bluuebunny/crossref_metadata_2025 huggingface dataset:
Advanced Electron Microscopy Investigation of Ceria–Zirconia‐Based Catalysts
Authors: López‐Haro M. , Pérez‐Omil J. A. , Hernández‐Garrido J. C. , Trasobares S. , Hungría A. B. , Cíes J. M. , Midgley P. A. , Bayle‐Guillemaud P. , Martínez‐Arias A. , Bernal S. , Delgado J. J. , Calvino J. J.
Published: November 2010

The potentials of advanced transmission and scanning transmission electron microscopy in nanostructural studies of ceria–zirconia mixed oxides are overviewed. The crystallographic criteria that allow us to discriminate the different CeO2–ZrO2 polymorphs and the nanocrystal size range within which they can be applied are discussed. The combined use of high resolution electron microscopy (HREM) and high‐angle annular dark field scanning transmission electron microscopy (HAADF‐STEM) to detect disorder–order transitions in the cation sublattice of this family of oxides and the size limit down to which each of them can be used for that purpose are also analyzed. Criteria to discriminate, on the basis of HREM images, the oxygen arrangement of the so called κ‐Ce2Zr2O8 phase from that of an oxidized pyrochlore Ce2Zr2O8 phase are presented and applied to the interpretation of experimental HREM images. HAADF‐STEM tomography studies and detailed analysis of HAADF‐STEM images establish both the crystallographic and compositional features of the surfaces of the mixed oxides that give enhanced redox activity. These findings allow deeper understanding of the influence of different thermal ageing pretreatments on the redox behavior of this family of mixed oxides. Novel characterization data do evidence that this model does not only fruitfully apply to binary ceria–zirconia oxides but also to more complex ternary oxides containing terbium.
Controlled Synthesis and Self‐Assembly of Highly Monodisperse Ag and Ag2S Nanocrystals
Authors: Li Peng , Peng Qing , Li Yadong
Published: November 2010

A facile method to control the synthesis and self‐assembly of monodisperse Ag and Ag2S nanocrystals with a narrow‐size distribution is described. Uniform Ag nanoparticles of less than 4 nm were obtained by thermolysis of Ag–oleate complexes in the presence of oleic acid and dodecylamine, and monodisperse Ag nanoparticles of less than 10 nm were also prepared in one step by using dodecylamine and oleic acid as capping agents. Moreover, the surface‐enhanced Raman scattering (SERS) properties of the Ag substrates have also been investigated. It is worth mentioning that these Ag nanoparticles and assemblies show great differences in the SERS activities of Rhodamine B dye. In addition, the superlattices of Ag2S nanocrystals were synthesized with Ag–oleate complexes, alkanethiol, and sulfur as the reactants. The resulting highly monodisperse nanocrystals can easily self‐assemble into interesting superstructures in the solution phase without any additional assembly steps. This method may be extended to the size‐controlled preparation and assembly of many other noble‐metal and transition‐metal chalcogenide nanoparticles. These results will aid the study of the physicochemical properties of the superlattice assemblies and construction of functional macroscopic architectures or devices.
Platinum(II)‐Based Hydrogen‐Evolving Catalysts Linked to Multipendant Viologen Acceptors: Experimental and DFT Indications for Bimolecular Pathways
Authors: Ogawa Makoto , Ajayakumar Gopalakrishnan , Masaoka Shigeyuki , Kraatz Heinz‐Bernhard , Sakai Ken
Published: November 2010

Three new [PtCl2(bpy)] derivatives tethered to 2, 4, and 6 dicationic viologen moieties, [PtCl2(MV2)]4+ (1), [PtCl2(MV4)]8+ (2), and [PtCl2(MV6)]12+ (3), have been synthesized (MV24+=5‐ethoxycarbamoyl‐5′‐(N‐R1‐carbamoyl)‐2,2′‐bipyridine, MV48+=5,5′‐bis(N‐R1‐carbamoyl)‐2,2′‐bipyridine, and MV612+=5,5′‐bis(N‐R2‐carbamoyl)‐2,2′‐bipyridine, in which R1=Asp(NH‐VG)‐NH‐VG, R2=Asp(NH‐VG)‐Asp(NH‐VG)‐NH‐VG, and VG=‐(CH2)2‐+NC5H4‐C5H4N+‐CH3). In spite of the higher charge storage capacity of 2 and 3 due to the higher number of acceptor groups (VG groups), compound 1 with the lowest number of VG tethers has turned out to exhibit an outstanding catalytic performance towards the hydrogen evolution from water. Quantitative analysis of UV/Vis‐NIR absorption spectral changes during the photolysis for 2 and 3 reveal that approximately 2 electrons per molecule are stored over the acceptor groups during the photolysis, and the storage events saturate after 20 min. As for 1, the total number of electrons stored per molecule increases once during the initial 10 min and then abruptly decreases down to around 0.1 electrons per molecule at 20 min, during which the storage is maximized at 10–20 min with 0.6–0.7 electrons stored per molecule, thereby indicating that the rates of radical formation and consumption are balanced during the photochemical hydrogen evolution reaction. The electrical conductivity measurements reveal that ion‐pair adducts (adducts with PF6− ions in solution) are formed by 2 and 3 but are not given by 1 under the catalysis conditions. These, together with the results of molecular mechanics calculations, reveal that stack of two [PtCl2(bpy)] units becomes unfavorable as the number of sterically bulky and highly charged VG units per molecule increases. We have therefore concluded that dimerization that leads to the formation of a PtPt association is a key step in the effective catalytic enhancement with [PtCl2(bpy)]‐type catalysts.
Aromatic Hydroxylation at a Non‐Heme Iron Center: Observed Intermediates and Insights into the Nature of the Active Species
Authors: Makhlynets Olga V. , Rybak‐Akimova Elena V.
Published: November 2010

