bluuebunny/crossref_metadata_2025 huggingface dataset:
Nitroxide Radicals as Probes for Exploring the Binding Properties of the Cucurbit[7]uril Host
Authors: Mezzina Elisabetta , Cruciani Francesca , Pedulli Gian Franco , Lucarini Marco
Published: June 2007

EPR spectroscopy was used for the first time to explore the binding properties of cucurbit[7]uril (CB7), a representative member of the cucurbituril family. Evidence for the formation of a complex between nitroxide radicals and the host system in an aqueous solution was provided by large changes in the nitrogen hyperfine splitting, attributed to the different polar environments experienced by the included radical. In the presence of alkali cations, the EPR spectra of benzyl tert‐butyl nitroxide were characterised by new signals attributed to the radical hosted in the CB7 cavity in which one metal cation is in close contact with the nitroxidic oxygen. The formation of the coordination complex results in a substantial increase in the electron spin density on the nitrogen in inverse order with respect to the size of the cation owing to increased localisation of negative charge on the oxygen atom from bonding to the alkali cation. The EPR spectra showed selective line‐broadening effects as a result of metal exchange between bulk water and the coordination complex. Analysis of the EPR linewidth variations allowed us to measure the corresponding kinetic rate constants for the first time. NMR spectroscopy showed that this behaviour is not peculiar to nitroxides but is also exhibited by the related carbonyl compounds. These data allowed us to quantify the template effect and to reach the conclusion that, in the presence of a guest having a coordinating lone pair, the formation of ternary metal‐guest‐CB complexes must be taken into account when discussing the complexation behaviour of cucurbituril derivatives in the presence of salts.
Quantum Mechanical Calculations of Conformationally Relevant 1H and 13C NMR Chemical Shifts of N‐, O‐, and S‐Substituted Calixarene Systems
Authors: Bifulco Giuseppe , Riccio Raffaele , Gaeta Carmine , Neri Placido
Published: June 2007

QM GIAO calculations of 13C and 1H chemical shift values of the ArCH2Ar group in N‐, O‐, and S‐substituted calixarene systems were performed with a hybrid DFT functional MPW1PW91 and 6‐31G(d,p) basis set. A good reproduction of experimental data was obtained for some representative calixarenes and for a series of simplified calixarene models. This allowed the derivation of chemical shift surfaces versus ϕ and χ dihedral angles. The applicability of chemical shift surfaces in the study of calixarene conformational features is illustrated.
Synthesis and Conformational Analysis of Macrocyclic Dihydroxystilbenes Linked between thepara–paraPositions
Authors: Mateo Carmen , López Vilmarí , Medarde Manuel , Peláez Rafael
Published: June 2007

A new family of diphenylethanes has been synthesized as conformationally restricted analogues of antimitotic combretastatins. The two phenyl rings are linked between thepara‐phenolic positions through a 3‐oxapentamethylene or hexamethylene chain. The key macrocyclization step was achieved in moderate yields by using an intramolecular McMurry pinacol coupling of linked aromatic dialdehydes, except for the nitro‐substituted compounds. The relative stereochemistry of the isomeric pinacols was determined by a combination of spectroscopic, chemical derivatization, and molecular‐modeling approaches. The NMR spectra of these compounds (with a polyoxygenated crownophane skeleton) indicate severe conformational restrictions relative to their parent combretastatins; the rotation of the phenyl rings is hampered by interactions of their substituents and the linker and the conformational restrictions imposed by the substituted bridge.
High Temperature Oxidation of the Refractory Alloy Glass Nb35Ni60Sn5.
Authors: Gallino Isabella , Busch Ralf , Yim Haein Choi , Jastrow Lioba , Koester Uwe
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Palladium‐Catalyzed Three‐Component Coupling of Propargylic Oxiranes, Phenols and Carbon Dioxide.
Authors: Yoshida Masahiro , Murao Tomohiko , Sugimoto Kenji , Ihara Masataka
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
New 5‐Hydroxy‐2‐(hydroxymethyl)‐4H‐pyran‐4‐one Derivatives Has Both Tyrosinase Inhibitory and Antioxidant Properties
Authors: Rho Ho Sik , Baek Heung Soo , You Jae Won , Kim Sujong , Lee Jin Young , Kim Duck Hee , Chang Ih Seop
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
A Versatile Synthesis of Cyclic Diphenyl Ether‐Type Diarylheptanoids: Acerogenins, (.+‐.)‐Galeon, and (.+‐.)‐Pterocarine
Authors: Jeong Byeong‐Seon , Wang Qian , Son Jong‐Keun , Jahng Yurngdong
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Green HAZOP Analysis: Incorporating Green Engineering into Design, Assessment and Implementation of Chemical Processes
Authors: Garcia‐Serna Juan , Martinez Jose Luis , Cocero Maria Jose
Published: June 2007

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
Price competition during and after promotions
Authors: Sigué Simon Pierre , Karray Salma
Published: June 2007

