhamnoides L.
Authors: Gao Wen , Chen Chao , Zhang Jing , Cheng Liang , Kong De‐Yun
Published: January 2015

Two new triterpene saponins, named hippophosides E and F (1 and 2, resp.), together with two known compounds, were isolated from the seed residue of Hippophae rhamnoides L. Their structures were elucidated on the basis of chemical and spectral analysis, including 1D‐ and 2D‐NMR and HR‐MS experiments, and by comparison with literature data.
Further Alkaloids from the Leaves of Trigonostemon lii
Authors: Tan Cheng‐Jian , Zhang Yu , Kong Ning‐Chuan , Di Ying‐Tong , Hao Xiao‐Jiang
Published: January 2015

Four new indole alkaloids, trigonoliimines D–G (1–4, resp.), were isolated from Trigonostemon lii. Their structures were elucidated by spectroscopic methods, including extensive 1D‐ and 2D‐NMR experiments.
Stereoselective Total Synthesis of the Natural Oxylipin (6R,7E,9R,10S)‐6,9,10‐Trihydroxyoctadec‐7‐enoic Acid
Authors: Salva Reddy N. , Das Biswanath
Published: January 2015

The stereoselective total synthesis of the natural oxylipin, (6R,7E,9R,10S)‐6,9,10‐trihydroxyoctadec‐7‐enoic acid, has been accomplished using nonanal and hexane‐1,6‐diol as the starting materials. The synthesis involves Sharpless kinetic resolution, asymmetric epoxidation, and olefin cross‐metathesis as the key steps.
Two New Labdane‐Type Diterpene Acids from the Wood of Cunninghamia konishii
Authors: Chang Chi‐I , Li Yen‐Cheng , Yang Chang‐Syan , Chao Che‐Yi , Li Yi‐Jen , Chang Hsun‐Shuo , Huang Ching‐Jeng , Kuo Ching‐Chuan , Kuo Yueh‐Hsiung
Published: January 2015

Two new labdane‐type diterpene acids, (12S)‐12‐hydroxylabda‐8(17),13(16),14‐trien‐18‐oic acid (1) and (12R)‐12‐hydroxy‐15,16‐epoxylabda‐8(17),13‐dien‐18‐oic acid (2), along with a known labdane‐type diterpene, (11E)‐15,16‐bisnor‐13‐oxolabda‐8(17),11‐dien‐19‐oic acid (3), were isolated from the MeOH extract of the wood of Cunninghamia konishii. Their structures were determined by analysis of spectroscopic data and comparison with the data of known analogs.
Two New Degraded Triterpenoids and a Novel seco‐Norabietane Diterpene from the Root Bark of Azadirachta indica
Authors: Dilshad Iffat , Siddiqui Bina S. , Faizi Shaheen
Published: January 2015

Three new compounds, the degraded ring C‐seco‐tetranortriterpenoid nimbolicidin (1), the degraded hexanortriterpenoid nimbocin (2), and the seco‐norabietane diterpene nimbocinin (3), were isolated from the root bark of Azadirachta indica A.Juss. Compound 1 is O‐bearing both at C(28) and C(29), which has been hitherto unreported in tetranortriterpenoids; 2 represents the first hexanortriterpenoid with a truncated apotirucallane (or apoeuphane) skeleton; 3 is an unprecedented seco‐norabietane. Spectroscopic data and chemical transformations of these compounds provided their complete structures.
Xanthones with α‐Glucosidase Inhibitory Activities from Aspergillus versicolor, a Fungal Endophyte of Huperzia serrata
Authors: Ma Tian‐Tian , Shan Wei‐Guang , Ying You‐Min , Ma Lie‐Feng , Liu Wen‐Hong , Zhan Zha‐Jun
Published: January 2015

