bluuebunny/crossref_metadata_2025_split huggingface dataset:
Palladium‐Catalyzed CH Activation and Intermolecular Annulation with Allenes
Authors: Xia Xiao‐Feng , Wang Yu‐Qi , Zhang Lu‐Lu , Song Xian‐Rong , Liu Xue‐Yuan , Liang Yong‐Min 
Published: March 2014

AbstractA new and efficient PdII‐catalyzed intermolecular annulation of N‐benzoylsulfonamide with allenes for the synthesis of 3,4‐dihydroisoquinolin‐1(2H)‐ones is reported. This CH functionalization is compatible with ambient air and moisture, and it can be applied to terminal or internal allenes with diﬀerent synthetically attractive functional groups. Control experiments and a kinetic isotope effect study are conducted and a plausible mechanism is proposed.
Tandem CH Activation/Arylation Catalyzed by Low‐Valent Iron Complexes with Bisiminopyridine Ligands
Authors: Salanouve Elise , Bouzemame Ghania , Blanchard Sébastien , Derat Etienne , Desage‐El Murr Marine , Fensterbank Louis 
Published: March 2014

AbstractTandem CH activation/arylation between unactivated arenes and aryl halides catalyzed by iron complexes that bear redox‐active non‐innocent bisiminopyridine ligands is reported. Similar reactions catalyzed by first‐row transition metals have been shown to involve substrate‐based aryl radicals, whereas our catalytic system likely involves ligand‐centered radicals. Preliminary mechanistic investigations based on spectroscopic and reactivity studies, in conjunction with DFT calculations, led us to propose that the reaction could proceed through an inner‐sphere CH activation pathway, which is rarely observed in the case of iron complexes. This bielectronic noble‐metal‐like behavior could be sustained by the redox‐active non‐innocent bisiminopyridine ligands.
A Novel Pentadentate Redox‐Active Ligand and Its Iron(III) Complexes: Electronic Structures and O2 Reactivity
Authors: Metzinger Ramona , Demeshko Serhiy , Limberg Christian 
Published: March 2014

AbstractA novel redox‐active ligand, H4Ph2SLAP (1) which was designed to be potentially pentadentate with an O,N,S,N,O donor set is described. Treatment of 1 with two equivalents of potassium hydride gave access to octametallic precursor complex [H2Ph2SLAPK2(thf)]4 (2), which reacted with FeCl3 to yield iron(III) complex [H2Ph2SLAPFeCl] (3). Employing Fe[N(SiMe3)2]3 for a direct reaction with 1 led to ligand rearrangement through CS bond cleavage and thiolate formation, finally yielding [HLAPFe] (5). Upon exposure to O2, 3 and 5 are oxidized through formal hydrogen‐atom abstraction from the ligand NH units to form [Ph2SLSQFeCl] (4) and [LSQFe] (6) featuring two or one coordinated iminosemiquinone moieties, respectively. Mössbauer measurements demonstrated that the iron centers remain in their +III oxidation states. Compounds 3 and 5 were tested with respect to their potential as models for the catechol dioxygenase. Thus, they were treated with 3,5‐di‐tert‐butyl‐catechol, triethylamine and O2. It turned out that the iron–catecholate complexes react with O2 in dichloromethane at ambient conditions through CC bond cleavage mainly forming extradiol cleavage products. Intradiol products are only side products and quinone formation becomes negligible. This observation has been rationalized by a dissociation of two donor functions upon coordination of the catecholate.
Palladium(II)‐Catalyzed ortho‐CH Arylation/Alkylation of N‐Benzoyl α‐Amino Ester Derivatives
Authors: Misal Castro Luis C. , Chatani Naoto 
Published: March 2014

