bluuebunny/crossref_metadata_2025 huggingface dataset:
Formation of Intermetallic Compounds by Reactive Metal–Support Interaction: A Frequently Encountered Phenomenon in Catalysis
Authors: Penner Simon , Armbrüster Marc
Published: December 2014

This Review discusses the structural and catalytic aspects of the recently introduced reactive metal–support interaction. This special term was coined to account for the inability of the original concept of the strong metal–support interaction to accurately describe the structural, compositional, and electronic changes frequently occurring in oxide‐supported metal particle catalysts at very high temperatures upon reduction in hydrogen, in many cases leading to intermetallic compound or substitutional alloy formation. This inaccuracy predominantly refers to the requirement of full reversibility upon oxidation and mild reduction for a “strong” metal–support interaction. A close look at the formation of oxide‐supported intermetallic compounds upon high‐temperature reduction reveals that these compounds are very common in catalysis and the situation is much more complex compared to unsupported intermetallic compounds due to the presence of the intermetallic compound–oxide interface.
Metal Nanoparticles Immobilized on Carbon Nanodots as Highly Active Catalysts for Hydrogen Generation from Hydrazine in Aqueous Solution
Authors: Sun Jian‐Ke , Xu Qiang
Published: December 2014

Well‐dispersed PtNi nanoparticles (NPs) grown on carbon nanodots (CNDs) derived from a metal–organic framework (ZIF‐8) are synthesized by a simple reduction of metal precursors in the presence of CNDs, wherein the CNDs prove to be a powerful dispersion agent and distinct support for the PtNi NPs. The resultant PtNi‐CND catalyst exerts almost 100 % H2 selectivity and a high activity for the decomposition of hydrous hydrazine at room temperature. This excellent catalytic performance might be a result of the synergistic effect of the CND support and the PtNi NPs. The utilization of CNDs as a support to anchor the active component NPs and thus to facilitate the electron transfer and mass transport kinetics during the catalytic reaction process opens up new avenues to design high‐performance catalysts.
Exploration of the Substrate Promiscuity of Biosynthetic Tailoring Enzymes as a New Source of Structural Diversity for Polyene Macrolide Antifungals
Authors: Santos‐Aberturas Javier , Engel Jennifer , Dickerhoff Jonathan , Dörr Mark , Rudroff Florian , Weisz Klaus , Bornscheuer Uwe T.
Published: December 2014

Even though there is an urgent need for new antifungals with improved clinical properties, the substrate promiscuity of tailoring enzymes has been poorly studied as a source of new structural diversity for polyene macrolides. We explore the acceptance of different polyene macrolides by the glutamine amidotransferase PscA and the catalytic effect of different homologous P450 cytochromes on a common scaffold, the pimaricin precursor 4,5‐desepoxypimaricin. By combining these two parallel strategies, we present three new pimaricin derivatives and a new lucensomycin variant. Our results show that P450 cytochromes devoted to the modification of the polyol region of polyene macrolides are not as substrate‐specific as previously thought and highlight PscA as a versatile small‐ring polyene‐modifying enzyme that allows the preparation of new carboxamide derivatives. We also provide useful information for the future production of previously unconceived epoxidized polyene macrolide antifungals.
Transfer Hydrogenation of Ketones, Nitriles, and Esters Catalyzed by a Half‐Sandwich Complex of Ruthenium
Authors: Lee Sun‐Hwa , Nikonov Georgii I.
Published: December 2014

Half‐sandwich complexes [Cp(PiPr3)Ru(CH3CN)2]PF6 (1; Cp=cyclopentadienyl) and [Cp*(phen)Ru(CH3CN)]PF6 (2; Cp*=pentamethylcyclopentadienyl, phen=phenanthroline) catalyse the transfer hydrogenation of ketones to alcohols, aldimines to amines, and nitriles to imines under mild conditions. In the latter process, the imine products come from the coupling of the amines formed initially with acetone derived from the reducing solvent (isopropanol). Among functionally substituted nitriles, the aldo and keto groups are reduced concomitantly with the cyano group, whereas ester and amido groups are tolerated. Amides and alkyl esters are not reduced under these conditions even upon heating to 70 °C. However, phenylbenzoates and trifluoroacetates are reduced to alcohols. Kinetic studies on the reduction of acetophenone in isopropanol established that the reaction is first order in both the substrate and the alcohol. Stoichiometric mechanistic studies showed the formation of a hydride species. A hydride mechanism was proposed to account for these observations.
Continuous Flow Preparation of Iron Oxide Nanoparticles Supported on Porous Silicates
Authors: Yepez Alfonso , Lam Frank L. Y. , Romero Antonio A. , Kappe C. Oliver , Luque Rafael
Published: December 2014

A simple, innovative, and efficient continuous flow methodology for the direct preparation of supported nanoparticles on porous materials by using metal precursor solution flowing through heated packed‐bed reactors containing the support material has been developed. The effects of the flow rate of the precursor solution, temperature, and nature of the support material and metal loading have been investigated. Results indicated that optimum conditions comprised short residence times (with typical flow rates of 0.5 mL min−1 and below) under mild heating (100 °C) to achieve optimum materials in terms of nanoparticle size and structure and catalytic activity. The support was found to have a remarkable effect on both loading and distribution and agglomeration of nanoparticles in the system, with a previously reported Fe/Al synergy also observed in the prepared nanomaterials, which led to optimum results.
Effects of Viscous Dissipation and Rarefaction on Parallel Plates with Constant Heat Flux Boundary Conditions
Authors: Kushwaha Hari Mohan , Sahu Santosh K.
Published: December 2014

