bluuebunny/crossref_metadata_2025 huggingface dataset:
Microbial Electroreduction: Screening for New Cathodic Biocatalysts
Authors: de Campos Rodrigues Tatiana , Rosenbaum Miriam A.
Published: September 2014

Cathodic microbial electrocatalysis, where microorganisms consume electrons from a cathode to perform biochemical reductions, is currently of high interest. For an effective electrochemical screening of potential new cathode biocatalysts, we developed a time‐saving medium‐throughput potentiostatic BES system to evaluate microbial ability to accept reducing equivalents from an electrode in pure cultures. Of nine tested physiologically and phylogenetically different strains, five promising cathode‐active strains were identified: Acidithiobacillus ferrooxidans (jmax=−50 μA cm−2), Desulfosporosinus orientis (jmax=−4 μA cm−2), Thiobacillus denitrificans and Sulfurimonas denitrificans (jmax=−2 μA cm−2 for both), and Desulfovibrio piger (jmax=−1.5 μA cm−2). From this screening, hypotheses were formulated on possible electron consumption and utilization processes. This work serves as a foundation for deeper investigation and characterization of the identified cathode biocatalysts.
Dissymmetrical U‐Shaped π‐Stacked Supramolecular Assemblies by Using a Dinuclear CuI Clip with Organophosphorus Ligands and Monotopic Fully π‐Conjugated Ligands
Authors: El Sayed Moussa Mehdi , Guillois Kevin , Shen Wenting , Réau Régis , Crassous Jeanne , Lescop Christophe
Published: September 2014

Reactions between the U‐shaped binuclear CuI complex A that bears short metal–metal distances and the cyano‐capped monotopic π‐conjugated ligands 1–5 that carry gradually bulkier polyaromatic terminal fragments lead to the formation of π‐stacked supramolecular assemblies 6–10, respectively, in yields of 50–80 %. These derivatives have been characterized by multinuclear NMR spectroscopic analysis and X‐ray diffraction studies. Their solid‐state structures show the selective formation of U‐shaped supramolecular assemblies in which two monotopic π‐conjugated systems present large (6, 7, and 9) or medium (8 and 10) intramolecular π overlap, thus revealing π–π interactions. These assemblies self‐organize into head‐to‐tail π‐stacked dimers that in turn self‐assemble to afford infinite columnar π stacks. The nature, extent, and complexity of the intermolecular contacts within the head‐to‐tail π‐stacked dimer depend on the nature of the terminal polyaromatic fragment carried by the cyano‐capped monotopic ligand, but it does not alter the result of the self‐assembling process. These results demonstrate that the dinuclear molecular clip A that bears short metal–metal distances allows selective supramolecular assembly processes driven by the formation of intra‐ and intermolecular short π–π interactions in the resulting self‐assembled structures; thus, demonstrating that their shape is not only dictated by the symmetry of the building blocks. This approach opens perspectives toward the formation of extended π‐stacked columns based on dissymmetrical and functional π‐conjugated systems.
Targeted Functionalization of Porous Materials for Separation of Alcohol/Water Mixtures by Modular Assembly
Authors: Ren Cai‐Xia , Ji Min , Yao Qing‐Xia , Cai Li‐Xuan , Tan Bin , Zhang Jie
Published: September 2014

Three isoreticular hydrogen‐bonded frameworks with functionalized pore structures were constructed by a modular self‐assembly process in which a series of amino acids with various substituents serve as facile exchange subassemblies to decorate the pore wall. The ordered amino acid side‐chain groups in the pore channels play an important role in determining the adsorption behavior of the framework materials, and ensure exclusive adsorption of methanol/water over ethanol. Gas‐chromatographic separation experiments demonstrated that alcohols can be efficiently separated from ternary water/methanol/ethanol mixtures and revealed a key influence of the adsorbate–host framework interaction on the practical separation performance of mixtures.
A Bis(pyridine N‐oxide) Analogue of DOTA: Relaxometric Properties of the GdIII Complex and Efficient Sensitization of Visible and NIR‐Emitting Lanthanide(III) Cations Including PrIII and HoIII
Authors: Martins André F. , Eliseeva Svetlana V. , Carvalho Henrique F. , Teixeira João M. C. , Paula Carlos T. B. , Hermann Petr , Platas‐Iglesias Carlos , Petoud Stephane , Tóth Éva , Geraldes Carlos F. G. C.
Published: September 2014

We report the synthesis of a cyclen‐based ligand (4,10‐bis[(1‐oxidopyridin‐2‐yl)methyl]‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid=L1) containing two acetate and two 2‐methylpyridine N‐oxide arms anchored on the nitrogen atoms of the cyclen platform, which has been designed for stable complexation of lanthanide(III) ions in aqueous solution. Relaxometric studies suggest that the thermodynamic stability and kinetic inertness of the GdIII complex may be sufficient for biological applications. A detailed structural study of the complexes by 1H NMR spectroscopy and DFT calculations indicates that they adopt an anti‐Δ(λλλλ) conformation in aqueous solution, that is, an anti‐square antiprismatic (anti‐SAP) isomeric form, as demonstrated by analysis of the 1H NMR paramagnetic shifts induced by YbIII. The water‐exchange rate of the GdIII complex is ${k{{298\hfill \atop {\rm ex}\hfill}}}$=6.7×106 s−1, about a quarter of that for the mono‐oxidopyridine analogue, but still about 50 % higher than the ${k{{298\hfill \atop {\rm ex}\hfill}}}$ of GdDOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid). The 2‐methylpyridine N‐oxide chromophores can be used to sensitize a wide range of LnIII ions emitting in both the visible (EuIII and TbIII) and NIR (PrIII, NdIII, HoIII, YbIII) spectral regions. The emission quantum yield determined for the YbIII complex (${Q{{{\rm L}\hfill \atop {\rm Yb}\hfill}}}$=7.3(1)×10−3) is among the highest ever reported for complexes of this metal ion in aqueous solution. The sensitization ability of the ligand, together with the spectroscopic and relaxometric properties of its complexes, constitute a useful step forward on the way to efficient dual probes for optical imaging (OI) and MRI.
Quantitative Description of Structural Effects on the Stability of Gold(I) Carbenes
Authors: Ringger David H. , Kobylianskii Ilia J. , Serra Daniel , Chen Peter
Published: September 2014