Three new xanthones, namely huperxanthones A–C (1–3, resp.), were obtained from the cultures of Aspergillus versicolor, a fungal endophyte of Huperzia serrata, together with 1,7‐dihydroxy‐8‐(methoxycarbonyl)xanthone‐3‐carboxylic acid (4), β‐diversonolic acid methyl ester (5), 4‐hydroxyvertixanthone (6), and sydowinin B (7). The structures of the new compounds were established by detailed NMR and MS analysis, especially by 2D‐NMR experiments. All xanthones were evaluated for their effects on α‐glucosidase. Compound 4 exhibited a potent inhibitory activity against α‐glucosidase with an IC50 value of 0.24 mM (vs. 0.38 mM for acarbose). The rest of the compounds showed weak or no activity against α‐glucosidase.
Mapping Bone Changes at the Proximal Femoral Cortex of Postmenopausal Women in Response to Alendronate and Teriparatide Alone, Combined or Sequentially
Authors: Whitmarsh Tristan , Treece Graham M , Gee Andrew H , Poole Kenneth ES
Published: January 2015

Combining antiresorptive and anabolic drugs for osteoporosis may be a useful strategy to prevent hip fractures. Previous studies comparing the effects of alendronate (ALN) and teriparatide (TPTD) alone, combined or sequentially using quantitative computed tomography (QCT) in postmenopausal women have not distinguished cortical bone mineral density (CBMD) from cortical thickness (CTh) effects, nor assessed the distribution and extent of more localized changes. In this study a validated bone mapping technique was used to examine the cortical and endocortical trabecular changes in the proximal femur resulting from an 18-month course of ALN or TPTD. Using QCT data from a different clinical trial, the global and localized changes seen following a switch to TPTD after an 18-month ALN treatment or adding TPTD to the ALN treatment were compared. Ct.Th increased (4.8%, p < 0.01) and CBMD decreased (−4.5%, p < 0.01) in the TPTD group compared to no significant change in the ALN group. A large Ct.Th increase could be seen for the switch group (2.8%, p < 0.01) compared to a significantly smaller increase for the add group (1.5%, p < 0.01). CBMD decreased significantly for the switch group (–3.9%, p < 0.01) and was significantly different from no significant change in the add group. Ct.Th increases were shown to be significantly greater for the switch group compared to the add group at the load bearing regions. This study provides new insights into the effects of ALN and TPTD combination therapies on the cortex of the proximal femur and supports the hypothesis of an increased bone remodeling by TPTD being mitigated by ALN. © 2014 American Society for Bone and Mineral Research.
Single-Limb Irradiation Induces Local and Systemic Bone Loss in a Murine Model
Authors: Wright Laura E , Buijs Jeroen T , Kim Hun-Soo , Coats Laura E , Scheidler Anne M , John Sutha K , She Yun , Murthy Sreemala , Ma Ning , Chin-Sinex Helen J , Bellido Teresita M , Bateman Ted A , Mendonca Marc S , Mohammad Khalid S , Guise Theresa A
Published: January 2015

Increased fracture risk is commonly reported in cancer patients receiving radiotherapy, particularly at sites within the field of treatment. The direct and systemic effects of ionizing radiation on bone at a therapeutic dose are not well-characterized in clinically relevant animal models. Using 20-week-old male C57Bl/6 mice, effects of irradiation (right hindlimb; 2 Gy) on bone volume and microarchitecture were evaluated prospectively by microcomputed tomography and histomorphometry and compared to contralateral-shielded bone (left hindlimb) and non-irradiated control bone. One week postirradiation, trabecular bone volume declined in irradiated tibias (–22%; p < 0.0001) and femurs (–14%; p = 0.0586) and microarchitectural parameters were compromised. Trabecular bone volume declined in contralateral tibias (–17%; p = 0.003), and no loss was detected at the femur. Osteoclast number, apoptotic osteocyte number, and marrow adiposity were increased in irradiated bone relative to contralateral and non-irradiated bone, whereas osteoblast number was unchanged. Despite no change in osteoblast number 1 week postirradiation, dynamic bone formation indices revealed a reduction in mineralized bone surface and a concomitant increase in unmineralized osteoid surface area in irradiated bone relative to contralateral and non-irradiated control bone. Further, dose-dependent and time-dependent calvarial culture and in vitro assays confirmed that calvarial osteoblasts and osteoblast-like MC3T3 cells were relatively radioresistant, whereas calvarial osteocyte and osteocyte-like MLO-Y4 cell apoptosis was induced as early as 48 hours postirradiation (4 Gy). In osteoclastogenesis assays, radiation exposure (8 Gy) stimulated murine macrophage RAW264.7 cell differentiation, and coculture of irradiated RAW264.7 cells with MLO-Y4 or murine bone marrow cells enhanced this effect. These studies highlight the multifaceted nature of radiation-induced bone loss by demonstrating direct and systemic effects on bone and its many cell types using clinically relevant doses; they have important implications for bone health in patients treated with radiation therapy. © 2015 American Society for Bone and Mineral Research.
Spatiotemporal Analyses of Osteogenesis and Angiogenesis via Intravital Imaging in Cranial Bone Defect Repair
Authors: Huang Chunlan , Ness Vincent P , Yang Xiaochuan , Chen Hongli , Luo Jiebo , Brown Edward B , Zhang Xinping
Published: January 2015