We provide a framework for setting regular prices and using promotional discounts in a duopoly where long‐term promotional effects are present and the firms' pricing and promotional strategies are common knowledge (e.g., as in online markets). We show that at equilibrium, the two firms may not promote and instead adopt an Everyday Low Price (EDLP) strategy. Consumers' tendency to stockpile promoted products, the level of brand loyalty and product differentiation, and the possibility of a postpromotional sales increase critically influence regular prices, price discount rates, and profits. Under some conditions consumer stockpiling intensifies promotional competition and reduces firms' profits while the possibility of attracting new consumers reduces the need to heavily promote and ensures better profits. Managerial implications are discussed. Copyright © 2007 ASAC. Published by John Wiley & Sons, Ltd.
Catalytic Kinetics of the Schiff Base Metal Complexes Bearing Side Chain of Cyclic morpholine in Carboxylic Ester Hydrolysis
Authors: Zhang Shu‐Lin , Li Min‐Jiao , Ou Zhong‐Wen , Chen Guo‐Xu , Liu Fu‐An , Xie Jia‐Qing
Published: June 2007

It has been reported that two Schiff base transition metal complexes bearing the side chain of the morpholine ring were synthesized and characterized, and two complexes with the same base agent but different metal ions were used as a simulant hydrolase in the catalytic hydrolysis of p‐nitrophenyl picolinate in this paper. The mechanism of PNPP catalytic hydrolysis is proposed and supported by the results of the spectral analysis and the kinetic calculation. A kinetic mathematical model, applied to the calculation of the kinetic and thermodynamics parameters of PNPP catalytic hydrolysis, has been established on the foundation of the mechanism proposed. The result of the study shows that the two complexes have a good catalytic activity in PNPP catalytic hydrolysis, and the rate of the PNPP catalytic hydrolysis was increased with the increase of the pH values in the buffer solution and affected by the polarization effect of metal ion of the complexes.
Some Interface Electrochemical Properties of Kaolinite
Authors: Jiao Yan‐Ni , Hou Wan‐Guo
Published: June 2007

The interface electrochemical properties of clay were theoretically analyzed to obtain some relationships among point of zero net charge (PZNC), point of zero net proton charge (PZNPC), intrinsic surface reaction equilibrium constants (K in 1‐pK model, Kinta1 and Kinta2 in 2‐pK model, *KintNa and *Kint in inert electrolyte chemical binding model) and structural negative charge density (σst) of clay, and some interface electrochemical parameters of kaolinite were measured. The following main conclusions were obtained. For clay possessing structural negative charges, the PZNC independent of electrolyte concentration (c) should exist just as amphoteric solid without structural charges such as oxides or hydroxides. A common intersection point (CIP) should appear among the potentiometric (or acid‐base) titration curves at different c and the pH at the CIP should be pHPZNC. A CIP among potentiometric titration curves at different c for kaolinite was observed, and the value of pHPZNC of kaolinite was 2.16. The values of pHPZNPC were decreased with increasing c, which arises from the presence of structural negative charges of kaolinite. In addition, it was observed that a good linear relationship existed between pHPZNPC and lg c. According to the values of pHPZNC and σst measured, the intrinsic surface reaction equilibrium constants, pK and pKinta1 and pKinta2 of 1‐pK and 2‐pK models could be directly calculated for clay, and the values of pK, pKinta1 and pKinta2 for kaolinite were 2.93, 1.90 and 3.97, respectively. These experimental values of pKinta1 and pKinta2 for kaolinite are obviously lower than those optimized with fitting programs in literatures, which maybe arises from the introduction of a type of permanent negatively charged sites in the models of literatures. An interesting result obtained in this study is that the inert electrolyte chemical binding does not exist for kaolinite, which also arises from the presence of structural negative charges.
Study on Cyclometalated Palladium‐azo Complexes as Colorimetric Probes for Hazardous Gas in Water
Authors: Yu Chun‐Wei , Li Shun‐Hua , Zheng Hong , Xu Jin‐Gou
Published: June 2007

A synthesized cyclometalated palladium‐azo complex was explored as a multifunctional probe for visual detection of SO2, H2S and NH3 in water. In acidic aqueous environment, the sensing solution underwent a sharp color change from poor violet to deep blue when titrated with Na2SO3 standard solution. But the color changed from poor violet to bright yellow when titrated with Na2S standard solution. In basic environment, the sensing solution rapidly changed to magenta when titrated by NH4Cl‐NH3 standard buffer solution at high concentration. However, the color of sensing solution changed to blue when titrated by NH4Cl‐NH3 standard buffer solution at low concentration although the pH was kept constant during the titration. Different species of these hazardous gases at environmentally relevant concentration levels were differentiated by independent optical signal outputs, and the interference from other inorganic ions commonly existing in water was very small.
Dehydration Kinetics of Zinc Phosphate Tetrahydrate α‐Zn3(PO4)2·4H2O Nanoparticle
Authors: Yuan Ai‐Qun , Wu Jian , Huang Zai‐Yin , Zhou Ze‐Guang , Wen Yan‐Xuan , Tong Zhang‐Fa
Published: June 2007