The gas‐phase bond‐dissociation energies of a SO2–imidazolylidene leaving group of three gold(I) benzyl imidazolium sulfone complexes are reported (E0=46.6±1.7, 49.6±1.7, and 48.9±2.1 kcal mol−1). Although these energies are similar to each other, they are reproducibly distinguishable. The energy‐resolved collision‐induced dissociation experiments of the three [L]–gold(I) (L=ligand) carbene precursor complexes were performed by using a modified tandem mass spectrometer. The measurements quantitatively describe the structural and electronic effects a p‐methoxy substituent on the benzyl fragment, and trans [NHC] and [P] gold ligands, have towards gold carbene formation. Evidence for the formation of the electrophilic gold carbene in solution was obtained through the stoichiometric and catalytic cyclopropanation of olefins under thermal conditions. The observed cyclopropane yields are dependent on the rate of gold carbene formation, which in turn is influenced by the ligand and substituent. The donation of electron density to the carbene carbon by the p‐methoxy benzyl substituent and [NHC] ligand stabilizes the gold carbene intermediate and lowers the dissociation barrier. Through the careful comparison of gas‐phase and solution chemistry, the results suggest that even gas‐phase leaving‐group bond‐dissociation energy differences of 2–3 kcal mol−1 enormously affect the rate of gold carbene formation in solution, especially when there are competing reactions. The thermal decay of the gold carbene precursor complex was observed to follow first‐order kinetics, whereas cyclopropanation was found to follow pseudo‐first‐order kinetics. Density‐functional‐theory calculations at the M06‐L and BP86‐D3 levels of theory were used to confirm the observed gas‐phase reactivity and model the measured bond‐dissociation energies.
BrettPhos Ligand Supported Palladium‐Catalyzed CO Bond Formation through an Electronic Pathway of Reductive Elimination: Fluoroalkoxylation of Activated Aryl Halides
Authors: Rangarajan T. M. , Singh Rajendra , Brahma Raju , Devi Kavita , Singh Rishi Pal , Singh R. P. , Prasad Ashok K.
Published: September 2014

We report an unprecedented BrettPhos ligand supported Pd‐catalyzed CO bond‐forming reaction of activated aryl halides with primary fluoroalkyl alcohols. We demonstrate that the Phosphine ligand (BrettPhos) possesses the property of altering the mechanistic pathway of reductive elimination from nucleophile to nucleophile. The Pd/BrettPhos catalyst system facilitates the reductive elimination of the oxygen nucleophile through an electronic pathway.
Structure–Activity Relationship of Tumor‐Selective 5‐Substituted 2‐Amino‐3‐carboxymethylthiophene Derivatives
Authors: Thomas Joice , Jejcic Alenka , Vervaeke Peter , Romagnoli Romeo , Liekens Sandra , Balzarini Jan , Dehaen Wim
Published: September 2014

Methyl‐2‐amino‐5‐[2‐(4‐methoxyphenethyl)]thiophene‐3‐carboxylate (8 c) is the prototype of a well‐defined class of tumor‐selective agents. Compound 8 c preferentially inhibited the proliferation of a number of tumor cell lines including many human T‐lymphoma/leukemia cells, but also several prostate, renal, central nervous system and liver tumor cell types. Instead, a broad variety of other tumor cell lines including B‐lymphomas and HeLa cells were not affected. The tumor selectivity (TS; selectivity index or preferential suppression of CEM lymphoma (IC50=0.90 μM) versus HeLa tumor cell carcinoma (IC50=39 μM)) amounted up to ∼43 for 8 c. At higher concentrations, the compound proved cytotoxic rather than cytostatic. The antiproliferative potency and selectivity of 8 c could be preserved by replacing the ethyl linker between the 2‐amino‐3‐carboxymethylthiophene and the substituted aryl by a thioalkyl but not by an oxyalkyl nor an aminoalkyl. Among >50 novel 8 c derivatives, the 5‐(4‐ethyl‐ and 4‐isopropylarylmethylthio)thiophene analogues, methyl‐2‐amino‐5‐((4‐ethylphenylthio)methyl)thiophene‐3‐carboxylate (13 m) and methyl‐2‐amino‐5‐((4‐isopropylphenylthio)methyl)thiophene‐3‐carboxylate (13 n), were more potent (IC50: 0.3–0.4 μM) and selective (TS: 100–144) anti‐T‐lymphoma/leukemia agents than the prototype compound.
Design and Structural Analysis of Aromatic Inhibitors of Type II Dehydroquinase from Mycobacterium tuberculosis
Authors: Howard Nigel I. , Dias Marcio V. B. , Peyrot Fabienne , Chen Liuhong , Schmidt Marco F. , Blundell Tom L. , Abell Chris
Published: September 2014

3‐Dehydroquinase, the third enzyme in the shikimate pathway, is a potential target for drugs against tuberculosis. Whilst a number of potent inhibitors of the Mycobacterium tuberculosis enzyme based on a 3‐dehydroquinate core have been identified, they generally show little or no in vivo activity, and were synthetically complex to prepare. This report describes studies to develop tractable and drug‐like aromatic analogues of the most potent inhibitors. A range of carbon–carbon linked biaryl analogues were prepared to investigate the effect of hydrogen bond acceptor and donor patterns on inhibition. These exhibited inhibitory activity in the high‐micromolar range. The addition of flexible linkers in the compounds led to the identification of more potent 3‐nitrobenzylgallate‐ and 5‐aminoisophthalate‐based analogues.
Psychiatric implications of cancer genetic testing
Authors: Hirschberg April Malia , Chan‐Smutko Gayun , Pirl William F.
Published: September 2014