Mechanism of substrate oxidations with hydrogen peroxide in the presence of a highly reactive, biomimetic, iron aminopyridine complex, [FeII(bpmen)(CH3CN)2][ClO4]2 (1; bpmen=N,N'‐dimethyl‐N,N'‐bis(2‐pyridylmethyl)ethane‐1,2‐diamine), is elucidated. Complex 1 has been shown to be an excellent catalyst for epoxidation and functional‐group‐directed aromatic hydroxylation using H2O2, although its mechanism of action remains largely unknown.1, 2 Efficient intermolecular hydroxylation of unfunctionalized benzene and substituted benzenes with H2O2 in the presence of 1 is found in the present work. Detailed mechanistic studies of the formation of iron(III)–phenolate products are reported. We have identified, generated in high yield, and experimentally characterized the key FeIII(OOH) intermediate (λmax=560 nm, rhombic EPR signal with g=2.21, 2.14, 1.96) formed by 1 and H2O2. Stopped‐flow kinetic studies showed that FeIII(OOH) does not directly hydroxylate the aromatic rings, but undergoes rate‐limiting self‐decomposition producing transient reactive oxidant. The formation of the reactive species is facilitated by acid‐assisted cleavage of the OO bond in the iron–hydroperoxide intermediate. Acid‐assisted benzene hydroxylation with 1 and a mechanistic probe, 2‐Methyl‐1‐phenyl‐2‐propyl hydroperoxide (MPPH), correlates with OO bond heterolysis. Independently generated FeIVO species, which may originate from OO bond homolysis in FeIII(OOH), proved to be inactive toward aromatic substrates. The reactive oxidant derived from 1 exchanges its oxygen atom with water and electrophilically attacks the aromatic ring (giving rise to an inverse H/D kinetic isotope effect of 0.8). These results have revealed a detailed experimental mechanistic picture of the oxidation reactions catalyzed by 1, based on direct characterization of the intermediates and products, and kinetic analysis of the individual reaction steps. Our detailed understanding of the mechanism of this reaction revealed both similarities and differences between synthetic and enzymatic aromatic hydroxylation reactions.
Fluorine–Protein Interactions and 19F NMR Isotropic Chemical Shifts: An Empirical Correlation with Implications for Drug Design
Authors: Dalvit Claudio , Vulpetti Anna
Published: November 2010

An empirical correlation between the fluorine isotropic chemical shifts, measured by 19F NMR spectroscopy, and the type of fluorine–protein interactions observed in crystal structures is presented. The CF, CF2, and CF3 groups present in fluorinated ligands found in the Protein Data Bank were classified according to their 19F NMR chemical shifts and their close intermolecular contacts with the protein atoms. Shielded fluorine atoms, i.e., those with increased electron density, are observed primarily in close contact to hydrogen bond donors within the protein structure, suggesting the possibility of intermolecular hydrogen bond formation. Deshielded fluorines are predominantly found in close contact with hydrophobic side chains and with the carbon of carbonyl groups of the protein backbone. Correlation between the 19F NMR chemical shift and hydrogen bond distance, both derived experimentally and computed through quantum chemical methods, is also presented. The proposed “rule of shielding” provides some insight into and guidelines for the judicious selection of appropriate fluorinated moieties to be inserted into a molecule for making the most favorable interactions with the receptor.
Differences in survival among women with stage III inflammatory and noninflammatory locally advanced breast cancer appear early
Authors: Dawood Shaheenah , Ueno Naoto T. , Valero Vicente , Woodward Wendy A. , Buchholz Thomas A. , Hortobagyi Gabriel N. , Gonzalez‐Angulo Ana Maria , Cristofanilli Massimo
Published: November 2010

BACKGROUND:

Significant improvements in the survival of women with breast cancer have been observed and are attributed to a multidisciplinary approach and the introduction of polychemotherapy and endocrine regimens. The objective of this population‐based study was to determine whether women with inflammatory breast cancer (IBC) who received treatment in a modern era had a poorer survival compared those with non‐IBC locally advanced breast cancer (LABC).

METHODS:

The Surveillance, Epidemiology, and End Results program registry was searched to identify women with stage IIIB/C breast cancer diagnosed between 2004 and 2007 who had undergone surgery and radiotherapy. Patients were categorized as either having IBC or non‐IBC LABC according the sixth edition of the American Joint Committee on Cancer (AJCC) criteria. Breast cancer‐specific survival (BCS) was estimated using the Kaplan‐Meier product limit method and compared across groups using the log‐rank statistic. Cox models were then fitted to compare the association between breast cancer type and BCS after adjusting for patient and tumor characteristics.

RESULTS:

A total of 828 (19.2%) women and 3476 (80.8%) women had stage IIIB/C IBC and non‐IBC LABC, respectively. The median follow‐up was 19 months. The 2‐year BCS rate was 90% (95% confidence interval [95% CI], 88%‐91%) for the entire cohort and 84% (95%CI, 80%‐87%) and 91% (95%CI, 90%‐91%) among women with IBC and non‐IBC LABC, respectively. In the multivariable model, patients with IBC were found to have a 43% increased risk of death from breast cancer compared with patients with non‐IBC LABC (hazard ratio, 1.43; 95%CI, 1.10‐1.86 [P = .008]).