The effect of viscous dissipation and rarefaction on heat transfer characteristics of hydrodynamically and thermally fully developed flow between parallel plates with constant heat flux conditions is analyzed. Three different types of heat flux boundary conditions, i.e., both plates kept at different constant heat fluxes, both plates kept at equal constant heat fluxes, and one plate insulated, are applied. In all cases, closed form expressions are obtained for the temperature distribution and Nusselt number. Viscous dissipation, rarefaction, and heat flux ratio are found to influence the heat transfer substantially. The present predictions are verified for the cases which neglect the microscale and viscous heating effect. The obtained results are in good agreement with other analytical results.
Esterification of Renewable Levulinic Acid to n‐Butyl Levulinate over Modified H‐ZSM‐5
Authors: Nandiwale Kakasaheb Y. , Bokade Vijay V.
Published: December 2014

The synthesis of n‐butyl levulinate, one of the most important biodiesel additives, by catalytic esterification of biomass‐derived levulinic acid (LA) with n‐butanol over modified H‐ZSM‐5 (micro/meso‐HZ‐5) in a closed‐batch system is reported for the first time. The optimization of the reaction conditions such as the reactant molar ratio, the catalyst loading, the reaction time and the temperature was performed in view to maximize the yield of n‐butyl levulinate. Micro/meso‐HZ‐5 was found to be the most efficient catalyst, with 98 % yield of n‐butyl levulinate and a reusability for six cycles, which is higher than reported in the literature. A possible catalytic mechanism for the esterification reaction is also proposed. A second‐order pseudo‐homogeneous model with R2 > 0.97 confirmed that the esterification reaction is performed in the kinetic regime due to the high activation energy of 23.84 kJ mol−1.
Design and Control of Ionic Liquid‐Catalyzed Reactive Distillation for n‐Butyl Acetate Production
Authors: Peng Xuan , Wang Likun
Published: December 2014

A simulation study of n‐butyl acetate production with the [Hpy][HSO4] ionic liquid catalyst was performed. Due to the lack of phase equilibrium data, the binary interaction parameters of the NRTL model for ionic liquid and reactive species were calculated by the COSMO‐RS technique. A reactive distillation process with recycled ionic liquid stream was proposed, and the column configuration was optimized by minimization of the total annual capital. The novel process is considerably efficient and economic compared to the traditional reactive distillation process of nonionic liquids. With the steady‐state parameters, a plant‐wide control structure was further developed to evaluate the robustness of the control system by exerting the disturbances of feed flow rate and feed composition. Dynamic simulation results suggest that the control scheme with a composition controller is timely and effective.
Manipulating the Hydrocarbon Selectivity of Copper Nanoparticles in CO2 Electroreduction by Process Conditions
Authors: Kas Recep , Kortlever Ruud , Yılmaz Hasan , Koper Marc T. M. , Mul Guido
Published: December 2014

The formation of ethylene in CO2 electroreduction over rough copper electrodes is often explained by the presence of specific surface crystal steps, edges and defects. We demonstrate that an identical electrode covered with copper nanoparticles can yield either predominantly ethylene or methane, depending on the electrolyte concentration and applied CO2 pressure. Calculations of the pH near the electrode surface suggest that ethylene formation is favored by a relatively high (local) pH. Furthermore, the conditions leading to the formation of significant amounts of methane result in rapid deterioration of hydrocarbon production rates, whereas electrode performance in conditions favoring ethylene production can be sustained for hours. This study substantially alters the mechanistic interpretation of formation of ethylene over rough copper surfaces and implies that applied process conditions inducing pH variations near the electrode surface need to be taken into consideration.
Insights into Functional‐Group‐Tolerant Polymerization Catalysis with Phosphine–Sulfonamide Palladium(II) Complexes
Authors: Jian Zhongbao , Falivene Laura , Wucher Philipp , Roesle Philipp , Caporaso Lucia , Cavallo Luigi , Göttker‐Schnetmann Inigo , Mecking Stefan
Published: December 2014

Two series of cationic palladium(II) methyl complexes {[(2‐MeOC6H4)2PC6H4SO2NHC6H3(2,6‐R1,R2)]PdMe}2[A]2 (X1+‐A: R1=R2=H: H1+‐A; R1=R2=CH(CH3)2: DIPP1+‐A; R1=H, R2=CF3: CF31+‐A; A=BF4 or SbF6) and neutral palladium(II) methyl complexes {[(2‐MeOC6H4)2PC6H4SO2NC6H3(2,6‐R1,R2)]PdMe(L)} (X1‐acetone: L=acetone; X1‐dmso: L=dimethyl sulfoxide; X1‐pyr: L=pyridine) chelated by a phosphine–sulfonamide were synthesized and fully characterized. Stoichiometric insertion of methyl acrylate (MA) into all complexes revealed that a 2,1 regiochemistry dominates in the first insertion of MA. Subsequently, for the cationic complexes X1+‐A, β‐H elimination from the 2,1‐insertion product X2+‐AMA‐2,1 is overwhelmingly favored over a second MA insertion to yield two major products X4+‐AMA‐1,2 and X5+‐AMA. By contrast, for the weakly coordinated neutral complexes X1‐acetone and X1‐dmso, a second MA insertion of the 2,1‐insertion product X2MA‐2,1 is faster than β‐H elimination and gives X3MA as major products. For the strongly coordinated neutral complexes X1‐pyr, no second MA insertion and no β‐H elimination (except for DIPP2‐pyrMA‐2,1) were observed for the 2,1‐insertion product X2‐pyrMA‐2,1. The cationic complexes X1+‐A exhibited high catalytic activities for ethylene dimerization, affording butenes (C4) with a high selectivity of up to 97.7 % (1‐butene: 99.3 %). Differences in activities and selectivities suggest that the phosphine–sulfonamide ligands remain coordinated to the metal center in a bidentate fashion in the catalytically active species. By comparison, the neutral complexes X1‐acetone, X1‐dmso, and X1‐pyr showed very low activity towards ethylene to give traces of oligomers. DFT analyses taking into account the two possible coordination modes (O or N) of the sulfonamide ligand for the cationic system CF31+ suggested that the experimentally observed high activity in ethylene dimerization is the result of a facile first ethylene insertion into the O‐coordinated PdMe isomer and a subsequent favored β‐H elimination from the N‐coordinated isomer formed by isomerization of the insertion product. Steric hindrance by the N‐aryl substituent in the neutral systems CF31 and H1 appears to contribute significantly to a higher barrier of insertion, which accounts for the experimentally observed low activity towards ethylene oligomerization.
Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η2:η1:η1 Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization
Authors: Zhang Guangchao , Wei Yun , Guo Liping , Zhu Xiancui , Wang Shaowu , Zhou Shuangliu , Mu Xiaolong
Published: December 2014