Osteogenesis and angiogenesis are two integrated components in bone repair and regeneration. A deeper understanding of osteogenesis and angiogenesis has been hampered by technical difficulties of analyzing bone and neovasculature simultaneously in spatiotemporal scales and in 3D formats. To overcome these barriers, a cranial defect window chamber model was established that enabled high-resolution, longitudinal, and real-time tracking of angiogenesis and bone defect healing via multiphoton laser scanning microscopy (MPLSM). By simultaneously probing new bone matrix via second harmonic generation (SHG), neovascular networks via intravenous perfusion of fluorophore, and osteoblast differentiation via 2.3-kb collagen type I promoter-driven GFP (Col2.3GFP), we examined the morphogenetic sequence of cranial bone defect healing and further established the spatiotemporal analyses of osteogenesis and angiogenesis coupling in repair and regeneration. We showed that bone defect closure was initiated in the residual bone around the edge of the defect. The expansion and migration of osteoprogenitors into the bone defect occurred during the first 3 weeks of healing, coupled with vigorous microvessel angiogenesis at the leading edge of the defect. Subsequent bone repair was marked by matrix deposition and active vascular network remodeling within new bone. Implantation of bone marrow stromal cells (BMSCs) isolated from Col2.3GFP mice further showed that donor-dependent bone formation occurred rapidly within the first 3 weeks of implantation, in concert with early angiogenesis. The subsequent bone wound closure was largely host-dependent, associated with localized modest induction of angiogenesis. The establishment of a live imaging platform via cranial window provides a unique tool to understand osteogenesis and angiogenesis in repair and regeneration, enabling further elucidation of the spatiotemporal regulatory mechanisms of osteoprogenitor cell interactions with host bone healing microenvironment. © 2015 American Society for Bone and Mineral Research.
The Anti-Osteoanabolic Function of Sclerostin Is Blunted in Mice Carrying a High Bone Mass Mutation of Lrp5
Authors: Yorgan Timur A , Peters Stephanie , Jeschke Anke , Benisch Peggy , Jakob Franz , Amling Michael , Schinke Thorsten
Published: January 2015

Activating mutations of the putative Wnt co-receptor Lrp5 or inactivating mutations of the secreted molecule Sclerostin cause excessive bone formation in mice and humans. Previous studies have suggested that Sclerostin functions as an Lrp5 antagonist, yet clear in vivo evidence was still missing, and alternative mechanisms have been discussed. Moreover, because osteoblast-specific inactivation of β-catenin, the major intracellular mediator of canonical Wnt signaling, primarily affected bone resorption, it remained questionable, whether Sclerostin truly acts as a Wnt signaling antagonist by interacting with Lrp5. In an attempt to address this relevant question, we generated a mouse model (Col1a1-Sost) with transgenic overexpression of Sclerostin under the control of a 2.3-kb Col1a1 promoter fragment. These mice displayed the expected low bone mass phenotype as a consequence of reduced bone formation. The Col1a1-Sost mice were then crossed with two mouse lines carrying different high bone mass mutations of Lrp5 (Lrp5A170V and Lrp5G213V), both of them potentially interfering with Sclerostin binding. Using µCT-scanning and histomorphometry we found that the anti-osteoanabolic influence of Sclerostin overexpression was not observed in Lrp5A213V/A213V mice and strongly reduced in Lrp5A170V/A170V mice. As a control we applied the same strategy with mice overexpressing the transmembrane Wnt signaling antagonist Krm2 and found that the anti-osteoanabolic influence of the Col1a1-Krm2 transgene was not affected by either of the Lrp5 mutations. Taken together, our data support the concept that Sclerostin inhibits bone formation through Lrp5 interaction, yet their physiological relevance remains to be established. © 2015 American Society for Bone and Mineral Research.
Isolation and characterization of an antimicrobial lipopeptide produced by Paenibacillus ehimensis MA2012
Authors: Naing Kyaw Wai , Lee Yong Seong , Nguyen Xuan Hoa , Jeong Min Hae , Anees Muhammad , Oh Byeong Seok , Cho Jeong Yong , Moon Jae Hak , Kim Kil Yong
Published: January 2015