CONCLUSIONS:

In the era of multidisciplinary management and anthracycline‐based and taxane‐based polychemotherapy regimens, women with IBC continue to have worse survival outcomes compared with those with non‐IBC LABC. Cancer 2011. © 2010 American Cancer Society.
Predicting individual risk of neutropenic complications in patients receiving cancer chemotherapy
Authors: Lyman Gary H. , Kuderer Nicole M. , Crawford Jeffrey , Wolff Debra A. , Culakova Eva , Poniewierski Marek S. , Dale David C.
Published: November 2010

BACKGROUND:

A prospective cohort study was undertaken to develop and validate a risk model for neutropenic complications in cancer patients receiving chemotherapy.

METHODS:

The study population consisted of 3760 patients with common solid tumors or malignant lymphoma who were beginning a new chemotherapy regimen at 115 practice sites throughout the United States. A regression model for neutropenic complications was developed and then validated by using a random split‐sample selection process.

RESULTS:

No significant differences in the derivation and validation populations were observed. The risk of neutropenic complications was greatest in cycle 1 with no significant difference in predicted risk between the 2 cohorts in univariate analysis. After adjustment for cancer type and age, major independent risk factors in multivariate analysis included: prior chemotherapy, abnormal hepatic and renal function, low white blood count, chemotherapy and planned delivery ≥85%. At a predicted risk cutpoint of 10%, model test performance included: sensitivity 90%, specificity 59%, and predictive value positive and negative of 34% and 96%, respectively. Further analysis confirmed model discrimination for risk of febrile neutropenia over multiple chemotherapy cycles.

CONCLUSIONS:

A risk model for neutropenic complications was developed and validated in a large prospective cohort of patients who were beginning cancer chemotherapy that may guide the effective and cost‐effective use of available supportive care. Cancer 2011. © 2010 American Cancer Society.
Practical advice for determining the role of BCR‐ABL mutations in guiding tyrosine kinase inhibitor therapy in patients with chronic myeloid leukemia
Authors: Jabbour Elias , Branford Susan , Saglio Giuseppe , Jones Dan , Cortes Jorge E. , Kantarjian Hagop M.
Published: November 2010

Data demonstrating the superiority of nilotinib over imatinib in the frontline treatment of chronic myeloid leukemia (CML) and ongoing studies with dasatinib and bosutinib are rapidly changing the treatment landscape for CML. In this review, the authors discuss currently available therapies for CML, focusing on mechanisms of resistance to imatinib and treatment strategies to overcome resistance. Relevant articles were identified through searches of PubMed and abstracts from international hematology/oncology congresses. Additional information sources were identified from the bibliographies of these references and from the authors' own libraries and expertise. In vitro 50% inhibitory concentration (IC50) data alone are not sufficient to guide the choice of a tyrosine kinase inhibitor (TKI) in the presence of a mutant breakpoint cluster region‐v‐abl Abelson murine leukemia viral oncogene homolog (BCR‐ABL) clone, because there is a lack of data regarding how well such IC50 values correlate with clinical response. A small subset of BCR‐ABL mutant clones have been associated with impaired responses to second‐generation TKIs (tyrosine to histidine mutation at codon 253 [Y253H], glutamic acid to lysine or valine mutation at codon 255 [E255K/V], and phenylalanine to cysteine or valine mutation at codon 359 [F359C/V] for nilotinib; valine to leucine mutation at codon 299 [V299L] and F317L for dasatinib); neither nilotinib nor dasatinib is active against the threonine to isoleucine mutation at codon 315 (T315I). For each second‐generation TKI, the detection of 1 of a small subset of mutations at the time of resistance may be helpful in the selection of second‐line therapy. For the majority of patients, comorbidities and drug safety profiles should be the basis for choosing a second‐line agent. Clinical trial data from an evaluation of the response of specific mutant BCR‐ABL clones to TKIs is needed to establish the role of mutation testing in the management of CML. Cancer 2011. © 2010 American Cancer Society.
The prognostic contribution of clinical breast cancer subtype, age, and race among patients with breast cancer brain metastases
Authors: Anders Carey K. , Deal Allison M. , Miller C. Ryan , Khorram Carmen , Meng Hong , Burrows Emily , Livasy Chad , Fritchie Karen , Ewend Matthew G. , Perou Charles M. , Carey Lisa A.
Published: November 2010

BACKGROUND:

Brain metastases (BM) arising from triple‐negative breast cancer (TNBC) portend a poor prognosis. TNBC is more common in premenopausal and African‐American (AA) patients; both of these characteristics also confer a poor prognosis. In a single‐institution cohort study, the authors attempted to determine whether the inferior outcome noted with TNBC brain metastases is more reflective of a higher risk population or the subtype itself.

METHODS:

The University of North Carolina Breast Cancer Database identified patients with BC brain metastases who were diagnosed between 1988 and 2008. BC subtype was assigned by immunohistochemistry: hormone receptor (HR) positive (+);(HR, estrogen receptor [ER]+ and/or progesterone receptor [PR]+)/human epidermal growth factor receptor 2 (HER2) negative (‐), HR+/HER2+, HR‐/HER2+, and TN (ER‐/PR‐/HER2‐). Survival and disease recurrence patterns were evaluated by subtype, patient age (<40 years vs ≥40 years), and race (AA vs non‐AA) using the Kaplan‐Meier method and Cox regression analysis.

RESULTS:

Among 119 patients with BC brain metastases, 33% were AA and 31% were aged <40 years. BC subtype was confirmed in 98 patients (30% with HR+/HER2‐, 21% with HR+/HER2+, 18% with HR‐/HER2+, and 31% with TNBC). Survival after BM was found to be impacted by subtype (P = .002), and was shortest for patients with TNBC (0.24 years; 95% confidence interval, 0.17 years‐0.48 years). There were no age‐specific (P = .84) or race‐specific (P = .09) differences in survival noted after brain metastases; stratification of BC subtypes by age and race revealed no difference (all, P > .1). The receipt of systemic therapy after BC brain metastases was found to be an important predictor of survival after BC brain metastases (hazard ratio, 0.29; P = .002) when adjusted for race, age, number of central nervous system lesions, and BC subtype.