As genetic testing for hereditary cancer syndromes has transitioned from research to clinical settings, research regarding its accompanying psychosocial effects has grown. Men and women being tested for hereditary cancer syndromes may experience some psychological distress while going through the process of testing or after carrier status is identified. Psychological distress appears to decrease over the course of the first year and it is typically not clinically significant. Longer term studies show mixed results with some mutation carriers continuing to experience elevated distress. Baseline distress is the greatest risk factor for both immediate (weeks‐12 months) and long‐term psychological distress (18 mo‐8 years post genetic testing). In addition to baseline psychological distress, other risk factors can be identified to help identify individuals who may need psychosocial interventions during the genetic testing process. The challenges of providing clinical care to the growing population of individuals identified to be at increased risk for heritable cancers present opportunities for research and new models of care. Cancer 2015;121:341–360. © 2014 American Cancer Society.
Quo vadis: Advanced prostate cancer—clinical care and clinical research in the era of multiple androgen receptor‐directed therapies
Authors: Kim Won , Ryan Charles J.
Published: September 2014

The novel androgen receptor‐directed therapies abiraterone acetate and enzalutamide, having demonstrated improved survival in randomized phase 3 studies of men with metastatic castration‐resistant prostate cancer, have ushered in a new era in the treatment of this disease. Additional novel androgen receptor‐directed therapies, such as ARN‐509 and orteronel, are in various phases of clinical trials and development. However, the emergence of therapeutic resistance and clinical disease progression is inevitable. Although advances in genomic technologies have led to unprecedented understanding of the biology of castration‐resistant prostate cancer, efforts only now are underway to elucidate the mechanisms of resistance associated with abiraterone and enzalutamide. A tremendous challenge in the near future will be to determine the optimal sequence or combination of therapies to overcome resistance mechanisms. In this review, the current landscape of androgen receptor‐directed therapies and future directions necessary to enhance their clinical efficacy for the maximal benefit of patients are discussed. Cancer 2015;121:361–371. © 2014 American Cancer Society.
Endoscopic ultrasonography in esophageal cancer leads to improved survival rates: Results from a population‐based study
Authors: Wani Sachin , Das Ananya , Rastogi Amit , Drahos Jennifer , Ricker Winifred , Parsons Ruth , Bansal Ajay , Yen Roy , Hosford Lindsay , Jankowski Meghan , Sharma Prateek , Cook Michael B.
Published: September 2014

BACKGROUND

The advantages of endoscopic ultrasound (EUS) and computed tomography (CT)–positron emission tomography (PET) with respect to survival for esophageal cancer patients are unclear. This study aimed to assess the effects of EUS, CT‐PET, and their combination on overall survival with respect to cases not receiving these procedures.

METHODS

Patients who were ≥66 years old when diagnosed with esophageal cancer were identified in the Surveillance, Epidemiology, and End Results–Medicare linked database. Cases were split into 4 analytic groups: EUS only (n = 318), CT‐PET only (n = 853), EUS+CT‐PET (n = 189), and no EUS or CT‐PET (n = 2439). Survival times were estimated with the Kaplan‐Meier method and were compared with the log‐rank test for each group versus the no EUS or CT‐PET group. Multivariate Cox proportional hazards models were used to compare 1‐, 3‐, and 5‐year survival rates.

RESULTS

Kaplan‐Meier analyses showed that EUS, CT‐PET, and EUS+CT‐PET patients had improved survival for all stages (with the exception of stage 0 disease) in comparison with patients undergoing no EUS or CT‐PET. Receipt of EUS increased the likelihood of receiving endoscopic therapies, esophagectomy, and chemoradiation. Multivariate Cox proportional hazards models showed that receipt of EUS was a significant predictor of improved 1‐ (hazard ratio [HR], 0.49; 95% confidence interval [CI], 0.39‐0.59; P < .0001), 3‐ (HR, 0.57; 95% CI, 0.48‐0.66; P < .0001), and 5‐year survival (HR, 0.59; 95% CI, 0.50‐0.68). Similar results were noted when the results were stratified on the basis of histology and for the CT‐PET and EUS+CT‐PET groups.

CONCLUSIONS

Receipt of either EUS or CT‐PET alone in esophageal cancer patients was associated with improved 1‐, 3‐, and 5‐year survival. Future studies should identify barriers to the dissemination of these staging modalities. Cancer 2015;121:194–201. © 2014 American Cancer Society.
Significant clinical impact of recurrent BRCA1 and BRCA2 mutations in Mexico
Authors: Villarreal‐Garza Cynthia , Alvarez‐Gómez Rosa María , Pérez‐Plasencia Carlos , Herrera Luis A. , Herzog Josef , Castillo Danielle , Mohar Alejandro , Castro Clementina , Gallardo Lenny N. , Gallardo Dolores , Santibáñez Miguel , Blazer Kathleen R. , Weitzel Jeffrey N.
Published: September 2014

BACKGROUND

Frequent recurrent mutations in the breast and ovarian cancer susceptibility (BRCA) genes BRCA1 and BRCA2 among Hispanics, including a large rearrangement Mexican founder mutation (BRCA1 exon 9‐12 deletion [ex9‐12del]), suggest that an ancestry‐informed BRCA‐testing strategy could reduce disparities and promote cancer prevention by enabling economic screening for hereditary breast and ovarian cancer in Mexico.