In this study, a novel lipopeptide antibiotic was isolated from the culture supernatant of Paenibacillus ehimensis strain MA2012. After analyses by mass spectrometry (MS), nuclear magnetic resonance (NMR), and high resolution mass spectrometry (HR‐MS/MS) the compound was identified to be polypeptin C consisting of 3‐hydroxy‐4‐methyl‐hexanoic acid moiety and nine amino acids as peptide body. It has the same molecular mass (1115 Da) with that of polypeptin A and B but the amino acid positions differ. A relatively low concentration (125 ppm) of polypeptin C lowered the surface tension of water from 72.2 to 36.4 mN/m. It showed antimicrobial activity against several plant pathogenic bacteria and fungi. When the polypeptin C was applied to the ripe pepper fruits previously inoculated with conidia of Colletotrichum gloeosporioides, the hyphal growth on the fruit was significantly suppressed. Moreover, the hyphal morphology of C. gloeosporioides was greatly affected by the purified compound. All these data suggest the great potential of P. ehimensis MA2012 to control plant fungal and bacterial diseases.
Elemental biochemical analysis of the polysaccharides in the extracellular matrix of the yeast Saccharomyces cerevisiae
Authors: Faria‐Oliveira Fábio , Carvalho Joana , Belmiro Celso LR , Ramalho Gustavo , Pavão Mauro , Lucas Cândida , Ferreira Célia
Published: January 2015

In yeast multicellular aggregates, such as biofilms and colonies, cells are supported by a yeast extracellular matrix (yECM) of glycosidic nature, the composition of which is mostly unknown. Saccharomyces cerevisiae ECM was produced, extracted and partitioned. An analytical‐grade pure glycoside fraction was obtained, fractionated by anionic exchange liquid chromatography and analyzed by gas chromatography–mass spectrometry and polyacrylamide gel electrophoresis. Two different molecular weight polysaccharides were found, composed of glucose, mannose and small relative amounts of galactose. One of the polysaccharides had a low molecular weight, compatible with the association with glycoproteins abundantly occurring in yECM. In addition, these polysaccharide species were separated by diaminopropane agarose gel electrophoresis and induced metachromatic shift, suggesting chemical substitution, which was corroborated by anticoagulation activity. This was shown to be associated with the double deletion of the yeast homologues of the mammalian Hedgehog modulators Hhatl and Hhat, respectively yeast Gup1 and Gup2. These results pioneer the study of the molecular biology of the ECM supporting S. cerevisiae multicellular aggregates such as biofilms.
Raman spectroscopy study of the interaction of 3,5,3′‐triiodo‐L‐thyronine with phosphatidylglycerol lipid bilayers
Authors: Sosa Morales Marcelo C. , Juárez Ana C. , Álvarez Rosa M. S.
Published: January 2015

A Raman spectroscopic study of anionic model membranes and their structural alterations exerted by a relatively small biomolecule, such as the hormone 3,5,3′‐triiodo‐L‐thyronine (T3), is presented. Spectral differences between pure dipalmitoylphosphatidylglycerol (DPPG) multilamellar vesicles and DPPG–T3 mixture and between pure dilauroylphosphatidylglycerol (DLPG) and DLPG–T3 mixture were evaluated in order to determine the response of lipid membranes in gel and liquid‐crystalline phases to the hormone incorporation. Density functional theory (DFT) calculations support the band analysis of the complex 1150–1050 cm−1 Raman region. Geometry optimizations and vibrational behaviors of a model charged molecule that mimics the phosphatidylglycerol lipid moiety in solvated state were taken into account for the spectral interpretation of this specific region. The anionic nature of the lipid polar head plays an important role in the interaction with the hormone, as is evidenced by the CO and PO2− stretching bands. In addition, the differential penetration of T3 into the hydrophobic region of the membranes shows to be dependent on the lipid phase. The spectral data were compared with those previously obtained for zwitterionic membranes. Copyright © 2015 John Wiley & Sons, Ltd.
Raman spectroscopy for future planetary exploration: photodegradation, self‐absorption and quantification of carotenoids in microorganisms and mineral matrices
Authors: Hooijschuur Jan‐Hein , Verkaaik Mattheus F.C. , Davies Gareth R. , Ariese Freek
Published: January 2015