Two series of new dinuclear rare‐earth metal alkyl complexes supported by indolyl ligands in novel μ‐η2:η1:η1 hapticities are synthesized and characterized. Treatment of [RE(CH2SiMe3)3(thf)2] with 1 equivalent of 3‐(tBuNCH)C8H5NH (L1) in THF gives the dinuclear rare‐earth metal alkyl complexes trans‐[(μ‐η2:η1:η1‐3‐{tBuNCH(CH2SiMe3)}Ind)RE(thf)(CH2SiMe3)]2 (Ind=indolyl, RE=Y, Dy, or Yb) in good yields. In the process, the indole unit of L1 is deprotonated by the metal alkyl species and the imino CN group is transferred to the amido group by alkyl CH2SiMe3 insertion, affording a new dianionic ligand that bridges two metal alkyl units in μ‐η2:η1:η1 bonding modes, forming the dinuclear rare‐earth metal alkyl complexes. When L1 is reduced to 3‐(tBuNHCH2)C8H5NH (L2), the reaction of [Yb(CH2SiMe3)3(thf)2] with 1 equivalent of L2 in THF, interestingly, generated the trans‐[(μ‐η2:η1:η1‐3‐{tBuNCH2}Ind)Yb(thf)(CH2SiMe3)]2 (major) and cis‐[(μ‐η2:η1:η1‐3‐{tBuNCH2}Ind)Yb(thf)(CH2SiMe3)]2 (minor) complexes. The catalytic activities of these dinuclear rare‐earth metal alkyl complexes for isoprene polymerization were investigated; the yttrium and dysprosium complexes exhibited high catalytic activities and high regio‐ and stereoselectivities for isoprene 1,4‐cis‐polymerization.
Catalyst‐Dependent Selectivity in the Relay Catalytic Branching Cascade
Authors: Bansode Avinash H. , Shaikh Aslam C. , Kavthe Rahul D. , Thorat Shridhar , Gonnade Rajesh G. , Patil Nitin T.
Published: December 2014

The synthesis of small organic molecules as probes for discovering new therapeutic agents has been an important aspect of chemical biology. One of the best ways to access collections of small molecules is to use various techniques in diversity‐oriented synthesis (DOS). Recently, a new form of DOS, namely “relay catalytic branching cascades” (RCBCs), has been introduced, wherein a common type of starting material reacts with several scaffold‐building agents (SBAs) to obtain structurally diverse molecular scaffolds under the influence of catalysts. Herein, the RCBC reaction of a common type of substrate with SBAs is reported to give two different types of molecular scaffolds and their formation is essentially dependent on the type of catalyst used.
Asymmetric Reduction of Ketones by Biocatalysis Using Clementine Mandarin (Citrus reticulata) Fruit Grown in Annaba or by Ruthenium Catalysis for Access to Both Enantiomers
Authors: Bennamane Manhel , Zeror Saoussen , Aribi‐Zouioueche Louisa
Published: December 2014

Biocatalytic reduction of prochiral ketones using freshly ripened clementine mandarin (Citrus reticulata) in aqueous medium is reported. High enantioselectivities were observed, especially for the bioreduction of indanone 3, tetralone 4, and thiochromanone 5 with respectively 95%, 99%, and 86% enantiomeric excess (ee). Enantioselective bio‐ and metal‐catalyzed reactions were compared. Chiral ruthenium catalysts afforded good asymmetric inductions (>75% ee) in most cases, enantiomeric excesses depending on the nature of substrate and ligand. N‐aminoindanol prolinamide L3 was revealed as the best ligand for most ketones. Interestingly, for several substrates both enantiomers could be obtained using either Citrus reticulata or ruthenium complex. Chirality 27:205–210, 2015. © 2014 Wiley Periodicals, Inc.
Bedrohung durch den Islamischen Staat (IS)?
Authors: Wöhrle Dieter
Published: December 2014

In ChiuZ 5/2014 wurde auf die Rolle und Bedeutung der Chemie im Terrorismus betreffend Missbrauch u.a. von Explosivstoffen, toxischen Chemikalien und radiologischen Waffen eingegangen. Der erst kürzlich ausgerufene Islamische Staat stellt ein neues terroristisches Gefahrenpotential dar, dessen mögliche Auswirkungen in dem Artikel nicht mehr berücksichtigt werden konnten. Daher ist es notwendig, auf mögliche Gefahren ganz neuer Quantität hinzuweisen.
Teichrosen, Bibergeil und traditionelle Medizin
Authors: Oltmanns Dörte
Published: December 2014