TG‐DTG technique and Harcourt‐Esson integrated equation were used to study the dehydration process of zinc phosphate tetrahydrate α‐Zn3(PO4)2·4H2O nanoparticle and its thermal decomposition kinetics. The results show that there are three stages of dehydration between 300 and 800 K during the thermal decomposition of α‐Zn3(PO4)2·4H2O nanoparticle. The first stage is controlled by chemical reaction with an activation energy of 69.48 kJ·mol−1 and a pre‐exponential factor of 1.77×106 s−1. The second is controlled by nucleation and growth with an activation energy of 78.74 kJ·mol−1 and a pre‐exponential factor of 5.86×109 s−1. The third is controlled by nucleation and growth with an activation energy of 141.5 kJ·mol−1 and a pre‐exponential factor of 1.01×1012 s−1. The kinetic compensative effects not only exist in Arrhenius equation but also in Harcourt‐Esson equation. Activation energy E is dependent on both the decomposition fraction α and temperature T.
Synthesis, Photophysical and Photochemical Properties of Poly(oxyethylene)‐Substituted Phthalocyaninato Oxotitanium(IV) Complexes
Authors: Atilla Devrim , Durmuş Mahmut , Yılmaz Özgür , Gürek Ayşe Gül , Ahsen Vefa , Nyokong Tebello
Published: June 2007

The synthesis, photophysical and photochemical properties of tetra‐ and chlorotetrapoly(oxyethylene)‐substituted oxotitanium(IV) phthalocyanines are reported for the first time. The new compounds were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. These complexes showed monomeric behaviour in solution. General trends are described for photodegredation, singlet oxygen, triplet state and fluorescence quantum yields, and triplet and fluorescence lifetimes of these compounds in dimethyl sulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The complexes showed high triplet quantum yields and triplet lifetimes in DMSO. The singlet oxygen quantum yields (ΦΔ), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism), were 0.72 and 0.78 for 3a and 5a, respectively. Thus, these complexes show potential as Type II photosensitizers. These complexes were also quenched by benzoquinone for fluorescence quenching studies.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Neodymium(III)‐Mediated Reformatsky‐Type Reactions of α‐Halo Ketones with Carbonyl Compounds
Authors: Kirsch Stefan F. , Liébert Clémence
Published: June 2007

In a neodymium(III) iodide induced process, α‐bromo ketones 1 and aldehydes 2 are effectively converted into aldol products 3. This Reformatsky‐type reaction proceeds through the formation of a neodymium enolate at room temperature in CH2Cl2. The analogous reaction in the presence of NdBr3/NaI at 50 °C in THF favors the formation of corresponding aldol–Tishchenko products 5 in good yields. Studies to define the scope and limitations of these reactions mediated by neodymium(III) salts are also described.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Rapid Organocatalytic Aldehyde‐Aldehyde Condensation Reactions
Authors: Erkkilä Anniina , Pihko Petri M.
Published: June 2007

We report the results of the systematic optimization of the α‐methylenation of aldehydes with aqueous formaldehyde. A simple combination of a secondary amine catalyst and a weak acid co‐catalyst has been identified, allowing access to α‐substituted acroleins in a matter of minutes. In the absence of formaldehyde, the catalytic system promoted the self‐condensation reaction of α,β‐unsaturated aldehydes. Both of these reactions exhibited linear relationships between co‐catalyst acidities and reaction rates. A second‐order dependence of catalyst concentration was observed, pointing to the involvement of two molecules of the ammonium catalyst in the rate‐determining step. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Comparison of anoxic sulfide biooxidation using nitrate/nitrite as electron acceptor
Authors: Mahmood Qaisar , Zheng Ping , Cai Jing , Wu Donglei , Hu Baolan , Islam Ejazul , Rashid Azim Muhammad
Published: June 2007

The performance of two lab‐scale Anoxic Sulfide Oxidizing Reactors (ASOR) utilizing diverse electron acceptors was compared to evaluate the loading potential for treating synthetic wastewaters. The nitrite utilizing reactor tolerated very high influent substrate concentrations compared with the nitrate using reactor and displayed better performance at HRT of 2 days and shorter. Under steady‐state denitrifying conditions, the maximal sulfide and nitrite removal rates were 13.53 kg/(m3 days) and 16.31 kg/(m3 days), respectively, while the maximal removal rates with nitrate as electron acceptor were 4.18 kg/(m3 days) and 1.73 kg/(m3 days), respectively. The reactor with nitrite as electron acceptor was able to tolerate high sulfide concentrations up to 1920 mg/L as compared with one using nitrate with influent concentrations up to 580 mg/L. ASORs could endure high nitrite concentrations of 2265 mg/L, while tolerating moderately lower nitrate concentrations of 110 mg/L. The process utilizing nitrite as electron acceptor could tolerate shorter HRTs, as compared with one using nitrate. Superior performance of the nitrite using ASO reactor may be due to more nitrite reactivity. Nitrite might have induced cytochrome production accepting electrons efficiently from sulfide that helped to overcome nitrite toxicity to the denitrifiers involved. Nitrite as an electron acceptor could be a better choice to treat wastewaters containing sulfides. © 2007 American Institute of Chemical Engineers Environ Prog, 2007
Linear trend tests for case–control genetic association that incorporate random phenotype and genotype misclassification error
Authors: Gordon Derek , Haynes Chad , Yang Yaning , Kramer Patricia L. , Finch Stephen J.
Published: June 2007