Carotenoids are among the key biomarkers in the search for life on other planets, and non‐destructive Raman spectroscopy on future rover missions is a potential sensitive detection method, especially under resonant conditions. In this research, reflectance spectra of minerals and microorganisms were measured using ultraviolet/visible diffuse reflectance spectroscopy in order to evaluate potential resonance Raman conditions and the possible degree of sample damage during laser irradiation. We report a photodegradation and semi‐quantitative Raman study of β‐carotene and the carotenoid‐containing extremophile Deinococcus radiodurans mixed with calcite at excitation wavelengths of 440 nm, 532 nm and 785 nm. A different type of carotenoid was detected in a culture of Chroococcidiopsis. Carotenoids embedded in bacterial membranes were found to be less sensitive to photodegradation than in a mineral matrix. Corrections for self‐absorption effects were performed using the 1085 cm−1 peak of calcite as an internal standard. Carotenoid‐type signals from 1 mg g−1 D. radiodurans in calcite could be detected, corresponding to about 5 µg g−1 β‐carotene in calcite (≈0.5% cell weight). This research emphasizes the potential suitability of Raman spectroscopy in the detection of organic biomarkers in future planetary exploration. Copyright © 2015 John Wiley & Sons, Ltd.
Portable FTIR analyzers for the rapid determination of total trans fat
Authors: Mossoba Magdi M. , Srigley Cynthia T. , Kramer John K.G.
Published: January 2015

Mid‐infrared spectroscopy (MIS) has been a particularly valuable, rapid analytical tool because it provides the total trans fat content of lipids in a single measurement. In recent years, portable Fourier transform infrared (FTIR) analyzers, which are most useful for field laboratories, have become commercially available. Their performance in the transmission or attenuated total reflection (ATR) modes and application to the rapid determination of total trans fat content of fats, oils and lipids extracted from fast foods were recently found to be equivalent to those of bench top FTIR spectrometers.
Evidence of MTCBP‐1 interaction with the cytoplasmic domain of MT1‐MMP: Implications in the autophagy cell index of high‐grade glioblastoma
Authors: Pratt Jonathan , Iddir Mustapha , Bourgault Steve , Annabi Borhane
Published: January 2015

Progression of astrocytic tumors is, in part, related to their dysregulated autophagy capacity. Recent evidence indicates that upstream autophagy signaling events can be triggered by MT1‐MMP, a membrane‐bound matrix metalloproteinase that contributes to the invasive phenotype of brain cancer cells. The signaling functions of MT1‐MMP require its intracellular domain, and recent identification of MTCBP‐1, a cytoplasmic 19 kDa protein involved in the inhibition of MT1‐MMP‐mediated cell migration, suggests that modulation of MT1‐MMP cytoplasmic domain‐mediated signaling may affect other carcinogenic processes. Using qPCR and screening of cDNA generated from brain tumor tissues of grades I, II, III, and IV, MT1‐MMP gene expression was found to correlate with increased grade of tumors. Inversely, MTCBP‐1 expression decreased with increasing grade of brain tumor. Confocal microscopy and fluorescence resonance energy transfer (FRET) analysis revealed that overexpressing a cytoplasmic‐deleted MT1‐MMP recombinant protein mutant prevented MTCBP‐1 recruitment to the intracellular leaf of plasma membrane in U87 glioblastoma cells. The interaction between MTCBP‐1 and the 20 amino acids peptide representing the MT1‐MMP cytoplasmic domain was confirmed by surface plasmon resonance. Overexpression of a full‐length Wt‐MT1‐MMP triggered acidic autophagy vesicle formation and autophagic puncta formation for green fluorescent microtubule‐associated protein 1 light chain 3 (GFP‐LC3). Autophagic vesicles and GFP‐LC3 puncta formation were abrogated in the presence of MTCBP‐1. Our data elucidate a new role for MTCBP‐1 regulating the intracellular function of MT1‐MMP‐mediated autophagy. The inverse correlation between MTCBP‐1 and MT1‐MMP expression with brain tumor grades could also contribute to the decreased autophagic index observed in high‐grade tumors. © 2015 Wiley Periodicals, Inc.
A biphasic response pattern of lipid metabolomics in the stage progression of hepatitis B virus X tumorigenesis
Authors: Teng Chiao‐Fang , Hsieh Wen‐Chuan , Yang Ching‐Wen , Su Hui‐Min , Tsai Ting‐Fen , Sung Wang‐Chou , Huang Wenya , Su Ih‐Jen
Published: January 2015