Teichrosen als Bestandteil traditioneller japanischer Medizin enthalten Nuphar‐Alkaloide. Pflanzen sind jedoch nicht die alleinige Quelle dieser Alkaloide: Sie finden sich auch in Bibergeil, dem in Antike und Mittelalter große Heilkräfte zugesprochen wurden. Ein Nuphar‐Alkaloid konnte nun enantiospezifisch in neun Schritten aus N‐Boc‐(L)‐Prolin synthetisiert und die Struktur mittels Röntgenstrukturanalyse bestimmt werden. Biologische Untersuchungen zeigen die medizinische Wirkung dieses Naturstoffs.
Bio oder nicht – lassen sich die Produkte durch 1H‐NMR‐Spektroskopie unterscheiden?
Authors: Hohmann Monika , Christoph Norbert , Wachter Helmut , Holzgrabe Ulrike
Published: December 2014

Die Nachfrage nach ökologisch produzierten Lebensmitteln steigt an. Da diese zu höheren Preisen als entsprechende konventionell produzierte Ware verkauft werden können, steigt gleichzeitig das Betrugsrisiko. Deshalb bedarf es geeigneter Analyseverfahren, um biologisch und konventionell hergestellte Lebensmittel unterscheiden zu können. Allerdings beschreibt die Deklaration “bio” die Anforderungen an die Herstellungsmethode und nicht an das Produkt. Mit den bisher verfügbaren Analysemethoden ist eine eindeutige Zuordnung der Anbaumethode nicht immer gegeben.
Supramolecular Assembly Models of siRNA Delivery Systems
Authors: Sun Jing , Wang Jiancheng , Yang Zhenjun
Published: December 2014

Small interfering RNA (siRNA) technology, which could be able to silence specific targeted mRNAs rapidly and efficiently, has been regarded as a novel and potent gene therapeutic approach for diseases, such as cancers, infections, inflammations and neurological disorders. However, some conspicuous intrinsic defects of siRNA including the poor cellular uptake, low biological stability, unfavorable pharmacokinetics and bio‐distribution properties, have hindered further applications in clinic. Therefore, it is prerequisite to design safe and effective siRNA delivery systems for the successful development of siRNA‐based various diseases therapeutics. This review aims to analyze and summarize these supramolecular assembly models in the process of siRNA delivery, namely recent nanotechnological strategies for carrying siRNA by using diverse non‐viral vehicles such as cationic liposomes, stable nucleic acid lipid particles (SNALPs), cationic polymers, cationic dendrimers, inorganic nanoparticles and others. Eventually, it is concluded with future perspectives of siRNA therapeutics in the field of non‐viral carriers.
Second Generation Nitrogen Doped Titania Nanoparticles: A Comprehensive Electronic and Microstructural Picture
Authors: Spadavecchia Francesca , Ceotto Michele , Presti Leonardo Lo , Aieta Chiara , Biraghi Iolanda , Meroni Daniela , Ardizzone Silvia , Cappelletti Giuseppe
Published: December 2014

A state‐of‐the‐art overview of N‐dopant characterizations in nano‐TiO2 second‐generation photocatalysts is provided. The related literature is very rich and sometimes offers contrasting interpretations. Here we critically discuss up‐to‐date literature results and our own findings, as retrieved by several experimental (BET, HR‐TEM, XPS, DRS, HR‐XRPD, EXAFS, electrochemical tools) and theoretical (periodic DFT) techniques. Our intent is to pull together outcomes from very different and complementary sources to make an as much as possible coherent picture of the morphological, electrochemical and electronic properties of N‐TiO2 materials. It is commonly accepted that critical issues to be considered in the design of high‐performing N‐TiO2 photocatalysts are synthetic strategy, defect concentration and chemical nature of the lattice point defects. We focus on the latter two issues, with emphasis on sol‐gel prepared materials, according to the specific area of expertise of our group. The problem of the chemical nature of guest N species into the lattice is crucial, as substitutional (Ns) or interstitial (Ni) nitrogen place their valence states just above the valence band or deeper into the band gap. Overall, we show how synergism among experimental and theoretical techniques is decisive to disentangle structural, electronic and morphological effects in complex N‐doped TiO2 matrices.
Recent Progress in the Synthesis and Application of Saddle‐shaped Cyclooctatetrathiophenes and Their Derivatives
Authors: Zhao Chunmei , Xu Li , Wang Yong , Li Chunli , Wang Hua
Published: December 2014

Cyclooctatetrathiophene (COTh) shows a novel saddle‐shaped molecular structure, which has been applied in organic synthesis and material science. In this paper, the design and synthesis of COThs and their derivatives were described. The derivatives of COThs include mainly four types. One is isomer with different sequences of the four thiophene rings; the second is oligomer such as dimmer and dendrimer; the third is derivative functionalized by substituent groups at the four α positions; the last is the one planarized by sulfur, silicon or sulfone bridges. The applications of COThs and their derivatives in molecular muscles and field effect transistors were also discussed.
Smart Supramolecular Nanosystems for Bioimaging and Drug Delivery
Authors: Yang Peipei , Wang Lei , Wang Hao
Published: December 2014

The application of smart supramolecular nanosystems in biomedicine increases rapidly and offers promising prospects for disease diagnostics and therapeutics. Supramolecular nanosystems such as liposomes, micelles, organic nanoaggregates and metallic nanostructures etc. have been widely explored as diagnostic/therapeutic tools. Here, we review the recent advances in supramolecular nanosystems with different built‐in reporters, e.g., fluorescent, magnetic and photoacoustic signals for bioimaging. In addition, the substantial progress of supramolecular nanosystems as drug delivery carriers for cancer therapy, including chemotherapy, photothermal and photodynamic therapies is also summarized.
An Efficient Synthesis of Spiroquinoxalinones via Tandem Reactions
Authors: Leong Seh Yong , Smith Paul W. , Zou Bin
Published: December 2014

