bluuebunny/crossref_metadata_2025 huggingface dataset:
ComuniCode: do jornalismo multimídia hiperlocal à esfera pública internacional
Authors: Barcellos Zanei Ramos , Bozza Gabriel Alexandre
Published: August 2013

Este trabalho discute teoricamente a possibilidade do estabelecimento da esfera pública internacional no ciberespaço com o enfraquecimento do Estado-Nação e fortalecimento do poder decisório local e da cidadania, ao mesmo tempo em que mostra o jornalismo em constante reconfiguração para apresentar notícias segmentadas voltadas ao público (hiper)local, em tempo real, distribuídas pela rede mundial de computadores ubíqua e recebidas pelos cidadãos do mundo em seus aparatos móveis, que replicam e interferem na sua produção e viram emissores de comunicação em massa. Assim apresentamos a experiência laboratorial de um produto jornalístico hiperlocal distribuído por QR Code, o ComuniCode, pela turma do terceiro ano de Jornalismo da PUCPR, no segundo semestre de 2011. Os alunos acharam uma forma de utilizar o código em produto jornalístico com a criação de um jornal digital multimídia hiperlocal, com distribuição via QR Code com leitura e acessibilidade por mobiles, como em smarthphones 3G.
Chromonic‐Like Physical Luminescent Gels Formed by Ionic Octahedral Iridium(III) Complexes in Diluted Water Solutions
Authors: Yadav Yogesh Jivajirao , Heinrich Benoît , De Luca Giuseppina , Talarico Anna Maria , Mastropietro Teresa Fina , Ghedini Mauro , Donnio Bertrand , Szerb Elisabeta Ildyko
Published: August 2013

The first example of spontaneous self‐assembly of ionic octahedral Ir(III) complexes containing carboxylates counterions into luminescent ordered aqueous gel phases is reported. The gel phases formed at 2.5% w/w (“Ir‐Ci”:H20) are investigated by POM, 1H and 2H NMR and UV–vis spectroscopies, whereas a detailed structural analysis by WAXS, SAXS, and SANS experiments is performed for the acetate complex, in both anisotropic gel and isotropic phases. This comprehensive investigation shows that the complex with the shortest carboxylate self‐assembles into double string polyelectrolyte‐type supramolecular columns surrounded by the counterions, at low concentrations in the isotropic solution (1.0% w/w). Upon increasing concentration, these supramolecular columns grow one‐dimensionally, and eventually gelation occurs and birefringent textures begin to be observed by POM, resembling the textures developed by chromonic systems. The gelation occurs with the close packing of the supramolecular columns sheathed in their solvation shell into a 2D rectangular lattice. Furthermore, a significant enhancement of the luminescence quantum yield is observed for all the complexes in the gel phases with respect to the isolated molecule.
Mapping Spatially Resolved Charge Collection Probability within P3HT:PCBM Bulk Heterojunction Photovoltaics
Authors: Dissanayake D. M. Nanditha M. , Ashraf Ahsan , Pang Yutong , Eisaman Matthew D.
Published: August 2013

Material properties in polymer and fullerene bulk heterojunctions (BHJs) such as donor to acceptor volume fraction, morphology, and molecular orientation critically influence light absorption, exciton dissociation, charge transport, and recombination, all of which are crucial device properties in organic photovoltaics (OPV). Spatial variation of BHJ properties normal to the substrate, caused by phase segregation, can thereby create corresponding spatial variations in the OPVs optoelectronic properties. Here, normally incident and wave‐guided optical modes are used to selectively excite localized regions within an inverted poly(3‐hexythiophene‐2,5‐diyl) and phenyl‐C61‐butyric acid methyl ester BHJ OPV and corresponding internal quantum efficiencies are measured to study the spatial‐dependent charge carrier collection probability within the BHJ. An electron‐limited charge collection profile is observed for a thick (920 nm) BHJ due to fullerene‐poor regions as a result of phase segregation. As the thickness of the BHJ is reduced (100 nm), charge transport is seen to be unaffected by the phase segregation. This has the potential to be a versatile non‐destructive characterization technique for measuring the spatially varying charge collection probability in thin film photovoltaics and will help enable optimum device design and characterization.
The combination of lenalidomide and dexamethasone reduces bone resorption in responding patients with relapsed/refractory multiple myeloma but has no effect on bone formation: Final results on 205 patients of the Greek myeloma study group
Authors: Terpos Evangelos , Christoulas Dimitrios , Kastritis Efstathios , Katodritou Eirini , Papatheodorou Athanasios , Pouli Anastasia , Kyrtsonis Marie‐Christine , Michalis Eurydiki , Papanikolaou Xenophon , Gkotzamanidou Maria , Koulieris Efstathios , Gavriatopoulou Maria , Zervas Konstantinos , Dimopoulos Meletios A. ,   on behalf of the Greek Myeloma Study Group
Published: August 2013

