bluuebunny/crossref_metadata_2025_split huggingface dataset:
Complexes of Copper(I) Thiocyanate with Monodentate Phosphine and Pyridine Ligands and the P(,N)‐Donor Diphenyl(2‐pyridyl)phosphine
Authors: Bowmaker Graham A. , Hanna John V. , King Scott P. , Marchetti Fabio , Pettinari Claudio , Pizzabiocca Adriano , Skelton Brian W. , Sobolev Alexandre N. , Tăbăcaru Aurel , White Allan H. 
Published: November 2014

AbstractCopper(I) thiocyanate derivatives were prepared by the reaction of CuNCS with pyridine (py) and tertiary monophosphine ligands [PR3 in general; in detail: PPh3, triphenylphosphine, P(4‐FPh)3, tris(4‐fluorophenyl)phosphine)], as well as the potentially bidentate ligand diphenyl(2‐pyridyl)phosphine (PPh2py). Mechanochemical methods were used in some cases to investigate stoichieometries that were not easily accessible by conventional solution syntheses. Three forms of the resulting adducts of CuNCS/PR3/py‐base (1:3–n:n) stoichiometry―all containing four‐coordinate copper(I) atoms and monodentate N‐thiocyanate groups―were confirmed crystallographically. Mononuclear arrays are defined for [(PPh2py)3–n(py)nCuNCS], n = 0, 1, 2, the monodentate thiocyanate being N‐coordinated in all; two polymorphs are observed for the n = 2 complex, both crystallizing in monoclinic P21 (Z = 2) cells with similar cell dimensions, but with aromatic components eclipsed about the Cu–P bond in the PPh3 complex, and staggered in the PPh2py complex. Bridging thiocyanate groups are found in the 1:1:1 CuNCS/PPh2py/2‐methylpyridine (mpy) and P(4‐FPh)3/mpy complexes, wherein centrosymmetric dimers with eight‐membered central rings are obtained: [(R3P)(mpy)Cu(NCS)2Cu(PR3)(mpy)], as is also the case in the parent 1:2 CuNCS/PPh2py adduct [(pyPh2P)2Cu(NCS)2Cu(PPh2py)2]. For the 1:1:1 CuNCS/P(4‐FPh)3/py and PPh3/Brmpy (Brmpy = 3‐bromo‐4‐methylpyridine) adducts, and, likely, CuNCS/PPh2py/py (1:1:1), single‐stranded polymers of the form [···Cu(NCS)(PR3)(py‐base)(Cu)···](∞|∞) with linearly bridging NCS ligands were obtained. Some derivatives, representative of all forms, display medium to strong green to blue luminescence when excited with radiation at 365 nm. The 31P CPMAS NMR spectroscopic data clearly differentiate the inequivalent phosphorus positions within each system, showing a wide range of 1J(31P,63/65Cu) values ranging from 965 Hz for [Cu(NCS)(PPh2py)3] to 1540 Hz for dimeric [(4‐FPh)3P(mpy)Cu(NCS)2Cu(P(4‐FPh)3)(mpy)], reflecting the large variations in the Cu–P bond length.
Total Synthesis of (±)‐Oxalicumone C and Chiral Resolution and Elucidation of Its Absolute Configuration
Authors: Wink Christoph , Andernach Lars , Opatz Till , Waldvogel Siegfried R. 
Published: November 2014

AbstractThe racemic total synthesis, the chiral resolution, and the elucidation of the absolute configuration of the natural product oxalicumone C were investigated. The goal was achieved by a synthetic strategy beginning with the synthesis of a 5‐hydroxy‐7‐methylchromone precursor. Further modification possibilities were achieved by introduction of a vinyl moiety into the chromone, which was based on a selective iodination step in the 3‐position. Further transformations furnished the racemic natural product. To determinate the absolute configuration of naturally occurring oxalicumone C, both enantiomers were separated by chiral HPLC. Comparison of the calculated and experimental vibrational circular dichroism spectra unequivocally indicated that (S)‐oxalicumone C is the naturally occurring enantiomer.
Channel estimation techniques for 5G cellular networks: FBMC and multiuser asynchronous fragmented spectrum scenario
Authors: Doré Jean‐Baptiste , Berg Vincent , Kténas Dimitri 
Published: November 2014