The purpose of this work is the development of linear trend tests that allow for error (LTTae), specifically incorporating double‐sampling information on phenotypes and/or genotypes. We use a likelihood framework. Misclassification errors are estimated via double sampling. Unbiased estimates of penetrances and genotype frequencies are determined through application of the Expectation‐Maximization algorithm. We perform simulation studies to evaluate false‐positive rates for various genotype classification weights (recessive, dominant, additive). We compare simulated power between theLTTaeand its genotypic test equivalent, theLRTae, in the presence of phenotype and genotype misclassification, to evaluate power gains of theLTTaefor multi‐locus haplotype association with a dominant mode of inheritance. Finally, we applyLTTaeand a method without double‐sample information (LTTstd) to double‐sampled phenotype data for an actual Alzheimer's disease (AD) case–control study with ApoE genotypes. Simulation results suggest that theLTTaemaintains correct false‐positive rates in the presence of misclassification. For power simulations, theLTTaemethod is at least as powerful asLRTaemethod, with a maximum power gain of 0.42 over theLRTaemethod for certain parameter settings. For AD data,LTTaeprovides more significant evidence for association (permutationp=0.0522) thanLTTstd(permutationp=0.1684). This is due to observed phenotype misclassification. TheLTTaestatistic enables researchers to apply linear trend tests to case–control genetic data, increasing power to detect association in the presence of misclassification. If the disease MOI is known,LTTaemethods are usually more powerful due to the fact that the statistic has fewer degrees of freedom.Genet. Epidemiol. 2007. © 2007 Wiley‐Liss, Inc.
Methods for interaction analyses using family‐based case‐control data: conditional logistic regression versus generalized estimating equations
Authors: Hancock Dana B. , Martin Eden R. , Li Yi‐Ju , Scott William K.
Published: June 2007

A complex web of gene‐gene and gene‐environment interactions likely underlies late‐onset disease development. We compared conditional logistic regression (CLR) and generalized estimating equations (GEE) in modeling such interactions in pedigrees with missing parents. Using the simulation of linkage and association (SIMLA) program, disease genes, an environmental risk factor, gene‐gene interaction, and gene‐environment interaction were generated in family‐based data sets. Four scenarios for the relationship between the marker and disease loci were examined: linkage and association, linkage without association, association without linkage, and absence of both linkage and association. Models for CLR and GEE (with exchangeable and independence correlation matrices) were built, and type I error, power, average odds ratio (OR), standard deviation, and 95% confidence intervals were estimated. CLR and GEE were valid tests of association in the presence of linkage, but type I error was inflated for association without linkage, particularly with GEE. CLR generated estimates of the OR with lower bias but often more variability than the OR estimates observed for GEE. Further, GEE was more powerful than CLR in detecting main and interactive effects. Although GEE with both matrices had similar power, use of the independence matrix resulted in lower type I error and less biased OR estimation as compared to the exchangeable matrix. Our findings support the use of GEE in maximizing power to detect gene‐gene and gene‐environment interactions but caution its use under potential association without linkage (e.g., population stratification) and the interpretation of its OR estimates. Genet. Epidemiol. 2007. © 2007 Wiley‐Liss, Inc.
Great Benefits from the Smallest Particles
Authors: Odenbach Stefan
Published: June 2007

Magnetic fields can be used to apply forces to ferrofluids, a practice currently being used advantageously in biomedical research. For example, it is implemented in novel forms of therapy used to combat cancer
Communication in the Information Network
Authors: Hesse Friedrich W. , Buder Jürgen , Bauer Korinna
Published: June 2007

How can knowledge exchange in computer networks be meaningfully supported? Studies offer insight into the possibilities and risks associated with network‐based group communication, the success of which does not depend on the medium alone
Recurrent pleomorphic adenoma of the parotid gland: Analysis of 108 consecutive patients
Authors: Wittekindt Claus , Streubel Kristina , Arnold Georg , Stennert Eberhard , Guntinas‐Lichius Orlando
Published: June 2007

Background

Surgery for recurrent parotid pleomorphic adenoma is a challenging problem.

Methods

One hundred eight patients who underwent 134 reoperations for recurrent parotid pleomorphic adenoma (follow‐up, 22 years) were evaluated for histopathologic features and risk factors for recurrence.

Results

The number of reoperations for tumor recurrence ranged from 1 to 10. Twenty‐seven patients (25%) developed permanent facial nerve weakness. The risks for clinically evident rerecurrence after 1, 5, and 15 years were 16%, 42%, and 75%, respectively. Female sex, young age at initial treatment, and enucleation instead of parotidectomy for treatment of the first recurrence were significant risk factors for rerecurrence. The mean number of recurrent tumor nodules was 26.

Conclusions

Surgery for recurrent parotid pleomorphic adenoma has a high rate of facial nerve morbidity. The chance of rerecurrence is high. Extended parotidectomy seems to be the best approach for the reoperation to reduce the risk of rerecurrence. © 2007 Wiley Periodicals, Inc. Head Neck 2007
Salivary duct carcinoma: A clinical and histologic review with implications for trastuzumab therapy
Authors: Nabili Vishad , Tan Jesse W. , Bhuta Sunita , Sercarz Joel A. , Head Christian S.
Published: June 2007

Background

Salivary duct carcinoma (SDC) is an aggressive tumor of the head and neck with a poor prognosis. The objective was to study SDC and recommend the use of trastuzumab as adjuvant therapy.