The combination of lenalidomide plus dexamethasone (RD) is very effective for patients with relapsed/refractory myeloma. However, the effect of RD on bone metabolism has not been previously evaluated in these patients. To address this issue, we initially performed a retrospective study in 106 consecutive patients with relapsed or refractory myeloma who received RD. We measured the following bone indices on Cycle 1/Day 1 and then on Cycles 3 and 6/Day 28: dickkopf‐1 (Dkk‐1), sRANKL, osteoprotegerin (OPG), bone resorption markers (C‐telopeptide of collagen type‐I, CTX and TRACP‐5b) and bone formation markers (bone‐specific alkaline phosphatase‐bALP and osteocalcin). RD produced a reduction of CTX only in responders, with no effect on bone formation. To validate these results, we then evaluated prospectively 99 patients who received either RD (n = 50) or VRD (bortezomib + RD, n = 49). RD reduced CTX, mainly in responders but showed no effect on bone formation, confirming the result of the retrospective study. However, the addition of bortezomib to RD (VRD arm) reduced Dkk‐1, sRANKL/OPG, and CTX, while it increased bALP and OC after six cycles of therapy. These changes were irrespective of treatment response, which was similar between treatment arms. No skeletal‐related events were observed in the VRD arm while two, nonresponding patients treated with RD developed a vertebral fracture. We conclude that RD reduces bone resorption only in responding patients with relapsed/refractory myeloma but has no effect on bone formation. Combination with bortezomib, which enhances bone formation, seems to be preferred for the management of myeloma patients with osteolytic disease. Am. J. Hematol. 89:34–40, 2014. © 2013 Wiley Periodicals, Inc.
A prospective newborn screening and treatment program for sickle cell anemia in Luanda, Angola
Authors: McGann Patrick T. , Ferris Margaret G. , Ramamurthy Uma , Santos Brigida , de Oliveira Vysolela , Bernardino Luis , Ware Russell E.
Published: August 2013

Over 300,000 infants are born annually with sickle cell anemia (SCA) in sub‐Saharan Africa, and >50% die young from infection or anemia, usually without diagnosis of SCA. Early identification by newborn screening (NBS), followed by simple interventions dramatically reduced the mortality of SCA in the United States, but this strategy is not yet established in Africa. We designed and implemented a proof‐of‐principle NBS and treatment program for SCA in Angola, with focus on capacity building and local ownership. Dried bloodspots from newborns were collected from five birthing centers. Hemoglobin identification was performed using isoelectric focusing; samples with abnormal hemoglobin patterns were analyzed by capillary electrophoresis. Infants with abnormal FS or FSC patterns were enrolled in a newborn clinic to initiate penicillin prophylaxis and receive education, pneumococcal immunization, and insecticide‐treated bed nets. A total of 36,453 infants were screened with 77.31% FA, 21.03% FAS, 1.51% FS, and 0.019% FSC. A majority (54.3%) of affected infants were successfully contacted and brought to clinical care. Compliance in the newborn clinic was excellent (96.6%). Calculated first‐year mortality rate for babies with SCA compares favorably to the national infant mortality rate (6.8 vs. 9.8%). The SCA burden is extremely high in Angola, but NBS is feasible. Capacity building and training provide local healthcare workers with skills needed for a functional screening program and clinic. Contact and retrieval of all affected SCA infants remains a challenge, but families are compliant with clinic appointments and treatment. Early mortality data suggest screening and early preventive care saves lives. Am. J. Hematol. 88:984–989, 2013. © 2013 Wiley Periodicals, Inc.
Staphylococcus aureus biofilm activates the nucleotide‐binding oligomerization domain containing 2 (Nod2) pathway and proinflammatory factors on a human sinonasal explant model
Authors: Cantero Daniel , Cooksley Clare , Bassiouni Ahmed , Wormald Peter‐John , Vreugde Sarah
Published: August 2013

Background

The presence of Staphylococcus aureus biofilms on sinonasal mucosal surfaces is associated with recalcitrant chronic rhinosinusitis (CRS), but little is known about the innate immune response they trigger. We aimed to study the human pattern recognition receptor (PRR) nucleotide‐binding oligomerization domain containing 2 (Nod2) receptor and downstream pathway in response to initial S. aureus biofilm infection.

Methods

Using a validated protocol, sinonasal mucosae from 4 non‐CRS donors were cultured with and without S. aureus biofilms and planktonic cells. After 24 hours, RNA was extracted and gene expression was analyzed using a human antibacterial response polymerase chain reaction (PCR) array. Immunohistochemistry was performed to confirm the presence and determine the immunolocalization of selected proteins.

Results

C‐X‐C motif (CXC) chemokine ligands 1 and 2, interleukin‐6 (IL‐6), and genes related to the Nod2 pathway were significantly upregulated in biofilm‐treated tissues compared with control samples. Nod2 pathway–specific gene expression was increased in biofilm‐treated tissues compared with planktonic S. aureus–treated explants. Enhanced expression of Nod2 and nuclear factor kappa B1 (NF‐κB1) was also detected with immunohistochemistry in control and biofilm‐treated tissues.

Conclusion

S. aureus biofilms exerted a proinflammatory response in the mucosa and activation of the Nod2 pathway, indicating this receptor to be involved in the innate immune response to S. aureus biofilms. Further studies are required to elucidate the role of this pathway in CRS.
Regional disparities and practice patterns in surgical approaches to pituitary tumors in the United States
Authors: Svider Peter F. , Keeley Brieze R. , Husain Qasim , Mauro Kevin M. , Setzen Michael , Liu James K. , Eloy Jean Anderson
Published: August 2013

Background

Traditional microscopic and endoscopic transsphenoidal approaches (TSAs) are the most common surgical techniques in pituitary surgery. Examining regional practice patterns in pituitary surgery can provide valuable insights into which surgical strategies are most accessible, effective, and cost‐efficient. In this study we investigated regional variations in surgical approaches to pituitary tumors and evaluated evolving practice patterns in pituitary surgery.

Methods

The 2010 Medicare Part B Carrier Summary Database and Medicare Part B National Summary Database from 2003–2010 were examined using pituitary surgery Current Procedure Terminology (CPT) codes 61548 (microscopic transsphenoidal approach), 62165 (endoscopic transsphenoidal approach), and 61546 (transcranial approach).