CONCLUSIONS:

TNBC confers a high risk of death after brain metastases regardless of patient race and age, supporting the need for novel agents capable of controlling both intracranial and extracranial TNBC across all races and ages. Cancer 2011. © 2010 American Cancer Society.
Overall survival and PD‐L1 expression in metastasized malignant melanoma
Authors: Gadiot Jules , Hooijkaas Anna I. , Kaiser Andrew D. M. , van Tinteren Harm , van Boven Hester , Blank Christian
Published: November 2010

BACKGROUND:

Cancers are known to elude the immune system, for example, by MHC loss, FAS up‐regulation, or increased secretion of TGF‐beta. Recently, ligands of coinhibitory receptors like programmed cell death ligand–1 (PD‐L1, B7‐H1) have come to attention for their role in tumor immune escape. Various tumors have been tested for PD‐L1 expression, and conflicting results were obtained regarding its correlative impact on patient survival. This study aimed to determine the prognostic relevance of PD‐L1 expression for the survival of melanoma patients.

METHODS:

Paraffin‐embedded nevi, primary melanoma, and in‐transit, lymph node, and distant organ metastases from a set of 63 stages III‐IV melanoma patients referred to the Netherlands Cancer Institute between 2000 and 2004 for a sentinel‐node procedure or systemic therapy were studied. A large effort was invested in validating specific PD‐L1 staining. In addition to immunological factors such as T‐cell infiltration (CD8, CD4, and regulatory T cells), TGF‐beta and MHC‐I expression were assessed.

RESULTS:

Longitudinal analysis revealed no relevant PD‐L1 expression on primary melanoma compared with metastatic disease. No significant correlations with prognosis were found regarding immunological factors, whereas known prognostic markers such as Breslow thickness and sex could be confirmed. Analyses of the overall survival of our patient cohort did not reveal a negative association with PD‐L1 expression.

CONCLUSIONS:

Correlation of overall survival with PD‐L1 expression by melanoma cells remains controversial, and future clinical studies should focus on antibody validation and time of analysis in respect to disease progression. Cancer 2011. © 2010 American Cancer Society.
Prostate cancer risk in the Swedish AMORIS study
Authors: Van Hemelrijck Mieke , Garmo Hans , Holmberg Lars , Walldius Göran , Jungner Ingmar , Hammar Niklas , Lambe Mats
Published: November 2010

BACKGROUND:

In a cohort including 5112 prostate cancer (pCa) patients, the authors investigated associations among triglycerides (TG), total cholesterol (TC), and pCa while taking into account glucose.

METHODS:

A cohort (n = 200,660) based on 4 groups of men, according to age at cohort entry, with TG, TC, and glucose measurements was selected from the Apolipoprotein MOrtality RISk (AMORIS) database. Of these, 5112 men developed pCa. Multivariate Cox proportional hazard models were used to analyze associations among TG, TC, and pCa. Competing risks were assessed graphically.

RESULTS:

Age‐stratified analyses for quartiles of TG, TC, and glucose showed a negative association between glucose and pCa risk (HR, 0.93; 95% CI, 0.86‐1.01), 0.93 (0.86‐1.01), 0.87 (0.81‐0.94) for the second, third, and fourth quartiles compared with the first (Ptrend = .001). Stratified analysis by glucose levels (<6.11 or ≥6.11 mmol/L) showed a positive association between hypertriglyceridemia (TG≥1.71 mmol/L) and pCa risk, when there were high glucose levels (HR, 1.23; 95% CI, 1.01‐1.48). No association was found for hypercholesterolemia (TC≥6.50 mmol/L). Competing risk analysis showed that protective effects of glucose were overestimated in conventional Cox proportional hazard models and strengthened positive findings between TG and pCa risk.

CONCLUSIONS:

The authors'; findings supported the hypothesis that factors of the glucose and lipid metabolism influence pCa risk. Competing risk assessment showed that it is important to take into account the long natural history and age distribution of pCa when interpreting results. The authors'; findings indicate another reason to fight the increasing prevalence of obesity and dyslipidemia. Cancer 2011. © 2010 American Cancer Society.
A phase 2 trial of dasatinib in advanced melanoma
Authors: Kluger Harriet M. , Dudek Arkadiuz Z. , McCann Carrie , Ritacco Jean , Southard Nadine , Jilaveanu Lucia B. , Molinaro Annette , Sznol Mario
Published: November 2010

BACKGROUND:

Inhibiting src kinases (non‐receptor tyrosine kinase signaling intermediates) reduces melanoma cell proliferation and invasion. Dasatinib inhibits c‐kit, PDGFβR, and EPHA2 and src kinases c‐src, c‐Yes, Lck, and Fyn. A phase 2 trial of dasatinib in melanoma was conducted to assess response rate (RR), progression‐free survival (PFS), and toxicity.

METHODS:

Adults with stage 3/4 chemotherapy‐naïve unresectable melanoma were eligible. Dasatinib was initially administered at 100 mg twice daily continuously to 17 patients. Due to toxicity, the starting dosage was decreased to 70 mg twice daily. Tumor assessments occurred every 8 weeks.

RESULTS:

Thirty‐nine patients were enrolled, 36 of whom were evaluable for activity and toxicity. Five, 4, and 3 patients had acral‐lentiginous, ocular, or mucosal primaries, respectively. Two patients had confirmed partial responses lasting 64 and 24 weeks (RR 5%). Three patients had minor responses lasting 136, 64, and 28 weeks, and 1 patient who was responding discontinued due to noncompliance. The median PFS was 8 weeks; the 6‐month PFS rate was 13%. One patient with an exon‐13 c‐kit mutation had a partial response, whereas disease in another patient with an exon‐11 c‐kit mutation progressed. Common toxicities were fatigue, dyspnea, and pleural effusion.