METHODS

In a multistage approach, 188 patients with cancer who were unselected for family cancer history (92 with ovarian cancer and 96 with breast cancer) were screened for BRCA mutations using a Hispanic mutation panel (HISPANEL) of 115 recurrent mutations in a multiplex assay (114 were screened on a mass spectroscopy platform, and a polymerase chain reaction assay was used to screen for the BRCA1 ex9‐12del mutation). This was followed by sequencing of all BRCA exons and adjacent intronic regions and a BRCA1 multiplex ligation‐dependent probe amplification assay (MLPA) for HISPANEL‐negative patients. BRCA mutation prevalence was calculated and correlated with histology and tumor receptor status, and HISPANEL sensitivity was estimated.

RESULTS

BRCA mutations were detected in 26 of 92 patients (28%) with ovarian cancer, in 14 of 96 patients (15%) with breast cancer overall, and in 9 of 33 patients (27%) who had tumors that were negative for estrogen receptor, progesterone receptor, and human epithelial growth factor 2 (triple‐negative breast cancer). Most patients with breast cancer were diagnosed with locally advanced disease. The Mexican founder mutation (BRCA1 ex9‐12del) accounted for 35% of BRCA‐associated ovarian cancers and 29% of BRCA‐associated breast cancers. At 2% of the sequencing and MLPA cost, HISPANEL detected 68% of all BRCA mutations.

CONCLUSIONS

In this study, a remarkably high prevalence of BRCA mutations was observed among patients with ovarian cancer and breast cancer who were not selected for family history, and the BRCA1 ex9‐12del mutation explained 33% of the total. The remarkable frequency of BRCA1 ex9‐12del in Mexico City supports a nearby origin of this Mexican founder mutation and may constitute a regional public health problem. The HISPANEL mutation panel presents a translational opportunity for cost‐effective genetic testing to enable breast and ovarian cancer prevention. Cancer 2015;121:372–378. © 2014 American Cancer Society.
Digital pathology: Get on board—the train is leaving the station
Authors: Wilbur David C.
Published: September 2014

The digital revolution clearly is underway, and the new technologies will affect the practice of pathology in general. In the coming years, cytology will be particularly affected by these technologic advances.
A Theoretical Analysis of the Potential Role of π–π Stacking Interactions in the Photoprotolytic Cycle of Firefly Luciferin
Authors: Pinto da Silva Luís , Esteves da Silva Joaquim C. G.
Published: September 2014

Firefly oxyluciferin is a photoacid that presents a pH‐sensitive fluorescence, which results from pH‐dependent changes on the conformation of self‐aggregated π–π stacking complexes. Luciferin is a derivative of oxyluciferin with very similar fluorescence and photoacidic properties. This similarity indicates that luciferin is also expected to be able to form π–π stacking complexes, but no pH‐sensitive fluorescence is found for this compound. Here, a theoretical approach is used to rationalize this finding. We have found that luciferin only forms π–π stacking complexes in the ground state at acidic pH. At basic pH and in the excited state, luciferin is present as a dianion. This species is not able to self‐aggregate, owing to repulsive electrostatic interactions. Thus, this emissive species is not subject to π–π stacking interactions; this explains its pH‐insensitive fluorescence.
Substitution‐Controlled Excited State Processes in Heteroleptic Copper(I) Photosensitizers Used in Hydrogen Evolving Systems
Authors: Tschierlei Stefanie , Karnahl Michael , Rockstroh Nils , Junge Henrik , Beller Matthias , Lochbrunner Stefan
Published: September 2014

Four different heteroleptic [Cu(N^N)(P^P)]PF6 complexes, which combine classical bidentate diimine ligands and sterically demanding diphosphine ligands, are studied by a combination of ultrafast time‐resolved spectroscopy and quantum chemical calculations. The light‐induced excited state processes, accompanied by a structural change, are discussed with respect to the application of these complexes as a new class of noble‐metal‐free photosensitizers in proton reducing systems. In particular, the influence of different substituents in the ligand backbone on the photophysical properties is highlighted.
Harmonic modelling of PV systems for probabilistic harmonic load flow studies
Authors: Ruiz‐Rodriguez Francisco‐Javier , Hernandez Jesus‐Casa , Jurado Francisco
Published: September 2014

Probabilistic harmonic load flow (HLF) is currently enjoying renewed popularity. This is not surprising since in the near future, thousands of photovoltaic (PV) systems will be integrated into distribution systems. However, as yet, there is no model capable of explaining PV harmonic current behaviour in probabilistic HLF studies. To fill this gap, the harmonic modelling of PV systems proposed in this paper has three key points. First, it provides an effective model of the relationship between PV harmonic current emission and background harmonic voltages. Second, it statistically characterises PV harmonic currents (relative magnitude and phase angle) at different fundamental‐frequency current output intervals using historical time‐series data. In this statistical characterisation, the first fifth moments of each PV harmonic current are used to accurately approximate the raw probability density function (PDF) by means of the Legendre series. Finally, the third key point of this harmonic modelling is a method capable of determining the distribution functions of PV harmonic currents (absolute magnitude and phase angle), based on the statistical characterisation and a fundamental‐frequency probabilistic PV model. The numerical results obtained confirm the effectiveness of this PV model. Copyright © 2014 John Wiley & Sons, Ltd.
Quantitative urine confirmatory testing for synthetic cannabinoids in randomly collected urine specimens
Authors: Castaneto Marisol S. , Scheidweiler Karl B. , Gandhi Adarsh , Wohlfarth Ariane , Klette Kevin L. , Martin Thomas M. , Huestis Marilyn A.
Published: September 2014

Synthetic cannabinoid intake is an ongoing health issue worldwide, with new compounds continually emerging, making drug testing complex. Parent synthetic cannabinoids are rarely detected in urine, the most common matrix employed in workplace drug testing. Optimal identification of synthetic cannabinoid markers in authentic urine specimens and correlation of metabolite concentrations and toxicities would improve synthetic cannabinoid result interpretation. We screened 20 017 randomly collected US military urine specimens between July 2011 and June 2012 with a synthetic cannabinoid immunoassay yielding 1432 presumptive positive specimens. We analyzed all presumptive positive and 1069 negative specimens with our qualitative synthetic cannabinoid liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) method, which confirmed 290 positive specimens. All 290 positive and 487 randomly selected negative specimens were quantified with the most comprehensive urine quantitative LC‐MS/MS method published to date; 290 specimens confirmed positive for 22 metabolites from 11 parent synthetic cannabinoids. The five most predominant metabolites were JWH‐018 pentanoic acid (93%), JWH‐N‐hydroxypentyl (84%), AM2201 N‐hydroxypentyl (69%), JWH‐073 butanoic acid (69%), and JWH‐122 N‐hydroxypentyl (45%) with 11.1 (0.1‐2,434), 5.1 (0.1‐1,239), 2.0 (0.1‐321), 1.1 (0.1‐48.6), and 1.1 (0.1‐250) µg/L median (range) concentrations, respectively.