ABSTRACTIn order to reduce constant exchange of control signalling, relaxed synchronisation is considered for the fifth generation of wireless cellular networks. This requirement combined with dynamic spectrum access has led to reconsider conventional orthogonal frequency division multiple access. Frequency division multiple access for filter bank multicarrier (FBMC) modulation has emerged as a serious contender for these asynchronous fragmented spectrum access scenarios. In this paper, it is demonstrated that the frequency‐spreading FBMC receiver architecture is particularly adapted to deal with these scenarios and is robust to severe channel conditions. Channel estimation has however so far only been partially addressed in this context. The challenges of this essential signal processing block are presented in this paper. Interference approximation methods have been applied to the so‐called frequency‐spreading FBMC receiver to propose and evaluate preamble structures and channel estimation schemes. A flexible preamble structure is finally described and analysed. Copyright © 2014 John Wiley & Sons, Ltd.
Quantifying uncertainty in the trophic magnification factor related to spatial movements of organisms in a food web
Authors: McLeod Anne M , Arnot Jon A , Borgå Katrine , Selck Henriette , Kashian Donna R , Krause Ann , Paterson Gord , Haffner G Doug , Drouillard Ken G 
Published: November 2014

Abstract
Trophic magnification factors (TMFs) provide a method of assessing chemical biomagnification in food webs and are increasingly being used by policy makers to screen emerging chemicals. Recent reviews have encouraged the use of bioaccumulation models as screening tools for assessing TMFs for emerging chemicals of concern. The present study used a food web bioaccumulation model to estimate TMFs for polychlorinated biphenyls (PCBs) in a riverine system. The uncertainty associated with model predicted TMFs was evaluated against realistic ranges for model inputs (water and sediment PCB contamination) and variation in environmental, physiological, and ecological parameters included within the model. Finally, the model was used to explore interactions between spatial heterogeneity in water and sediment contaminant concentrations and theoretical movement profiles of different fish species included in the model. The model predictions of magnitude of TMFs conformed to empirical studies. There were differences in the relationship between the TMF and the octanol–water partitioning coefficient (KOW) depending on the modeling approach used; a parabolic relationship was predicted under deterministic scenarios, whereas a linear TMF–KOW relationship was predicted when the model was run stochastically. Incorporating spatial movements by fish had a major influence on the magnitude and variation of TMFs. Under conditions where organisms are collected exclusively from clean locations in highly heterogeneous systems, the results showed bias toward higher TMF estimates, for example the TMF for PCB 153 increased from 2.7 to 5.6 when fish movement was included. Small underestimations of TMFs were found where organisms were exclusively sampled in contaminated regions, although the model was found to be more robust to this sampling condition than the former for this system. Integr Environ Assess Manag 2014;X:000–000. ©2014 SETAC Integr Environ Assess Manag 2015;11:306–318. © 2014 SETAC
Key Points
The model predictions of magnitude of TMFs conformed to empirical studies. Sampling regimes had an important influence on the magnitude and variation of TMFs, as did incorporation of spatial movements by fish. When organisms were sampled exclusively from clean locations in highly heterogeneous systems the TMF showed bias towards high estimates when fish movements were allowed for. Small underestimations of TMFs were found when organisms were sampled exclusively in contaminated regions for this system.
RNA‐Seq‐based toxicogenomic assessment of fresh frozen and formalin‐fixed tissues yields similar mechanistic insights
Authors: Auerbach Scott S. , Phadke Dhiral P. , Mav Deepak , Holmgren Stephanie , Gao Yuan , Xie Bin , Shin Joo Heon , Shah Ruchir R. , Merrick B. Alex , Tice Raymond R. 
Published: November 2014