CONCLUSIONS:

Daily dasatinib has minimal activity in unselected melanoma patients, excluding those with c‐kit mutations. The study did not meet the prespecified endpoints of 30% response rate or 6‐month PFS. Dasatinib was poorly tolerated overall, often requiring dose reduction or interruption. Because activity was observed in a small subset without c‐kit mutations, identifying predictive biomarkers is important for future development of dasatinib in melanoma alone or in combination trials. Cancer 2011. © 2010 American Cancer Society.
Nucleation Rates of Methanol Using the SAFT‐0 Equation of State
Authors: Obeidat Abdalla , Gharaibeh Maen , Ghanem Hasan , Hrahsheh Fawaz , Al‐Zoubi Nora , Wilemski Gerald
Published: November 2010

Classical and nonclassical calculations of nucleation rates are presented for methanol, an associating vapor system. The calculations use an equation of state (EOS) that accounts for the effects of molecular association based on the statistical association fluid theory (SAFT). Two forms of classical nucleation theory (CNT) were studied: a Gibbsian form known as the P‐form and the standard or S‐form. CNT P‐form calculations and nonclassical gradient theory (GT) calculations were made using the SAFT‐0 EOS. Calculated rates were compared to the experimental rates of Strey, et al. [J. Chem. Phys. 1986, 84, 2325–2335]. Very little difference was found between the two forms of CNT for either the temperature (T) or supersaturation (S) dependence of the rates. Nucleation rates based on GT showed improved T and S dependence compared to CNT. The GT rates were also improved by factors of 100‐1000 compared to CNT. Despite these improvements, GT does not describe the reported T and S dependence of the nucleation rates. To explore this further, the GT and experimental rates were analyzed using Hale’s scaled model [J. Chem. Phys. 2005, 122, 204 509]. This analysis reveals an inconsistency between the predictions of GT, which scale relatively well, and the experimental data, which do not scale. It also shows that the measured rate data have an anomalous T and S dependence. A likely source of this anomaly is the inadequate thermodynamic data base for small cluster properties that was used originally to correct the raw rate data for the effects of association.
Reusable Task‐Specific Ionic Liquids for a Clean ε‐Caprolactam Synthesis under Mild Conditions
Authors: Turgis Raphaël , Estager Julien , Draye Micheline , Ragaini Vittorio , Bonrath Werner , Lévêque Jean‐Marc
Published: November 2010

Brønsted‐acidic ionic liquids that bear a sulfonic acid group, known as Forbes acids, show a good catalytic activity for the Beckmann rearrangement, used to prepare ε‐caprolactam, which is a precursor of Nylon 6. The activity essentially stems from the acidity of the sulfonic acid group. Although these task specific ionic liquids suffer from a high viscosity, this drawback can be circumvented at higher temperatures. A combination of the hydrogen sulfate anion and the sulfonic acid group of the cation is needed to obtain the rearrangement product rapidly under mild conditions. When using an excess of ionic liquid, we postulate that the internal pressure of the ionic medium, generated by the high viscosity and the high number of hydrogen‐bonds, is strong enough to contribute to a decrease of the thermodynamic barrier. In accordance with the “Principles of Green Chemistry,” we have developed a synthesis of ε‐caprolactam that requires no additional chemicals except cyclohexanone oxime and the reusable TSIL.
Role of estrogen in spermatogenesis in initial phase males of the three‐spot wrasse (Halichoeres trimaculatus): Effect of aromatase inhibitor on the testis
Authors: Kobayashi Yasuhisa , Nozu Ryo , Nakamura Masaru
Published: November 2010

The three‐spot wrasse, Halichoeres trimaculatus, is a protogynous hermaphrodite. Under appropriate social conditions, female fish can become male. Previous studies indicated that estrogens are important regulators of sex change in this fish. However, the role of estrogen in the male is not known. To clarify the involvement of estrogen in spermatogenesis in hermaphrodite fish, we treated initial phase (IP) males for 10 weeks with exemestane, an aromatase inhibitor (AI), to block estrogen synthesis. Fish treated with AI exhibited decreases in gonadal weight, plasma estrogen levels, and spermatogonial proliferation in the testis, together with increases in androgen levels. Additionally, we confirmed that exogenous estrogen treatments stimulated the renewal and proliferation of spermatogonia in the testis of IP males. These results indicate that estrogens play an important role in regulating spermatogenesis in this fish. Developmental Dynamics, 2011. © 2010 Wiley‐Liss, Inc.
An automatic control parameter tuning method for differential evolution
Authors: Yamaguchi Satoshi
Published: November 2010

Differential Evolution (DE) is an evolutionary algorithm that has shown excellent ability for solving global optimization problems over continuous spaces. DE has a few control parameters that must be set by the user. The ability of DE depends on these control parameters, and in many cases, trial‐and‐error processes are required for finding suitable values. This paper proposes a method for tuning the DE control parameters automatically. The control parameters are tuned within the DE search process. When this method is used, the finding of appropriate control parameter values by trial and error is not required. To evaluate its performance, the proposed method was applied to nine benchmark function optimization problems. The results indicate that the proposed method achieved 100% success in solving optimization problems without a major increase in the number of generations required for finding the optimum solution. © 2010 Wiley Periodicals, Inc. Electr Eng Jpn, 174(3): 25–33, 2011; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/eej.21047
Sensorless suppression control for frame vibration of PMSM
Authors: Shimada Arinori , Kawai Kenji , Zanma Tadanao , Doki Shinji , Ishida Muneaki
Published: November 2010