Methods

A retrospective chart review of patients seen between 1993 and 2006 was performed. Tumor specimens were examined for HER‐2 protein overexpression via immunohistochemistry (IHC) and fluorescence in situ hybridization (FISH) methods.

Results

Of the 7 patients with SDC, 57% had tumors arising in the parotid gland, the majority having facial nerve paralysis, 71% with nodal disease, and 43% having recurrence. All samples were HER‐2 positive on IHC. Three patients had FISH‐positive tumors, recurrent disease, and recieved trastuzumab therapy; 1 of the 3 died after 20 months and a second has shown disappearance of metastatic disease.

Conclusions

Trastuzumab is effective in treating HER‐2‐positive breast cancer. Given immunohistochemical similarities between SDC and ductal carcinoma of the breast, patients with FISH‐positive HER‐2/neu SDC should be considered for trastuzumab therapy. © 2007 Wiley Periodicals, Inc. Head Neck 2007
Clinical impact of, and prognostic stratification by, F‐18 FDG PET/CT in head and neck mucosal squamous cell carcinoma
Authors: A. Connell Caroline , Corry June , Milner Alvin D. , Hogg Annette , Hicks Rodney J. , Rischin Danny , Peters Lester J.
Published: June 2007

Background

The aim of this study was to determine prospectively the incremental value of positron emission tomography/computed tomography (PET/CT) over conventional assessment (clinical examination and CT/MRI imaging).

Methods

All patients undergoing 18F‐fluorodeoxyglucose (FDG)‐PET/CT for primary head and neck mucosal squamous cell carcinoma between January 2002 and December 2003 (inclusive) were included in this study provided they had undergone contemporaneous conventional assessment of the head and neck region and had 12 months minimum follow‐up.

Results

Seventy‐six patients underwent 100 PET/CT scans. The majority of patients (74%) were treated with definitive (chemo)radiotherapy. Median follow‐up time was 28 months. PET/CT led to a TNM classification alteration in 34% (12/35), a change in radiotherapy planning technique and/or dose in 29% (10/35), and altered treatment response assessment in 43% (13/30). A complete metabolic response was predictive of overall survival (p = .037).

Conclusion

Our results support incorporation of PET/CT into the management paradigm of head and neck mucosal squamous cell carcinoma. © 2007 Wiley Periodicals, Inc. Head Neck 2007
Prognostic significance of cyclin D1 and p16 in patients with intermediate‐risk head and neck squamous cell carcinoma treated with docetaxel and concurrent radiotherapy
Authors: Higuchi Eisaku , Oridate Nobuhiko , Homma Akihiro , Suzuki Fumiyuki , Atago Yoshihiro , Nagahashi Tatsumi , Furuta Yasushi , Fukuda Satoshi
Published: June 2007

Background

The current study aimed to evaluate the significance of the cell‐cycle‐control proteins cyclin D1 and p16 as prognostic markers in head and neck squamous cell carcinoma (HNSCC) patients treated with docetaxel and radiotherapy.

Methods

Cyclin D1 and/or p16 protein expression was retrospectively evaluated by immunohistochemistry in 53 patients with stage T1‐3N0‐2M0 (except T1N0 glottis) HNSCC who were treated with 10 mg/m2/week docetaxel 4 to 6 times and received concurrent chemoradiotherapy.

Results

Kaplan–Meier univariate analysis revealed that patients with cyclin D1‐positive tumors or p16‐negative tumors had a worse prognosis compared with those with cyclin D1‐negative tumors or p16‐positive tumors (p = .0004 and p = .025, respectively). The prognostic significance of cyclin D1 expression, not p16 expression, was confirmed using a proportional hazard regression model.

Conclusions

An assessment of cyclin D1 and p16 levels might be of clinical use in defining subgroups of patients with poor prognosis. © 2007 Wiley Periodicals, Inc. Head Neck 2007
Systematic screening and treatment evaluation of hereditary neck paragangliomas
Authors: Fish John H. , Klein‐Weigel Peter , Biebl Matthias , Janecke Andreas , Tauscher Thomas , Fraedrich Gustav
Published: June 2007

Familial paragangliomas of the neck are often bilateral and more aggressive than spontaneous forms. Tumors appear earlier (2nd–4th decade) often with diffuse, multifocal involvement. Without treatment, these tumors can lead to significant morbidity. Three families withsuccinate dehydrogenase subunit D(SDHD) germline mutations underwent clinical and genetic evaluation. Patients were screened using ultrasound and evaluated further with conventional and functional imaging. Tumors with a diameter >1.5 cm were surgically removed. Multicentric and bilateral tumors were detected in 9/13 (69%) and 8/13 (62%) patients, respectively. Surgical morbidity occurred in 64% of patients. Local recurrence was 57%, although this was lower in tumors with a diameter <2 cm. We recommend an algorithm for a systematic approach to the diagnosis, monitoring, and treatment of familial head and neck paragangliomas. Operative treatment in advanced stages often leads to unwanted morbidity, such that earlier detection and treatment of smaller tumors seems to be of benefit. © 2007 Wiley Periodicals, Inc. Head Neck 2007
Convergence between physiological, facial and verbal self‐report measures of affective empathy in children
Authors: Anastassiou‐Hadjicharalambous Xenia , Warden David
Published: June 2007