AbstractFormalin‐fixed, paraffin‐embedded (FFPE) pathology specimens represent a potentially vast resource for transcriptomic‐based biomarker discovery. We present here a comparison of results from a whole transcriptome RNA‐Seq analysis of RNA extracted from fresh frozen and FFPE livers. The samples were derived from rats exposed to aflatoxin B1 (AFB1) and a corresponding set of control animals. Principal components analysis indicated that samples were separated in the two groups representing presence or absence of chemical exposure, both in fresh frozen and FFPE sample types. Sixty‐five percent of the differentially expressed transcripts (AFB1 vs. controls) in fresh frozen samples were also differentially expressed in FFPE samples (overlap significance: P < 0.0001). Genomic signature and gene set analysis of AFB1 differentially expressed transcript lists indicated highly similar results between fresh frozen and FFPE at the level of chemogenomic signatures (i.e., single chemical/dose/duration elicited transcriptomic signatures), mechanistic and pathology signatures, biological processes, canonical pathways and transcription factor networks. Overall, our results suggest that similar hypotheses about the biological mechanism of toxicity would be formulated from fresh frozen and FFPE samples. These results indicate that phenotypically anchored archival specimens represent a potentially informative resource for signature‐based biomarker discovery and mechanistic characterization of toxicity. Copyright © 2014 John Wiley & Sons, Ltd.
Multimodal and multiplex spectral imaging of rat cornea ex vivo using a white‐light laser source
Authors: Segawa Hiroki , Kaji Yuichi , Leproux Philippe , Couderc Vincent , Ozawa Takeaki , Oshika Tetsuro , Kano Hideaki 
Published: November 2014

We applied our multimodal nonlinear spectral imaging microscope to the measurement of rat cornea. We successfully obtained multiple nonlinear signals of coherent anti‐Stokes Raman scattering (CARS), third‐order sum frequency generation (TSFG), and second harmonic generation (SHG). Depending on the nonlinear optical processes, the cornea tissue was visualized with different image contrast mechanism simultaneously. Due to white‐light laser excitation, multiplex CARS and TSFG spectra were obtained. Combined multimodal and spectral analysis clearly elucidated the layered structure of rat cornea with molecular structural information. This study indicates that our multimodal nonlinear spectral microscope is a promising bioimaging method for tissue study.
Multimodal nonlinear spectral images of rat cornea at corneal epithelium and corneal stroma in the in‐plane (XY) direction. With use of the combinational analysis of different nonlinear optical processes, detailed molecular structural information is available without staining or labelling.magnified imageMultimodal nonlinear spectral images of rat cornea at corneal epithelium and corneal stroma in the in‐plane (XY) direction. With use of the combinational analysis of different nonlinear optical processes, detailed molecular structural information is available without staining or labelling.
Endoscopic ultrasonography‐guided pancreatic cyst ablation (with video)
Authors: Oh Hyoung‐Chul , Seo Dong Wan 
Published: November 2014

Abstract Pancreatic cystic lesions are being diagnosed with increasing frequency owing to the widespread use of cross‐sectional imaging. Although most pancreatic cysts are detected incidentally, they represent a wide spectrum of histopathology, and neoplastic cysts appear to be more prevalent than previously estimated. Some histologic types have malignant potential. Considering the perioperative morbidity associated with surgical resection, deciding whether to operate or observe an indeterminate pancreatic cyst is challenging, and there is a strong clinical need to develop a minimally invasive approach. EUS‐guided pancreatic cyst ablation has been investigated in several clinical trials, and may represent a viable alternative to surgical resection.
The effects of bruising and temperature on enzyme activity and textural qualities of tomato juice
Authors: Held Matthew T , Anthon Gordon E , Barrett Diane M 
Published: November 2014

AbstractBACKGROUNDDuring harvest and transportation, processing tomatoes are exposed to elevated temperatures, compression and vibration in the harvester and truck, making them prone to bruising. The objective of this study was to determine how bruising and exposure to high temperatures affect pectin methylesterase (PME) activation and the textural quality of tomato juice.RESULTSTomatoes were both hand and mechanically harvested using current harvest practices. Mechanically harvested fruits were significantly softer, had greater PME activity and greater juice consistency than hand harvested fruits. In a controlled bruising study, whole tomatoes were exposed to various compressive forces at 21 or 40 °C and held for 0 or 4 h. Greater bruising force and higher temperature resulted in a decrease in firmness and an increase in PME activity. Consistency of tomato juice improved when tomatoes were exposed to 40 °C. Tomatoes subjected to a temperature range from 21 to 65 °C had activated PME at 40 °C and increased activity as temperature increased. Consistency increased at 35 °C but decreased with increasing temperature.CONCLUSIONTomatoes harvested using current mechanical techniques are likely to be less firm and have increased PME activity; however, increased consistency of processed juice is observed. Tomatoes harvested at higher temperatures are also likely to have better consistency when processed. © 2014 Society of Chemical Industry
Identification of 19 phthalic acid esters in dairy products by gas chromatography with mass spectrometry
Authors: Wu Pinggu , Cai Chenggang , Yang Dajin , Wang Liyuan , Zhou Yan , Shen Xianghong , Ma Bingjie , Tang Jun 
Published: November 2014