Results

Endoscopic TSAs increased by over 10‐fold in the past decade, while usage of microscopic TSAs decreased by 23.3%. Nevertheless, the microscopic approach was still the most common TSA (64.7%) in 2010 compared to the endoscopic approach (35.3%). The microscopic TSA was predominant in the Southern and Western United States (74% and 69%, respectively). In the Northeast and Midwest, the rates of microscopic and endoscopic TSAs were roughly equivalent. However, the rate of endoscopic TSAs was statistically significantly higher (p < 0.05) in the Northeast and Midwest (47% and 45%, respectively) than in the South and West (26% and 31%, respectively). Transcranial approaches continued to decline from 4% to 2% over the last decade.

Conclusion

Regional disparities in transsphenoidal practice patterns exist in the United States. Although the microscopic approach is still more common overall, there has been an evolving shift toward endoscopic TSAs in the last decade.
Aqueous core polystyrene microspheres fabricated via suspension polymerization basing on a multiple pickering emulsion
Authors: Zhou Haiou , Shi Tiejun , Zhou Xun
Published: August 2013

Multi‐hollow or hollow polymer particles are of great interest in many fields. Here we successfully fabricate polystyrene microspheres with aqueous cores through w/o/w Pickering emulsion stabilized by modified SiO2 nanoparticles. The final structure and constituents of the microspheres is investigated via SEM, X‐ray photoelectron spectra, and thermo‐gravimetric analysis. The results demonstrate that the size and amount of aqueous cores in the microspheres can be tuned by the original structure of the multiple emulsions: when the volume fraction of inner water is 0.2, the inner structure of the microspheres obtained is porous and each pore is not interconnected; when the volume fraction of inner water is increased to 0.7, the resulting products are hollow microspheres and when 0.3% wt/vol of salt is added to the inner aqueous phase, the inner pores of the resulting microspheres enlarge or even coalesce. The multi‐hollow or hollow polystyrene microspheres with aqueous cores are expected to be candidates for encapsulation in biotechnology. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39761.
Synthesis of fluoroalkyl‐modified polyester and its application in improving the hydrophobicity and oleophobicity of cured polyester coatings
Authors: Xiong Jinsu , Xia Lei , Shentu Baoqing , Weng Zhixue
Published: August 2013

The fluoroalkyl‐modified polyester (PE‐Fn) was synthesized by the reaction of polyester resin (PE) and fluorinated isocyanate, and the structure of the synthesized product was characterized by proton nuclear magnetic resonance (1H‐NMR) and fluorine nuclear magnetic resonance (19F‐NMR). The water and oil wettability of the cured PE coatings with PE‐Fn as additives was investigated by contact angle meter. The results showed that the introduction of an extremely low concentration of PE‐Fn into PE led to the increase in contact angle of water and diiodomethane on cured PE coatings, and the decrease in the surface free energy. The X‐ray photoelectron spectroscopic (XPS) analysis showed that the F/C molar ratio in the outer few nanometers was significantly higher than that in the bulk, indicating that the fluoroalkyl groups in PE‐Fn had enriched on the coating surface. It was also found that longer fluoroalkyl groups and fluoroalkyl groups with CF3 at its end had the higher tendency to aggregate on the coating surface. The topological structures of the cured coatings were recorded by an atomic force microscope under tapping mode and the results revealed that there was a strong surface segregation of fluorinated species. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39812.
Preparation of aromatic poly(1,3,4‐oxadiazoles) pulps and their paper properties
Authors: Liu Jianrong , Jia Erpeng , Liu Pengqing , Ye Guangdou , Xu Jianjun
Published: August 2013

To improve the paper properties of the poly(1,3,4‐oxadiazoles) (POD), the POD pulps were prepared by prechemical and mechanical methods to increase their polarity, contact area, and interaction. The fibrillated degree of the staple fibers was evaluated by the Canadian Standard Freeness and the specific surface area, while the surface free energy was calculated by the Micro–wilhelmy method. Meanwhile, the functional groups and compositions on the surface of the POD fibers were confirmed by the FTIR–ATR and the X‐ray photoelectron spectroscopy, and the surface morphological structure and the crystalline structure of the POD fibers were observed by the fiber analyzer, scanning electron microscope, and Wide‐angle X‐ray diffraction, respectively. It was found that the pronounced abrasive and distinctive grooves were formed on the surface of the POD fibers after prechemical and mechanical treatment. The surface free energy of POD fibers increased 8.41%, and the polar part increased by 32.10% after treatment. It was confirmed that the polar functional groups and fibril were formed after chemical and mechanical treatment, so the interaction of the POD fibers was highly enhanced, and as a result the apparent density, tensile strength, fold endurance, and tear strength of the paper formed by those treated fibers were all improved apparently. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2014,131, 39818.
Preparation and characterization of poly(ethylene terephthalate) copolyesters modified with sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate and poly(ethylene glycol)
Authors: Zhao Ming‐Liang , Li Fa‐Xue , Yu Jian‐Yong , Wang Xue‐Li
Published: August 2013