AbstractThe palladium‐catalyzed arylation/alkylation of ortho‐CH bonds in N‐benzoyl α‐amino ester derivatives is described. In such a system both the NH‐amido and the CO2R groups in the α‐amino ester moieties play a role in successful CH activation/CC bond formation using iodoaryl coupling partners. A wide variety of functional groups and electron‐rich/deficient iodoarenes are tolerated. The yields obtained range from 20 to 95 %.
Recognition and Site‐Selective Transformation of Monosaccharides by Using Copper(II) Catalysis
Authors: Chen I‐Hon , Kou Kevin G. M. , Le Diane N. , Rathbun Colin M. , Dong Vy M. 
Published: March 2014

AbstractWe demonstrate copper(II)‐catalyzed acylation and tosylation of monosaccharides. Various carbohydrate derivatives, including glucopyranosides and ribofuranosides, are obtained in high yields and regioselectivities. Using this versatile strategy, the site of acylation can be switched by choice of ligand. Preliminary mechanistic studies support nucleophilic addition of a copper–sugar complex to the acyl chloride to be turnover limiting.
On the Synthesis, Characterization and Reactivity of N‐Heteroaryl–Boryl Radicals, a New Radical Class Based on Five‐Membered Ring Ligands
Authors: Tehfe Mohamad‐Ali , Schweizer Stéphane , Chany Anne‐Caroline , Ysacco Cédric , Clément Jean‐Louis , Gigmes Didier , Morlet‐Savary Fabrice , Fouassier Jean‐Pierre , Neuburger Markus , Tschamber Théophile , Blanchard Nicolas , Lalevée Jacques 
Published: March 2014

AbstractThe synthesis and physical characterization of a new class of N‐heterocycle–boryl radicals is presented, based on five membered ring ligands with a N(sp2) complexation site. These pyrazole–boranes and pyrazaboles exhibit a low bond dissociation energy (BDE; BH) and accordingly excellent hydrogen transfer properties. Most importantly, a high modulation of the BDE(BH) by the fine tuning of the N‐heterocyclic ligand was obtained in this series and could be correlated with the spin density on the boron atom of the corresponding radical. The reactivity of the latter for small molecule chemistry has been studied through the determination of several reaction rate constants corresponding to addition to alkenes and alkynes, addition to O2, oxidation by iodonium salts and halogen abstraction from alkyl halides. Two selected applications of N‐heterocycle–boryl radicals are also proposed herein, for radical polymerization and for radical dehalogenation reactions.
Combining Electronic and Steric Effects for Highly Stable Unsymmetric Pentacenes
Authors: Zhang Jingjing , Pawle Robert H. , Haas Terry E. , Thomas Samuel W. 
Published: March 2014

AbstractThis paper describes the reactivity of unsymmetrically substituted pentacenes to photochemical oxidation. Acenes in general, and pentacenes in particular, are a key family of compounds for a variety of organic electronics applications. The instability of many pentacene derivatives, particularly to oxidation, is an important restriction in their applicability. Several substitution strategies for decreasing the reactivity of pentacene exist, but these almost always involve symmetrically substituted derivatives, restricting the chemical space of structures from which to choose. In this paper, we demonstrate that combining electronic and steric effects yields highly stable unsymmetrically substituted pentacenes.
Process Development of Enantioselective Extraction in Miniaturized Lab Columns
Authors: Holbach Alexander , Jaritsch Dimitri , Godde Julia , Kockmann Norbert 
Published: March 2014

AbstractDie Enantioselektive Extraktion stellt neben bestehenden Verfahren der Racematspaltung eine kostengünstige und flexible Alternative dar. In einer neuen, miniaturisierten Laborkolonne wurde sie experimentell und theoretisch untersucht. Ein Racemat in einem wässrig/organischen Zweiphasensystem wurde dabei mithilfe eines Selektormoleküls getrennt. Für eine vollständige Separation der Enantiomere sind viele theoretische Trennstufen nötig, da die operative Selektivität des Systems gering ist. Höhere Überschüsse des Selektormoleküls führen dabei zu höheren Enantiomerüberschüssen und geringeren Ausbeuten.
Helical Poly(α,β‐unsaturated ketone) with Bulky Pendant of Binaphthyl from Anionic Polymerization of ((−)‐Menthyl (S)‐6′‐Acrylyl‐2′‐methyloxy‐1,1′‐binaphthalene‐2‐carboxylate
Authors: Chen Yehui , Yang Liwen , Yang Nianfa , Yang Zhusheng , Zhang Jin 
Published: March 2014