A mild and efficient synthesis of spiroquinoxalinones via tandem condensation of chlorooxoindoline 1 with benzene‐1,2‐diamines 2 is described. And a plausible mechanism for the reaction is proposed.
Ultrasmall particles for Gd‐MRI and 68Ga‐PET dual imaging
Authors: Truillet Charles , Bouziotis Penelope , Tsoukalas Charalambos , Brugière Jérémy , Martini Matteo , Sancey Lucie , Brichart Thomas , Denat Franck , Boschetti Frédéric , Darbost Ulrich , Bonnamour Isabelle , Stellas Dimitris , Anagnostopoulos Constantinos D. , Koutoulidis Vassilis , Moulopoulos Lia A. , Perriat Pascal , Lux François , Tillement Olivier
Published: December 2014

Nanoparticles made of a polysiloxane matrix and surrounded by 1,4,7,10‐tetraazacyclododecane‐1‐glutaric anhydride‐4,7,10‐triacetic acid (DOTAGA)[Gd3+] and 2,2'‐(7‐(1‐carboxy‐4‐((2,5‐dioxopyrrolidin‐1‐yl)oxy)‐4‐oxobutyl)‐1,4,7‐triazonane‐1,4‐diyl)diacetic acid) NODAGA[68Ga3+] have been synthesized for positron emission tomography/magnetic resonance (PET/MRI) dual imaging. Characterizations were carried out in order to determine the nature of the ligands available for radiolabelling and to quantify them. High radiolabelling purity (>95%) after 68Ga labelling was obtained. The MR and PET images demonstrate the possibility of using the nanoparticles for a combined PET/MR imaging scanner. The images show fast renal elimination of the nanoparticles after intravenous injection.Copyright © 2014 John Wiley & Sons, Ltd.
Insurance status and risk of cancer mortality among adolescents and young adults
Authors: Rosenberg Abby R. , Kroon Leah , Chen Lu , Li Christopher I. , Jones Barbara
Published: December 2014

BACKGROUND

Adolescents and young adults with cancer have inferior survival outcomes compared with younger pediatric patients and older adult patients. Lack of insurance may partly explain this disparity. The objective of this study was to identify associations between insurance status and both advanced‐stage cancer and cancer‐specific mortality.

METHODS

Using the Surveillance, Epidemiology, and End Results (SEER) 18 registries, 57,981 patients ages 15 to 39 years were identified who were diagnosed between 2007 and 2010 and had complete insurance and staging information. Multinomial logistic regression models were used to identify associations between insurance type and disease stage, with the models adjusted for sex, age, and race. Cox proportional hazards models were used to estimate cancer‐specific mortality.

RESULTS

Overall, 84% of patients were aged ≥25 years, 64% were women, and 79% were privately insured. Compared with patients who had private insurance, those who had nonprivate insurance tended to present with more advanced‐stage disease and to die more quickly and more commonly from their cancer. Patients ages 25 to 39 years who had Medicaid coverage or no insurance had 3.2 times and 2.4 times higher odds of having stage IV disease, respectively, than privately insured patients (95% confidence interval [CI], 3.0‐3.5 times higher odds and 2.1‐2.6 times higher odds, respectively). Among those with stage I/II and III/IV cancers, the risk of death was 2.9 times greater (95% CI, 2.2‐3.9 times greater) and 1.7 times greater (95% CI, 1.5‐1.9 times greater), respectively, than the risk for privately insured patients. Patients who died from stage III/IV cancers survived at least 2 months longer if they had private insurance.

CONCLUSIONS

Among young adults, insurance status is independently associated with advanced‐stage cancer and the risk of death from cancer, even for patients who have low‐stage disease. Broader insurance coverage and access to health care may improve some of the disparate outcomes of adolescents and young adults with cancer. Cancer 2015;121:1279–1286. © 2014 American Cancer Society.
Increasing time to treatment initiation for head and neck cancer: An analysis of the National Cancer Database
Authors: Murphy Colin T. , Galloway Thomas J. , Handorf Elizabeth A. , Wang Lora , Mehra Ranee , Flieder Douglas B. , Ridge John A.
Published: December 2014

BACKGROUND

The objective of this study was to identify trends and predictors of the time to treatment initiation (TTI) for patients with head and neck squamous cell carcinoma (HNSCC).

METHODS

The National Cancer Database (NCDB) was reviewed for the following head and neck cancer sites: oral tongue, oropharynx, larynx, and hypopharynx. TTI was defined as the number of days from diagnosis to the initiation of definitive treatment and was measured according to covariates. Significant differences in the median TTI across each covariate were measured using the Kruskal‐Wallis test, and the Spearman test was used to measure trends within covariates. For multivariate analysis, a zero‐inflated, negative, binomial regression model was used to estimate the expected TTI, which was expressed in the predicted number of days; and the Vuong test was used to identify the predictors of TTI.

RESULTS

In total, 274,630 patients were included. Between 1998 and 2011, the median TTI for all patients was 26 days, and it increased from 19 days to 30 days (P < .0001). Treatment with chemoradiation (CRT) (P < .0001), treatment at academic facilities (P < .0001), and stage IV disease (P < .0001) were associated with increased TTI. TTI significantly increased for each disease stage (P < .0001), treatment modality (P < .0001), and facility type (P < .0001) over time. In addition, patients became more likely to transition care between facilities after diagnosis for treatment initiation (P < .0001) over time. On multivariate analysis, treatment at academic facilities (33 days), transitioning care (37 days), and receipt of CRT (39 days) predicted for a longer TTI.