It is well known that frame vibration occurs in driving permanent magnet synchronous motors (PMSM). The authors have suggested a method for suppression of frame vibration by means of Fourier series and repetitive control. The method requires an acceleration sensor and a position sensor. However, the use of such a sensor is not desirable from the point of view of system cost. Therefore, this paper proposes a method of sensorless suppression control of frame vibration. The effectiveness of the proposed method is illustrated by experiments. © 2010 Wiley Periodicals, Inc. Electr Eng Jpn, 174(3): 53–61, 2011; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/eej.21048
Two‐degree‐of‐freedom model matching control of shift‐by‐wire system with emergency mechanical link
Authors: Osamura Kensuke , Kobayashi Sinya , Nagano Masaharu , Hirata Mitsuo , Adachi Shuichi
Published: November 2010

A new shift‐by‐wire system having a standby mechanical link with backlash is proposed. The link directly connects the select lever and the manual lever of the automatic transmission in case of emergency. Thus, it is necessary to keep the backlash free during normal operations without generating a force. The angles of the manual lever driven by an actuator should follow the angles of the select lever exactly and quickly. A two‐degree‐of‐freedom model matching control is developed to meet this requirement. It is shown that the backlash is kept free during the range select operation. © 2010 Wiley Periodicals, Inc. Electr Eng Jpn, 174(3): 45–52, 2011; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/eej.21049
Model‐based feedforward compensation for disturbance during inching and reciprocating motions
Authors: Yamamoto Masafumi , Iwasaki Makoto , Ito Kazuaki , Matsui Nobuyuki
Published: November 2010

This paper presents a feedforward compensation approach for nonlinear disturbances in ball‐screw‐driven table positioning systems. The compensator design is focused on minimizing the effects of nonlinear disturbances on positioning performance. This is achieved through the use of a mathematical model of precise micrometer disturbance characteristics produced by nonlinear spring behaviors during inching and reciprocating motions. Based on this model, feedforward disturbance compensation is applied in order to improve the disturbance suppression capability. The effectiveness of the proposed positioning control approach has been verified by experiments using a table drive system on a machine stand. © 2010 Wiley Periodicals, Inc. Electr Eng Jpn, 174(3): 34–44, 2011; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/eej.21054
Field trial on a rack‐mounted DC power supply system with 80‐Ah lithium‐ion batteries
Authors: Matsushima Toshio
Published: November 2010

Using an industrial lithium‐ion battery that has higher energy density than conventional valve‐regulated lead‐acid batteries, a rack‐mounted DC power supply system was assembled and tested at a base transceiver station (BTS) offering actual services. The nominal output voltage and maximum output current of the system are 53.5 V and 20 A, respectively. An 80‐Ah lithium‐ion battery composed of 13 cells connected in series was applied in the system and maintained by the floating charge method. The DC power supply system was installed in a 19‐inch power rack in the telecommunications equipment box at BTS. The characteristics of the 80‐Ah lithium‐ion battery, the specifications of the DC power supply system, and field‐test results are presented in this paper. \copy 2010 Wiley Periodicals, Inc. Electr Eng Jpn, 174(3): 1–8, 2011; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/eej.21067
Guiding the “misguided” – functional conditioning of dendritic cells for the DC‐based immunotherapy against tumours
Authors: Huang Fang‐Ping , Chen Yu‐Xiao , To Christina KW
Published: November 2010

The concept of DC‐based tumour vaccine has been tested both clinically and experimentally for the past two decades. Even though only limited success has been achieved to date, DC vaccination remains a promising immunological approach against tumours and deserves further exploration. It aims to elicit and establish specific immunity to destroy tumours. By such an approach, DC are used not only as a vector to deliver tumour antigens, but also as a “natural adjuvant” to boost vaccine efficacy. Tumours are however of mutated “self”, to which the host immune system is essentially tolerated in the absence of external perturbation otherwise. Such a live cell‐based approach is unfortunately extremely sensitive to, hence its efficacy inevitably limited by, the tumour microenvironment. Certain immunosuppressive mechanisms triggered by the tumour cells are therefore major obstacles against successful DC vaccination. Attempts have since been made in order to overcome these hurdles. This brief review summarises some of the earlier and current findings, and compares the effectiveness of various approaches used in these studies. It focuses particularly on strategies aimed at enhancing DC immunogenicity, through molecular modifications and functional conditioning of the cell vectors, targeting both the positive and negative regulators of DC functions. By dissecting the roles of DC in immunity versus tolerance induction, and the very mechanisms underlying autoimmunity, we examine further and try to explain how the suppressed or “misguided” immunity may be alternatively switched‐on and more effectively redirected for cancer therapy.
Counter‐regulation mechanism of IL‐4 and IFN‐α signal transduction through cytosolic retention of the pY‐STAT6:pY‐STAT2:p48 complex
Authors: Kim Seol‐Hee , Lee Choong‐Eun
Published: November 2010