Two types of poly(ethylene terephthalate) (PET) copolyesters were successfully prepared with sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate (SIPE) and poly(ethylene glycol) (PEG) units with different molecular weights named as cationic dyeable polyester and easy cationic dyeable polyester. Their chemical and crystalline structures were characterized by the nuclear magnetic resonance (NMR), wide angle X‐ray diffraction (WAXD), and small angle X‐ray scattering measurement, and their thermal properties were tested by differential scanning calorimetry and thermogravimetric analysis, respectively. NMR experimental results showed that the actual molar ratio of comonomers was basically consistent with the correlative feed ratio. WAXD results indicated that the crystalline structures of prepared copolyesters were similar to that of PET. Moreover, the glass transition temperature, melting temperature, and thermal degradation temperature were found to decrease with the reduction of theof PEG units as the incorporation of lowerof PEG units brought more ether bonds into molecular chains, which increased the irregularity of molecular chain arrangement and led to lower crystallinity. In addition, because the incorporation of PEG units with lower molecular weight led to more ether bonds and hydroxyl end‐groups in molecular chains, the value of contact angle of PET copolyesters dropped, manifesting PET copolyesters had better hydrophilicity with the decreasing molecular weight of PEG units.© 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2014,131, 39823.
Synthesis of Peripherally Nitrated, Aminated, and Arylaminated Subporphyrins
Authors: Tsurumaki Eiji , Osuka Atsuhiro
Published: August 2013

2‐Nitro‐5,10,15‐tri(4‐tert‐butylphenyl)subporphyrin 2 was prepared by the nitration of 5,10,15‐tri(4‐tert‐ butylphenyl)subporphyrin 1a with five equivalents of Cu(NO3)2⋅5 H2O in a mixed EtOAc/Ac2O solution and was reduced into 2‐amino‐5,10,15‐tri(4‐tert‐butylphenyl)subporphyrin 3. Bromination of 5,10,15‐triphenylsubporphyrin 1b with 1.5 equivalents of N‐bromosuccinimide (NBS) gave 2‐bromo‐5,10,15‐triphenylsubporphyrin, which was converted into various 2‐arylamino‐5,10,15‐triphenylsubporphyrins (4a, 4b, 4c, 4d) and 2‐benzamido‐5,10,15‐triphenylsubporphyrin 5 through Pd‐catalyzed cross‐coupling reactions. These molecules constitute the first examples of mono‐β‐substituted subporphyrins. These subporphyrins exhibit significantly perturbed optical and electrochemical properties, which reflect a large influence of the peripherally attached substituents on the electronic networks of subporphyrins.
Fluctuating Asymmetry as Risk Marker for Stress and Structural Defects in a Toxicologic Experiment
Authors: Breno Matteo , Bots Jessica , De Schaepdrijver Luc , Van Dongen Stefan
Published: August 2013

Fluctuating asymmetry (the directionally random asymmetry of bilateral structures, FA) is commonly used as a measure of developmental instability, and may increase with stress. As several studies reported a relation between FA and developmental abnormalities, we investigate whether FA could be an additional perhaps more sensitive marker of developmental toxicity. The aim of this work is analyzing patterns of FA in multiple traits in a large dataset of rabbit fetuses, which were prenatally exposed to a toxic compound and sacrificed just before natural delivery. Gravid females were exposed to three doses of this compound, inducing abnormalities in the fetuses at the high dose only. The average FA, however, was already higher than control in rabbit fetuses of the low‐dose group but did not further increase with higher concentrations. Moreover, the increase in FA differed between traits, with the hindlimbs showing the strongest response. In addition, we did not find any association between FA and the presence of fetal abnormalities at the individual level. Although these results suggest that FA may act as “an early warning system,” we did not find a dose–response relationship with increasing stress and effects were trait‐specific. Further testing is needed before FA may be considered as a sensitive marker in developmental toxicity studies.
Teratology Study of Amide Derivatives of Branched Aliphatic Carboxylic Acids with 4‐Aminobenzensulfonamide in NMRI Mice
Authors: Onishi Yuko , Okada Akinobu , Noyori Hiroko , Okamura Ai , Hen Naama , Yagen Boris , Bialer Meir , Fujiwara Michio
Published: August 2013

BACKGROUND

Valproic acid (VPA), widely used to treat epilepsy, bipolar disorders, and migraine prophylaxis, is known to cause neural tube and skeletal defects in humans and animals. Aminobenzensulfonamide derivatives of VPA with branched aliphatic carboxylic acids, namely 2‐methyl‐N‐(4‐sulfamoyl‐phenyl)‐pentanamide (MSP), 2‐ethyl‐N‐(4‐sulfamoyl‐phenyl)‐butyramide (ESB), 2‐ethyl‐4‐methyl‐N‐(4‐sulfamoyl‐phenyl)‐pentanamide (EMSP), and 2‐ethyl‐N‐(4‐sulfamoyl‐benzyl)‐butyramide (ESBB), have shown more potent anticonvulsant activity than VPA in preclinical testing. Here, we investigated the teratogenic effects of these analogous compounds of VPA in NMRI mice.

METHODS

Pregnant NMRI mice were given a single subcutaneous injection of either VPA at 1.8 or 3.6 mmol/kg, or MSP, ESB, EMSP, or ESBB at 1.8, 3.6, or 4.8 mmol/kg on gestation day (GD) 8. Cesarean section was performed on GD 18, and the live fetuses were examined for external and skeletal malformations.

RESULTS

Compared with VPA, which induced neural tube defects (NTDs) in fetuses at 1.8 and 3.6 mmol/kg, the analog derivatives induced no NTDs at dose levels up to 4.8 mmol/kg (except for a single case of exencephaly at 4.8 mmol/kg MSP). Skeletal examination showed several abnormalities mainly at the axial skeletal level with VPA at 1.8 mmol/kg. Fused vertebrae and/or fused ribs were also observed with MSP, ESB, EMSP, and ESBB, they were less severe and seen at a lower incidence that those induced by VPA at the same dose level.