The present study investigated the degree of convergence between three different measures of vicarious affective responsiveness (affective empathy)—verbal self‐report, facial expression and change in heart rate—in typically developing children (N=29, aged 8–10 years), when presented with an emotionally evocative film. Although convergence between physiological and verbal measures was only at chance levels, convergence between facial and physiological measures, and between facial and verbal measures was statistically significant, but low (κ=0.30 and 0.22, respectively, p<0.01). These findings have important implications for the assessment of empathy in children and indicate that generalization of results across methods should be undertaken with caution. Copyright © 2007 John Wiley & Sons, Ltd.
The relation between 3‐ and 15‐month olds' cry vocalizations and their mothers' affective involvement during inoculation
Authors: Stormark Kjell Morten
Published: June 2007

This study examined if infant immunization distress is related to their mothers' affective involvement prior to the injection. The duration of infant cry vocalizations and the amount of maternal behaviour before and after the syringe injection were observed in 18 mother–infant dyads, of whom nine comprised 3‐month‐old and nine 15‐month‐old infants. The maternal behaviour was scored in terms of various soothing strategies used to calm infants in distress. Infant cry duration, in both the 3‐ and the 15‐month olds, was associated with amount of maternal eye‐gaze before the injection. For the 15‐month olds, also face‐to‐face contact and rocking the infant was associated with more crying. Even though the small scale of the study warrants some caution in the interpretation, the overall findings suggest that young infants have a referential understanding of caregiver affective involvement prior to a stressor. Copyright © 2007 John Wiley & Sons, Ltd.
Expression of S100A4 by a variety of cell types present in the tumor microenvironment of human breast cancer
Authors: Cabezón Teresa , Celis Julio E. , Skibshøj Inge , Klingelhöfer Jörg , Grigorian Mariam , Gromov Pavel , Rank Fritz , Myklebust June Helen , Mælandsmo Gunhild M. , Lukanidin Eugene , Ambartsumian Noona
Published: June 2007

The S100A4 protein, which is involved in the metastasis process, is a member of the S100 superfamily of Ca‐binding proteins. Members of this family are multifunctional signaling proteins with dual extra and intracellular functions involved in the regulation of diverse cellular processes. Several studies have established a correlation between S100A4 protein expression and worse prognosis for patients with various malignancies including breast cancer. In this article, we have used specific antibodies in combination with immunohistochemistry (IHC) to identify the cell types that express S100A4 in human breast cancer biopsies obtained from high‐risk patients. IHC analysis of 68 tumor biopsies showed that the protein is expressed preferentially by various cell types present in the tumor microenvironment (macrophages, fibroblasts, activated lymphocytes), rather than by the tumor cells themselves. Moreover, we show that the protein is externalized by the stroma cells to the fluid that bathes the tumor microenvironment, where it is found in several forms that most likely correspond to charge variants. Using a specific ELISA test, we detected a significant higher concentration of S100A4 in the tumor interstitial fluid (TIF) as compared to their corresponding normal counterparts (NIF). © 2007 Wiley‐Liss, Inc.
Id1 expression is transcriptionally regulated in radial growth phase melanomas
Authors: Ryu Byungwoo , Kim Dave S. , DeLuca Amena M. , Healey Megan A. , Dunlap Shariff , Fackler Mary Jo , Herman James , Alani Rhoda M.
Published: June 2007

Id genes have been demonstrated to be upregulated in a wide variety of human malignancies and their expression has been correlated with disease prognosis; however, little is known about the mechanisms of Id gene activation in tumors. We have previously shown that the helix‐loop‐helix transcription factor, Id1, is highly expressed in primary human melanomas during the radial growth phase and that Id1 is a transcriptional repressor of the familial melanoma gene CDKN2A. Here we use a series of melanoma cell lines that recapitulate the phenotypic characteristics of melanomas at varying stages of malignant progression to evaluate the expression levels of Id1 in this model system and determine the mechanism of Id1 dysregulation in these tumor cells. We find elevated protein levels of Id1 to be present consistently in radial growth phase tumor cells in accordance with our primary tumor data. Id1 transcript levels were also found to be elevated in these radial growth phase melanoma cells without any appreciable evidence of gene amplification and Id1 promoter activity was found to correlate with Id expression levels. We therefore conclude that Id1 expression is primarily regulated at the transcriptional level in radial growth phase melanomas and expect that therapies that target Id1 gene expression may be useful in the treatment of Id‐associated malignancies. © 2007 Wiley‐Liss, Inc.
A prospective pilot study of antibodies against human papillomaviruses and cutaneous squamous cell carcinoma nested in the Oxford component of the European Prospective Investigation into Cancer and Nutrition
Authors: Casabonne Delphine , Michael Kristina M. , Waterboer Tim , Pawlita Michael , Forslund Ola , Burk Robert D. , Travis Ruth C. , Key Tim J. , Newton Robert
Published: June 2007