Metabolic syndrome has closely linked to the development of human hepatocellular carcinoma (HCC). By using the hepatitis B virus (HBV) X (HBx) transgenic mouse model, we studied the dynamic evolution of serum and liver profiles of lipids and global cDNA expression at different stages of HBx tumorigenesis. We observed that the lipid (triglycerides, cholesterol, and fatty acids) profiles revealed a biphasic response pattern during the progression of HBx tumorigenesis: a small peak at early phase and a large peak or terminal switch at the tumor phase. By analyzing cDNA microarray data, the early peak correlated to the oxidative stress and pro‐inflammatory response, which then resolved at the middle phase and were followed by the terminal metabolic switch in the tumor tissues. Five lipid metabolism‐related genes, the arachidonate 5‐lipoxygenase, lipoprotein lipase, fatty acid binding protein 4, 1‐acylglycerol‐3‐phosphate O‐acyltransferase 9, and apolipoprotein A‐IV were identified to be significantly activated in HBx transgenic HCCs and further validated in human HBV‐related HCCs. Inhibition of these lipid genes could reverse the effect of HBx on lipid biosynthesis and suppress HBx‐induced cell proliferation in vitro. Our results support the concept that metabolic syndrome plays an important role in HBV tumorigenesis. The dysregulation of lipid metabolic genes may predict the disease progression to HCC in chronic hepatitis B patients. © 2015 Wiley Periodicals, Inc.
Urokinase is a negative modulator of Egf‐dependent proliferation and motility in the two breast cancer cell lines MCF‐7 and MDA‐MB‐231
Authors: Kozlova Nina , Samoylenko Anatoly , Drobot Lyudmyla , Kietzmann Thomas
Published: January 2015

The epidermal growth factor receptor (EGFR) is involved in the regulation of various cellular processes and dysregulation of its signalling plays a critical role in the etiology of a variety of malignancies like breast cancer. At the same time, elevated levels of urokinase (uPA), its receptor uPAR, and other components of the plasminogen activation system are found to be correlated with a poor prognosis in breast cancer. Interestingly, EGFR appears to participate in transducing the signal generated upon binding of uPA to uPAR. However, whether uPA signalling would thereby interfere with ligand‐driven EGFR signalling was not described before. Therefore, it was the aim of the present study to investigate the combined effects of uPA and EGF in the low invasive and high invasive breast adenocarcinoma cell lines MCF‐7 and MDA‐MB‐231, respectively. Simultaneous exposure of cells to both signals negatively affected ERK1/2 and AKT activation whereas positive effects on p38 and Src kinase phosphorylation were noted in both cell lines. Furthermore, uPA attenuated the mitogenic effect of EGF on cellular proliferation, invasion and motility in both MCF‐7 and MDA‐MB‐231 cells. Experiments with the uPA amino terminal fragment (ATF) revealed that the negative effects of uPA were independent from its protease activity. Together, these data suggest that enhanced levels of uPA in breast cancer modulate the mitogenic effects of EGF and thus, this knowledge may help to better understand breast cancer pathogenesis as well as to develop new therapeutic options. © 2015 Wiley Periodicals, Inc.
Photolytic determination of charge state for large proteins and fragments in an ion trap mass spectrometer
Authors: Lyon Yana A. , Julian Ryan R.
Published: January 2015

Rationale

One of the major shortcomings of linear ion trap mass spectrometers is poor resolution. Failure to resolve isotopic peaks makes charge state determination for large proteins very difficult, hindering the ability to perform top‐down proteomics.