IFN‐α and IL‐4 induce Th1 and Th2 responses, respectively, and often display antagonistic actions against each other. To elucidate the molecular mechanism of counter‐regulation, we have investigated the signal interception by IFN‐α and IL‐4, employing a human B‐cell line Ramos, sensitive to both cytokines. In these cells, IFN‐α effectively inhibited IL‐4‐induced Fc epsilon receptor II (CD23) expression, whereas IL‐4 suppressed IFN‐α‐mediated IRF7 expression. The counter‐regulatory action by IL‐4 and IFN‐α proceeded with a delayed kinetics requiring 4 h. Notably, IFN‐α did not affect the IL‐4‐induced tyrosine phosphorylation of STAT6, but induced a time‐dependent cytoplasmic accumulation of phosphotyrosine(pY)‐STAT6 and a corresponding decrease in nuclear pY‐STAT6. By confocal analysis and co‐immunoprecipitation assays, we demonstrated the colocalization and molecular interaction of IL‐4‐induced pY‐STAT6 with IFN‐α‐induced pY‐STAT2:p48 in the cytosol. In addition, the over‐expression of STAT2 or STAT6 induced the concomitant cytosolic accumulation of pY‐STAT6 or pY‐STAT2, leading to the suppression of IL‐4‐induced CD23 or IFN‐α‐induced IRF7 gene expression, respectively. Our data suggest that the signals ensued by IFN‐α and IL‐4 induce cytoplasmic sequestration of IL‐4‐activated STAT6 and IFN‐α‐activated STAT2:p48 in B cells through the formation of pY‐STAT6:pY‐STAT2:p48 complex, which provides a novel mechanism by which IFN‐α and IL‐4 cross‐regulate their signaling into the nucleus.
Supercritical fluid extraction of lipids from broccoli leaves
Authors: Arnáiz Esther , Bernal José , Martín María Teresa , García‐Viguera Cristina , Bernal José Luis , Toribio Laura
Published: November 2010

The supercritical fluid extraction (SFE) and fractionation of lipids from broccoli leaves is presented in this work. For this purpose the effect of the different variables on the extraction was studied, obtaining the best results at 60°C, 300 bar and 3 mL/min. Two different fractions were obtained: First, the samples were extracted with pure CO2, and afterward the residual material was extracted using CO2 modified with 15% of methanol. The total fatty acid content of the extracts was determined by GC‐MS and compared with those results obtained by Soxhlet extraction with hexane and a chloroform/methanol (2:1) mixture. The SFE extracts presented a higher percentage of unsaturated fatty acids, especially the polyunsaturated 18:3 n − 3. The methodology was successfully applied to the analysis of the fatty acid composition of the leaves from five different cultivars of broccoli. In all the samples the main fatty acids were α‐linolenic (18:3 n − 3), linoleic (18:2 n − 6), and palmitic (16:0). Among the different cultivars analyzed, Naxos variety presented the highest levels in fatty acids, while Parthenon and Viola the lowest.

Practical applications: The proposed method allows the fractionation of lipids from broccoli leaves using a small volume of organic solvent and mild conditions. This is advantageous compared to conventional methods where large volumes or organic solvents are used, and the cost and time for the removal of these solvents, along with the possibility of degradation and toxicity, are the major disadvantages. The results obtained contribute to a better compositional characterization and a possible revaluation of this by‐product as a source of biologically active compounds.
Efficient and Complementary Methods Offering Access to Synthetically Valuable 1,2‐Dibromobenzenes
Authors: Diemer Vincent , Leroux Frédéric R. , Colobert Françoise
Published: November 2010

1,2‐Dibromobenzenes are highly valuable precursors for various organic transformations, in particular, reactions based on the intermediate formation of benzynes. This report describes short sequences for the synthesis of various derivatives based on regioselective bromination,ortho‐metalation, and halogen/metal permutations. 1,2‐Dibromo‐3‐iodobenzene (2f), 1,2‐dibromo‐4‐iodobenzene (4c), and 2,3‐dibromo‐1,4‐diiodobenzene (5e) act as intermediates in these syntheses.
New Umpolung Catalysts: Reactivity and Selectivity of Terpenol‐Based Lithium Phosphonates in Enantioselective Benzoin‐Type Couplings
Authors: Gliga Anca , Klare Helge , Schumacher Maria , Soki Francis , Neudörfl Jörg M. , Goldfuss Bernd
Published: November 2010

Two new classes of terpenol‐based lithium phosphonates, i.e. phenylfenchyl phosphonates and 2,2′‐biphenyldiylbis(terpenyl) phosphonates, are employed as umpolung catalysts for the enantioselective cross benzoin coupling. The structural characteristics of the phosphonates were investigated by means of X‐ray, 31P‐NMR analyses as well as DFT computations. The chiral lithium phosphonates were found to catalyze the cross benzoin coupling with enantioselectivities up to 54 % ee. For the phenylfenchyl phosphonates, the catalyst reactivities highly depend on the substituents in benzylic position. Modification of benzylic >CH2 to >C(CF3)2 significantly increases the yield from 19 to 92 %. For phenylfenchyl phosphonate pre‐catalysts, substitution of the benzylic >CH2 group by >C(CF3)2 changes the sense of enantioselectivity from S‐ to the R‐configured benzoin product.
A Cascade Annulation Based Convergent Approach to Racemic Tetrodotoxin (Eur. J. Org. Chem. 35/2010)
Authors: Cagide‐Fagín Fernando , Alonso Ricardo
Published: November 2010

The cover picture shows furfural and dihydroxyacetone, which are two compounds that can be obtained from plant sources, for example, from olive stones and sugar beets, respectively. These compounds can be used as building blocks for a convergent, cascade annulation based synthetic approach to the sodium channel blocker tetrodotoxin isolated from puffer fish. Details are discussed in the article by F. Cagide‐Fagín and R. Alonso on p. 6741 ff.
openWNS—a simulation platform for IMT‐advanced systems
Authors: Bültmann D. , Mühleisen M. , Max S. , Klagges K. , Schinnenburg M. , Walke B.
Published: November 2010