CONCLUSIONS

In addition to exerting more potent preclinical antiepileptic activity, teratology comparison indicates that aminobenzensulfonamide analogs are generally more weakly teratogenic than VPA.
Biophysical Studies of the Amyloid β‐Peptide: Interactions with Metal Ions and Small Molecules
Authors: Wärmländer Sebastian , Tiiman Ann , Abelein Axel , Luo Jinghui , Jarvet Jyri , Söderberg Kajsa L. , Danielsson Jens , Gräslund Astrid
Published: August 2013

Alzheimer's disease is the most common of the protein misfolding (“amyloid”) diseases. The deposits in the brains of afflicted patients contain as a major fraction an aggregated insoluble form of the so‐called amyloid β‐peptides (Aβ peptides): fragments of the amyloid precursor protein of 39–43 residues in length. This review focuses on biophysical studies of the Aβ peptides: that is, of the aggregation pathways and intermediates observed during aggregation, of the molecular structures observed along these pathways, and of the interactions of Aβ with Cu and Zn ions and with small molecules that modify the aggregation pathways. Particular emphasis is placed on studies based on high‐resolution and solid‐state NMR methods. Theoretical studies relating to the interactions are also included. An emerging picture is that of Aβ peptides in aqueous solution undergoing hydrophobic collapse together with identical partners. There then follows a relatively slow process leading to more ordered secondary and tertiary (quaternary) structures in the growing aggregates. These aggregates eventually assemble into elongated fibrils visible by electron microscopy. Small molecules or metal ions that interfere with the aggregation processes give rise to a variety of aggregation products that may be studied in vitro and considered in relation to observations in cell cultures or in vivo. Although the heterogeneous nature of the processes makes detailed structural studies difficult, knowledge and understanding of the underlying physical chemistry might provide a basis for future therapeutic strategies against the disease. A final part of the review deals with the interactions that may occur between the Aβ peptides and the prion protein, where the latter is involved in other protein misfolding diseases.
Acenaphthylene‐Fused Cyclo[8]pyrroles with Intense Near‐IR‐Region Absorption Bands
Authors: Okujima Tetsuo , Ando Chie , Mack John , Mori Shigeki , Hisaki Ichiro , Nakae Takahiro , Yamada Hiroko , Ohara Keishi , Kobayashi Nagao , Uno Hidemitsu
Published: August 2013

An acenaphthylene‐fused cyclo[8]pyrrole was synthesized by using an oxidative coupling reaction of the corresponding 2,2′‐bipyrrole. Two conformational isomers 1 a and 1 b were isolated, and their molecular structures were elucidated by X‐ray crystallographic studies. The less‐polar and lower‐symmetry 1 b isomer can be converted into the 1 a isomer through a thermal ring flip. Application of the perimeter model developed by Michl to magnetic circular dichroism spectroscopic data and theoretical calculations demonstrate that there is a marked redshift of the near‐IR absorption maxima relative to cyclo[8]isoindole because there is a significant stabilization of the LUMO due to the differing effects of a fused ring expansion with acenaphthylene and benzene moieties on the frontier π molecular orbitals.
Synthetic and DFT Studies Towards a Unified Approach to Phlegmarine Alkaloids: Aza‐Michael Intramolecular Processes Leading to 5‐Oxodecahydroquinolines
Authors: Bradshaw Ben , Luque‐Corredera Carlos , Saborit Gisela , Cativiela Carlos , Dorel Ruth , Bo Carles , Bonjoch Josep
Published: August 2013

A diastereoselective synthesis of cis‐5‐oxodecahydroquinolines is described in which three stereocenters are generated in a one‐pot reaction. The reaction involves a lithium hydroxide‐promoted Robinson annulation/intramolecular aza‐Michael domino process from an achiral acyclic tosylamine‐tethered β‐keto ester. The development and scope of this reaction was facilitated through the use of DFT‐based mechanistic studies, which enabled the observed diastereodivergent course of the azacyclization to be rationalized. The varying stereochemistry and stability of the resulting decahydroquinolines was found to depend on whether a β‐keto ester or ketone were embedded in the substrates undergoing aminocyclization. This synthetic approach gave access not only to both diastereomeric cis‐decahydroquinolines from the same precursor, but also to the corresponding trans isomers, through an epimerization processes of the corresponding N‐unsubstituted cis‐5‐oxodecahydroquinolines. The described methodology provides advanced building‐blocks with the three relative stereochemistries required for the total synthesis of phlegmarine alkaloids.
Oxaphospholes and Bisphospholes from Phosphinophosphonates and α,β‐Unsaturated Ketones
Authors: Arkhypchuk Anna I. , Orthaber Andreas , Mihali Viorica Alina , Ehlers Andreas , Lammertsma Koop , Ott Sascha
Published: August 2013