Methods

Peptides, proteins and corresponding fragments modified with para‐iodobenzoate were trapped and irradiated with 266 nm light from an Nd:YAG laser. Loss of iodine due to photodissociation was then used to assign charge states by measuring the corresponding m/z shifts.

Results

Initial experiments on small peptides illustrate the feasibility of the method. Further studies performed on larger proteins in higher charge states yielded similar results, revealing that fragment ions over a significant mass range either remain in or are quickly cooled to the laser overlap region of the ion trap.

Conclusions

Rapid charge state assignment for both whole molecules and collision‐induced dissociation (CID) fragments can be obtained by photoactivation of chromophores with labile carbon–iodine bonds. Copyright © 2015 John Wiley & Sons, Ltd.
Imaging and identification of endogenous peptides from rat pituitary embedded in egg yolk
Authors: Sosnowski Piotr , Zera Tymoteusz , Wilenska Beata , Szczepanska‐Sadowska Ewa , Misicka Aleksandra
Published: January 2015

Rationale

Mass spectrometry imaging (MSI) can provide accurate data containing the spatial distribution of endogenous peptides in tissue sections without previous treatment. One of the key issues in analyzing small samples is establishing a proper technique for mounting and manipulating collected tissue in order to avoid contamination of the sample with optimal cutting temperature (OCT) resin.

Methods

We present a method for embedding rat pituitary tissue in a frozen egg yolk block, which enables its further imaging in experiments on a matrix‐assisted laser desorption/ionization (MALDI) mass spectrometer with time‐of‐flight (TOF) analyzer. Embedding the sample in the egg yolk prevents contamination from the OCT resin, which decreases MALDI signal quality.

Results

In the present study we detected numerous m/z peaks related to endogenous peptides. We identified fifteen peptides and their post‐translational modifications by tandem mass spectrometry (MS/MS) directly on tissue sections of the hypophysis posterior and intermediate lobes; among these peptides were vasopressin, oxytocin, copeptin, melanocyte‐stimulating hormones and beta‐endorphin. We also showed that egg yolk itself does not affect localization of peptides in the pituitary.

Conclusions

Egg yolk embedding enables preparation of tissue sections from small tissue fragments to organs such as the pituitary gland, which is suitable for localization and identification of endogenous peptides by the MALDI‐MSI and MALDI‐MS/MS techniques. Copyright © 2015 John Wiley & Sons, Ltd.
Urban Economies and Spatial Governmentalities in the World Heritage City of Antigua, Guatemala
Authors: Little Walter E.
Published: January 2015

As one of 725 UNESCO World Heritage Properties, Antigua, Guatemala, is subject to local international regulations related to building codes and how streets and public places are occupied. These regulations are discussed within the theoretical framework of spatial governmentality to explore that relationship between governance and Maya street vendors' economic practices. I situate the scholarly discussion of spatial governmentality within a specific economic context by highlighting how street economies are affected by what Foucault calls the “era of ‘governmentality,’” especially in an ethnographic context. In this article, I argue that horizontal and vertical forms of governmentality affect the economic practices of street vendors within Antigua's sociopolitically constructed spaces. Understanding how spatial governmentalities work in a particular place helps explain why street economies persist and why new ones emerge. In Antigua's case, a new mobile form of street vending emerged because of newly implemented municipal regulations and policing priorities.
A Model Socialist Steel Town Enters the Neoliberal Age: The Changing Political Economy of Nowa Huta, Poland
Authors: Pozniak Kinga
Published: January 2015

This article examines how changing political and economic ideologies and projects—first socialism, then neoliberal capitalism—were worked out in a Polish industrial town called Nowa Huta. Nowa Huta was initially built after World War II as a town that would embody the socialist state's goals of industrialization, urbanization, and the creation of a working class. Following the collapse of the socialist government in 1989 and the ensuing market reforms, Nowa Huta experienced deindustrialization, privatization of state enterprise, unemployment, and decay of urban infrastructure. The article traces how this changing political economy was worked out in the cityscape and in the relationship between place, work, and community. It argues that the case of Nowa Huta allows us to see how global processes, such as industrialization and deindustrialization, and the changing organization of economy and work, are domesticated in local places and in relation to local politics and histories.