The open source wireless network simulator (openWNS) is presented. It has been released in January 2009 as open source software. openWNS is a dynamic event driven system level simulation platform useful for investigation of dynamic protocol behaviour in multi‐cellular mobile radio network scenarios with detailed signal interference modelling. The platform follows a modular design down to atomic protocol building blocks, making possible to rapidly modify and extend a protocol stack implemented. openWNS includes models from physical to application layer and is supported by a large number of Unit Tests. The tool has been used for IMT‐Advanced evaluation within the European WINNER+ evaluation group. Copyright © 2010 John Wiley & Sons, Ltd.
Coexistence of Hashimoto's thyroiditis with papillary thyroid carcinoma: The influence of lymph node metastasis
Authors: Kim Sang Soo , Lee Byung Joo , Lee Jin Choon , Kim Seong‐Jang , Jeon Yun Kyung , Kim Mi Ra , Huh Jeong Eun , Mok Ji Young , Kim Bo Hyun , Kim Yong Ki , Kim In Joo
Published: November 2010

Background

The aim of this study was to evaluate the influence of coexistent Hashimoto's thyroiditis with papillary thyroid carcinoma on lymph node metastasis.

Methods

The coexistent Hashimoto's thyroiditis group was defined by the presence of thyroid autoantibodies or pathologic confirmation. The control group did not have autoantibodies, disease, or ultrasound findings of Hashimoto's thyroiditis.

Results

For the Hashimoto's thyroiditis group, only central lymph node metastasis had a lower frequency and the mean number of central metastatic lymph nodes was lower than in the control group after adjustment. With regard to lateral lymph node involvement, there was no significant difference between the 2 groups. The multivariate analysis showed a negative association between the coexistence of Hashimoto's thyroiditis and central lymph node metastasis.

Conclusions

Coexisting Hashimoto's thyroiditis in patients with papillary thyroid carcinoma was identified as a negative independent predictive factor for central lymph node metastasis. © 2010 Wiley Periodicals, Inc. Head Neck, 2010
Significant correlation of peptidyl‐prolyl isomerase overexpression in merkel cell carcinoma with overall survival of patients
Authors: Lill Claudia , Schneider Sven , Pammer Johannes , Loewe Robert , Gedlicka Wilhelm , Houben Roland , Heiduschka Gregor , Brunner Markus , Thurnher Dietmar
Published: November 2010

Background

An overexpression of PIN1, the peptidyl‐prolyl cis‐trans isomerase, might cause cell cycle arrest and growth inhibition by binding to the p53 protein, a process leading to p53 stabilization. The rationale of this retrospective analysis was to evaluate the expression pattern of PIN1 in Merkel cell carcinomas (MCCs) and its suitability as a prognostic factor.

Methods

Samples of 27 MCCs were immunhistochemically stained for PIN1 expression and correlated with overall and disease‐free survival of patients.

Results

All samples expressed PIN1. We showed a significantly better overall survival in patients with an overexpression of PIN1 than in patients with a weak PIN1 expression (p= .031), but expression was not significant for disease‐free survival (p= .821). The 5‐year overall survival rate was 14.4% in patients with weak and 50.9% in patients with overexpression of PIN1.

Conclusions

PIN1 seems to be a prognostic factor for a better overall survival rate of patients with MCC. © 2010 Wiley Periodicals, Inc. Head Neck, 2010
Stair‐step flap for secondary lower lip revision after lip and cheek composite defects reconstruction
Authors: Fujiwara Takashi , Chen Chien‐Chang , Shih Hsiang‐Shun , Nebres Rico P. , Jeng Seng‐Feng , Kuo Yur‐Ren
Published: November 2010

Background

Free flap reconstruction is a common procedure for through‐and‐through lip and cheek complex defects after cancer ablation. However, oral incompetence with unacceptable bulky flap appearance invariably occurs and needs a secondary revisionary procedure. The purpose of this article was to present our method to improve the oral competence and cosmetic appearance by the stair‐step technique of flap revision.

Methods

Fourteen patients who had undergone flap folding reconstruction of the lip and cheek complex defect resulting in oral incontinence were involved in this study. Thirteen patients had been treated with an anterolateral thigh flap and 1 patient had been treated with a fibular osteocutaneous flap. This revisionary stair‐step technique was combined with simultaneous liposuction of the bulky flap in all cases.

Results

Adequate oral continence and good contour was achieved in 12 patients. The remaining 2 patients still had mild drooling, which was managed successfully with a second stair‐step flap.

Conclusion

This technique is a valuable option for revision of lower lip deformity. © 2010 Wiley Periodicals, Inc. Head Neck, 2010
Comparison of morbidity between sentinel node biopsy and elective neck dissection for treatment of the n0 neck in patients with oral squamous cell carcinoma
Authors: Murer Karin , Huber Gerhard F. , Haile Sarah R. , Stoeckli Sandro J.
Published: November 2010

Background

Sentinel node biopsy (SNB) has been proposed for staging of the cN0 neck in early oral/oropharyngeal squamous cell carcinomas (SCC). Because SNB is a minimally invasive procedure, it is thought to be associated with less morbidity than elective neck dissection.

Methods

Sixty‐two consecutive patients were included from 2000 to 2009. Two groups were analyzed consisting of 33 patients after SNB and 29 after elective neck dissection. Subjective impairment and functional shoulder status were assessed with the Neck Dissection Impairment Index (NDII) questionnaire and the modified individual relative Constant Score. Postoperative complications were retrieved from the clinical charts.

Results

The investigated scores were significantly better in the SNB group. All postoperative complications occurred in the elective neck dissection group.

Conclusion

SNB is associated with significantly less postoperative morbidity and better shoulder function than elective neck dissection. This supports our opinion that patients with nodal negative early SCC of the oral cavity should be offered SNB. © 2010 Wiley Periodicals, Inc. Head Neck, 2010