Alkyl hydroxy and carboxy metabolites provided suitable biomarkers for 11 parent synthetic cannabinoids; although hydroxyindoles were also observed. This is by far the largest data set of synthetic cannabinoid metabolites urine concentrations from randomly collected workplace drug testing specimens rather than acute intoxications or driving under the influence of drugs. These data improve the interpretation of synthetic cannabinoid urine test results and suggest suitable urine markers of synthetic cannabinoid intake. This article is a U.S. Government work and is in the public domain in the USA.
Novel water sources restore plant and animal communities along an urban river
Authors: Bateman H. L. , Stromberg J. C. , Banville M. J. , Makings E. , Scott B. D. , Suchy A. , Wolkis D.
Published: September 2014

Many projects have been undertaken to restore urban rivers in arid regions. At the same time, passive discharge of urban water sources has stimulated redevelopment of wetlands and riparian forests along stretches of dewatered rivers. In Phoenix, Arizona, for example, some segments of the dewatered Salt River have been actively restored by planting and irrigation, whereas others have revegetated in response to runoff from storm drains and effluent drains. Our research documents how biotic communities differ between these actively restored and ‘accidentally’ restored areas, and between wetter and drier urban reaches. We addressed these objectives with a multi‐taxa, multi‐season sampling approach along reaches of the Salt River. We quantified plants using cover estimates in quadrats, birds using fixed radius, point‐count surveys, and herpetofauna (amphibians and reptiles) using visual‐encounter surveys. One notable finding was that wetland plants had greater richness and cover at accidentally restored sites compared with actively restored, dry urban, and non‐urban reference sites. Birds and herpetofauna, however, were most species‐rich at actively restored and non‐urban reference sites, and riparian birds were more abundant at sites with perennial flows compared with ephemeral reaches. From a landscape perspective, the range of management approaches along the river (including laissez‐faire) is sustaining a diverse riparian and wetland mosaic. Urban water subsidies are sustaining freshwater forests and marshlands, the latter a regionally declining ecosystem. In urbanized rivers of arid regions, mapping and conserving perennial stream flows arising from stormwater and effluent discharge can be an important complement to active restoration. Copyright © 2014 John Wiley & Sons, Ltd.
Heterogeneous Foldamers from Aliphatic–Aromatic Amino Acid Building Blocks: Current Trends and Future Prospects
Authors: Nair Roshna V. , Vijayadas Kuruppanthara N. , Roy Arup , Sanjayan Gangadhar J.
Published: September 2014

Chemists' constant pursuit of understanding of the underlying principles of nature's most intricate phenomenon such as protein folding has led to the development of the field of “foldamers”. The emergence of diverse classes of unnatural amino acid building blocks has unleashed countless opportunities to design, develop and explore the structural and functional aspects of synthetic peptides. One current trend in foldamer chemistry is the heterofoldamer approach, which involves systematic stoichiometric variation of various natural/unnatural amino acid residues, leading to conformational ordering with intriguing structural architectures. In this regard, the incorporation of aromatic amino acids provides efficient structural rigidification and tunability to the molecular scaffolds, which can exhibit a range of secondary structural features. Recent times have witnessed an upsurge of foldamers featuring aliphatic‐aromatic residues with diverse structural propensities. This review is an effort to cover this rapidly developing field of foldamer science and also to envisage its future perspectives.
Electrochemical Studies on Glucose Oxidation in an Enzymatic Fuel Cell with Enzyme Immobilized on to Reduced Graphene Oxide Surface
Authors: Das Debalina , Ghosh Susanta , Basumallick I.
Published: September 2014

The present study reports fabrication and characterization of glucose oxidase (GOx) immobilized reduced graphene oxide (rGO), gold nanoparticles (AuNp) and rGO/AuNp composite electrodes. The study further evaluated their electrochemical behaviors using cyclic voltammetry (CV) at different scan rates (10–150 mV/s) and different glucose concentrations (0.1–0.9 M) in phosphate buffer solution (PBS) at pH 7.4. Electron transfer rate constants (ks) for glucose oxidation onto these enzyme immobilized electrodes have been calculated from the plot of Ep vs. log ν ( peak potential vs. log of scan rate) which showed faster electron transfer rate onto rGO/AuNp composite surface compared to AuNp or rGO surfaces alone. A laboratory model enzymatic fuel cell (EFC) was constructed by coupling the anode with a potassium ferrocyanide‐ferricyanide cathode under argon atmosphere. From the discharge studies, the rGO/AuNp/GOx/C‐felt electrode was found to be better than AuNp/GOx/C‐felt or rGO/GOx/C‐felt electrodes. This better performance in rGO/AuNp/GOx/C‐felt electrode has been related to the enhanced attachment of GOx enzyme onto AuNp surface through “S” atoms of sulfur containing amino acids and better electronic conductivity of rGO surface. Hence, the current study concluded that the rGO/AuNp/GOx/C‐felt electrode is a promising electrode for glucose oxidation in EFCs.
Chiral Recognition of Proline Enantiomers by the Catalytic Oxygen Reduction and Formation of Cu(II)‐Polymer Complex Crystals
Authors: Kim Dong‐Min , Won Mi‐Sook , Yoon Jang‐Hee , Kim Jung Ho , Goyal Rajendra N. , Shim Yoon‐Bo
Published: September 2014