The reaction of a {W(CO)5}‐stabilized phosphinophosphonate 1, (CO)5WPH(Ph)P(O)(OEt)2, with ethynyl‐ (2 a–f) and diethynylketones (7–11, 18, and 19) in the presence of lithium diisopropylamide (LDA) is examined. Lithiated 1 undergoes nucleophilic attack in the Michael position of the acetylenic ketones, as long as this position is not sterically encumbered by bulky (iPr)3Si substituents. Reaction of all other monoacetylenic ketones with lithiated 1 results in the formation of 2,5‐dihydro‐1,2‐oxaphospholes 3 and 4. When diacetylenic ketones are employed in the reaction, two very different product types can be isolated. If at least one (Me)3Si or (Et)3Si acetylene terminus is present, as in 7, 8, and 19, an anionic oxaphosphole intermediate can react further with a second equivalent of ketone to give cumulene‐decorated oxaphospholes 14, 15, 24, and 25. Diacetylenic ketones 10 and 11, with two aromatic acetylene substituents, react with lithitated 1 to form exclusively ethenyl‐bridged bisphospholes 16 and 17. Mechanisms that rationalize the formation of all heterocycles are presented and are supported by DFT calculations. Computational studies suggest that thermodynamic, as well as kinetic, considerations dictate the observed reactivity. The calculated reaction pathways reveal a number of almost isoenergetic intermediates that follow after ring opening of the initially formed oxadiphosphetane. Bisphosphole formation through a carbene intermediate G is greatly favored in the presence of phenyl substituents, whereas the formation of cumulene‐decorated oxaphospholes is more exothermic for the trimethylsilyl‐containing substrates. The pathway to the latter compounds contains a 1,3‐shift of the group that stems from the acetylene terminus of the ketone substrates. For silyl substituents, the 1,3‐shift proceeds along a smooth potential energy surface through a transition state that is characterized by a pentacoordinated silicon center. In contrast, a high‐lying transition state TS(E′–F′)R=Ph of 37 kcal mol−1 is found when the substituent is a phenyl group, thus explaining the experimental observation that aryl‐terminated diethynylketones 10 and 11 exclusively form bisphospholes 16 and 17.
Simultaneous Degradation of Trichloroethylene and Toluene by Burkholderia cepacia G4 and the Effect of Biotransformation on Bacterial Density
Authors: Hamid Shanawar , Amin Muhammad Tahir , Alazba Abdulrahman Ali , Manzoor Umair
Published: August 2013

The effect of biomass density, effect of different ratios of trichloroethylene (TCE) and toluene on biomass, and strategies to cope with problems using acclimated Burkholderia cepacia G4 were investigated. Complete degradation of TCE was achieved when B. cepacia G4 was exposed to 0.5 mg/L TCE and 10 mg/L toluene after starvation of 100 h. Overall results of this study show that degradation rates of toluene decreased as TCE concentration increased. On the contrary, degradation rates of TCE increased up to 10 mg/L TCE and then decreased. Transformation capacity of B. cepacia G4 increased as toluene concentration increased but transformation yield decreased showing that excessive substrate supply may not help to improve specific performance parameters. Results of these experiments bear that instead of simultaneous injection of TCE and substrate, the supply of substrate in pulses can increase the efficiency of B. cepacia G4 or similar bacterial strains.
Small orangiophilic squamous‐like cells: An underrecognized and useful morphological feature for the diagnosis of malignant mesothelioma in pleural effusion cytology
Authors: Chen Longwen , Caldero Sonia Gatius , Gmitro Stephen , Smith Maxwell L. , De Petris Giovanni , Zarka Mathew A.
Published: August 2013

BACKGROUND

The cytological diagnosis of malignant mesothelioma (MM) on serous effusion is challenging due to significant morphologic overlap with reactive mesothelial cells and adenocarcinoma. One of the morphologic features of MM in effusion cytology, small orangiophilic squamous‐like cells (SOSLC), has received little attention. To the best of the authors' knowledge, the current study is the first to assess the sensitivity and specificity of SOSLC in serous effusion specimens from histology‐proven MM cases along with those of reactive mesothelial and adenocarcinoma cases.

METHODS

A total of 130 cases of pleural (86 cases) and peritoneal (44 cases) effusion cytology cases (30 with histology‐proven MM, 41 with adenocarcinoma, and 59 with reactive mesothelial cells) were studied. The presence or absence of SOSLC was recorded in each case.

RESULTS

The cytological diagnoses of the 30 histology‐proven MM cases included 1) atypical mesothelial cells, favor reactive (4 cases); 2) atypical mesothelial cells, suspicious for or cannot exclude mesothelioma (18 cases); and 3) positive for MM (8 cases). SOSLC were found in 10 of the 30 MM effusion cases (33.3%), 1 of the 41 adenocarcinoma cases (2.4%), and 5 of the 59 reactive mesothelial cell cases (8.5%). SOSLC were more likely to be present in MM effusions compared with either adenocarcinoma (P < .0001) or reactive mesothelial cell (P < .02) effusions. All 10 cases of MM with SOSLC were from pleural fluids. One case of peritoneal serous adenocarcinoma had SOSLC and 5 cases of reactive mesothelial cells in peritoneal fluid were found to have SOSLC.

CONCLUSIONS

Although not sensitive, the presence of SOSLC is quite specific for MM in pleural fluid cytology specimens. Finding this morphological feature in pleural fluid should alert the pathologist to a possible diagnosis of MM.

Cancer (Cancer Cytopathol) 2014;122:70–75. © 2013 American Cancer Society.
Kinetically Limited CO Adsorption: Spill‐Over as a Highly Effective Adsorption Pathway on Bimetallic Surfaces
Authors: Hartmann Heinrich , Diemant Thomas , Behm R. Jürgen
Published: August 2013

We demonstrate that the (local) adsorbed carbon monoxide, COad, coverage on the Pt‐free areas of bimetallic Pt/Ru(0001) surfaces (a Ru(0001) substrate partly covered by Pt monolayer islands) can be increased to ∼0.80 monolayers (ML), well above the established saturation COad coverage of 0.68 ML, even under ultrahigh vacuum conditions by using spill‐over of CO adsorbed on the Pt islands to the Ru areas as an highly effective adsorption channel. The apparent COad saturation coverage of 0.68 ML on pure Ru(0001) is identified as due to kinetic limitations, hindering further uptake from the gas phase, rather than being caused by thermodynamic reasons. This spill‐over mechanism is proposed to be a general phenomenon for adsorption on bimetallic surfaces.
Composition and morphological characteristics of sialoliths
Authors: Faklaris I. , Bouropoulos N. , Vainos N. A.
Published: August 2013