Abstract((−)‐Menthyl (S)‐6′‐acrylyl‐2′‐methyloxy‐1,1′‐binaphthalene‐2‐carboxylate (3) was synthesized and anionically polymerized using n‐BuLi as an initiator in toluene. The monomer 3 was levorotatory and had an [α]D25 value of −72.4, but its corresponding polymer poly‐3 was dextrorotatory and showed an [α]D25 value of +162.0. Poly‐3 was confirmed to exist in the form of one‐handed helical structure in solution by means of comparing the specific optical rotation and the CD spectra with that of 3 and the model compounds such as (−)‐menthyl (S)‐6′‐propionyl‐2′‐methyloxy‐1,1′‐binaphthalene‐2‐carboxylate 2b and (−)‐menthyl (S)‐6′‐heptanoyl‐2′‐methyloxy‐1,1′‐binaphthalene‐2‐carboxylate 2c. This conclusion was also confirmed by the fact that the g‐value of poly‐3 is about 11 times of that of monomer 3.
Characterizing fatigue associated with sunitinib and its impact on health‐related quality of life in patients with metastatic renal cell carcinoma
Authors: Cella David , Davis Mellar P. , Négrier Sylvie , Figlin Robert A. , Michaelson M. Dror , Bushmakin Andrew G. , Cappelleri Joseph C. , Sandin Rickard , Korytowsky Beata , Charbonneau Claudie , Matczak Ewa , Motzer Robert J. 
Published: March 2014

BACKGROUNDUsing phase 3 trial data for sunitinib versus interferon (IFN)‐α in treatment‐naive patients with metastatic renal cell carcinoma, retrospective analyses characterized sunitinib‐associated fatigue and its impact on patient‐reported health‐related quality of life (HRQoL).METHODSPatients received sunitinib at a dose of 50 mg/day on a schedule of 4 weeks on/2 weeks off (375 patients) or IFN‐α at a dose of 9 MU subcutaneously 3 times per week (360 patients). HRQoL was self‐assessed using the Functional Assessment of Cancer Therapy‐Kidney Symptom Index–15‐item (FKSI‐15) questionnaire, with fatigue assessed using its Disease‐Related Symptoms subscale. Fatigue was also assessed by providers using Common Terminology Criteria for Adverse Events (CTCAE). A repeated‐measures model (M1) and random intercept‐slope model (M2) characterized sunitinib‐associated fatigue over time. Another repeated‐measures model examined the relationship between HRQoL scores and CTCAE fatigue grade.RESULTSM1 demonstrated that the initial increase in patient‐reported fatigue with sunitinib was worst during cycle 1, with mean values numerically better at subsequent cycles; most pairwise comparisons of consecutive CTCAE fatigue cycle means were not found to be statistically significant. M2 demonstrated that the overall trend (slope) for patient‐reported and CTCAE fatigue with sunitinib was not statistically different from 0. The relationship between most HRQoL scores and CTCAE fatigue was close to linear regardless of treatment, with lower scores (worse HRQoL) corresponding to higher fatigue grade. The majority of HRQoL scores were better with sunitinib versus IFN‐α for the same CTCAE fatigue grade.CONCLUSIONSPatients reported worse fatigue during the first sunitinib cycle. However, in subsequent consecutive cycles, less fatigue was reported with no statistically significant worsening. CTCAE fatigue assessment may not fully capture patient treatment experience. Cancer 2014;120:1871–1880. © 2014 The Authors. Cancer published by Wiley Periodicals, Inc. on behalf of American Cancer Society. This is an open access article under the terms of the Creative Commons Attribution NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
The role of targeted protein degradation in early neural development
Authors: Saritas‐Yildirim Banu , Silva Elena M. 
Published: March 2014