A Cu(II)‐Poly(terthiophene carboxylic acid) (pTTC)/Nafion modified glassy carbon electrode has been used for the chiral recognition and discrimination of d‐ and l‐prolines by the catalytic oxygen reduction process and the shape of crystals formed on the electrode surface. The cyclic voltammetry with the modified electrode in the presence of oxygen recognized d‐ and l‐form of prolines by exhibiting a difference in the peak potential and the peak current of the oxygen reduction. The effect of pH and proline concentration on the peak current and the peak potential of oxygen have been studied. The SEM studies on the nature of crystals formed on a proline‐Cu(II)pTTC complex. The oxidation state of the copper species present at the electrode surface was characterized by ESCA.
One‐Dimensional, Additive‐Free, Single‐Crystal TiO2 Nanostructured Anodes Synthesized by a Single‐Step Aerosol Process for High‐Rate Lithium‐Ion Batteries
Authors: Chadha Tandeep S. , Tripathi Alok M. , Mitra Sagar , Biswas Pratim
Published: September 2014

Highly oriented, single crystal dendritic columnar nanostructures of titanium dioxide (TiO2) were fabricated by using single‐step aerosol chemical vapor deposition (ACVD) on stainless‐steel current collectors for use as high‐rate lithium‐ion battery anodes. The synthesized nanostructures exhibited the highest specific capacity (183.5 mAh g−1 after 100 cycles at 1 C rate) ever reported for anatase TiO2 without the use of any conductive additive or binding agents. Exceptional cycling performance and rate capability were also demonstrated making the structures an ideal electrode for high‐rate applications, exhibiting no change in nanostructure morphology even after 100 cycles. At a current density of 16.75 A g−1 (50 C rate), the specific charge capacity of the columnar nanostructures was 278 % higher than that of granular nanostructures synthesized by using the same technique. This facile, low‐cost synthesis of high‐performance anodes thus provides a single‐step, scalable alternative to the conventional fabrication of anode materials.
Thermodynamic Analysis and Characterization of Syngas Production by Autothermal Reforming of Biodiesel Byproducts
Authors: Liu Yujia , Lawal Adeniyi
Published: September 2014

As the demand for and production of biodiesel increase exponentially, the utilization of the biodiesel byproducts will be of increasing commercial significance. The autothermal reforming (ATR) of biodiesel byproducts into synthesis gas (syngas) was experimentally studied by using the BASF Pt and Rh/Pt (rhodium/platinum) dual‐layer monolith catalyst. A total gaseous carbon yield as high as 98 % was obtained with near‐equilibrium concentrations of H2, CO, CO2, and CH4. The optimum operating conditions to produce high yields of syngas with minimal coke formation were also determined to be at atmospheric pressure, a temperature of 750 °C, a steam/carbon (S/C) molar ratio of 3, and an O2/C molar ratio of 0.1. The Aspen simulation software package was used to calculate the equilibrium product composition for autothermal reforming of biodiesel byproducts on molecular basis. A comparison between the equilibrium and experimental data was made, and the agreement was generally good, indicating that close‐to‐equilibrium conditions were attained for the selected reaction conditions.
The influence of diameter of vortex finder on cyclone collection efficiency
Authors: Ficici Ferit , Ari Vedat
Published: September 2014

Cyclones, which are used to separate particles from particle–gas mixtures by spinning movement of centrifugal forces, are stationary pieced devices, main advantages of which are their simplicity and also operability under heavy conditions such as high temperature and high pressure. From an engineering point of view, there are two important parameters in cyclones, namely the cyclone pressure loss and particle collection efficiency. In this work, three different vortex finders' diameters of 80, 120, and 160 mm were designed and fabricated to investigate experimentally the effects of various lengths of vortex finders, inlet velocities and concentrations of inlet particles on particle collection efficiency of preheat cyclones. Increases in all the operating parameters led to increases in the collection efficiency of all cyclones. Also, the experimental study clearly pointed out a critical diameter of vortex finder of 120 mm. © 2014 American Institute of Chemical Engineers Environ Prog, 2014 34: 669–673, 2015
Environmentally benign catalytic process for esterification of renewable levulinic acid to various alkyl levulinates biodiesel
Authors: Nandiwale Kakasaheb Y. , Bokade Vijay V.
Published: September 2014

This study explores, the use of modified zeolite (Micro/Meso‐HZ‐5) obtained by desilication post‐treatment as heterogeneous catalyst for esterification of biomass derived renewable levulinic acid (LA) with different alkyl alcohols such as methanol, ethanol, n‐butanol, and n‐octanol aiming to produce corresponding alkyl levulinate. This method of production of alkyl levulinates would be sustainable process, as it can be used as novel miscible diesel biofuels preventing global warming by decreasing atmospheric CO2.

The LA conversion obtained over Micro/Meso‐HZ‐5 was higher than H‐ZSM‐5, which is due to the combined effect of increase in Brönsted acid sites, total acidity, and other properties such as BET surface area and the generation of mesoporosity. The maximum LA conversion of 91, 95, 96, and 98% with 100% selectivity toward alkyl levulinate was obtained, when LA was being esterified over Micro/Meso‐HZ‐5 with methanol, ethanol, n‐butanol, and n‐octanol, respectively, at optimal process parameters. Micro/Meso‐HZ‐5 catalyst was found to be reusable for six cycles.