Sialolithiasis refers to pathological minerilazation in the salivary glands and ducts. Aiming to a better understanding of the formation phenomena, structural and morphological analysis of a relatively large ensemble of sialoliths extracted from 22 patients via sielendoscopy was performed. Characterization methods, including Fourier Transform Infrared (FTIR) Spectroscopy, X‐Ray Diffraction, Raman spectroscopy and Scanning Electron Microscopy (SEM), showed that the large majority of 90% of sialoliths were composed of carbonate apatite as the inorganic phase, while SEM imaging revealed the presence of bacteria in 13 cases. Furthermore, carbonate apatite crystals in the form of parallel or randomly oriented sheets were observed and in some cases rhombohedral calcite‐type nanocrystals were detected. The present findings may contribute to a better understanding of the formation mechanisms in vivo and and contribute to the treatment of sialolithiasis.
Current knowledge on cannabinoids in oral fluid
Authors: Lee Dayong , Huestis Marilyn A.
Published: August 2013

Oral fluid (OF) is a new biological matrix for clinical and forensic drug testing, offering non‐invasive and directly observable sample collection reducing adulteration potential, ease of multiple sample collections, lower biohazard risk during collection, recent exposure identification, and stronger correlation with blood than urine concentrations. Because cannabinoids are usually the most prevalent analytes in illicit drug testing, application of OF drug testing requires sufficient scientific data to support sensitive and specific OF cannabinoid detection. This review presents current knowledge of OF cannabinoids, evaluating pharmacokinetic properties, detection windows, and correlation with other biological matrices and impairment from field applications and controlled drug administration studies. In addition, onsite screening technologies, confirmatory analytical methods, drug stability, and effects of sample collection procedure, adulterants, and passive environmental exposure are reviewed. Delta‐9‐tetrahydrocannabinol OF concentrations could be >1000 µg/L shortly after smoking, whereas minor cannabinoids are detected at 10‐fold and metabolites at 1000‐fold lower concentrations. OF research over the past decade demonstrated that appropriate interpretation of test results requires a comprehensive understanding of distinct elimination profiles and detection windows for different cannabinoids, which are influenced by administration route, dose, and drug use history. Thus, each drug testing program should establish cut‐off criteria, collection/analysis procedures, and storage conditions tailored to its purposes. Building a scientific basis for OF testing is ongoing, with continuing OF cannabinoids research on passive environmental exposure, drug use history, donor physiological conditions, and oral cavity metabolism needed to better understand mechanisms of cannabinoid OF disposition and expand OF drug testing applicability. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.
Role ofSp5as an essential early regulator of neural crest specification inxenopus
Authors: Park Dong‐Seok , Seo Jeong‐Han , Hong Mina , Bang Wonseon , Han Jin‐Kwan , Choi Sun‐Cheol
Published: August 2013

Background:The neural crest (NC) is a multipotent embryonic cell population, which is induced by an integration of secreted signals including BMP, Wnt, and FGF and, subsequently, NC cell fates are specified by a regulatory network of specific transcription factors. This study was undertaken to identify a role ofSp5transcription factor in vertebrates.Results:Xenopus Sp5is expressed in the prospective neural crest regions from gastrulation through the tadpole stages in early development. Knockdown ofSp5caused severe defects in craniofacial cartilage, pigmentation, and dorsal fin. Gain‐ and loss‐of‐function ofSp5led to up‐ and down‐regulation of the expression of NC markers in the neural fold, respectively. In contrast,Sp5had no effect on neural induction and patterning.Sp5regulated the expression of neural plate border (NPB) specifiers,Msx1andPax3, and these regulatory factors recovered the expression of NC marker in theSp5‐deficient embryos. Depletion ofSp5impaired NC induction by Wnt/β‐catenin or FGF signal, whereas its co‐expression rescued NC markers in embryos in which either signal was blocked.Conclusions:These results suggest thatSp5functions as a critical early factor in the genetic cascade to regulate NC induction downstream of Wnt and FGF pathways.Developmental Dynamics 242:1382–1394, 2013. © 2013 Wiley Periodicals, Inc.
Design of Porphyrin‐dota‐Like Scaffolds as All‐in‐One Multimodal Heterometallic Complexes for Medical Imaging
Authors: Eggenspiller Antoine , Michelin Clément , Desbois Nicolas , Richard Philippe , Barbe Jean‐Michel , Denat Franck , Licona Cynthia , Gaiddon Christian , Sayeh Amira , Choquet Philippe , Gros Claude P.
Published: August 2013

A series of four multimodal ligands incorporating one porphyrin moiety and one or more dota‐like macrocycles all‐in‐one in the same molecular architecture have been synthesized and full characterized. The corresponding gadolinium(III) complexes were also synthesized and heterometallic complexes incorporating both gadolinium(III) and copper(II) ions were prepared as potential MRI/PET multimodal contrast agents. One ligand (L4) includes an amine moiety that can be activated for easy conversion into an isothiocyanate group for further anchoring to a biological vector. Preliminary relaxivity, cytotoxicity, and MRI studies showed that the complexes developed in this work are very promising medical‐imaging agents for the enhancement of contrast in bimodal MRI techniques.
Achievable rate regions for a three‐user multiple access channel with partial side information
Authors: Bahmani Elham , Hodtani Ghosheh Abed
Published: August 2013