SummaryAs neural stem cells differentiate into neurons during neurogenesis, the proteome of the cells is restructured by de novo expression and selective removal of regulatory proteins. The control of neurogenesis at the level of gene regulation is well documented and the regulation of protein abundance through protein degradation via the Ubiquitin/26S proteasome pathway is a rapidly developing field. This review describes our current understanding of the role of the proteasome pathway in neurogenesis. Collectively, the studies show that targeted protein degradation is an important regulatory mechanism in the generation of new neurons. genesis 52:287–299, 2014. © 2014 Wiley Periodicals, Inc.
Facile Synthesis of Carbon‐Encapsulated Li4Ti5O12@C Hollow Microspheres as Superior Anode Materials for Li‐Ion Batteries
Authors: Liu Jun , Liu Wei , Ji Shaomin , Wan Yanling , Yin Huaqi , Zhou Yichun 
Published: March 2014

AbstractAn in situ carbon‐encapsulating solution route for the synthesis of Li4Ti5O12@C composite hollow microspheres has been developed. The finally obtained Li4Ti5O12@C hollow microspheres possess a microsized spherical shape, embedded Li4Ti5O12 nanocrystals, and fully encapsulating conductive carbon shells, which endow this Li4Ti5O12 anode material with high specific capacity, rate capability, and cycle stability. Owing to their unique microstructure characteristics, these hollow Li4Ti5O12@C microsphere composites are promising anode materials for highly efficient Li‐ion batteries with an excellent rate capability (discharge capacity of 169, 152, 130, 116, 93, and 76 mA h g–1 at 0.2, 1, 2, 5, 30 and 60C, respectively) and a significantly enhanced cycling performance.
Direct In Situ Determination of Ascorbic Acid in Fruits by Screen‐Printed Carbon Electrodes Modified with Nylon‐6 Nanofibers
Authors: Fuenmayor Carlos Alberto , Benedetti Simona , Pellicanò Alessandro , Cosio Maria Stella , Mannino Saverio 
Published: March 2014

AbstractA simple sensing unit based on a disposable screen printed carbon electrode coated by an electrospun nylon‐6 nanofibrous membrane was developed for in situ selective determination of ascorbic acid (AA) in different types of fruits. The membrane, prepared by electrospinning, represents a selective barrier to possible interferents, such as phenolic compounds, allowing an improved selectivity towards AA. No sample preparation and/or dilution is necessary since the new device is applied directly “pricking” the fruit with the electrode. A good correlation was obtained between the amperometric in situ method and a reference chromatographic methodology (HPLC‐UV) when applied to various fruit samples.
Hyaluronidase modulates bleomycin‐induced lung injury detected noninvasively in small rodents by radial proton MRI
Authors: Egger Christine , Cannet Catherine , Gérard Christelle , Dunbar Andrew , Tigani Bruno , Beckmann Nicolau 
Published: March 2014