Furthermore, pseudo homogeneous (P‐H) kinetic model of the esterification of LA with the studied four alcohols were established with R2 > 0.99, using the experimental data. A P‐H kinetic model implies that, the esterification reaction follows second order reversible kinetics. © 2014 American Institute of Chemical Engineers Environ Prog, 34: 795–801, 2015
EGR strategy for DME engine‐out NOx to meet euro V
Authors: Zhao Danping , Wei Yanju , Chen Xiao , Song Ruizhi , Liu Shenghua
Published: September 2014

In this article, a 2102QB diesel engine was retrofitted to run on DME. The effects of EGR on the DME engine power output, DME fuel consumption, and emission characteristics were investigated. Experimental results show that, DME engine power and fuel economy are both improved. The stoichiometric air/fuel ratio of DME is 9/1. DME engine can run properly if the air/fuel ratio is leaner than that due to the introduction of EGR. Only under fuel rich conditions, DME engine power output, fuel economy, HC and CO emissions become worse. NOx emissions can be reduced easily by the use of EGR.

Based on the experimental data, the specific NOx emissoin was calculated and then it was used to set the rate of EGR under the ESC 13 operating conditions. By the designed EGR strategies, the DME engine NOx emissions under ESC operating conditions meets the requirement of Euro IV and V. At the mean time, HC and CO emissions of the DME engine were evaluated. The increase of CO and HC emissions require oxidation after treatment to meet their own standards. © 2014 American Institute of Chemical Engineers Environ Prog, 2014 34: 881–889, 2015
Diesel engine applications for evaluation of performance and emission behavior of biodiesel from different oil stocks
Authors: Behcet Rasim , Aydın Hüseyin , İlkılıç Cumali , İşcan Bahattin , Aydın Selman
Published: September 2014

Extensive researches on alternative fuels have been carried out since the fossil‐based fuels are limited. Many of these studies have ever been on the usability of vegetable oils in diesel engines. In the current work, biodiesel were produced from waste fish oil (FOB), hazelnut oil (HOB), rapeseed oil (ROB), and waste cooking oil (WCOB) by transesterification method. The same optimized variables of 6:1 methanol/oil molar ratio (mol/mol), 0.4% sodium methoxide concentration (wt.%), 60°C reaction temperature, 1000 rpm agitation speed and 2 h reaction time conditions were performed for biodiesel production from all kinds of above mentioned oils. Some of the important chemical and physical properties of test fuels were found. Without making blends with diesel fuel, pure biodiesels were used in a diesel engine in order to clarify how their usage effects on engine performance and exhaust emission parameters. When compared with those of diesel fuel, average torque and power were reduced while brake specific fuel consumption was increased for biodiesels. Besides, carbon monoxide (CO), hydrocarbon (HC) emissions were considerably lower for biodiesel usage while oxides of nitrogen (NOx) emissions were higher than that of diesel fuel. Furthermore, emissions of carbon dioxide (CO2) and smoke opacity were reduced for biodiesel usage. Oxygen (O2) contained in the exhaust gases were higher for biodiesels while they contain more oxygen molecules in their structure. © 2014 American Institute of Chemical Engineers Environ Prog, 2014 34: 890–896, 2015
Remediation of chromite ore processing residue using solidification and stabilization process
Authors: Kameswari K. Sri Bala , Pedaballe Vihita , Narasimman L.M. , Kalyanaraman Chitra
Published: September 2014

Disposal of Chromite Ore Processing Residue (COPR) is a major concern from an environmental point of view because it consists mainly of Cr(VI) in addition to Cr(III). Cr(VI) is more soluble and mobile when compared to Cr(III). The study primarily concentrated on treatment of COPR using solidification and stabilization (S/S) process. Prior to the S/S process, there was a need for reduction of Cr(VI) fraction present in COPR to Cr(III). In order to reduce Cr(VI) fraction present in COPR to Cr(III), experiments were carried with a variety of reducing agents like Calcium Polysulfide, Silica Gel, Gaur Gum and an optimum dose was arrived at. Further, the chemically treated COPR was solidified with Ordinary Portland Cement along with lime as the binding material in various mix proportions, with Water/COPR plus binder ratio of 0.55. The performance of the above reducing agents and S/S process was verified by conducting leaching tests like Toxicity Characteristic Leaching Procedure, Extraction Procedure Toxicity Test, and American Nuclear Society Leach Test. With these tests, the leaching process in acidic and neutral mediums and the influence of the size of the waste particles on the reduction process as well as leaching were studied. The economics of the process was also arrived at based on cost of chemicals (reducing agents) and materials (cement, lime) needed for remediation of one tonne of COPR. © 2014 American Institute of Chemical Engineers Environ Prog, 34: 674–680, 2015
Occurrence and behavior of the chiral anti-inflammatory drug naproxen in an aquatic environment
Authors: Suzuki Toshinari , Kosugi Yuki , Hosaka Mitsugu , Nishimura Tetsuji , Nakae Dai
Published: September 2014

The present study reports on the occurrence and chiral behavior of the anti-inflammatory drug (S)-naproxen (NAP)—(S)-2-(6-methoxynaphthalen-2-yl)propionic acid—in an aquatic environment under both field and laboratory conditions. In influents and effluents of sewage treatment plants (STPs) in the Tama River basin (Tokyo), (S)-NAP was detected at concentrations of 0.03 µg L−1 to 0.43 µg L−1 and 0.01 µg L−1 to 0.11 µg L−1, respectively. The concentrations of a major metabolite, 6-O-desmethyl NAP (DM-NAP) were up to 0.47 µg L−1 and 0.56 µg L−1 in influents and effluents, respectively. (R)-naproxen was not detected in STP influents, although it was present in effluents, and the enantiomeric faction (= S/[S + R]) of NAP ranged from 0.88 to 0.91. Under laboratory conditions with activated sludge from STPs, rapid degradation of (S)-NAP to DM-NAP and chiral inversion of (S)-NAP to (R)-NAP were observed. During river die-away experiments, degradation and chiral inversion of NAP were extremely slow. In addition, chiral inversion of (S)-NAP to (R)-NAP was not observed during photodegradation experiments. In the river receiving STP discharge, NAP and DM-NAP concentrations reached 0.08 µg L−1 and 0.16 µg L−1, respectively. The enantiomeric faction of NAP in the river ranged from 0.84 to 0.98 and remained almost unchanged with the increasing contribution of rainfall to the river water. These results suggest that the absence and decrease of (R)-NAP in river waters could indicate the inflow of untreated sewage. Environ Toxicol Chem 2014;33:2671–2678. © 2014 SETAC
Championing Culturally Responsive Leadership for Evaluation Practice
Authors: Aponte‐Soto Lisa , Ling Grant Deborah S. , Carter‐Johnson Frances , Colomer Soria E. , Campbell Johnavae E. , Anderson Karen G.
Published: September 2014