CONCLUSIONS

TTI is rising for patients with HNSCC. Those who have advanced‐stage disease, receive treatment with CRT, are treated at academic facilities, and who have a transition in care realized the greatest increases in TTI. Cancer 2015;121:1204–1213. © 2014 American Cancer Society.
Cancer disparities research: It is time to come of age
Authors: Halpern Michael T.
Published: December 2014

Although cancer disparities research has been an extremely productive field, much of this research has been largely descriptive. Researchers need to prioritize disparity areas with knowledge gaps and focus on understanding both the causes of and approaches to addressing and reducing disparities.
Cytomorphologic and clinicoradiologic analysis of primary nonhematologic central nervous system tumors with positive cerebrospinal fluid
Authors: Ho Cheng‐Ying , VandenBussche Christopher J. , Huppman Alison R. , Chaudhry Rabia , Ali Syed Z.
Published: December 2014

BACKGROUND

Positive cerebrospinal fluid (CSF) cytology typically indicates leptomeningeal dissemination of metastatic, secondary, or rarely, primary central nervous system (CNS) tumors. To the authors' knowledge, large‐scale studies on clinicocytologic features of various primary CNS tumors in CSF are lacking.

METHODS

The authors performed a retrospective cytomorphologic study on 127 positive CSF specimens from 87 patients with a history of primary nonhematologic CNS tumors. Pertinent clinical, radiological, and histologic findings were reviewed.

RESULTS

Pediatric tumors accounted for the majority (82.6%) of the primary CNS tumors with positive CSF cytology. The most common radiological finding of neuraxial dissemination was diffuse leptomeningeal enhancement. Greater than 95% of the cases with positive CSF cytology were high‐grade or malignant tumors. The most common tumor type was central primitive neuroectodermal tumors (47.2%). Overall, the frequency of initial metastasis was found to be lowest in central primitive neuroectodermal tumors and retinoblastomas (approximately one‐third). They also had the longest latency (1.5‐2 years) in cases without initial metastasis. The majority of metastatic tumors in CSF demonstrated distinct cytomorphology reminiscent of the histologic features of the primary tumor, such as prominent nucleoli, cell wrapping, and apoptosis in large cell/anaplastic medulloblastomas; rhabdoid morphology and cytoplasmic inclusions in atypical teratoid/rhabdoid tumors; large clusters of cells with scant cytoplasm and nuclear molding in retinoblastomas; nuclear pleomorphism and hyperchromasia in high‐grade infiltrating astrocytomas; and small clusters/rosettes of epithelioid cells in ependymomas.

CONCLUSIONS

The results of the current study provide useful clinicoradiological information and cytomorphologic findings for both common and rare primary CNS tumors that cytopathologists might encounter on CSF examination. Cancer (Cancer Cytopathol) 2015;123:123–135. © 2014 American Cancer Society.
Multielement Crystalline and Pseudocrystalline Oxides as Efficient Catalysts for the Direct Transformation of Glycerol into Acrylic Acid
Authors: Chieregato Alessandro , Soriano M. Dolores , García‐González Ester , Puglia Giuseppe , Basile Francesco , Concepción Patricia , Bandinelli Claudia , López Nieto José M. , Cavani Fabrizio
Published: December 2014

Glycerol surplus from biodiesel synthesis still represents a major problem in the biofuel production chain. Meanwhile, those in the acrylic acid market are looking for new processes that are able to offer viable alternatives to propylene‐based production. Therefore, acrylic acid synthesis from glycerol could be an effective solution to both issues. Among the viable routes, one‐pot synthesis theoretically represents the most efficient process, but it is also highly challenging from the catalyst design standpoint. A new class of complex WMoV mixed‐oxide catalysts, which are strongly related to the hexagonal tungsten bronze structure, able to directly convert glycerol into acrylic acid with yields of up to 51 % are reported.
A bag of cells approach for antinuclear antibodies HEp‐2 image classification
Authors: Wiliem Arnold , Hobson Peter , Minchin Rodney F. , Lovell Brian C.
Published: December 2014

The antinuclear antibody (ANA) test via indirect immunofluorescence applied on Human Epithelial type 2 (HEp‐2) cells is a pathology test commonly used to identify connective tissue diseases (CTDs). Despite its effectiveness, the test is still considered labor intensive and time consuming. Applying image‐based computer aided diagnosis (CAD) systems is one of the possible ways to address these issues. Ideally, a CAD system should be able to classify ANA HEp‐2 images taken by a camera fitted to a fluorescence microscope. Unfortunately, most prior works have primarily focused on the HEp‐2 cell image classification problem which is one of the early essential steps in the system pipeline. In this work we directly tackle the specimen image classification problem. We aim to develop a system that can be easily scaled and has competitive accuracy. ANA HEp‐2 images or ANA images are generally comprised of a number of cells. Patterns exhibiting in the cells are then used to make inference on the ANA image pattern. To that end, we adapted a popular approach for general image classification problems, namely a bag of visual words approach. Each specimen is considered as a visual document containing visual vocabularies represented by its cells. A specimen image is then represented by a histogram of visual vocabulary occurrences. We name this approach as the Bag of Cells approach. We studied the performance of the proposed approach on a set of images taken from 262 ANA positive patient sera. The results show the proposed approach has competitive performance compared to the recent state‐of‐the‐art approaches. Our proposal can also be expanded to other tests involving examining patterns of human cells to make inferences. © 2014 International Society for Advancement of Cytometry
3‐acetylpyridine‐induced degeneration in the adult ascidian neural complex: Reactive and regenerative changes in glia and blood cells
Authors: Medina Bianca N. S. P. , Santos de Abreu Isadora , Cavalcante Leny A. , Silva Wagner A. B. , da Fonseca Rodrigo N. , Allodi Silvana , de Barros Cintia M.
Published: December 2014