PurposeTo assess whether hyaluronic acid, a building block of proteoglycans and extracellular matrix with hydrophilic characteristics, might contribute to magnetic resonance imaging (MRI)‐detected proton signals elicited by bleomycin in the lung. To this end, hyaluronidase, which degrades hyaluronic acid, was administered to bleomycin‐challenged animals.Materials and MethodsFibrosis was induced by oropharyngeal aspiration (OA) of bleomycin. Mice received bleomycin once daily (0.1 mg/kg) on 6 consecutive days, while rats were given a single dose (2 or 4 mg/kg). Hyaluronidase, budesonide, and the respective vehicles were also administered via OA. Animals were examined using a radial ultrashort echo time sequence. Histology of picrosirius reflecting collagen and tissue gene analysis were performed postmortem.ResultsIn mice, hyaluronidase induced an increase of high intensity signals by 34 ± 12 μL (means ± SD, P = 0.007), consistent with the ability of the degradation products of hyaluronic acid to provoke acute inflammation. Budesonide was able to resolve hyaluronidase‐induced signals or to prevent their formation. Combined administration of budesonide and hyaluronidase to bleomycin‐treated rats resulted in an overall decrease (−17.1 ± 7%, P = 0.02) of the MRI‐detected bleomycin‐induced signals. Moreover, the relative gene expression of hyaluronidase was reduced (−61.8 ± 10.2%, P < 0.001) in fibrotic lungs.ConclusionThe present data indicate that hyaluronic acid contributes to the bleomycin‐induced responses detected by MRI in the lung. J. Magn. Reson. Imaging 2015;41:755–764. © 2014 Wiley Periodicals, Inc.
High‐resolution mass spectrometry to evaluate the influence of cross‐breeding segregating populations on the phenolic profile of virgin olive oils
Authors: Sánchez de Medina Verónica , Calderón‐Santiago Mónica , El Riachy Milad , Priego‐Capote Feliciano , Luque de Castro María Dolores 
Published: March 2014

AbstractBACKGROUNDThe growing demand for high‐quality virgin olive oils (VOOs) has increased the interest in olive breeding programs. Cross‐breeding is considered, within these programs, the best strategy to generate new cultivars as an attempt to improve the present cultivars. In this research, the phenolic profile of VOOs from target crosses (Arbequina × Arbosana, Picual × Koroneiki and Sikitita × Arbosana) and their corresponding genitors (Arbequina, Arbosana, Koroneiki, Picual and Sikitita) has been evaluated using a targeted metabolomics approach.RESULTSThe phenolic profiles were obtained by liquid chromatographic–hybrid quadrupole time‐of‐flight mass spectrometric targeted analysis of 37 phenols or compounds involved in the main pathways for their biosynthesis. Statistical multivariate analysis by principal component analysis was applied to study the influence of genotype on phenol composition. Phenolic compounds with the highest contribution to explain the observed variability associated to genotype were identified through fold change algorithms (cut‐off > 2.0) and t‐test analysis.CONCLUSIONA total of nine phenols (viz. quercetin, ligstroside aglycon (p‐HPEA‐EA), demethyl oleuropein aglycon, oleuropein aglycon (3,4‐DHPEA‐EA), hydroxypinoresinol, hydroxytyrosol and phenolic acids such as p‐coumaric acid, ferulic acid and protocatechuic acid) contributed to explain the observed variability with 99% confidence (P<0.01). © 2014 Society of Chemical Industry
Mismatch repair system and p53 expression in patients with T1 and T2 colorectal cancer: Predictive role of lymph node metastasis and survival
Authors: Huh Jung Wook , Kim Hee Cheol , Kim Seok Hyung , Park Yoon Ah , Cho Yong Beom , Yun Seong Hyeon , Lee Woo Yong , Chun Ho‐Kyung 
Published: March 2014

AbstractBackgroundThe aim of this study was to evaluate the predictive role of the mismatch repair (MMR) system and p53 expression for lymph node metastasis and long‐term survival in patients with T1 and T2 colorectal cancer.MethodsA total of 543 patients with T1 or T2 colorectal cancers who underwent radical surgery with regional lymphadenectomy from December 2007 to December 2009 were analyzed. Predictive factors for lymph node metastasis and prognostic factors were analyzed.ResultsDuring the median follow‐up period of 4 years, the 5‐year disease‐free survival rate for patients without lymph node metastasis was 94.8%, which was significantly higher than that for those with lymph node metastases (85.2%; P < 0.001). On multivariate analysis, gender, tumor location, N category, lymphatic invasion, vascular invasion, and perineural invasion were independent prognostic factors for disease‐free survival; however MMR defect, p53 expression, and microsatellite instability (MSI) were not. The presence of lymphatic invasion, vascular invasion, and tumor budding were independent predictors of lymph node metastasis.ConclusionsIn patients with T1 or T2 colorectal cancer, lymphatic invasion, vascular invasion, and tumor budding were predictive of lymph node metastasis; however, MMR defect, p53 expression, and MSI were not predictive. J. Surg. Oncol. 2014 109:848–852. © 2014 Wiley Periodicals, Inc.
Anatomical study of critical features on the posterior wall of the maxillary sinus: Clinical implications
Authors: Wang Liang , Gun Ramazan , Youssef Ahmed , Carrau Ricardo L. , Prevedello Daniel M. , Otto Bradley A. , Ditzel Leo 
Published: March 2014