In a prospective pilot study nested in the EPIC‐Oxford cohort, we examined the seroprevalence of antibodies against the L1 antigen of 38 human papilloma virus (HPV) types among 39 cases of cutaneous squamous cell carcinoma (SCC) for whom plasma was collected prior to diagnosis (incident) and 80 controls. Fifteen cases having already developed SCC at blood collection (prevalent) were also tested. There were no statistically significant differences in the seroprevalence of antibodies against any of the HPV types examined between incident cases and controls, nor was there a difference in the seroprevalence of multiple infections. However, consistent with results from published case–control studies, the seroprevalence of many β‐HPV types was higher among prevalent cases than among either incident cases or controls. For example the seroprevalence of antibodies against HPV‐8 was 20% (16/80) in controls, 23% (9/39) among incident cases and 40% (6/15) among prevalent cases. Among the incident cases only, the seroprevalence was 16% (5/32) among those for whom blood was collected 18+ months prior to diagnosis, but 57% (4/7) among those for whom diagnosis was within 18 months of blood collection, a pattern seen for many of the HPV types. This might suggest that if HPV is involved in the aetiology of SCC, the process occurs close to the time of diagnosis, or that the antibody response observed in people with SCC is a consequence of tumor formation. Further and larger prospective studies are needed to clarify the role of HPV in the aetiology of cutaneous SCC. © 2007 Wiley‐Liss, Inc.
Innovative processes for electropolishing of medical devices made of stainless steels
Authors: Eliaz Noam , Nissan Oded
Published: June 2007

Currently, many medical devices are made of implantable metals such as 316LVM stainless steel. Electropolishing is a common process to obtain a smooth surface, free of contaminants and more passive, which allows for minimizing the foreign body response and cell adhesion. However, polishing of small implants with a highly complicated geometry and nonuniform metallurgy might result in unsatisfactory results. The objective of this work was to develop an electropolishing process effective for complex metallic implants such as artificial heart valve frames and miniature glaucoma implants. Polishing in an ultrasonic bath and pulsed voltage polishing processes were studied and compared to the standard ASTM process. Current‐voltage curves were constructed for different solutions and bath temperatures. The polished parts were evaluated by stereomicroscopy, optical microscopy, atomic force microscopy, noncontact surface profilometry, and X‐ray diffraction. Pulse polishing was found useful in eliminating the erosion effects of gas bubbles in solution. Electropolishing in an ultrasonic bath was found useful when a rough, patterned surface is needed, e.g. for osseointegration purposes. Preliminary animal studies followed by histopathology indicated that the polished surfaces stimulated only a moderate body reaction, as desired in such applications. The pronounced dependence of the measured roughness values on both the measurement technique and scanned area should inspire the preparation of a new test‐method standard. © 2007 Wiley Periodicals, Inc. J Biomed Mater Res, 2007
Electronic structure and physical properties of MiXi clusters (M = B, Al; X = N, P; i = 1, 2, 3): Ab initio study
Authors: Ončák Milan , Srnec Martin
Published: June 2007

Ab initio calculations of structural stability and properties of selected IIIa–Va monomers (BN, BP, AlN, AlP), and dimers and trimers thereof are presented. It was demonstrated that multireference methods are needed for an appropriate description of the electronic structure of the diatomics under study. The energy differences between the quasi‐degenerated states of monomers were determined: in the range of 220–257 cm−1 for the X3Π → A1Σ+ in BN, 277–311 cm−1 for the X3Π → A3Σ− in AlN, and 344–768 cm−1 for the X3Σ− → A3Π in the AlP molecule. Many stable isomers of dimers and trimers were optimized and the structural patterns of the species were established. Although the (BN)i isomers prefer linear and cyclic geometries with a metal‐nonmetal sequence, the structure of the (AlN)i species is determined by strong NN interactions; the geometric patterns of the (BP)i and (AlP)i systems are more involved. The electronic structure and physical and chemical properties of the most stable dimers and trimers were calculated. As to electronic spectra, absorption bands in the visible and infrared region were found. The calculated low‐lying excited states, electron distribution and partially biradical character of structures along with the variety of stable isomers indicate high chemical reactivity of the studied IIIa–Va microclusters. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008
Assessment of theoretical methods for the calculation of methyl cation affinities
Authors: Wei Y. , Singer T. , Mayr H. , Sastry G. N. , Zipse H.
Published: June 2007

The methyl cation affinity (MCA; 298 K) of a variety of neutral and anionic bases has been examined computationally with a wide variety of theoretical methods. These include high‐level composite procedures such as W1, G3, G3B3, and G2, conventional ab initio methods such as CCSD(T) and MP2, as well as a selection of density functional theory (DFT) methods. Experimental results for a variety of small model systems are well reproduced with practically all these methods, and the performance of DFT based methods are far superior in comparison to their MP2 analogs for these small models. For larger model, systems including motifs frequently encountered in organocatalysts, the performance deteriorates somewhat for DFT methods, while it improves significantly for MP2, rendering the former methods unreliable for common organic bases. Thus, MP2 calculations performed in combination with basis sets such as 6‐31+G(2d, p) or larger, appear to offer a practical and reliable approach to compute MCAs of organic bases. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008
Intracellular phospholipase A2 expression and location in human macrophages: Influence of synthetic material surface chemistry
Authors: Dinnes Donna Lee M. , Santerre J. Paul , Labow Rosalind S.
Published: June 2007