A detection method for 19 kinds of phthalic acid ester compounds analyzed by n‐hexane/ether/acetonitrile 1:7:8 v/v/v mixed solvent extraction, quick, easy, cheap, effective, rugged, and safe purification and internal standard method of quantitative gas chromatography with mass spectrometry was established. This method can effectively remove interfering materials, such as lipids, fatty acids, and pigments, from dairy products. The 19 kinds of phthalic acid ester compounds were within a 0.025–0.2 mg/kg range, the recovery rate was 65.2–125.7%, relative standard deviation was 7.9–15.4% (n = 6), and the limit of detection was 0.005–0.02 mg/kg. Concentrations of the 19 kinds of phthalic acid ester compounds ranged between 0.01 and 0.12 mg/kg in ten dairy materials and 20 dairy products. The established method is simple, rapid, accurate, and highly sensitive.
Determination of the polyphenolic content of a Capsicum annuum L. extract by liquid chromatography coupled to photodiode array and mass spectrometry detection and evaluation of its biological activity
Authors: Mokhtar Meriem , Soukup Jan , Donato Paola , Cacciola Francesco , Dugo Paola , Riazi Ali , Jandera Pavel , Mondello Luigi 
Published: November 2014

The present study was aimed to investigate the polyphenolic profile of a pepper (Capsicum annuum L.) extract from Algeria and evaluate its biological activity. The total polyphenol content of the extract was determined as 1.373 mg of gallic acid equivalents (±0.0046), whereas the flavonoids were determined as 0.098 mg of quercetin (±0.0015). The determination of the complete polyphenolic profile of the extract was achieved by liquid chromatography with an RP‐amide column in combination with photodiode array and mass spectrometry detection through an electrospray ionization interface. A total of 18 compounds were identified, of which five were reported for the first time in the sample tested. Quercetin rhamnoside was the most abundant compound (82.6 μg/g of fresh pepper) followed by quercetin glucoside (19.86 μg/g). The antioxidant activity and antimicrobial effects were also determined. For the antimicrobial tests assessed against Gram‐positive and Gram‐negative bacteria, kaempferol showed the strongest inhibitory effect followed by quercetin and caffeic acids. In the study of the cytotoxicity of the extract, the cancer cells (U937) were more affected than the normal cells (peripheral blood mononucleated cells), with more than 62% inhibition at the highest concentration.
Sinonasal and ventral skull base Inflammatory pseudotumor: A systematic review
Authors: Desai Stuti V. , Spinazzi Eleonora F. , Fang Christina H. , Huang Grace , Tomovic Senja , Liu James K. , Baredes Soly , Eloy Jean Anderson 
Published: November 2014

Objectives/HypothesisInflammatory pseudotumor is a benign idiopathic inflammatory process often misdiagnosed as an infection or neoplasm. This review analyzes all reported cases of sinonasal and ventral skull base inflammatory pseudotumor to date, and provides a framework for evaluation and management of this uncommon condition.Data SourcesMEDLINE/PubMed database.Review MethodsA search for articles related to sinonasal and ventral skull base inflammatory pseudotumor, along with bibliographies of those articles, was performed. Demographics, presentation, radiographic findings, treatment, follow‐up, and outcome were analyzed.ResultsThirty‐three articles were reviewed, including a total of 87 patients. The most common presenting symptom was vision change (58.6%). Sinonasal and ventral skull base inflammatory pseudotumor was found in the cavernous sinus in 46.0% of cases. The lesion appeared isointense (66.7% of cases) and homogeneously enhancing on T1‐weighted magnetic resonance imaging (MRI), whereas it appeared hypointense on T2‐weighted MRI in 90.7% of cases. Inflammatory pseudotumor appeared hyperdense on computed tomography in 78.9% of cases. Histopathological analysis of biopsied specimens revealed presence of inflammatory cells (94.4%) and fibrosis (80.3%). Corticosteroids alone were the most common treatment modality (55.2%), resulting in disease‐free patients in 22.9% of cases over a median follow‐up period of 17.6 months. Surgical management alone was uncommon (8.0%), but showed high success rate (57.1%).ConclusionThis review is the most comprehensive analysis of sinonasal and ventral skull base inflammatory pseudotumor to date. Radiologic findings and histopathological analysis are essential for diagnosis. Corticosteroids are the most common treatment modality. Surgery, although uncommon, appears to be an efficacious treatment modality.Level of EvidenceN/A Laryngoscope, 125:813–821, 2015
Oxyethylation of carbochain and heterochain polyamides
Authors: Rafikov S. R. , Chelnokova G. N. , Zhuravleva I. V. , Gribkova P. N. 
Published: November 2014