Objectives/HypothesisEndonasal approaches to the pterygopalatine fossa for epistaxis or as part of a transpterygoid approach have been popularized somewhat by the ability to control the terminal branches of the maxillary artery (MA). Surgical landmarks are useful to identify these arteries. Therefore, identification of surface features on the posterior wall of the antrum that reflect the position of deeper structures within the pterygopalatine fossa would help predict anatomical position and orientation.Study DesignDescribe the incidence of identifiable markings on the posterior wall of the maxillary sinus and ascertain their nature.MethodsAn anatomical study of 18 cadaveric specimens noting and recording the presence, location, and number of prominences on the posterior wall of the antrum. After removing the bony wall, structure in the pterygopalatine fossa corresponding to the surface markings was noted.ResultsTwo prominences were identified. Prominence (P)1 extended from the upper part of the posterior wall of the maxillary sinus to the inferior orbit and corresponded to the infraorbital nerve. P2 was located at the middle part of the posterior wall, below P1, and corresponded to the MA. P2 was located medial to a vertical “drop line” where P1 connected to the posterior wall. P1 and P2 were found in 41.7% and 22.2%, respectively, of the specimens.ConclusionsThis study defines features on the maxillary sinus posterior wall from an endoscopic perspective. These landmarks may be useful to identify the MA and its branches during surgery within the pterygopalatine fossa.Level of EvidenceN/A. Laryngoscope, 124:2451–2455, 2014
Hand Exercise Intervention in Patients with Polymyositis and Dermatomyositis: A Pilot Study
Authors: Regardt Malin , Schult Marie‐Louise , Axelsson Yvonne , Aldehag Anna , Alexanderson Helene , Lundberg Ingrid E. , Henriksson Elisabet Welin 
Published: March 2014

AbstractObjectiveThe aim of the present study was to develop a 12‐week hand exercise intervention for patients with polymyositis (PM) and dermatomyositis (DM) and evaluate adherence, patients' opinions of the programme design and overall feasibility, and the effect on hand function and activity limitation after the intervention.MethodA pilot hand exercise intervention was conducted on a convenience sample of 15 patients with reduced handgrip strength and established, inactive PM and DM. Acceptable adherence was set at 75%. The programme was evaluated based on patients' opinions regarding exertion, the movements involved and overall feasibility. Hand‐ and pinch‐grip strength, grip ability, dexterity and activity limitation were assessed.ResultsEleven of 15 patients completed the intervention, with acceptable adherence of 78–100%. Measures of handgrip strength, dexterity and activity limitation were reduced at baseline compared with normative data from the literature. Throughout the intervention, rates of perceived exertion were scored between ‘moderate’ and ‘fairly strong’. Finger abduction and adduction were excluded from the hand exercise programme because they were not feasible to perform. Repetitions of the exercise increased gradually to a maximum of 30 per movement. Patients regarded this as too time‐consuming and suggested ten repetitions daily or 10–20 repetitions 2–4 times per week. There were some individual, clinically meaningful improvements in hand function and activity limitation. A comparison between baseline and after the intervention showed that the three‐jaw (tripod) pinch‐grip strength (left hand) had increased (p < 0.007; z = –2.7).ConclusionA hand exercise programme was found to be feasible to perform by patients with established PM or DM. The effect was limited, with few individual improvements in hand function and activity limitation, indicating a need to increase the resistance in the movements and to limit the duration of each exercise session. Copyright © 2014 John Wiley & Sons, Ltd.