Phospholipase A2 (PLA2) enzymes participate in a potent inflammatory pathway through the liberation of arachidonic acid upon hydrolysis of membrane glycerophospholipids. The presence of implanted polycarbonate‐urethane (PCNU) materials, used in several medical applications, has the ability to influence inflammatory responses of human macrophages that are recruited to a tissue‐material interface; however, the specific inflammatory pathways that are activated upon macrophage attachment to PCNU are largely unknown. Previous studies suggested the participation of PLA2 pathways in material degradation with the use of chemical inhibitors, such as aristolochic acid (ARIST), however not accurately defining the specific PLA2 enzymes involved. The current study aimed to establish specific groups of PLA2 involved in the macrophage foreign body response to PCNU. ARIST was assessed for specific effects on secretory PLA2 (sPLA2) protein expression and non‐specific effects on key proteins, β‐actin and monocyte‐specific esterase, implicated in the macrophage attack on PCNU materials. Macrophage attachment to PCNU materials induced increased intracellular expression of cytosolic PLA2 (cPLA2), but not sPLA2, relative to tissue culture polystyrene (TCPS) as detected by immunoblot analysis, demonstrating an early and delayed stimulation during the time course of increased cPLA2 protein expression. Laser scanning confocal microscopy images indicated a change in location of cPLA2 in macrophages adherent to PCNU surfaces compared to TCPS. This study has illustrated changes in macrophage cPLA2 expression in response to cell‐attachment to PCNU surfaces, demonstrating that the macrophage foreign body response to biomaterials induces a potent inflammatory pathway, which may lead to tissue damage near the site of material implantation. J. Cell. Physiol. 214:136–144, 2008. © 2007 Wiley‐Liss, Inc.
Alcohol biomarker analysis: simultaneous determination of 5‐hydroxytryptophol glucuronide and 5‐hydroxyindoleacetic acid by direct injection of urine using ultra‐performance liquid chromatography‐tandem mass spectrometry
Authors: Stephanson Nikolai , Helander Anders , Beck Olof
Published: June 2007

A direct ultra‐performance liquid chromatography‐tandem mass spectrometry method (UPLC‐MS/MS) for simultaneous measurement of urinary 5‐hydroxytryptophol glucuronide (GTOL) and 5‐hydroxyindoleacetic acid (5‐HIAA) was developed. The GTOL/5‐HIAA ratio is used as an alcohol biomarker with clinical and forensic applications. The method involved dilution of the urine sample with deuterated analogues (internal standards), reversed‐phase chromatography with gradient elution, electrospray ionisation and monitoring of two product ions per analyte in selected reaction monitoring mode. The measuring ranges were 6.7–10 000 nmol/l for GTOL and 0.07–100 µmol/l for 5‐HIAA. The intra‐ and inter‐assay imprecision, expressed as the coefficient of variation, was below 7%. Influence from ion suppression was noted for both compounds but was compensated for by the use of co‐eluting internal standards. The accuracy in analytical recovery of added substance to urine samples was 96 and 98%, respectively, for GTOL and 5‐HIAA. Method comparison with GC‐MS for GTOL in 25 authentic patient samples confirmed the accuracy of the method with a median ratio between methods (GC‐MS to UPLC‐MS/MS) of 1.14 (r2 = 0.975). The difference is explained by the fact that the GC‐MS method also measures unconjugated 5‐hydroxytryptophol naturally present in urine. The comparison with data for 5‐HIAA obtained by an HPLC method demonstrated a median ratio of 1.05 between the methods. The UPLC‐MS/MS method was capable of measuring endogenous GTOL and 5‐HIAA levels in urine, which agreed with the literature data. In conclusion, a fully validated and robust direct method for the routine measurement of urinary GTOL and 5‐HIAA was developed. Copyright © 2007 John Wiley & Sons, Ltd.
Analysis of intracellular short organic acid‐coenzyme A esters from actinomycetes using liquid chromatography‐electrospray ionization‐mass spectrometry
Authors: Park Je Won , Jung Won Seok , Park Sung Ryeol , Park Byoung Chul , Yoon Yeo Joon
Published: June 2007

A method employing silicone oil density centrifugation, solid‐phase extraction (SPE) cleanup, and LC‐ESI‐MS/MS analysis was developed for the rapid, selective, sensitive, and quantitative detection of an intracellular pool of short organic acid‐CoA esters in actinomycetes. The detection limit was determined to be approximately 0.8 pmol (1.2 ng/ml) for each standard CoA‐ester analyzed by the present LC‐ESI‐MS/MS method. A selected ion chromatogram for a typical fragment ion (m/z 428) specific to CoA‐esters enabled the detection of eight intracellular CoA‐esters involved in both primary and secondary metabolisms. The application of this method to bacterial metabolomic study is demonstrated by the profiling of the intracellular CoA‐ester pools in the wild‐type Streptomyces venezuelae strain producing polyketide antibiotics (methymycin and pikromycin), a polyketide synthase (PKS)‐deleted S. venezuelae mutant, and a S. venezuelae mutant expressing the heterologous PKS genes. By quantifying the individual CoA‐esterlevel in three different genotypes of the S. venezuela e strain, further insight could be gained into the role of CoA‐estersin polyketide biosynthesis. This analytical approach can be extended to the quantification of the size and composition of in vivo CoA‐ester pools in various microbes, and can provide a detailed understanding of the relationship between the in vivo CoA‐ester pool and the production of pharmaceutically important polyketides. Copyright © 2007 John Wiley & Sons, Ltd.