Ascidians are interesting neurobiological models because of their evolutionary position as a sister‐group of vertebrates and the high regenerative capacity of their central nervous system (CNS). We investigated the degeneration and regeneration of the cerebral ganglion complex of the ascidian Styela plicata following injection of the niacinamide antagonist 3‐acetylpyridine (3AP), described as targeting the CNS of several vertebrates. For the analysis and establishment of a new model in ascidians, the ganglion complex was dissected and prepared for transmission electron microscopy (TEM), routine light microscopy (LM), immunohistochemistry and Western blotting, 1 or 10 days after injection of 3AP. The siphon stimulation test (SST) was used to quantify the functional response. One day after the injection of 3AP, CNS degeneration and recruitment of a non‐neural cell type to the site of injury was observed by both TEM and LM. Furthermore, weaker immunohistochemical reactions for astrocytic glial fibrillary acidic protein (GFAP) and neuronal βIII‐tubulin were observed. In contrast, the expression of caspase‐3, a protein involved in the apoptotic pathway, and the glycoprotein CD34, a marker for hematopoietic stem cells, increased. Ten days after the injection of 3AP, the expression of markers tended toward the original condition. The SST revealed attenuation and subsequent recovery of the reflexes from 1 to 10 days after 3AP. Therefore, we have developed a new method to study ascidian neural degeneration and regeneration, and identified the decreased expression of GFAP and recruitment of blood stem cells to the damaged ganglion as reasons for the success of neuroregeneration in ascidians. © 2014 Wiley Periodicals, Inc. Develop Neurobiol 75: 877–893, 2015
Analysis of dextromethorphan and dextrorphan in decomposed skeletal tissues by microwave assisted extraction, microplate solid‐phase extraction and gas chromatography‐ mass spectrometry (MAE‐MPSPE‐GCMS)
Authors: Fraser Candice D. , Cornthwaite Heather M. , Watterson James H.
Published: December 2014

Analysis of decomposed skeletal tissues for dextromethorphan (DXM) and dextrorphan (DXT) using microwave assisted extraction (MAE), microplate solid‐phase extraction (MPSPE) and gas chromatography‐mass spectrometry (GC‐MS) is described. Rats (n = 3) received 100 mg/kg DXM (i.p.) and were euthanized by CO2 asphyxiation roughly 20 min post‐dose. Remains decomposed to skeleton outdoors and vertebral bones were recovered, cleaned, and pulverized. Pulverized bone underwent MAE using methanol as an extraction solvent in a closed microwave system, followed by MPSPE and GC‐MS. Analyte stability under MAE conditions was assessed and found to be stable for at least 60 min irradiation time. The majority (>90%) of each analyte was recovered after 15 min. The MPSPE‐GCMS method was fit to a quadratic response (R2 > 0.99), over the concentration range 10‒10 000 ng⋅mL‐1, with coefficients of variation <20% in triplicate analysis. The MPSPE‐GCMS method displayed a limit of detection of 10 ng⋅mL‐1 for both analytes. Following MAE for 60 min (80 °C, 1200 W), MPSPE‐GCMS analysis of vertebral bone of DXM‐exposed rats detected both analytes in all samples (DXM: 0.9‐1.5 µg⋅g‐1; DXT: 0.5‐1.8 µg⋅g‐1). Copyright © 2014 John Wiley & Sons, Ltd.
Hydrological impacts of climate and land‐use changes in a mountain watershed: uncertainty estimation based on model comparison
Authors: Morán‐Tejeda Enrique , Zabalza Javier , Rahman Kazi , Gago‐Silva Ana , López‐Moreno J. Ignacio , Vicente‐Serrano Sergio , Lehmann Anthony , Tague Christina L. , Beniston Martin
Published: December 2014

This paper evaluates the response of streamflow and other components of the water balance to changes in climate and land use in a Pyrenean watershed. It further provides a measure of uncertainty in water resources forecasts by comparing the performance of two hydrological models: the Soil and Water Assessment Tool (SWAT) and Regional Hydro‐ecological Simulation System (RHESSys). Regional climate model outputs for the 2021–2050 time frame and hypothetical (but plausible) land‐use scenarios considering re‐vegetation and wildfire processes were used as inputs to the models. Results indicate an overall decrease in river flows (up to 30%, depending on the combination of scenarios) when the scenarios are considered, except for the post‐fire vegetation scenario, in which streamflows are simulated to increase (between 2% and 10%). However, the magnitude of these projections varies between the two models used, as SWAT tends to produce larger hydrological changes under climate change scenarios and RHESSys shows more sensitivity to changes in land cover. The final prediction will therefore depend largely on the combination of the land‐use and climate scenarios and on the model used. Copyright © 2014 John Wiley & Sons, Ltd.
Genomic expression profiling of NK cells in health and disease
Authors: Wang Fuyan , Tian Zhigang , Wei Haiming
Published: December 2014

NK cells are important components of innate and adaptive immunity. Functionally, they play key roles in host defense against tumors and infectious pathogens. Within the past few years, genomic‐scale experiments have provided us with a plethora of gene expression data that reveal an extensive molecular and biological map underlying gene expression programs. In order to better explore and take advantage of existing datasets, we review here the genomic expression profiles of NK cells and their subpopulations in resting or stimulated states, in diseases, and in different organs; moreover, we contrast these expression data to those of other lymphocytes. We have also compiled a comprehensive list of genomic profiling studies of both human and murine NK cells in this review.
Interleukin‐17 and interleukin‐22 promote tumor progression in human nonmelanoma skin cancer
Authors: Nardinocchi Lavinia , Sonego Giulio , Passarelli Francesca , Avitabile Simona , Scarponi Claudia , Failla Cristina Maria , Simoni Stefano , Albanesi Cristina , Cavani Andrea
Published: December 2014