The Graduate Education Diversity Internship (GEDI) program empowers students of color to become adaptive leaders, change agents, partners, and facilitators through exposure to theory, experiential training, leadership development, and mentorship in order to advance culturally responsive evaluation (CRE) practices that respond to context and community values in a respectful and positive manner (Nelson‐Barber, LaFrance, Trumbull, & Aburto, ). A case study of the first six GEDI cohorts was conducted to evaluate the program's impact on CRE leadership development. This chapter validates how GEDI transformative leadership strategies can be applied by any profession to champion CRE practitioners and promote a society that values social justice, equity, and democratic change.
Comprehensive exploration of novel chimeric transcripts in clear cell renal cell carcinomas using whole transcriptome analysis
Authors: Gotoh Masahiro , Ichikawa Hitoshi , Arai Eri , Chiku Suenori , Sakamoto Hiromi , Fujimoto Hiroyuki , Hiramoto Masaki , Nammo Takao , Yasuda Kazuki , Yoshida Teruhiko , Kanai Yae
Published: September 2014

The aim of this study was to clarify the participation of expression of chimeric transcripts in renal carcinogenesis. Whole transcriptome analysis (RNA sequencing) and exploration of candidate chimeric transcripts using the deFuse program were performed on 68 specimens of cancerous tissue (T) and 11 specimens of non‐cancerous renal cortex tissue (N) obtained from 68 patients with clear cell renal cell carcinomas (RCCs) in an initial cohort. As positive controls, two RCCs associated with Xp11.2 translocation were analyzed. After verification by reverse transcription (RT)‐PCR and Sanger sequencing, 26 novel chimeric transcripts were identified in 17 (25%) of the 68 clear cell RCCs. Genomic breakpoints were determined in five of the chimeric transcripts. Quantitative RT‐PCR analysis revealed that the mRNA expression levels for the MMACHC, PTER, EPC2, ATXN7, FHIT, KIFAP3, CPEB1, MINPP1, TEX264, FAM107A, UPF3A, CDC16, MCCC1, CPSF3, and ASAP2 genes, being partner genes involved in the chimeric transcripts in the initial cohort, were significantly reduced in 26 T samples relative to the corresponding 26 N samples in the second cohort. Moreover, the mRNA expression levels for the above partner genes in T samples were significantly correlated with tumor aggressiveness and poorer patient outcome, indicating that reduced expression of these genes may participate in malignant progression of RCCs. As is the case when their levels of expression are reduced, these partner genes also may not fully function when involved in chimeric transcripts. These data suggest that generation of chimeric transcripts may participate in renal carcinogenesis by inducing dysfunction of tumor‐related genes. © 2014 The Authors. Genes, Chromosomes & Cancer Published by Wiley Periodicals, Inc.
A genetic dichotomy between pure sclerosing epithelioid fibrosarcoma (SEF) and hybrid SEF/low‐grade fibromyxoid sarcoma: A pathologic and molecular study of 18 cases
Authors: Prieto‐Granada Carlos , Zhang Lei , Chen Hsiao‐Wei , Sung Yun‐Shao , Agaram Narasimhan P , Jungbluth Achim A , Antonescu Cristina R
Published: September 2014

Sclerosing epithelioid fibrosarcoma (SEF) is a rare soft tissue tumor exhibiting considerable morphologic overlap with low‐grade fibromyxoid sarcoma (LGFMS). Moreover, both SEF and LGFMS show MUC4 expression by immunohistochemistry. While the majority of LGFMS cases are characterized by a FUS‐CREB3L1 fusion, both FUS‐CREB3L2 and EWSR1‐CREB3L1 fusions were recently demonstrated in a small number of LGFMS and SEF/LGFMS hybrid tumors. In contrast, recent studies pointed out that SEF harbor frequent EWSR1 rearrangements, with only a minority of cases showing FUS‐CREB3L2 fusions. In an effort to further characterize the molecular characteristics of pure SEF and hybrid SEF/LGFMS lesions, we undertook a clinicopathologic, immunohistochemical and genetic analysis of a series of 10 SEF and 8 hybrid SEF/LGFMS tumors. The mortality rate was similar between the two groups, 44% within the pure SEF group and 37% in the hybrid SEF/LGFMS with a mean overall follow‐up of 66 months. All but one pure SEF and all hybrid SEF/LGFMS‐tested cases showed MUC4 immunoreactivity. The majority (90%) of pure SEF cases showed EWSR1 gene rearrangements by fluorescence in situ hybridization with only one case exhibiting FUS rearrangement. Of the nine EWSR1 positive cases, six cases harbored CREB3L1 break‐apart, two had CREB3L2 rearrangement (a previously unreported finding) and one lacked evidence of CREB3L1/2 abnormalities. In contrast, all hybrid SEF/LGFMS tumors exhibited FUS and CREB3L2 rearrangements. These results further demarcate a relative cytogenetic dichotomy between pure SEF, often characterized by EWSR1 rearrangements, and hybrid SEF/LGFMS, harboring FUS‐CREB3L2 fusion; the latter group recapitulating the genotype of LGFMS. © 2014 Wiley Periodicals, Inc.