AbstractCarbochain and heterochain polyamides are highly reactive compounds and may be quite easily converted to various polymer analogs, including compounds with graft side chains. We have studied the relations in the polyoxyethylation of heterochain and carbochain polyamides of various structure under different conditions. Under heterogeneous conditions the reaction takes place not only at the surface, but in the entire body of the film or fiber, although not to the same degree. On heterogeneous polyoxyethylation of heterochain polyamides graft polymers were obtained with up to 55% content of polyethylene oxide, with varying polyethylene oxide chain lengths and with different degrees of substitution of the groups. The formation of polyoxyethylated polyamides with high polyethylene oxide contents is facilitated by the use of a large excess of ethylene oxide and a lower degree of orientation of the films and fibers. In the polyoxyethylation of heterochain polyamides, as a result of crosslinking insoluble products may form which are greatly swelled in the various solvents. The branching and crosslinking of the macromolecules has been found to result from the reaction of the terminal carboxyl groups of the polyamides and the hydroxyl groups of the polyethylene oxide graft. On polyoxyethylation of polyamides not containing terminal carboxyl groups non‐cross‐linked, soluble, graft polymers are formed. In the heterogeneous polyoxyethylation of Polyacrylamide films, graft polymers with up to 65% polyethylene oxide content were obtained. In this case the reaction is also accompanied by the formation of crosslinks. In the reaction process one or both of the hydrogens of an amide group may be replaced by polyethylene oxide chains.
Thermal aging of polychloroprene
Authors: Kössler I. , Matyska B. , Poláček J. 
Published: November 2014

AbstractThe aging of polychloroprene has been studied at normal and elevated temperatures in air, in oxygen, and in nitrogen. A comparison of the molecular weight distribution curves for fresh specimens and for specimens aged under various conditions showed that on aging the polymer becomes heterogeneous. A large increase in the high molecular fractions shows that reactions leading to crosslinking prevail over those leading to degradation. Crosslinking (at least in the beginning) is caused mainly by peroxide bonds, as indicated by the spontaneous and ultrasonic degradation of the first fractions of the aged polymer. This conclusion has also received support in a comparison of the ultrasonic degradation of unfractionated fresh and aged polymer. It can be seen from the infrared spectra that on aging in air there is an increase in the carboxyl, aldehyde, CO, and OH group content, as well as in the number of conjugated double bonds. The number of CCl==CH, CH2, and CR1R2==CHR3 groups diminishes. The formation of conjugated double bonds was also found to take place during crystallization. The ultimate degree of crystallization greatly fell during the aging process (from 34 to 0%); the rate of crystallization, obeying well the Avrami equation for n = 2, changed only to an insignificant extent. On the basis of the measurements made it has been concluded that on lowering the crystallization capacity to 3.5% the degree of crosslinking is larger than in the case of vulcanized natural rubber with a 0.05% sulfur content. The chemical reactions leading to loss in crystallizability proceed with an activation energy of 8.5 kcal./mole, which approaches the value for the energy of activation of hydrogen chloride evolution (9.5 kcal./mole). The evolution of hydrogen chloride is initiated by oxidation reactions and is related to the polymer structure. Products of the decomposition of tetraethylthiuram disulfide or polysulfides were detected in considerable amounts among the gaseous aging products.