A generalisation of the Gaussian doubly dirty multiple access channel to a Gaussian triply dirty multiple access channel (GTD‐MAC) is considered, where there are three additive interference signals, each one non‐causally known to only associated transmitter. Same as in the Gaussian doubly dirty multiple access channel, Costa's strategy (i.e. random binning scheme) cannot achieve positive rates in the limit of strong interferences. In contrast, it is shown that positive rates independent of the interferences can be achieved by lattice strategies. In fact in some cases—which depend on the noise variance and power constraints—lattice strategies are optimal, in particular, in the high signal‐to‐noise ratio (SNR) regime. For the GTD‐MAC, two models are considered, full side information and partial side information at the transmitters. The results show that partiality in side information reduces the achievable rates as numerical illustrations confirm. Also, the results for the GTD‐MAC can be extended to the K‐user case. Copyright © 2013 John Wiley & Sons, Ltd.
Germline variation in NCF4, an innate immunity gene, is associated with an increased risk of colorectal cancer
Authors: Ryan Bríd M. , Zanetti Krista A. , Robles Ana I. , Schetter Aaron J. , Goodman Julie , Hayes Richard B. , Huang Wen‐Yi , Gunter Mark J. , Yeager Meredith , Burdette Laurie , Berndt Sonja I. , Harris Curtis C.
Published: August 2013

Chronic inflammation has been implicated in the etiology of colorectal adenoma and cancer; however, few key inflammatory genes mediating this relationship have been identified. In this study, we investigated the association of germline variation in innate immunity genes in relation to the risk of colorectal neoplasia. Our study was based on the analysis of samples collected from the prostate, lung, colorectal and ovarian (PLCO) Cancer Screening Trial. We investigated the association between 196 tag single nucleotide polymorphisms (SNPs) in 20 key innate immunity genes with risk of advanced colorectal adenoma and cancer in 719 adenoma cases, 481 cancer cases and 719 controls. Logistic regression was used to estimate odds ratios (OR) and 95% confidence intervals (CIs). After Bonferroni correction, the AG/GG genotype of rs5995355, which is upstream of NCF4, was associated with an increased risk of colorectal cancer (OR = 2.43, 95% CI = 1.73–3.39; p < 0.0001). NCF4 is part of the NAPDH complex, a key factor in biochemical pathways and the innate immune response. While not definitive, our analyses suggest that the variant allele does not affect expression of NCF4, but rather modulates activity of the NADPH complex. Additional studies on the functional consequences of rs5995355 in NCF4 may help to clarify the mechanistic link between inflammation and colorectal cancer.
Transport barriers and strategies of antitumor nanocarriers delivery system
Authors: Zhang Lin , Wang Yazhou , Cao Yang , Lou Deshuai , Wang Bochu
Published: August 2013

Nanocarriers with unique characteristics have attracted great attentions in tumor treatment, but therapeutic efficacy of drugs is limited by the nonuniform delivery of nanocarriers to tumor by three progresses blood circulation system, tumor vessels and tumor interstitium. The total number of nanocarriers usually was reduced dramatically into tumor, because nanocarriers in blood vessels always can be cleared by RES system or accumulated in kidney and liver. Abnormal vessels are almost uneven allocation on tumor surface and cannot contribute to deliver nanocarriers to all the region of tumors, especially the interior of tumors. In addition, nanocarriers will be retained in perivascular space of tumor under high interstitial fluid pressure (IFP) and heterogeneous structure of tumor matrix. In this article, we reviewed the structure of nanocarriers and the barriers in tumor microenvironment influencing delivery of nanocarriers. With the aim of transport over these barriers to increase the delivery efficiency of nanocarriers, two strategies tumor microenvironment normalization and nanocarriers optimization were proposed and designed. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 101A: 3661–3669, 2013.
EphA4 Receptor Is a Novel Negative Regulator of Osteoclast Activity
Authors: Stiffel Virginia , Amoui Mehran , Sheng Matilda H-C , Mohan Subburaman , Lau K-H William
Published: August 2013

Of the ephrin (Eph) receptors, mature osteoclasts express predominantly EphA4. This study sought to determine if EphA4 has a regulatory role in osteoclasts. Treatment of RAW/C4 cells with Epha4 small interfering RNAs (siRNAs) increased average size, Ctsk mRNA expression level, and bone resorption activity of the derived osteoclast-like cells. Activation of the EphA4 signaling in osteoclast precursors with EfnA4-fc chimeric protein reduced cell size and resorption activity of the derived osteoclasts. Homozygous Epha4 null mice had substantially less trabecular bone in femur and vertebra compared to wild-type controls. The bone loss was due to a decrease in trabecular number and an increase in trabecular spacing, but not to an increase in osteoclast-lined bone surface or an increase in the number of osteoclasts on bone surface. Dynamic histomorphometry and serum biomarker analyses indicate that bone formation in Epha4 null mice was reduced slightly but not significantly. Osteoclasts of Epha4 null mice were also larger, expressed higher levels of Mmp3 and Mmp9 mRNAs, and exhibited greater bone resorption activity than wild-type osteoclasts in vitro. Deficient Epha4 expression had no effects on the total number of osteoclast formed in response to receptor activator of NF-κB ligand nor on apoptosis of osteoclasts in vitro. It also did not affect the protein-tyrosine phosphorylation status of its ligands, EfnB2, EfnA2, and EfnA4, in osteoclasts. Deficient Epha4 expression in Epha4 null osteoclasts activated the β3-integrin signaling through reduced phosphorylation of the tyr-747 residue, which led to increased binding of the stimulatory talin and reduced binding of the inhibitory Dok1 to β3-integrin. This in turn activated Vav3 and the bone resorption activity of osteoclasts. In conclusion, we demonstrate for the first time that EphA4 is a potent negative regulator of osteoclastic activity, mediated in part through increased Dok1 binding to β3-integrin via an increase in EphA4-dependent tyr-747 phosphorylation. © 2014 American Society for Bone and Mineral Research.