Interleukin‐17 (IL‐17) and IL‐22 have been reported to play critical roles in autoimmunity and inflammation but information about their role in cancer is limited. In this study, we investigated the role of IL‐17 and IL‐22 in the progression of human skin basal‐cell carcinoma (BCC) and squamous‐cell carcinoma (SCC). We found that both tumor types are infiltrated with an high number of IL‐17+ and IL‐22+ T lymphocytes, as demonstrated by immunohistochemistry and by FACS analysis performed on peritumoral T‐cell lines isolated from skin biopsies. In vitro studies demonstrated that proliferation and migration of the BCC‐ and SCC‐cell lines M77015 and CAL27 were increased by IL‐17 and IL‐22. Moreover, IL‐17, alone or in combination with TNF‐α, was able to induce the production of two cytokines important for tumor progression, IL‐6 and IL‐8, in CAL27. We also showed that IL‐17 upregulated NF‐κB signaling, while IL‐22 activated the STAT3 pathway and the antiapoptotic AKT protein in M77015 and CAL27. Finally, in vivo experiments demonstrated that IL‐17 and IL‐22 enhanced tumor growth in nude mice injected with CAL27. Altogether, our findings indicate that high levels of IL‐22 and IL‐17 in the BCC and SCC microenvironment promote tumor progression.
Using Click Chemistry to Tune the Properties and the Fluorescence Response Mechanism of Structurally Similar Probes for Metal Ions
Authors: Ast Sandra , Kuke Stefanie , Rutledge Peter J. , Todd Matthew H.
Published: December 2014

Four cyclam‐based fluorescent molecular probes were prepared using “click” chemistry and investigated to determine the effect of the triazole connectivity and fluorophore substitution on the photophysical properties and metal‐ion response mechanism. The fluorescence of the ligands is turned on in the presence of ZnII but varies in intensity depending on the solvent; the highest signal changes are found in MeCN. Complexation with CuII leads to fluorescence quenching, but only in the aqueous solvent, in which the triazole is involved in coordination of the metal. The length of the pendant triazole arm influences the ligand field around pentacoordinate CuII to yield a distorted square‐planar coordination geometry in the ligands with an ethylene linker. The quantum yield (QY) of the emission intensity can be tuned by the triazole substitution, thereby resulting in increases in QY of more than one order of magnitude (ligand 1 versus 3). Changing the fluorophore opens up alternative radiative processes, thus leading to phosphorescence‐like behavior in coumarin probe 2. Steady‐state fluorescence emission spectra of the free ligands and their respective CuII complexes in a “glass environment” reveal two different inherent fluorescence quenching mechanisms. In the free ligands an electron‐transfer deactivates the excited chromophore, whereas in the CuII complexes it is energy transfer that results in complete quenching of the emission of the ligands.
Perfluorinated Cobalt Phthalocyanine Effectively Catalyzes Water Electrooxidation
Authors: Morlanés Natalia , Joya Khurram S. , Takanabe Kazuhiro , Rodionov Valentin
Published: December 2014

Efficient electrocatalysis of water oxidation under mild conditions at neutral pH was achieved by a fluorinated cobalt phthalocyanine immobilized on fluorine‐doped tin oxide (FTO) surfaces with an onset potential at 1.7 V vs. RHE. Spectroscopic, electrochemical, and inhibition studies indicate that phthalocyanine molecular species are the operational active sites. Neither free cobalt ions nor heterogeneous cobalt oxide particles or films were observed. During long‐term controlled‐potential electrolysis at 2 V vs. RHE (phosphate buffer, pH 7), electrocatalytic water oxidation was sustained for at least 8 h (TON ≈ 1.0 × 105), producing about 4 μmol O2 h–1 cm–2 with a turnover frequency (TOF) of about 3.6 s–1 and no measurable catalyst degradation.
Trimethylsilyl Iodide Mediated One‐Pot Synthesis of 2‐Allyl‐2H‐chromenes
Authors: Padhi Birakishore , Reddy D. Srinivas , Mohapatra Debendra K.
Published: December 2014

A new and efficient metal‐free trimethylsilyl iodide (TMSI) catalyzed one‐pot synthesis of 2‐allyl‐2H‐chromenes has been developed that takes place under mild conditions. The synthesis proceeds through a Wittig reaction by using (triphenylphosphoranylidene)acetaldehyde to form an o‐hydroxycinnamaldehyde derivative followed by a tandem isomerization and C–O and C–C bond‐forming reactions. The procedure was carried out at room temperature in the presence of 20 mol‐% of TMSI and allyltrimethylsilane in tetrahydrofuran (THF) and provided the 2‐allyl‐2H‐chromenes in good to excellent yields.
Design and Characterization of 4,5‐Bis(diarylamino)phthalic Acid Diesters as a New Class of Fluorophores Exhibiting Efficient Blue Emission in the Solid State
Authors: Shimizu Masaki , Tamagawa Tomokazu
Published: December 2014

We developed 4,5‐bis(diarylamino)phthalic acid diesters as blue fluorophores exhibiting efficient photoluminescence in powder and in a thin film of pol(methyl methacrylate). Increasing the electron‐donating nature of the substituents in the para positions of the diarylamino moieties in the dimethyl esters increased the redshift in the fluorescence spectrum. Replacing the methoxycarbonyl groups with aryloxylcarbonyl groups also induced a bathochromic shift in the fluorescence spectrum. Thus, the color of the emission was finely tuned by simple molecular modification. Single‐crystal X‐ray analysis revealed a twisted conformation with loose packing in the crystal. Density functional theory calculations suggested that the excitation process was governed by intramolecular charge transfer from the diarylamino moieties to the alkoxycarbonyl groups.
A General and Efficient Method to Access Tetracyclic Spirooxindole Derivatives
Authors: El Bouakher Abderrahman , Massip Stéphane , Jarry Christian , Troin Yves , Abrunhosa‐Thomas Isabelle , Guillaumet Gérald
Published: December 2014

An efficient, simple, and convenient synthetic procedure for the synthesis of tetracyclic spirooxindole derivatives, starting from N‐protected isatins and 2‐fluoropyridine, was successfully developed. It enables the facile formation of a new class of spirooxindoles in which the oxindole core is fused with various heterocycles at the C‐3 position.